CN104466244A - Non-aqueous organic high voltage electrolyte additive, non-aqueous organic high voltage electrolyte and lithium ion secondary battery - Google Patents

Non-aqueous organic high voltage electrolyte additive, non-aqueous organic high voltage electrolyte and lithium ion secondary battery Download PDF

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CN104466244A
CN104466244A CN201310416375.1A CN201310416375A CN104466244A CN 104466244 A CN104466244 A CN 104466244A CN 201310416375 A CN201310416375 A CN 201310416375A CN 104466244 A CN104466244 A CN 104466244A
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alkyl
water
organic high
voltage electrolyte
carbon number
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CN104466244B (en
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许梦清
邢丽丹
李伟善
杨同勇
安伟峰
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Honor Device Co Ltd
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Huawei Technologies Co Ltd
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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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A non-aqueous organic high voltage electrolyte additive, a non-aqueous organic high voltage electrolyte and a lithium ion secondary battery. An embodiment of the invention provides a non-aqueous organic high voltage electrolyte additive with a chemical structural formula shown as a formula (I), wherein R1 and R2 are independently selected from the group consisting of H, metal ions, alkyl, alkylene, alkyne, halogenated alkyl, halogenated alkylene, halogenated alkyne, aromatic base and halogenated aromatic base; the number of carbon atoms alkyl and alkyl halide is 1-20, the number of carbon atoms in the alkylene, alkyne, halogenated alkyl, halogenated alkylene and halogenated alkyne is 2-20, and the number of carbon atoms in the aromatic base and halogenated aromatic base ranges from 6 to 20. The non-aqueous organic high voltage electrolyte additive is oxidized and decomposed in the charging process of the lithium ion secondary battery, promotes the formation of cathode material surface protection film, and can improve the cycle performance and the discharge capacity of the lithium ion secondary battery under high voltage.

Description

A kind of non-water organic high-voltage electrolyte additive, the organic high-voltage electrolyte of non-water and lithium rechargeable battery
Technical field
The present invention relates to field of lithium ion secondary, particularly relate to a kind of non-water organic high-voltage electrolyte additive, the organic high-voltage electrolyte of non-water and lithium rechargeable battery.
Background technology
Along with the expansion of lithium rechargeable battery application, comprise large-scale energy-accumulating power station, base station in recent years and the introducing of new application scenarios such as to power, 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, operating voltage or research and development high-energy positive electrode generally by improving lithium rechargeable battery realize.The high-voltage anode material reported has LiCoPO 4, LiNiPO 4, and LiNi 0.5mn 1.5o 4deng, its charging voltage platform is close to or higher than 5V, but the non-water organic electrolyte matched seriously lags behind the development of high-voltage anode material, limits the application of lithium rechargeable battery.The electrolyte of lithium rechargeable battery conventional is at present mainly non-water organic electrolyte, such as 1MLiPF 6be dissolved in the non-water organic electrolyte formed in carbonate-based solvent, but this non-water organic electrolyte is in high voltage (more than 4.5V voltage) battery system, in charging process, meeting and positive electrode generation side reaction and then oxidized decomposition, produce CO 2, H 2the oxidation products such as O, CO 2generation potential threat is caused for the security performance of battery; H 2the generation of O makes LiPF 6/ carbonate electrolyte system generation self-catalyzed reaction, the production of its intermediate product HF can cause LiMn 1.5ni 0.5o 4the stripping of material metal ion Mn, Ni, causes the structure of material distortion occurs or caves in.Finally cause the decline of lithium rechargeable battery cycle performance, volumetric expansion and discharge capacity to decline, therefore cannot be applied to high-voltage lithium ion secondary battery system.
Summary of the invention
For solving the problem; embodiment of the present invention first aspect aims to provide the organic high-voltage electrolyte additive of a kind of non-water; the oxidized decomposition in the charging process of high-voltage lithium ion secondary battery of this non-water organic high-voltage electrolyte additive; thus form diaphragm on positive electrode surface, reduce positive pole to the oxidation of the organic high-voltage electrolyte of non-water.Embodiment of the present invention second aspect aims to provide a kind of organic high-voltage electrolyte of non-water comprising above-mentioned non-water organic electrolysis solution additive, and the organic high-voltage electrolyte of this non-water can meet 4.5V and above high-voltage lithium ion secondary battery is used.The embodiment of the present invention third aspect aims to provide a kind of lithium rechargeable battery comprising the organic high-voltage electrolyte of above-mentioned non-water, and lithium rechargeable battery has good cycle performance and discharge capacity under high voltages.
