CN104425841B - A kind of non-aqueous organic high-voltage electrolyte additive, non-aqueous organic high-voltage electrolyte and lithium rechargeable battery - Google Patents
A kind of non-aqueous organic high-voltage electrolyte additive, non-aqueous organic high-voltage electrolyte and lithium rechargeable battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The embodiments of the invention provide the non-aqueous organic high-voltage electrolyte additive of one kind, shown in chemical structural formula such as formula (I), wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes one kind in alkyl, alkylene, alkynes base, aromatic radical, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；X, n, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, and y is 0~(2x+1) integer.Non-aqueous organic high-voltage electrolyte additive is oxidized in the charging process of high-voltage lithium ion secondary battery and decomposed, and promotes the formation of positive electrode surface protection film, can improve the cycle performance and discharge capacity of lithium rechargeable battery under high voltage.
Description
Technical field
The present invention relates to field of lithium ion secondary, more particularly to a kind of non-aqueous organic high-voltage electrolyte addition
Agent, non-aqueous organic high-voltage electrolyte and lithium rechargeable battery.
Background technology
With the extension of lithium rechargeable battery application field, including in recent years large-scale energy-accumulating power station, base station power etc. it is new
Application scenarios introducing, people become more urgent to the demand with high energy lithium ion secondary batteries.
In order to realize the high-energy of lithium rechargeable battery, typically by the operating voltage that improves lithium rechargeable battery or
High-energy positive electrode is researched and developed to realize.It has been reported that high-voltage anode material have LiCoPO4、LiNiPO4And
LiNi0.5Mn1.5O4Deng its charging voltage platform is close to or higher than 5V, but matching non-aqueous organic electrolyte is seriously delayed
In the development of high-voltage anode material, the application of lithium rechargeable battery is limited.Such as 1M LiPF6It is dissolved in carbonates
The non-aqueous organic electrolyte formed in solvent, the non-aqueous organic electrolyte is in high voltage（More than 4.5V voltages）In battery system,
Can occur side reaction in charging process with positive electrode and then be oxidized to decompose, produce CO2、H2The oxidation products such as O, CO2Generation
Security performance for battery causes potential threat；H2O generation causes LiPF6Self-catalysis occurs for/carbonate electrolyte system
Reaction, its intermediate product HF generation can cause LiMn1.5Ni0.5O4Material metal atom Mn, Ni dissolution, cause the knot of material
Structure is distorted or caved in.Ultimately result under the decline of lithium rechargeable battery cycle performance, volumetric expansion and discharge capacity
Drop, therefore high-voltage lithium ion secondary battery system can not be applied to.
The content of the invention
Add to solve the above problems, first aspect of the embodiment of the present invention aims to provide a kind of non-aqueous organic high-voltage electrolyte
Plus agent, non-aqueous organic high-voltage electrolyte additive is oxidized in the charging process of high-voltage lithium ion secondary battery to be divided
Solution, promotes the formation of positive electrode surface protection film, suppresses oxidation of the positive electrode to non-aqueous organic electrolyte solvents.This
Inventive embodiments second aspect aims to provide a kind of non-aqueous organic high voltage electricity comprising above-mentioned non-aqueous organic electrolysis solution additive
Liquid is solved, non-aqueous organic high-voltage electrolyte disclosure satisfy that 4.5V and above high-voltage lithium ion secondary battery are used.It is of the invention real
Apply a third aspect and aim to provide a kind of lithium rechargeable battery for including above-mentioned non-aqueous organic high-voltage electrolyte, lithium ion two
Primary cell has preferable cycle performance and discharge capacity under high voltages.
In a first aspect, the embodiments of the invention provide the non-aqueous organic high-voltage electrolyte additive of one kind, described non-aqueous have
The chemical structural formula such as formula of machine high-voltage electrolyte additive（Ⅰ）It is shown：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes alkyl, alkylene, alkynes base, virtue
One kind in perfume base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；x、
N, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, y
For 0~(2x+1) integer.
Preferably, the Ra、Rb、RcAnd RdThe alkene that the alkyl for being 1~8 for oxygen, carbon number, carbon number are 2~8
Haloalkyl that aromatic radical that alkynes base that base, carbon number are 2~8, carbon number are 6~8, carbon number are 1~8, carbon
The halogenated aromatic that the acetylenic halide alkyl or carbon number that haloalkene alkyl that atomicity is 2~8, carbon number are 2~8 are 6~8
Base.
Preferably, the Ra、Rb、RcAnd RdAlkylene that the alkyl for being 2~6 for carbon number, carbon number are 2~6,
Haloalkene alkyl that haloalkyl that alkynes base that carbon number is 2~6, carbon number are 2~6, carbon number are 2~6 and
Carbon number is one kind in 2~6 acetylenic halide alkyl.
Preferably, the chemical structural formula of non-aqueous organic high-voltage electrolyte additive is one in the f of I a of formula~formula I
Kind：
A kind of non-aqueous organic high-voltage electrolyte additive that first aspect of the embodiment of the present invention is provided can be used in lithium ion
In the preparation of secondary cell, lithium rechargeable battery is in charging process, and anodic potentials are constantly raised, non-aqueous organic high voltage
Electrolysis additive will promote the formation of positive electrode surface protection film；Diaphragm can cover the active sites on positive electrode surface
Point, blocks avtive spot on positive electrode surface to be contacted with the direct of non-aqueous organic electrolyte, suppress positive electrode has to non-aqueous
The oxidation of machine electrolyte, solves non-aqueous organic electrolyte of the prior art in high voltage（More than 4.5V voltages）Battery
Side reaction easily occurs with positive electrode in system causes the decline of lithium rechargeable battery cycle performance, volumetric expansion and electric discharge to be held
The problem of the problem of amount declines, so as to improve the cycle performance and discharge capacity of lithium rechargeable battery under high voltage.
