CN104300174A - Non-aqueous electrolyte of lithium ion battery and lithium ion battery - Google Patents

Non-aqueous electrolyte of lithium ion battery and lithium ion battery Download PDF

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Publication number
CN104300174A
CN104300174A CN201410534841.0A CN201410534841A CN104300174A CN 104300174 A CN104300174 A CN 104300174A CN 201410534841 A CN201410534841 A CN 201410534841A CN 104300174 A CN104300174 A CN 104300174A
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lithium ion
carbonate
aqueous electrolyte
electrolyte
ion battery
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石桥
胡时光
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Priority to CN201410534841.0A priority Critical patent/CN104300174A/en
Priority to PCT/CN2014/089138 priority patent/WO2016054843A1/en
Publication of CN104300174A publication Critical patent/CN104300174A/en
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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
    • 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
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

The invention relates to non-aqueous electrolyte of a lithium ion battery. The non-aqueous electrolyte comprises an organic solvent, lithium salt and a phosphate-ester type compound. The invention also discloses the lithium ion battery. The non-aqueous electrolyte has the beneficial effect that the high-temperature storage performance and the circulating performance of the battery are improved.

Description

A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery
Technical field
The present invention relates to the battery of battery electrolytic solution and this electrolyte of use, particularly a kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery.
Background technology
In recent years, along with development and the market demand of electronic technology, consumer to portable type electronic product as volume, weight, the function of camera, Digital Video, mobile phone, notebook computer etc. and have higher requirement useful life.Therefore, develop the power supply product that matches with portable type electronic product, especially develop high-energy-density, active demand that the secondary cell of long-life and high security is industry development.
Compared with lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery, because of features such as its energy density is large, operating voltage is high, the life-span is long, environmental protections, is widely used in portable type electronic product.
Lithium ion battery forms primarily of positive and negative electrode, electrolyte and barrier film.Positive pole is mainly containing the transition metal oxide of lithium, and negative pole is Carbon Materials mainly.Because the average discharge volt of lithium ion battery is about 3.6-3.7V, need to select electrolyte component stable in the charging/discharging voltages of 0-4.2V.For this reason, lithium ion battery uses the organic solvent mixed liquor being dissolved with lithium salts as electrolyte.Preferred organic solvent should have high ionic conductivity, high dielectric constant and low viscosity.But single organic solvent is difficult to meet these requirements simultaneously, so, generally using the organic solvent of high-k and the low viscous organic solvent mixed liquor solvent as lithium-ion battery electrolytes.Such as: lithium ion battery uses the mixture comprising cyclic carbonate solvents (as ethylene carbonate) and linear carbonates solvent (as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate) as solvent usually, and lithium hexafluoro phosphate is as the electrolyte of solute.
Lithium ion battery is in initial charge process, and electrolyte and carbon anode surface react, and produces alkyl lithium carbonates, Li 2cO 3, Li 2the materials such as O, LiOH, thus form one deck passivating film at carbon anode surface, this passivating film is referred to as solid electrolyte interface (SEI) film.Owing to no matter being charging or electric discharge, lithium ion must pass through this layer of SEI film, so the performance of SEI film determines many performances (as cycle performance, high-temperature behavior, high rate performance) of battery.SEI film, after initial charge is formed, can stop the further decomposition of electrolyte solvent, and form ion channel in charge and discharge cycles subsequently.But along with the carrying out of discharge and recharge, the expansion that electrode repeats and contraction SEI film may break or dissolve gradually, the anode thereupon exposed continues to react with electrolyte, produce gas simultaneously, thus increase the interior pressure of battery, and significantly reduce the cycle life of battery.Especially battery stores under the high temperature conditions and carries out charge and discharge cycles under the high temperature conditions, and SEI film is more easily destroyed, thus causes battery bulging and cycle performance obviously to decline.In addition, in charge and discharge process, electrolyte also can in positive electrode surface generation decomposition reaction, and especially in high voltage system, electrolyte decomposes at positive electrode surface can be more serious.Electrolyte can consume limited active lithium in positive electrode surface decomposition, causes capacity attenuation.When electrolyte more than needed in battery system is consumed totally, circulating battery there will be diving phenomenon.Meanwhile, electrolyte can aggravate the stripping of cathode metal ion in positive electrode surface decomposition, causes the deterioration of battery performance further.