First aspect, embodiments provides the organic high-voltage electrolyte additive of a kind of non-water, and the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
Preferably, described metal ion is selected from Li +, Na +, Mg 2+and Al 3+in one.
Preferably, the carbon number of described alkyl and haloalkyl is 1 ~ 10, and the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 10, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 10.
Preferably, described R 1and R 2independently be selected from the one in ethyl, fluoroethyl groups, trifluoromethyl, fluorinated propyl, fluoro isopropyl, the fluoro tert-butyl group and benzyl.
The organic high-voltage electrolyte additive of a kind of non-water that embodiment of the present invention first aspect provides can be used in the preparation of lithium rechargeable battery, lithium rechargeable battery charging process in, anodic potentials constantly raises, high-voltage electrolyte additive will promote the formation of positive pole diaphragm, solve non-water organic electrolyte of the prior art lasting side reaction easily occurs with positive electrode in high voltage (more than 4.5V voltage) battery system to cause lithium rechargeable battery cycle performance to decline, the problem that volumetric expansion and discharge capacity decline, thus the cycle performance of lithium rechargeable battery and discharge capacity under raising high voltage.
Second aspect, embodiments provide the organic high-voltage electrolyte of a kind of non-water, comprise: the organic high-voltage electrolyte additive of lithium salts, non-aqueous organic solvent and non-water, the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
Preferably, described metal ion is selected from Li +, Na +, Mg 2+and Al 3+in one.
Preferably, the carbon number of described alkyl and haloalkyl is 1 ~ 10, and the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 10, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 10.
Preferably, described R 1and R 2independently be selected from the one in ethyl, fluoroethyl groups, trifluoromethyl, fluorinated propyl, fluoro isopropyl, the fluoro tert-butyl group and benzyl.
Wherein, lithium salts is selected from LiPF 6, LiBF 4, LiClO 4, LiBF 2c 2o 4, LiPF 4c 2o 4, Li(CF 3sO 2) 2n, LiBOB(di-oxalate lithium borate) and LiDFOB(difluorine oxalic acid boracic acid lithium) in one or more.
Non-aqueous organic solvent is selected from one or more in carbonic ester and halo derivatives thereof, ether, sulfone, nitrile, ionic liquid.Preferably, described non-aqueous organic solvent is ethylene carbonate (Ethylene Carbonate, be called for short EC), propene carbonate (Propylene Carbonate, be called for short PC), one or more in 1,2-vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), methyl ethyl ether, oxolane, sulfolane, acetonitrile and 1-methyl-3-ethyl imidazol(e) two (trimethyl fluoride sulfonyl) imines.
Preferably, by mass fraction, non-water organic high-voltage electrolyte additive accounts for 0.1 ~ 10% of the organic high-voltage electrolyte of non-water.
The organic high-voltage electrolyte of the non-water of the one that embodiment of the present invention second aspect provides contains the organic high-voltage electrolyte additive of above-mentioned non-water, therefore, it is possible to meet 4.5V and above high-voltage lithium ion secondary battery use, there is excellent chemical stability and electrochemical stability, the phenomenon that lithium rechargeable battery aerogenesis expands under high voltage can be avoided, and improve cycle performance and the discharge capacity of lithium rechargeable battery under high voltage.
The third aspect, embodiments provides a kind of lithium rechargeable battery, comprising:
Positive pole, positive pole comprises the positive electrode active materials that can embed or deviate from lithium ion;
Negative pole, negative pole comprises the negative active core-shell material that can embed or deviate from lithium ion;
Barrier film;
The organic high-voltage electrolyte of non-water, comprising: the organic high-voltage electrolyte additive of lithium salts, non-aqueous organic solvent and non-water, and the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
The organic high-voltage electrolyte of described non-water, as described in embodiment of the present invention second aspect, repeats no more herein.
The lithium rechargeable battery that the embodiment of the present invention third aspect provides has good cycle performance and discharge capacity.