Second aspect, the embodiments of the invention provide the non-aqueous organic high-voltage electrolyte of one kind, including：Lithium salts, non-aqueous have
Machine solvent and non-aqueous organic high-voltage electrolyte additive, the chemical structural formula of non-aqueous organic high-voltage electrolyte additive
Such as formula（Ⅰ）It is shown：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes alkyl, alkylene, alkynes base, virtue
One kind in perfume base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；x、
N, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, y
For 0~(2x+1) integer.
Preferably, the Ra、Rb、RcAnd RdThe alkene that the alkyl for being 1~8 for oxygen, carbon number, carbon number are 2~8
Haloalkyl that aromatic radical that alkynes base that base, carbon number are 2~8, carbon number are 6~8, carbon number are 1~8, carbon
The halogenated aromatic that the acetylenic halide alkyl or carbon number that haloalkene alkyl that atomicity is 2~8, carbon number are 2~8 are 6~8
Base.
Preferably, the Ra、Rb、RcAnd RdAlkylene that the alkyl for being 2~6 for carbon number, carbon number are 2~6,
Haloalkene alkyl that haloalkyl that alkynes base that carbon number is 2~6, carbon number are 2~6, carbon number are 2~6 and
Carbon number is one kind in 2~6 acetylenic halide alkyl.
Preferably, the chemical structural formula of non-aqueous organic high-voltage electrolyte additive is one in the f of I a of formula~formula I
Kind：
Wherein, lithium salts is selected from LiPF6、LiBF4、、LiClO4、Li（CF3SO2）2N、LiBOB（Di-oxalate lithium borate）、
LiDFOB（Difluorine oxalic acid boracic acid lithium）And LiPF4C2O4（Tetrafluoro oxalic acid lithium phosphate）In one or more.
One or more of the non-aqueous organic solvent in carbonic ester and its halo derivatives, ether, sulfone, nitrile, ionic liquid.
Preferably, the non-aqueous organic solvent is ethylene carbonate（Ethylene Carbonate, abbreviation EC）, propene carbonate
（Propylene Carbonate, abbreviation PC）, 1,2- vinylene carbonates（VC）, dimethyl carbonate（DMC）, carbonic acid diethyl
Ester（DEC）, methyl ethyl carbonate（EMC）, fluorinated ethylene carbonate（FEC）, gamma-butyrolacton, methyl ethyl ether, tetrahydrochysene furan
Mutter, the one or more in sulfolane, acetonitrile and (trimethyl fluoride sulfonyl) imines of 1- methyl -3- ethyl imidazol(e)s two.
Preferably, as mass fraction, non-aqueous organic high-voltage electrolyte additive accounts for non-aqueous organic high-voltage electrolyte
0.1~10%.
A kind of non-aqueous organic high-voltage electrolyte that second aspect of the embodiment of the present invention is provided contains above-mentioned non-aqueous organic high
Potential electrolysis solution additive, is used therefore, it is possible to meet 4.5V and above high-voltage lithium ion secondary battery, with excellent electrification
Stability is learned, the phenomenon that lithium rechargeable battery aerogenesis expands under high voltage can be avoided, and improve lithium ion two under high voltage
The cycle performance and discharge capacity of primary cell.
The third aspect, the embodiments of the invention provide a kind of lithium rechargeable battery, including：
Positive pole, positive pole includes to be embedded in or deviating from the positive electrode active materials of lithium ion；
Negative pole, negative pole includes to be embedded in or deviating from the negative active core-shell material of lithium ion；
Barrier film；
Non-aqueous organic high-voltage electrolyte, including：Lithium salts, non-aqueous organic solvent and non-aqueous organic high-voltage electrolyte addition
Agent, the chemical structural formula such as formula of non-aqueous organic high-voltage electrolyte additive（Ⅰ）It is shown：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes alkyl, alkylene, alkynes base, virtue
One kind in perfume base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；x、
N, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, y
For 0~(2x+1) integer.
Non-aqueous organic high-voltage electrolyte is as described in second aspect of the embodiment of the present invention, and here is omitted.
The lithium rechargeable battery that the third aspect of the embodiment of the present invention is provided has good cycle performance and discharge capacity.
A kind of non-aqueous organic high-voltage electrolyte additive that first aspect of the embodiment of the present invention is provided can be used in lithium ion
In the preparation of secondary cell, lithium rechargeable battery charging process in, anodic potentials are constantly raised, non-aqueous organic high electricity
Electrolysis additive is pressed to promote the formation of positive electrode surface protection film；Diaphragm can cover the active sites on positive electrode surface
Point, blocks avtive spot on positive electrode surface to be contacted with the direct of non-aqueous organic electrolyte, suppress positive electrode has to non-aqueous
The oxidation of machine electrolyte, solves non-aqueous organic electrolyte of the prior art in high voltage（More than 4.5V voltages）Battery
Easily occurring lasting side reaction in system with positive electrode causes the decline of lithium rechargeable battery cycle performance, volumetric expansion and puts
The problem of capacitance declines.A kind of non-aqueous organic high-voltage electrolyte that second aspect of the embodiment of the present invention is provided contains above-mentioned non-
The organic high-voltage electrolyte additive of water, is used therefore, it is possible to meet 4.5V and above high-voltage lithium ion secondary battery, with excellent
Different electrochemical stability, can avoid the phenomenon that lithium rechargeable battery aerogenesis expands under high voltage.The embodiment of the present invention the 3rd
The lithium rechargeable battery that aspect is provided has good cycle performance and discharge capacity.