Due to SEI film quality to the high-temperature storage performance of lithium ion battery and cycle performance most important, the quality therefore improving SEI film by regulation and control is very necessary to realizing high performance lithium ion battery.In order to address this problem, people attempt adding a small amount of additive in the electrolytic solution to improve SEI film, to improving the performance of lithium ion battery.Researcher develops a series of film for additive through great efforts as vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluorinated ethylene carbonate (FEC) etc., they can form more stable SEI on graphite cathode surface, thus significantly improve the cycle performance of lithium ion battery.In addition, Japanese Matsushita Electric Industrial Industry Co., Ltd is a kind of containing (R patent discloses of Chinese application number 00801010.2 1a) P=(O) (OR 2a) (OR 3a) (wherein, R 1a, R 2a, R 3arepresent that independently carbon number is the aliphatic alkyl of 7-12) electrolyte of compound, its effectively control the discharge capacity occurred along with the carrying out of charge and discharge cycles decline and High temperature storage time battery behavior decline phenomenon.Samsung SDI Co., Ltd of Korea S discloses a kind of containing (R in Chinese application number 200410001479.7 patent 1o) P=(OR 2) (CH=C (R 3) (R 4)) electrolyte of compound, its reliability effectively preventing cell expansion and improve battery.Application number is the electrolyte disclosing a kind of double bond containing phosphate compound in the Chinese patent of 201310046105.6, it improves high-temperature storage and the cycle performance of battery effectively, but we study discovery, double bond containing phosphate compound is unstable in the electrolytic solution, especially containing allylic phosphate compound, its content in the electrolytic solution passes continuous reduction in time, and this causes battery performance to be guaranteed.
Battery in above-mentioned patent is still not ideal enough in high-temperature storage performance and cycle performance, still there will be the decomposition of electrolyte at a higher temperature and cause inflatable, thus bring serious potential safety hazard, especially in high voltage system, the decomposition reaction of electrolyte can aggravate.Therefore be necessary to develop high-temperature storage performance and the high temperature cyclic performance that new additive improves lithium ion battery further.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of non-aqueous electrolyte for lithium ion cell that can improve high-temperature storage and cycle performance, and further providing package is containing the lithium ion battery of described non-aqueous electrolyte for lithium ion cell.
In order to solve the problems of the technologies described above, first aspect present invention provides a kind of non-aqueous electrolyte for lithium ion cell, comprises organic solvent, lithium salts and phosphate compounds.The structural formula of described phosphate compounds is:
Wherein, R 1, R 2, R 3separately be selected from the alkyl that carbon number is 1-4, and R 1, R 2, R 3in at least one is unsaturated alkyl containing three key.
Second aspect present invention provides a kind of lithium ion battery, comprises positive pole, negative pole and the barrier film be placed between positive pole and negative pole and electrolyte, the non-aqueous electrolyte for lithium ion cell that wherein said electrolyte provides for first aspect.
Beneficial effect of the present invention is:
Hinge structure, non-aqueous electrolyte for lithium ion cell provided by the invention, owing to adding the phosphate compound containing unsaturated three key, can form stable passivating film in negative terminal surface, can stop the decomposition of electrolyte further.In addition the phosphate containing unsaturated three key also can form diaphragm at positive electrode surface; electrolyte can be stoped further in the oxidized decomposition of positive electrode surface; suppress the stripping of cathode metal ion, especially when charging voltage is equal to or greater than 4.35V, its effect is more obvious simultaneously.Compared with double bond containing phosphate, the phosphate compound containing three key can stable existence in the electrolytic solution.Therefore the lithium ion battery provided of the present invention has better high-temperature storage performance and high temperature cyclic performance.
Embodiment
By describing technology contents of the present invention in detail, being realized object and effect, be explained below in conjunction with execution mode.
The invention provides a kind of nonaqueous electrolytic solution for lithium ion battery, comprise organic solvent, lithium salts and phosphate compounds, the structural formula of described phosphate compounds is:
Wherein, R 1, R 2, R 3separately be selected from the alkyl that carbon number is 1-4, and R 1, R 2, R 3in at least one is unsaturated alkyl containing three key.
Further, described R 2for acetenyl.
Seen from the above description, R in phosphate group in the structure of the phosphate compounds of the present embodiment 2be connected with acetylene.
Further, described R 2for propinyl.
Seen from the above description, R in phosphate group in the structure of the phosphate compounds of the present embodiment 2be connected with propine.