The organic high-voltage electrolyte additive of a kind of non-water that embodiment of the present invention first aspect provides can be used in the preparation of lithium rechargeable battery, lithium rechargeable battery charging process in, anodic potentials constantly raises, high-voltage electrolyte additive will promote the formation of positive pole diaphragm, solve non-water organic electrolyte of the prior art lasting side reaction easily occurs with positive electrode in high voltage (more than 4.5V voltage) battery system to cause lithium rechargeable battery cycle performance to decline, the problem that volumetric expansion and discharge capacity decline, thus the cycle performance of lithium rechargeable battery and discharge capacity under raising high voltage.The organic high-voltage electrolyte of the non-water of the one that embodiment of the present invention second aspect provides contains the organic high-voltage electrolyte additive of above-mentioned non-water, therefore, it is possible to meet 4.5V and above high-voltage lithium ion secondary battery use, there is excellent chemical stability and electrochemical stability, the phenomenon that lithium rechargeable battery aerogenesis expands under high voltage can be avoided, and improve cycle performance and the discharge capacity of lithium rechargeable battery under high voltage.The lithium rechargeable battery that the embodiment of the present invention third aspect provides has good cycle performance and discharge capacity.
Accompanying drawing explanation
Fig. 1 is that lithium rechargeable battery obtained in embodiment one ~ tetra-and comparative example carries out charge and discharge cycles result figure under room temperature condition within the scope of 3.5 ~ 4.9V potential region.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect aims to provide the organic high-voltage electrolyte additive of a kind of non-water, this non-water organic high-voltage electrolyte additive in the charging process of high-voltage lithium ion secondary battery by oxidized decomposition, thus form diaphragm on positive electrode surface, reduce positive electrode to the oxidation of the organic high-voltage electrolyte of non-water, embodiment of the present invention second aspect aims to provide a kind of non-water organic electrolyte comprising above-mentioned non-water organic electrolysis solution additive, the organic high-voltage electrolyte of this non-water can meet 4.5V and above high-voltage lithium ion secondary battery is used.The embodiment of the present invention third aspect aims to provide a kind of lithium rechargeable battery comprising the organic high-voltage electrolyte of above-mentioned non-water, and this lithium rechargeable battery has good cycle performance and discharge capacity under high voltages.
First aspect, embodiments provides the organic high-voltage electrolyte additive of a kind of non-water, and the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
Preferably, described metal ion is selected from Li +, Na +, Mg 2+and Al 3+in one.
Preferably, the carbon number of described alkyl and haloalkyl is 1 ~ 10, and the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 10, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 10.
Preferably, described R 1and R 2independently be selected from the one in ethyl, fluoroethyl groups, trifluoromethyl, fluorinated propyl, fluoro isopropyl, the fluoro tert-butyl group and benzyl.
The organic high-voltage electrolyte additive of a kind of non-water that embodiment of the present invention first aspect provides can be used in the preparation of lithium rechargeable battery, lithium rechargeable battery is in charging process, high-voltage electrolyte additive can oxidized decomposition, promote the formation of positive electrode surface protection film, solve the organic high-voltage electrolyte of non-water of the prior art lasting side reaction easily occurs with positive electrode in high voltage (more than 4.5V voltage) battery system to cause lithium rechargeable battery cycle performance to decline, the problem that volumetric expansion and discharge capacity decline, thus the cycle performance of lithium rechargeable battery and discharge capacity under raising high voltage.
Second aspect, embodiments provide the organic high-voltage electrolyte of a kind of non-water, comprise: the organic high-voltage electrolyte additive of lithium salts, non-aqueous organic solvent and non-water, the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
Wherein, lithium salts is selected from LiPF 6, LiBF 4, LiClO 4, LiBF 2c 2o 4, LiPF 4c 2o 4, Li(CF 3sO 2) 2n, LiBOB(di-oxalate lithium borate) and LiDFOB(difluorine oxalic acid boracic acid lithium) in one or more.Preferably, the final concentration of lithium salts in non-water organic electrolyte is 0.1 ~ 1.5mol/L.
Non-aqueous organic solvent is selected from one or more in carbonic ester and halo derivatives thereof, ether, sulfone, nitrile, ionic liquid.Preferably, described non-aqueous organic solvent is ethylene carbonate (Ethylene Carbonate, be called for short EC), propene carbonate (Propylene Carbonate, be called for short PC), one or more in 1,2-vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC), gamma-butyrolacton (GBL), methyl ethyl ether, oxolane, sulfolane, acetonitrile or 1-methyl-3-ethyl imidazol(e) two (trimethyl fluoride sulfonyl) imines.