Brief description of the drawings
Fig. 1 is obtained lithium rechargeable battery in embodiment one~five and comparative example in 3.5~4.9V voltage belts
Between in the range of charge and discharge cycles result figure is carried out under room temperature condition.
Embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, some improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
First aspect of the embodiment of the present invention aims to provide a kind of non-aqueous organic high-voltage electrolyte additive, and this is non-aqueous organic
High-voltage electrolyte additive is oxidized in the charging process of high-voltage lithium ion secondary battery and decomposed, and promotes positive electrode table
The formation of surface protective film, suppresses positive electrode to the oxidation of non-aqueous organic electrolyte, second aspect purport of the embodiment of the present invention
A kind of non-aqueous organic electrolyte for including above-mentioned non-aqueous organic electrolysis solution additive, non-aqueous organic high-voltage electrolyte are being provided
It disclosure satisfy that 4.5V and above high-voltage lithium ion secondary battery are used.The third aspect of the embodiment of the present invention aims to provide one kind and included
The lithium rechargeable battery of above-mentioned non-aqueous organic high-voltage electrolyte, the lithium rechargeable battery has preferable under high voltages
Cycle performance and discharge capacity.
In a first aspect, the embodiments of the invention provide the non-aqueous organic high-voltage electrolyte additive of one kind, described non-aqueous have
The chemical structural formula such as formula of machine high-voltage electrolyte additive（Ⅰ）It is shown：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes alkyl, alkylene, alkynes base, virtue
One kind in perfume base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；x、
N, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, y
For 0~(2x+1) integer.
Preferably, the Ra、Rb、RcAnd RdThe alkene that the alkyl for being 1~8 for oxygen, carbon number, carbon number are 2~8
Haloalkyl that aromatic radical that alkynes base that base, carbon number are 2~8, carbon number are 6~8, carbon number are 1~8, carbon
The halogenated aromatic that the acetylenic halide alkyl or carbon number that haloalkene alkyl that atomicity is 2~8, carbon number are 2~8 are 6~8
Base.
Preferably, the Ra、Rb、RcAnd RdAlkylene that the alkyl for being 2~6 for carbon number, carbon number are 2~6,
Haloalkene alkyl that haloalkyl that alkynes base that carbon number is 2~6, carbon number are 2~6, carbon number are 2~6 and
Carbon number is one kind in 2~6 acetylenic halide alkyl.
Preferably, the chemical structural formula of non-aqueous organic high-voltage electrolyte additive is one in the f of I a of formula~formula I
Kind：
A kind of non-aqueous organic high-voltage electrolyte additive that first aspect of the embodiment of the present invention is provided can be used in lithium ion
In the preparation of secondary cell, lithium rechargeable battery is in charging process, and anodic potentials are constantly raised, and high voltage additive can promote
Enter the formation of positive electrode surface protection film, the avtive spot on diaphragm covering positive electrode surface blocks positive electrode surface
Upper avtive spot is directly contacted with non-aqueous organic electrolyte, suppresses oxidation of the positive electrode to non-aqueous organic electrolyte,
The situation for avoiding lithium rechargeable battery volumetric expansion and discharge capacity from declining, so as to improve lithium ion secondary electricity under high voltage
The cycle performance and discharge capacity in pond.
Second aspect, the embodiments of the invention provide the non-aqueous organic high-voltage electrolyte of one kind, including：Lithium salts, non-aqueous have
Machine solvent and non-aqueous organic high-voltage electrolyte additive, the chemical structural formula of non-aqueous organic high-voltage electrolyte additive
Such as formula（Ⅰ）It is shown：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes alkyl, alkylene, alkynes base, virtue
One kind in perfume base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；x、
N, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, y
For 0~(2x+1) integer.
Preferably, the Ra、Rb、RcAnd RdThe alkene that the alkyl for being 1~8 for oxygen, carbon number, carbon number are 2~8
Haloalkyl that aromatic radical that alkynes base that base, carbon number are 2~8, carbon number are 6~8, carbon number are 1~8, carbon
The halogenated aromatic that the acetylenic halide alkyl or carbon number that haloalkene alkyl that atomicity is 2~8, carbon number are 2~8 are 6~8
Base.
Preferably, the Ra、Rb、RcAnd RdAlkylene that the alkyl for being 2~6 for carbon number, carbon number are 2~6,
Haloalkene alkyl that haloalkyl that alkynes base that carbon number is 2~6, carbon number are 2~6, carbon number are 2~6 and
Carbon number is one kind in 2~6 acetylenic halide alkyl.
Preferably, the chemical structural formula of non-aqueous organic high-voltage electrolyte additive is one in the f of I a of formula~formula I
Kind：
Wherein, lithium salts is selected from LiPF6、LiBF4、、LiClO4、、Li（CF3SO2）2N、LiBOB（Di-oxalate lithium borate）、
LiDFOB（Difluorine oxalic acid boracic acid lithium）And LiPF4C2O4（Tetrafluoro oxalic acid lithium phosphate）In one or more.Preferably, lithium salts exists
Final concentration of 0.1~1.5mol/L in non-aqueous organic electrolyte.