Separately the illustrative compounds in the compound described in structure 1 is illustrated in Table 1, but be not restricted to this.
Table 1
Further, described phosphate compounds accounts for the 0.01%-2% of electrolyte total weight.
Seen from the above description, when phosphate compounds content in the electrolytic solution lower than 0.01% time, effective passivating film cannot be formed at electrode surface, solvent molecule can not be stoped to decompose further at electrode surface.When phosphate compounds content in the electrolytic solution higher than 2% time, the passivating film formed at electrode surface is blocked up, causes battery impedance obviously to increase, thus causes battery performance to worsen.
Further, also comprise in vinylene carbonate (VC), PS (1,3-PS), fluorinated ethylene carbonate (FEC) and vinyl ethylene carbonate (VEC) one or more.
Seen from the above description, described film for additive can form more stable SEI film on graphite cathode surface, thus significantly improves the cycle performance of lithium ion battery.
Further, described organic solvent is that cyclic carbonate is or/and linear carbonate, described cyclic carbonate be selected from ethylene carbonate, propene carbonate and butylene one or more, described linear carbonate be selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate one or more.
Seen from the above description, the present embodiment adopts the cyclic carbonate organic solvent of high-k and the mixed liquor of low viscous linear carbonate organic solvent as the solvent of lithium-ion battery electrolytes, makes the mixed liquor of this organic solvent have high ionic conductivity, high dielectric constant and low viscosity simultaneously.
Further, described lithium salts is selected from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2cF 3) 2, LiN (SO 2c 2f 5) 2, LiC (SO 2cF 3) 3with LiN (SO 2f) 2in one or more.
Seen from the above description, the present embodiment provides the concrete scope chosen of lithium salts, described lithium salts preferably LiPF 6or LiPF 6with the mixture of other lithium salts.
A kind of lithium ion battery of the present invention, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, also comprises above-mentioned non-aqueous electrolyte for lithium ion cell.
Further, the positive electrode of described positive pole is selected from LiCoO 2, LiNiO 2, LiMn 2o 4, LiCo 1-ym yo 2, LiNi 1-ym yo 2, LiMn 2-ym yo 4and LiNi xco ymn zm 1-x-y-zo 2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
Embodiment 1
1) preparation of electrolyte
By ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) in mass ratio for EC:DEC:EMC=1:1:1 mixes, then add lithium hexafluoro phosphate (LiPF 6) to molar concentration be 1mol/L, add compound 1 (compound 1 referred in embodiment, the compound 2 by the gross mass 0.5% of electrolyte again ... refer to the compound of the reference numeral enumerated in table 1, below each example in like manner) shown in phosphate compound.
2) preparation of positive plate
By the quality of 93:4:3 than blended anode active material lithium nickel cobalt manganese oxide LiNi 0.5co 0.2mn 0.3o 2, then they are dispersed in METHYLPYRROLIDONE (NMP), obtain anode sizing agent by conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF).Be uniformly coated on by slurry on the two sides of aluminium foil, through drying, calendering and vacuumize, and burn-on after aluminum lead-out wire with supersonic welder and obtain positive plate, the thickness of pole plate is at 120-150 μm.
3) preparation of negative plate
By the mass ratio mixing negative active core-shell material modified natural graphite of 94:1:2.5:2.5, conductive carbon black Super-P, binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC), then by their dispersions in deionized water, obtain cathode size.Be coated on by slurry on the two sides of Copper Foil, through drying, calendering and vacuumize, and burn-on after nickel making outlet with supersonic welder and obtain negative plate, the thickness of pole plate is at 120-150 μm.
4) preparation of battery core
Between positive plate and negative plate, place thickness is that the polyethene microporous membrane of 20 μm is as barrier film, then the sandwich structure that positive plate, negative plate and barrier film form is reeled, square aluminum metal-back is put into after being flattened by coiling body again, the lead-out wire of both positive and negative polarity is welded on the relevant position of cover plate respectively, and with laser-beam welding machine, cover plate and metal-back are welded as a whole, obtain the battery core treating fluid injection.
5) battery core fluid injection and change into
In the glove box that dew point controls below-40 DEG C, the electrolyte of above-mentioned preparation is injected battery core by liquid injection hole, and the amount of electrolyte will ensure the space be full of in battery core.Then change into according to the following steps: 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min, after shelving 1hr, shaping is sealed, then further with the electric current constant current charge of 0.2C to 4.2V, after normal temperature shelf 24hr, with the electric current constant-current discharge of 0.2C to 3.0V.