Preferably, by mass fraction, non-water organic high-voltage electrolyte additive accounts for 0.1 ~ 10% of the organic high-voltage electrolyte of non-water.
More preferably, by mass fraction, non-water organic high-voltage electrolyte additive accounts for 0.2 ~ 8% of the organic high-voltage electrolyte of non-water.
In order to meet the organic high-voltage electrolyte of non-water application demand in certain situations, preferably, the organic high-voltage electrolyte of non-water also comprises function additive, and described function additive is high temperature additive, flame-retardant additive or overcharging additive.
More preferably, described high temperature additive is selected from 1,3 propane sultones, ethylene carbonate (FEC) and LiBF4 (LiBF 4) in one or more, described flame-retardant additive is selected from one or more in trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and phosphonitrile compounds, and described overcharging additive is selected from one or more in biphenyl and cyclohexyl benzene.
More preferably, by mass fraction, function additive accounts for 0.1 ~ 10% of the organic high-voltage electrolyte of non-water.
The organic high-voltage electrolyte of the non-water of the one that embodiment of the present invention second aspect provides contains the organic high-voltage electrolyte additive of above-mentioned non-water, therefore, it is possible to meet 4.5V and above high-voltage lithium ion secondary battery use, there is excellent chemical stability and electrochemical stability, the phenomenon that lithium rechargeable battery aerogenesis expands under high voltage can be avoided, and improve cycle performance and the discharge capacity of lithium rechargeable battery under high voltage.
The third aspect, embodiments provides a kind of lithium rechargeable battery, comprising:
Positive pole, positive pole comprises the positive electrode active materials that can embed or deviate from lithium ion;
Negative pole, negative pole comprises the negative active core-shell material that can embed or deviate from lithium ion;
Barrier film;
The organic high-voltage electrolyte of non-water, comprising: the organic high-voltage electrolyte additive of lithium salts, non-aqueous organic solvent and non-water, and the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
The organic high-voltage electrolyte of described non-water, as described in embodiment of the present invention second aspect, repeats no more herein.
Preferably, described positive electrode active materials has at 4.5V and more than 4.5V removal lithium embedded platform when discharge and recharge deintercalate lithium ions.More preferably, described positive electrode active materials is selected from LiCoPO 4, LiNiPO 4and LiNi 0.5mn 1.5o 4in one or more.
The form of a kind of lithium rechargeable battery that the embodiment of the present invention third aspect provides is not limit, can be square, cylinder or soft-package battery, be no matter takeup type or stacked, this lithium rechargeable battery has high-energy-density, good cycle performance and discharge capacity.
The preparation method of this lithium rechargeable battery is: positive pole, negative pole and barrier film are made Battery Pole Core, injects the organic high-voltage electrolyte of described non-water, obtains lithium rechargeable battery.Preparation method's simple and feasible of described lithium rechargeable battery.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can be known by the enforcement of the embodiment of the present invention.
Embodiment one
A preparation method for the organic high-voltage electrolyte additive of non-water, comprises the following steps:
In the glove box being full of high-purity argon gas, get diethyl phosphite (DEP), add in the flask filling anhydrous tetrahydro furan (THF) and (fill flask 2/5ths), produce glove box with after rubber plug sealing.Flask is proceeded in ice bath; under nitrogen atmosphere protection; with the n-BuLi/hexane solution of long needle aspirate stoichiometric proportion; and slowly add and fill in the mixed solution of DEP and THF, the ratio of the mole of the n-BuLi in the mole of described diethyl phosphite and described n-BuLi/hexane solution is 1:1.Whole course of reaction strong mixing, inflated with nitrogen protection, react after about 12 hours and stop.After reaction terminates, with vacuum line extraction solvent THF and n-hexane reaction dissolvent, obtain the non-water organic high-voltage electrolyte additive diethyl phosphorous acid lithium shown in I a.By the diethyl phosphorous acid lithium solid product drying more than 12 hours at 110 DEG C obtained, and deposit in high-purity argon gas glove box stand-by.
A preparation method for the organic high-voltage electrolyte of non-water, comprises the following steps:
By lithium salts LiPF 6be dissolved in non-aqueous organic solvent the lithium salt solution making 1mol/L, stir, whipping temp is 28 DEG C, the mixed solvent that the ratio of non-aqueous organic solvent to be ethylene carbonate (EC) and dimethyl carbonate (DMC) be by volume 3:7 mixes; Add such as formula the non-water organic high-voltage electrolyte additive diethyl phosphorous acid lithium shown in I a in lithium salt solution, stir, obtained non-water organic electrolyte A, by mass fraction, non-water organic electrolysis solution additive I a accounts for 0.3% of non-water organic electrolyte.