One or more of the non-aqueous organic solvent in carbonic ester and its halo derivatives, ether, sulfone, nitrile, ionic liquid.
Preferably, the non-aqueous organic solvent is ethylene carbonate（Ethylene Carbonate, abbreviation EC）, propene carbonate
（Propylene Carbonate, abbreviation PC）, 1,2- vinylene carbonates（VC）, dimethyl carbonate（DMC）, carbonic acid diethyl
Ester（DEC）, methyl ethyl carbonate（EMC）, fluorinated ethylene carbonate（FEC）, gamma-butyrolacton, methyl ethyl ether, tetrahydrochysene furan
Mutter, the one or more in sulfolane, acetonitrile or (trimethyl fluoride sulfonyl) imines of 1- methyl -3- ethyl imidazol(e)s two.
Preferably, as mass fraction, non-aqueous organic high-voltage electrolyte additive accounts for non-aqueous organic high-voltage electrolyte
0.1~10%.
It is highly preferred that as mass fraction, non-aqueous organic high-voltage electrolyte additive accounts for non-aqueous organic high voltage electrolysis
The 0.5~8% of liquid.
In order to meet the application demand of non-aqueous organic high-voltage electrolyte in certain situations, it is preferable that non-aqueous organic high
Potential electrolysis liquid also includes function additive, and the function additive is high temperature additive, flame-retardant additive or overcharging additive.
Preferably, the high temperature additive is selected from 1,3 propane sultones, fluoro ethylene carbonate (FEC) and tetrafluoro boric acid
Lithium (LiBF4) in one or more, the flame-retardant additive be selected from trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphorus
One or more in sour tributyl and phosphorus nitrile compounds, the one kind of the overcharging additive in biphenyl and cyclohexyl benzene
Or it is several.
It is highly preferred that as mass fraction, function additive accounts for the 0.1~10% of non-aqueous organic high-voltage electrolyte.
A kind of non-aqueous organic high-voltage electrolyte that second aspect of the embodiment of the present invention is provided contains above-mentioned non-aqueous organic high
Potential electrolysis solution additive, is used therefore, it is possible to meet 4.5V and above high-voltage lithium ion secondary battery, with excellent electrification
Stability is learned, the phenomenon that lithium rechargeable battery aerogenesis expands under high voltage can be avoided, and improve lithium ion two under high voltage
The cycle performance and discharge capacity of primary cell.
The third aspect, the embodiments of the invention provide a kind of lithium rechargeable battery, including：
Positive pole, positive pole includes to be embedded in or deviating from the positive electrode active materials of lithium ion；
Negative pole, negative pole includes to be embedded in or deviating from the negative active core-shell material of lithium ion；
Barrier film；
Non-aqueous organic high-voltage electrolyte, including：Lithium salts, non-aqueous organic solvent and non-aqueous organic high-voltage electrolyte addition
Agent, the chemical structural formula such as formula of non-aqueous organic high-voltage electrolyte additive（Ⅰ）It is shown：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group includes alkyl, alkylene, alkynes base, virtue
One kind in perfume base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；Wherein i, j, q and t are 0 or 1；x、
N, e and h are 1~4 integer, and f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, y
For 0~(2x+1) integer.
Non-aqueous organic high-voltage electrolyte is as described in second aspect of the embodiment of the present invention, and here is omitted.
Preferably, there is 4.5V and more than 4.5V voltages to put down during the discharge and recharge deintercalate lithium ions of the positive electrode active materials
Platform.It is highly preferred that the positive electrode active materials are selected from LiCoPO4、LiNiPO4And LiMn1.5Ni0.5O4In one or more.
A kind of form for lithium rechargeable battery that the third aspect of the embodiment of the present invention is provided is not limited, and can be square, circle
Post or soft-package battery, either takeup type or stacked, lithium rechargeable battery have good cycle performance and electric discharge
Capacity.
The preparation method of the lithium rechargeable battery is：Battery Pole Core is made in positive pole, negative pole and barrier film, is injected described non-
The organic high-voltage electrolyte of water, obtains lithium rechargeable battery.The preparation method of the lithium rechargeable battery is simple and feasible.
The advantage of the embodiment of the present invention will be illustrated partly in the following description, a part according to specification be it is aobvious and
It is clear to, or can be known by the implementation of the embodiment of the present invention.
Embodiment one
A kind of preparation method of non-aqueous organic high-voltage electrolyte additive, comprises the following steps：
In the glove box full of high-purity argon gas, hexafluoroisopropanol is taken, addition fills anhydrous tetrahydro furan（THF）Flask
In（Fill 2/5ths flasks）, with producing glove box after rubber plug sealing.Flask is transferred in ice bath, in nitrogen atmosphere protection
Under, with n-BuLi/hexane solution of long needle aspirate stoichiometric proportion, and it is slowly added to fill hexafluoroisopropanol and THF
Mixed solution in.Whole course of reaction strong mixing, nitrogen charging gas shielded, reaction stop after about 12 hours.Then inhaled with long syringe needle
Take tetrachloro silicane solution（SiCl4）, it is slowly added in the reacted mixed solution flask of the first step, hexafluoroisopropanol and tetrachloro silicon
The mol ratio of alkane is 4:1, reaction is reacted after nitrogen protection is carried out about 24 hours at ambient temperature to be stopped.Treat whole course of reaction
After end, filtered with sand mold funnel, remove byproduct of reaction filter residue（LiCl）, reclaim filtrate.Flask is removed with Rotary Evaporators
Middle remaining reaction dissolvent includes tetrahydrofuran and n-hexane, concentrates reaction product.Then, obtained enriched product is transferred to small
In number flask, sublimator is connected, and connect circulating condensing water.By oil bath heating, target production can be obtained at reduced pressure conditions
Thing crystal.Solid product recovery will be obtained, is dried in vacuo more than 12 hours and is stored in high-purity argon gas glove box at 110 DEG C and treat
With obtaining non-aqueous organic high-voltage electrolyte additive silicic acid-four-hexafluoro isopropyl ester shown in I a.