6) normal-temperature circulating performance test
At room temperature with the electric current constant current charge of 1C to 4.2V then constant voltage charge drop to 0.1C to electric current, then with the electric current constant-current discharge of 1C to 3.0V, circulation like this 300 weeks, records the discharge capacity of the 1st week and the discharge capacity of the 300th week, is calculated as follows the capability retention of normal temperature circulation:
The discharge capacity * 100% of discharge capacity/1st of capability retention=300th week week
7) high temperature cyclic performance test
Battery is placed in the baking oven of constant temperature 45 DEG C, with the electric current constant current charge of 1C to 4.2V then constant voltage charge drop to 0.1C to electric current, then with the electric current constant-current discharge of 1C to 3.0V, circulation like this 300 weeks, record the discharge capacity of the 1st week and the discharge capacity of the 300th week, be calculated as follows the capability retention of high temperature circulation:
The discharge capacity * 100% of discharge capacity/1st of capability retention=300th week week
8) high-temperature storage performance test
At room temperature with the electric current constant current charge of 1C to 4.2V then constant voltage charge drop to 0.1C to electric current, measure the thickness of battery, the baking oven then battery being placed in constant temperature 85 DEG C stores 4h, takes out relief battery cool to room temperature, measure the thickness of battery, be calculated as follows the thickness swelling of battery:
Cell thickness * 100% before thickness swelling=(cell thickness before the cell thickness-storage after storage)/storage
Embodiment 2
Except the compound 2 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 2.
Embodiment 3
Except the compound 4 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 2.
Embodiment 4
Except the compound 5 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 2.
Comparative example 1
Except not adding except compound 1 in the preparation of electrolyte, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 2.
Table 2
As can be seen from the data of table 2, compared with not containing the electrolyte of additive, with the addition of the normal-temperature circulating performance of the battery obtained by electrolyte of phosphate compound, high temperature cyclic performance and high-temperature storage performance and be all significantly improved.
Embodiment 5
Except the compound 1 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 0.01%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 3.
Embodiment 6
Except the compound 1 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 0.1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 3.
Embodiment 7
Except the compound 1 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 3.
Embodiment 8
Except the compound 1 in the preparation of electrolyte, the compound 1 of 0.5% being changed into 2%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 3.
Table 3
As can be seen from the data of table 3, when compound 1 addition in the electrolytic solution brings up to 0.1% from 0.01%, the normal-temperature circulating performance of battery, high temperature circulation and high-temperature storage performance improve gradually, but when addition reaches 2%, normal-temperature circulating performance and the high temperature cyclic performance of battery decline to some extent.
Embodiment 9
Except the compound 1 of 0.5% being changed in the preparation of electrolyte into the combination of the vinylene carbonate (VC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 4.
Embodiment 10
Except the compound 1 of 0.5% being changed in the preparation of electrolyte into the combination of the fluorinated ethylene carbonate (FEC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 4.
Embodiment 11
Except the compound 1 of 0.5% being changed in the preparation of electrolyte into the combination of the vinyl ethylene carbonate (VEC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 4.
Comparative example 2
Except the vinylene carbonate (VC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 4.
Comparative example 3
Except the fluorinated ethylene carbonate (FEC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 4.
Comparative example 4
Except the vinyl ethylene carbonate (VEC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 4.
Table 4
As can be seen from the data of table 4, on the basis using VC, FEC or VEC, add compound 1 further and battery can be made to obtain better high-temperature storage performance, normal-temperature circulating performance and high temperature cyclic performance are also improved simultaneously.
Embodiment 12
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiNi into 1/3co 1/3mn 1/3o 2and outside the combination in the preparation of electrolyte, the compound 1 of 0.5% being changed into the vinylene carbonate (VC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Embodiment 13
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiNi into 0.8co 0.15al 0.05o 2and outside the combination in the preparation of electrolyte, the compound 1 of 0.5% being changed into the vinylene carbonate (VC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Embodiment 14
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiCoO into 2and outside the combination in the preparation of electrolyte, the compound 1 of 0.5% being changed into the vinylene carbonate (VC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Embodiment 15
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiMn into 2o 4and outside the combination in the preparation of electrolyte, the compound 1 of 0.5% being changed into the vinylene carbonate (VC) of 1% and the compound 1 of 0.5%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Comparative example 5
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiNi into 1/3co 1/3mn 1/3o 2and outside the vinylene carbonate (VC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Comparative example 6
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiNi into 0.8co 0.15al 0.05o 2and outside the vinylene carbonate (VC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Comparative example 7
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiCoO into 2and outside the vinylene carbonate (VC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Comparative example 8
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiMn into 2o 4and outside the vinylene carbonate (VC) in the preparation of electrolyte, the compound 1 of 0.5% being changed into 1%, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 5.