Be made as example below with square coiled lithium ion secondary soft-package battery (model is for 423450-800mAh), the preparation method of embodiment of the present invention lithium rechargeable battery is described.
The preparation of positive plate
The positive electrode active materials that the embodiment of the present invention is selected is LiMn 1.5ni 0.5o 4scattered positive electrode active materials, conductive agent hydrocarbon black powder material and binding agent PVDF are mixed according to mass ratio 96:2:2, then add 1-METHYLPYRROLIDONE (NMP) solution and be prepared into oil system slurry, finally slurry is coated in aluminium collector two sides, makes lithium-ion secondary battery positive plate.
The preparation of negative plate
Negative active core-shell material Delanium powder, binding agent carboxymethyl cellulose (CMC), binding agent styrene butadiene ribber (SBR) emulsion are mixed according to mass ratio 97:1.5:1.5, then add deionized water and be prepared into water system cathode size, finally slurry is coated in copper current collector two sides, make lithium ion secondary battery negative pole sheet, negative plate Capacity design is 1.2 times of positive plate capacity.
The organic high-voltage electrolyte A of non-water that the organic high-voltage electrolyte of non-water adopts the embodiment of the present invention obtained above.
The making of lithium rechargeable battery
Between the anode pole piece that the composite diaphragm that polypropylene and polyethylene form is put into above-mentioned preparation and cathode pole piece, as sandwich structure, then 423450 square battery pole pieces are rolled into together, finally complete square winding soft-package battery, finally inject the organic high-voltage electrolyte A of non-water, obtain lithium rechargeable battery A.
For lithium rechargeable battery, no matter be square or cylinder or soft-package battery, be also no matter takeup type or stacked, adopt above-mentioned lithium rechargeable battery preparation method can obtain identical effect.
Embodiment two
The preparation method of the organic high-voltage electrolyte additive of a kind of non-water is with embodiment one.
A preparation method for the organic high-voltage electrolyte of non-water, comprises the following steps:
By lithium salts LiPF 4c 2o 4be dissolved in non-aqueous organic solvent the lithium salt solution making 1.2mol/L, stir, whipping temp is 20 DEG C, the mixed solvent that the ratio that non-aqueous organic solvent is ethylene carbonate (EC), gamma-butyrolacton (GBL), dimethyl carbonate (DMC) and diethyl carbonate (DEC) are 2:1:3:5 by volume mixes;
Add such as formula the non-water organic high-voltage electrolyte additive diethyl phosphorous acid lithium shown in I a in lithium salt solution, stir, obtained non-water organic electrolyte B, by mass fraction, non-water organic electrolysis solution additive I a, account for 1% of non-water organic electrolyte.
The preparation of positive plate
By positive electrode active materials LiMn 1.5ni 0.5o 4, conductive agent hydrocarbon black powder material and binding agent PVDF mix according to mass ratio 96:2:2, then add 1-METHYLPYRROLIDONE (NMP) solution and be prepared into oil system slurry, finally slurry is coated in aluminium collector two sides, makes lithium-ion secondary battery positive plate.
Other is by the manufacture method with the lithium rechargeable battery of embodiment one, obtained lithium rechargeable battery B.
Embodiment three
In the glove box being full of high-purity argon gas, get dibenzyl phosphite, add (2/5ths flasks) in the flask filling anhydrous tetrahydro furan (THF), produce glove box with after rubber plug sealing.Flask is proceeded in ice bath; under nitrogen atmosphere protection; with the n-BuLi/hexane solution of long needle aspirate stoichiometric proportion; and slowly adding in the mixed solution filling dibenzyl phosphite and THF, the ratio of the mole of the n-BuLi in the mole of described dibenzyl phosphite and described n-BuLi/hexane solution is 1:1.Whole course of reaction strong mixing, inflated with nitrogen protection, react after about 12 hours and stop.After reaction terminates, with vacuum line extraction solvent THF and n-hexane reaction dissolvent, obtain the non-water organic high-voltage electrolyte additive dibenzyl hydrogen phosphite lithium shown in I b.By the dibenzyl hydrogen phosphite lithium solid product drying more than 12 hours at 110 DEG C obtained, and deposit in high-purity argon gas glove box stand-by.