A kind of preparation method of non-aqueous organic high-voltage electrolyte, comprises the following steps：
By lithium salts LiPF6The lithium salt solution that 1mol/L is obtained in non-aqueous organic solvent is dissolved in, is stirred, whipping temp is 28
DEG C, non-aqueous organic solvent is ethylene carbonate（EC）And dimethyl carbonate（DMC）It is 1 by volume:What 2 ratio was mixed
Mixed solvent；
Non-aqueous organic high-voltage electrolyte additive silicic acid-four-hexafluoro isopropyl as shown in a of formula I is added to lithium salt solution
Non-aqueous organic electrolyte A is made, and as mass fraction, non-aqueous organic a of high-voltage electrolyte additive I accounts for non-aqueous in base ester, stirring
The 0.5% of organic electrolyte.
Below with the secondary soft-package battery of square coiled lithium ion（Model 423450-800mAh）Making exemplified by, it is right
The preparation method of lithium rechargeable battery of the embodiment of the present invention is illustrated.
The preparation of positive plate
The positive electrode active materials that the embodiment of the present invention is selected are LiMn1.5Ni0.5O4, by scattered positive electrode active materials,
Conductive agent hydrocarbon black powder material and binding agent PVDF are according to mass ratio 96:2:2 are mixed, and then add 1-METHYLPYRROLIDONE
（NMP）Solution is prepared into oil system slurry, and slurry finally is coated in into aluminium collector two sides, lithium ion secondary battery positive electrode is made
Piece.
The preparation of negative plate
By negative active core-shell material Delanium powder, binding agent carboxymethyl cellulose（CMC）, binding agent styrene butadiene
Rubber（SBR）Emulsion is according to mass ratio 97:1.5:1.5 are mixed, and are then added deionized water and are prepared into water system cathode size,
Slurry is finally coated in copper current collector two sides, lithium ion secondary battery negative pole piece is made, negative plate Capacity design is positive plate
1.2 times of capacity.
Non-aqueous organic high-voltage electrolyte uses obtained non-aqueous organic high-voltage electrolyte A above of the embodiment of the present invention.
The making of lithium rechargeable battery
The composite diaphragm that polypropylene and polyethylene are constituted is put between the anode pole piece of above-mentioned preparation and cathode pole piece, such as
Sandwich structure, then rolls into 423450 square battery pole pieces together, finally completes square winding soft-package battery, finally injects
Non-aqueous organic high-voltage electrolyte A, obtains lithium rechargeable battery A.
For lithium rechargeable battery, either square or cylinder or soft-package battery, also either takeup type is still folded
Chip, identical effect can be obtained using above-mentioned lithium rechargeable battery preparation method.
Embodiment two
A kind of preparation method of non-aqueous organic high-voltage electrolyte additive, comprises the following steps：
In the glove box full of high-purity argon gas, the high fluorine tert-butyl alcohol is taken, addition fills anhydrous tetrahydro furan（THF）Flask
In（Fill flask 2/5ths）, with producing glove box after rubber plug sealing.Flask is transferred in ice bath, in nitrogen atmosphere protection
Under, with n-BuLi/hexane solution of long needle aspirate stoichiometric proportion, and it is slowly added to fill the high fluorine tert-butyl alcohol and THF
Mixed solution in.Whole course of reaction strong mixing, nitrogen charging gas shielded, reaction stop after about 12 hours.Then inhaled with long syringe needle
Take tetrachloro silicane solution（SiCl4）, it is slowly added in the reacted mixed solution flask of the first step, high the fluorine tert-butyl alcohol and tetrachloro silicon
The mol ratio of alkane is 4:1, reaction is reacted after nitrogen protection is carried out about 24 hours at ambient temperature to be stopped.Treat whole course of reaction
After end, filtered with sand mold funnel, remove byproduct of reaction filter residue（LiCl）, reclaim filtrate.Flask is removed with Rotary Evaporators
Middle remaining reaction dissolvent includes tetrahydrofuran and n-hexane, concentrates reaction product.Then, obtained enriched product is transferred to small
In number flask, sublimator is connected, and connect circulating condensing water.By oil bath heating, target production can be obtained at reduced pressure conditions
Thing crystal.Solid product recovery will be obtained, is dried in vacuo more than 12 hours and is stored in high-purity argon gas glove box at 110 DEG C and treat
With obtaining non-aqueous organic high-voltage electrolyte additive silicic acid-four-high fluorine tert-butyl ester shown in I b.
A kind of preparation method of non-aqueous organic high-voltage electrolyte, comprises the following steps：
By lithium salts LiPF6The lithium salt solution that 1mol/L is obtained in non-aqueous organic solvent is dissolved in, is stirred, whipping temp is 28
DEG C, non-aqueous organic solvent is ethylene carbonate（EC）And dimethyl carbonate（DMC）It is 1 by volume:What 2 ratio was mixed
Mixed solvent；
Non-aqueous organic high-voltage electrolyte additive silicic acid-four-high fluorine uncle as shown in the b of formula I is added into lithium salt solution
Non-aqueous organic electrolyte B is made, and as mass fraction, non-aqueous organic b of high-voltage electrolyte additive I accounts for non-aqueous in butyl ester, stirring
The 1% of organic electrolysis solution additive.
The preparation of positive plate
By positive electrode active materials LiMn1.5Ni0.5O4, conductive agent hydrocarbon black powder material and binding agent PVDF dusty materials press again
According to mass ratio 96:2:2 are mixed, and then add 1-METHYLPYRROLIDONE（NMP）Solution is prepared into oil system slurry, finally will slurry
Material is coated in aluminium collector two sides, and lithium-ion secondary battery positive plate is made.
The preparation method of other lithium rechargeable batteries by be the same as Example one, is made lithium rechargeable battery B.
Embodiment three
The preparation method of non-aqueous organic high-voltage electrolyte additive of the present embodiment is identical with embodiment two；By embodiment
Tetrachloro silicane in two changes n-hexyl trichlorosilicane into, be made I c shown in non-aqueous organic high-voltage electrolyte additive just oneself
Base-three-high fluorine tert-butoxy silane, wherein, the mol ratio of high the fluorine tert-butyl alcohol and n-hexyl trichlorosilicane is 3:1.
A kind of preparation method of non-aqueous organic high-voltage electrolyte, comprises the following steps：
Lithium salts LiDFOB is dissolved in the lithium salt solution that 1mol/L is obtained in non-aqueous organic solvent, stirred, whipping temp is 20
DEG C, non-aqueous organic solvent is ethylene carbonate（EC）, propene carbonate（PC）And methyl ethyl carbonate（EMC）It is 2 by volume:1:
The mixed solvent that 5 ratio is mixed；
Non-aqueous organic high-voltage electrolyte additive n-hexyl-three-high fluorine as shown in the c of formula I is added into lithium salt solution
Non-aqueous organic electrolyte C, as mass fraction, non-aqueous organic c of high-pressure electrolysis solution additive I is made in tert-butoxy silane, stirring
Account for the 10% of non-aqueous organic electrolyte.
By the preparation method of the lithium rechargeable battery of be the same as Example one, lithium rechargeable battery C is made.
Example IV
The preparation method of non-aqueous organic high-voltage electrolyte additive of the present embodiment is identical with embodiment two；By embodiment
Silicon tetrachloride in two changes di-p-tolyl silicon dichloride into, and non-aqueous organic high-voltage electrolyte additive shown in I d is made
Two-p-methylphenyl-two-high fluorine tert-butoxy silane, wherein, the mol ratio of high the fluorine tert-butyl alcohol and di-p-tolyl silicon dichloride is
2:1。
A kind of preparation method of non-aqueous organic high-voltage electrolyte, comprises the following steps：
By lithium salts LiPF6The lithium salt solution that 1mol/L is obtained in non-aqueous organic solvent, LiPF are dissolved in LiDFOB6With
LiDFOB mol ratio is 4:1, stirring, whipping temp is 20 DEG C, and non-aqueous organic solvent is ethylene carbonate（EC）, propylene carbonate
Ester（PC）And methyl ethyl carbonate（EMC）It is 2 by volume:1:The mixed solvent that 5 ratio is mixed；
Non-aqueous organic high-voltage electrolyte additive as shown in the d of formula I is added into lithium salt solution, is stirred, is made non-aqueous
Organic electrolyte D, as mass fraction, non-aqueous organic d of high-pressure electrolysis solution additive I account for the 0.1% of non-aqueous organic electrolyte.
By the preparation method of the lithium rechargeable battery of be the same as Example one, lithium rechargeable battery D is made.
Embodiment five
The preparation method of non-aqueous organic high-voltage electrolyte additive of the present embodiment is identical with embodiment two；By embodiment
Silicon tetrachloride in two changes triethyl group silicon chloride into, and the tertiary fourth of non-aqueous organic high fluorine of high-voltage electrolyte additive shown in I e is made
Epoxide-triethyl silicane, wherein, the mol ratio of high the fluorine tert-butyl alcohol and triethyl group silicon chloride is 1:1.
A kind of preparation method of non-aqueous organic high-voltage electrolyte, comprises the following steps：
By lithium salts 0.8M LiPF6It is dissolved in 0.2M LiBOB in non-aqueous organic solvent, obtains 1mol/L lithium salt solution,
LiPF6Mol ratio with LiBOB is 4:1, then stir, whipping temp is 20 DEG C, and non-aqueous organic solvent is ethylene carbonate
（EC）And dimethyl carbonate（DMC）It is 1 by volume:The mixed solvent that 2 ratio is mixed；
Non-aqueous organic high-voltage electrolyte additive as shown in the e of formula I is added into lithium salt solution, is stirred, it is made non-aqueous
Organic electrolyte E, as mass fraction, non-aqueous organic e of high-pressure electrolysis solution additive I account for the 3% of non-aqueous organic electrolyte.