Lithium salts LiDFOB is dissolved in non-aqueous organic solvent the lithium salt solution obtaining 1mol/L, stir, whipping temp is 20 DEG C, and non-aqueous organic solvent is ethylene carbonate (EC), propene carbonate (PC) and methyl ethyl carbonate (EMC) are mixed solvent that the ratio of 2:1:5 mixes by volume; Add such as formula the non-water organic high-voltage electrolyte additive dibenzyl hydrogen phosphite lithium shown in I b in lithium salt solution, stir, obtained non-water organic electrolyte C, by mass fraction, non-water organic electrolysis solution additive I b accounts for 5% of non-water organic electrolyte.
Lithium rechargeable battery preparation method is with embodiment one, and battery is designated as C.
Embodiment four
In the glove box being full of high-purity argon gas, get two (2,2,2-trifluoroethyl) phosphite ester, add (2/5ths flasks) in the flask filling anhydrous tetrahydro furan (THF), produce glove box with after rubber plug sealing.Flask is proceeded in ice bath; under nitrogen atmosphere protection; with the n-BuLi/hexane solution of long needle aspirate stoichiometric proportion; and slowly add and fill (2; 2,2-trifluoroethyl) phosphite ester and THF mixed solution in, described two (2; 2,2-trifluoroethyl) ratio of mole of n-BuLi in the mole of phosphite ester and described n-BuLi/hexane solution is 1:1.Whole course of reaction strong mixing, inflated with nitrogen protection, react after about 12 hours and stop.After reaction terminates, with vacuum line extraction solvent THF and n-hexane reaction dissolvent, obtain two (2,2,2-trifluoroethyl) the phosphorous acid lithium of the organic high-voltage electrolyte additive of non-water shown in I c.By two (2,2,2-trifluoroethyl) the phosphorous acid lithium solid products drying more than 12 hours at 110 DEG C obtained, and deposit in high-purity argon gas glove box stand-by.
By lithium salts 0.5mol/L LiDFOB and 0.6mol/L LiPF 6be dissolved in non-aqueous organic solvent the lithium salt solution obtaining 1.1mol/L, stir, whipping temp is 28 DEG C, and non-aqueous organic solvent is ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) are mixed solvent that the ratio of 2:3:5 mixes by volume; Add such as formula two (2,2,2-trifluoroethyl) the phosphorous acid lithium of the organic high-voltage electrolyte additive of the non-water shown in I c in lithium salt solution, stir, obtained non-water organic electrolyte D, by mass fraction, non-water organic electrolysis solution additive I b accounts for 0.5% of non-water organic electrolyte.
Lithium rechargeable battery preparation method is with embodiment one, and battery is designated as D.
Embodiment five
The preparation method of the organic high-voltage electrolyte additive of a kind of non-water is with embodiment one.
A preparation method for the organic high-voltage electrolyte of non-water, comprises the following steps:
By lithium salts 0.3mol/L LiPF 4c 2o 4with 0.3mol/L LiPF 6be dissolved in non-aqueous organic solvent the lithium salt solution making 0.6mol/L, stir, whipping temp is 28 DEG C, and non-aqueous organic solvent is ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) are mixed solvent that the ratio of 2:4:4 mixes by volume;
Add such as formula the non-water organic high-voltage electrolyte additive diethyl phosphorous acid lithium shown in I a in lithium salt solution, stir, obtained non-water organic electrolyte E, by mass fraction, non-water organic electrolysis solution additive I a, account for 10% of non-water organic electrolyte.
The preparation of positive plate
By positive electrode active materials LiMn 1.5ni 0.5o 4, conductive agent hydrocarbon black powder material and binding agent PVDF mix according to mass ratio 96:2:2, then add 1-METHYLPYRROLIDONE (NMP) solution and be prepared into oil system slurry, finally slurry is coated in aluminium collector two sides, makes lithium-ion secondary battery positive plate.
Other is by the manufacture method with the lithium rechargeable battery of embodiment one, obtained lithium rechargeable battery E.
Comparative example
By lithium salts LiPF 6be dissolved in non-aqueous organic solvent, obtain the lithium salt solution of 1mol/L, stir, obtained non-water organic electrolyte, non-aqueous organic solvent is ethylene carbonate (EC) and dimethyl carbonate (DMC) is mixed solvent that 3:7 is mixed with by volume.The non-water organic electrolyte prepared is injected in the square coiled lithium ion secondary soft-package battery (model is 423450,800mAh) made, is designated as comparative example.