By the preparation method of the lithium rechargeable battery of be the same as Example one, lithium rechargeable battery E is made.
Embodiment six
The preparation method of non-aqueous organic high-voltage electrolyte additive of the present embodiment is identical with embodiment two；By embodiment
Silicon tetrachloride in two changes 17 fluorine decyltrichlorosilanes into, and non-aqueous organic high-voltage electrolyte additive shown in I f is made
Three-high fluorine decyl the silane of fluorine tert-butoxy 17, wherein, the mol ratio of the high fluorine tert-butyl alcohol and 17 fluorine decyltrichlorosilanes is 3:
1。
A kind of preparation method of non-aqueous organic high-voltage electrolyte, comprises the following steps：
By lithium salts 0.8M LiPF6With 0.2M LiBF4It is dissolved in non-aqueous organic solvent, obtains 1mol/L lithium salt solution, so
After stir, whipping temp be 20 DEG C, non-aqueous organic solvent is ethylene carbonate（EC）And dimethyl carbonate（DMC）It is by volume
1:The mixed solvent that 3 ratio is mixed；
Non-aqueous organic high-voltage electrolyte additive as shown in the f of formula I is added into lithium salt solution, is stirred, is made non-aqueous
Organic electrolyte F, as mass fraction, non-aqueous organic f of high-pressure electrolysis solution additive I account for the 0.5% of non-aqueous organic electrolyte.
By the preparation method of the lithium rechargeable battery of be the same as Example one, lithium rechargeable battery F is made.
Comparative example
By lithium salts LiPF6It is dissolved in non-aqueous organic solvent, obtains 1mol/L lithium salt solution, stir, is made non-aqueous organic
Electrolyte, non-aqueous organic solvent is ethylene carbonate（EC）And dimethyl carbonate（DMC）It is 1 by volume:2 ratio mixing and
Into mixed solvent.The non-aqueous organic electrolyte prepared is injected into the square coiled lithium ion made secondary soft
Bag battery（Model 423450-800mAh）In, it is designated as comparative example.
Obtained lithium rechargeable battery is experimental cell in above example and comparative example, in 3.5~4.9V electricity
Charge and discharge cycles are carried out under the conditions of room temperature in the interval range of position, test result is as shown in Figure 1.
From figure 1 it appears that with the addition of the non-aqueous organic electrolysis solution additive of first aspect of embodiment of the present invention offer
Performance of lithium-ion secondary battery be improved significantly, after 16 times circulate, the lithium rechargeable battery of embodiment 1~5 holds
Amount is held essentially constant, by contrast, and comparative example is not added with the lithium rechargeable battery of non-aqueous organic electrolysis solution additive
Capacity is begun to decline after circulation the 5th time, after circulation the 15th time, and lithium rechargeable battery in comparative example is from first
Beginning capacity is that 120mAh/g have decreased to 80mAh/g, and capacity have dropped 33.3%.This explanation, first aspect of the embodiment of the present invention is carried
The non-aqueous organic electrolysis solution additive supplied improves the cycle performance of lithium rechargeable battery under high voltages, and its reason is non-at this
The organic high-voltage electrolyte additive of water is oxidized in lithium rechargeable battery charging process and decomposed, and promotes positive electrode surface
The formation of diaphragm, the avtive spot on diaphragm covering positive electrode surface, block on positive electrode surface avtive spot with it is non-
The direct contact of water organic electrolyte, suppresses oxidation of the positive electrode to non-aqueous organic electrolyte, it is to avoid lithium ion secondary
The situation that battery volumetric expansion and discharge capacity decline, so as to improve the cycle performance of lithium rechargeable battery under high voltage.
Claims (10)
1. a kind of non-aqueous organic high-voltage electrolyte additive, it is characterised in that non-aqueous organic high-voltage electrolyte addition
Shown in the chemical structural formula of agent such as formula (I)：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group include alkyl, alkylene, alkynes base, aromatic radical,
One kind in haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；And Ra、Rb、RcAnd RdIn at least one
For oxygen, Ra、Rb、RcAnd RdIn at least one be aromatic radical or halogenated aromatic base；Wherein i, j, q and t are 1；X, n, e and h are 1
~4 integer, f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, and y is 0~(2x+
1) integer.
2. a kind of non-aqueous organic high-voltage electrolyte additive as claimed in claim 1, it is characterised in that the Ra、Rb、Rc
And RdAlkynes base that alkylene that the alkyl for being 1~8 for oxygen, carbon number, carbon number are 2~8, carbon number are 2~8,
Haloalkene alkyl that haloalkyl that aromatic radical that carbon number is 6~8, carbon number are 1~8, carbon number are 2~8, carbon
The halogenated aromatic base that the acetylenic halide alkyl or carbon number that atomicity is 2~8 are 6~8.
3. a kind of non-aqueous organic high-voltage electrolyte additive as claimed in claim 2, it is characterised in that the Ra、Rb、Rc
And RdAlkynes base that alkylene that the alkyl for being 2~6 for carbon number, carbon number are 2~6, carbon number are 2~6, carbon are former
In the acetylenic halide alkyl that the haloalkene alkyl and carbon number that haloalkyl that subnumber is 2~6, carbon number are 2~6 are 2~6
One kind.
4. a kind of non-aqueous organic high-voltage electrolyte additive as claimed in claim 1, it is characterised in that described non-aqueous organic
The chemical structural formula of high-voltage electrolyte additive is the d of formula I：
5. a kind of non-aqueous organic high-voltage electrolyte, it is characterised in that including：Lithium salts, non-aqueous organic solvent and non-aqueous organic high
Potential electrolysis solution additive, shown in the chemical structural formula such as formula (I) of non-aqueous organic high-voltage electrolyte additive：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group include alkyl, alkylene, alkynes base, aromatic radical,
One kind in haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；And Ra、Rb、RcAnd RdIn at least one
For oxygen, Ra、Rb、RcAnd RdIn at least one be aromatic radical or halogenated aromatic base；Wherein i, j, q and t are 1；X, n, e and h are 1
~4 integer, f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, and y is 0~(2x+
1) integer.
6. a kind of non-aqueous organic high-voltage electrolyte as claimed in claim 5, it is characterised in that the Ra、Rb、RcAnd RdFor
Alkynes base that alkylene that alkyl that oxygen, carbon number are 1~8, carbon number are 2~8, carbon number are 2~8, carbon atom
Haloalkene alkyl that haloalkyl that aromatic radical that number is 6~8, carbon number are 1~8, carbon number are 2~8, carbon number
For 2~8 acetylenic halide alkyl or carbon number be 6~8 halogenated aromatic base.
7. a kind of non-aqueous organic high-voltage electrolyte as claimed in claim 6, it is characterised in that the Ra、Rb、RcAnd RdFor carbon
Alkynes base that alkylene that alkyl that atomicity is 2~6, carbon number are 2~6, carbon number are 2~6, carbon number are 2
One kind in the acetylenic halide alkyl that the haloalkene alkyl and carbon number that~6 haloalkyl, carbon number are 2~6 are 2~6.
8. a kind of non-aqueous organic high-voltage electrolyte as claimed in claim 5, it is characterised in that non-aqueous organic high voltage
The chemical structural formula of electrolysis additive is the d of formula I：
9. a kind of non-aqueous organic high-voltage electrolyte as claimed in claim 5, it is characterised in that as mass fraction, described
Non-aqueous organic high-voltage electrolyte additive accounts for the 0.1~10% of non-aqueous organic electrolyte.
10. a kind of lithium rechargeable battery, it is characterised in that including：
Positive pole, positive pole includes to be embedded in or deviating from the positive electrode active materials of lithium ion；
Negative pole, negative pole includes to be embedded in or deviating from the negative active core-shell material of lithium ion；
Barrier film；
Non-aqueous organic high-voltage electrolyte, non-aqueous organic high-voltage electrolyte includes：Lithium salts, non-aqueous organic solvent and non-aqueous
Organic high-voltage electrolyte additive, shown in the chemical structural formula such as formula (I) of non-aqueous organic high-voltage electrolyte additive：
Wherein, Ra、Rb、RcAnd RdFor oxygen or organic group, the organic group include alkyl, alkylene, alkynes base, aromatic radical,
One kind in haloalkyl, haloalkene alkyl, acetylenic halide alkyl and halogenated aromatic base；And Ra、Rb、RcAnd RdIn at least one
For oxygen, Ra、Rb、RcAnd RdIn at least one be aromatic radical or halogenated aromatic base；Wherein i, j, q and t are 1；X, n, e and h are 1
~4 integer, f is 0~(2e+1) integer, and k is 0~(2h+1) integer, and m is 0~(2n+1) integer, and y is 0~(2x+
1) integer.
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| PCT/CN2014/078010 WO2015032215A1 (en) | 2013-09-05 | 2014-05-21 | Nonaqueous organic high-voltage electrolyte additive, nonaqueous organic high-voltage electrolyte and lithium ion secondary battery |
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| KR102112207B1 (en) * | 2017-01-26 | 2020-05-19 | 주식회사 엘지화학 | Non-aqueous electrolyte solution and lithium secondary battery comprising the same |
| KR102595175B1 (en) | 2018-03-14 | 2023-10-30 | 삼성전자주식회사 | Lithium secondary battery comprising the electrolyte containing trialkoxyalkylsilane compound |
| CN110994018B (en) * | 2019-12-20 | 2021-04-06 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| CN113161619B (en) * | 2021-04-29 | 2023-04-11 | 厦门大学 | Weak-polarity system electrolyte and application thereof |
| CN114583276B (en) * | 2022-03-10 | 2024-04-02 | 东莞凯德新能源有限公司 | High-wettability electrolyte and preparation method thereof |
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| DE10027626A1 (en) * | 2000-06-07 | 2001-12-13 | Merck Patent Gmbh | Electrolyte comprising a lithium containing inorganic or organic conductive salt contains a silane compound as an additive useful in electrochemical cells, batteries and secondary lithium batteries |
| CN101471455A (en) * | 2007-12-28 | 2009-07-01 | 张家港市国泰华荣化工新材料有限公司 | Additive for lithium ion battery non-aqueous electrolyte and non-aqueous electrolyte made by the same |
| JP2009245922A (en) * | 2008-03-13 | 2009-10-22 | Hitachi Maxell Ltd | Nonaqueous electrolyte secondary battery |
| JP2010033732A (en) * | 2008-07-25 | 2010-02-12 | Idemitsu Kosan Co Ltd | Coated solid electrolyte for lithium battery, and all-solid secondary battery using the same |
| JP5694833B2 (en) * | 2010-09-22 | 2015-04-01 | 富士フイルム株式会社 | Non-aqueous secondary battery electrolyte and lithium secondary battery |
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