Lithium rechargeable battery obtained in above embodiment one ~ tetra-and comparative example is experimental cell, and within the scope of 3.5 ~ 4.9V potential region, carry out 0.1C charge and discharge cycles under room temperature condition, test result as shown in Figure 1.As can be seen from Figure 1, do not add carry out of comparative example's lithium rechargeable battery with circulation of the organic high-voltage electrolyte additive of non-water, capability retention deep fades, after 20 charge and discharge cycles, capability retention only has 82%, illustrates that the organic high-voltage electrolyte of non-water is in charging process, in the oxidized decomposition of side of the positive electrode, thus causing lithium rechargeable battery system to be destroyed, chemical property is continuous worsening.The test result of embodiment one ~ tetra-illustrates, adding of the organic high-voltage electrolyte additive of non-water, significantly improves the high voltage applications performance of lithium rechargeable battery.What the organic high-voltage electrolyte additive of non-water was described adds the formation promoting positive electrode surface diaphragm; the organic high-voltage electrolyte of non-water is prevented to contact with the direct of positive electrode; inhibit the side reaction of the oxidized decomposition of the organic high-voltage electrolyte of non-water, so experimental cell has higher capability retention.

Claims (10)

1. the organic high-voltage electrolyte additive of non-water, is characterized in that, the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
2. the organic high-voltage electrolyte additive of a kind of non-water as claimed in claim 1, it is characterized in that, described metal ion is selected from Li +, Na +, Mg 2+and Al 3+in one.
3. the organic high-voltage electrolyte additive of a kind of non-water as claimed in claim 1, it is characterized in that, the carbon number of described alkyl and haloalkyl is 1 ~ 10, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 10, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 10.
4. the organic high-voltage electrolyte additive of a kind of non-water as claimed in claim 1, is characterized in that, described R 1and R 2independently be selected from the one in ethyl, fluoroethyl groups, trifluoromethyl, fluorinated propyl, fluoro isopropyl, the fluoro tert-butyl group and benzyl.
5. the organic high-voltage electrolyte of non-water, is characterized in that, comprising: the organic high-voltage electrolyte additive of lithium salts, non-aqueous organic solvent and non-water, and the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
6. the organic high-voltage electrolyte of a kind of non-water as claimed in claim 5, it is characterized in that, described metal ion is selected from Li +, Na +, Mg 2+and Al 3+in one.
7. the organic high-voltage electrolyte of a kind of non-water as claimed in claim 5, it is characterized in that, the carbon number of described alkyl and haloalkyl is 1 ~ 10, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 10, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 10.
8. the organic high-voltage electrolyte of a kind of non-water as claimed in claim 5, is characterized in that, described R 1and R 2independently be selected from the one in ethyl, fluoroethyl groups, trifluoromethyl, fluorinated propyl, fluoro isopropyl, the fluoro tert-butyl group and benzyl.
9. the organic high-voltage electrolyte of a kind of non-water as claimed in claim 5, is characterized in that, by mass fraction, described non-water organic high-voltage electrolyte additive accounts for 0.1 ~ 10% of non-water organic electrolyte.
10. a lithium rechargeable battery, is characterized in that, comprising:
Positive pole, positive pole comprises the positive electrode active materials that can embed or deviate from lithium ion;
Negative pole, negative pole comprises the negative active core-shell material that can embed or deviate from lithium ion;
Barrier film;
The organic high-voltage electrolyte of non-water, the organic high-voltage electrolyte of described non-water comprises: the organic high-voltage electrolyte additive of lithium salts, non-aqueous organic solvent and non-water, and the chemical structural formula of the organic high-voltage electrolyte additive of described non-water is such as formula shown in (I):
Wherein, R 1and R 2independently be selected from the one in H, metal ion, alkyl, alkylene, alkynes base, haloalkyl, haloalkene alkyl, acetylenic halide alkyl, aromatic radical, halogenated aromatic base, the carbon number of described alkyl and haloalkyl is 1 ~ 20, the carbon number of described alkylene, alkynes base, haloalkene alkyl and acetylenic halide alkyl is 2 ~ 20, and the carbon number of described aromatic radical and halogenated aromatic base is 6 ~ 20.
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