Table 5
As can be seen from the data of table 5, with LiNi 1/3co 1/3mn 1/3o 2, LiNi 0.8co 0.15al 0.05o 2, LiCoO 2, LiMn 2o 4for in the lithium ion battery of positive electrode, add the high-temperature storage performance that compound 1 also can improve battery, also can improve normal-temperature circulating performance and the high temperature cyclic performance of battery simultaneously.
Embodiment 16
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiCoO into 2and charging becomes beyond 4.35V by voltage, other is identical with embodiment 1, tests that the normal temperature that obtains circulates, the data of high temperature circulation and high-temperature storage are in table 6.
Embodiment 17
Except becoming except 4.35V by charging by voltage, other is identical with embodiment 1, test obtain normal temperature circulation, high temperature circulation and high-temperature storage data in table 6.
Comparative example 9
Except by positive electrode LiNi 0.5co 0.2mn 0.3o 2change LiCoO into 2becoming by current potential with charging does not add beyond compound 1 in 4.35V and electrolyte preparation, and other is identical with embodiment 1, tests that the normal temperature that obtains circulates, the data of high temperature circulation and high-temperature storage are in table 6.
Comparative example 10
Do not add except compound 1 except charging being become by voltage in 4.35V and electrolyte preparation, other is identical with embodiment 1, tests that the normal temperature that obtains circulates, the data of high temperature circulation and high-temperature storage are in table 6.
Table 6
As can be seen from the data of table 6, with LiNi 1/3co 1/3mn 1/3o 2, LiCoO 2for in the high-voltage lithium ion batteries of positive electrode, add the high-temperature storage performance that compound 1 also obviously can improve battery, also can improve normal-temperature circulating performance and the high temperature cyclic performance of battery simultaneously.
In sum, nonaqueous electrolytic solution for lithium ion battery provided by the invention effectively can improve SEI film thermal stability at high temperature, the SEI film of the electrode surface of lithium ion battery of the present invention has the advantage of good stability under the high temperature conditions, has good cycle performance and high-temperature storage performance.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalents utilizing description of the present invention to do, or be directly or indirectly used in relevant technical field, be all in like manner included in scope of patent protection of the present invention.

Claims (10)

1. a non-aqueous electrolyte for lithium ion cell, is characterized in that, comprises organic solvent, lithium salts and phosphate compounds, and the structural formula of described phosphate compounds is:
Wherein, R 1, R 2, R 3separately be selected from the alkyl that carbon number is 1-4, and R 1, R 2, R 3in at least one is unsaturated alkyl containing three key.
2. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described R 2for acetenyl.
3. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described R 2for propinyl.
4. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described phosphate compounds accounts for the 0.01%-2% of electrolyte total weight.
5. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, also comprises one or more in vinylene carbonate, PS, fluorinated ethylene carbonate and vinyl ethylene carbonate.
6. non-aqueous electrolyte for lithium ion cell according to claim 1, it is characterized in that, described organic solvent is the mixture of cyclic carbonate and linear carbonate, described cyclic carbonate be selected from ethylene carbonate, propene carbonate and butylene one or more, described linear carbonate be selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate one or more.
7. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described lithium salts is selected from LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiN (SO 2cF 3) 2, LiN (SO 2c 2f 5) 2, LiC (SO 2cF 3) 3with LiN (SO 2f) 2in one or more.
8. a lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, is characterized in that, also comprises the non-aqueous electrolyte for lithium ion cell described in claim 1 to 7 any one.
9. lithium ion battery according to claim 8, is characterized in that, described positive pole is selected from LiCoO 2, LiNiO 2, LiMn 2o 4, LiCo 1-ym yo 2, LiNi 1-ym yo 2, LiMn 2-ym yo 4and LiNi xco ymn zm 1-x-y-zo 2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
10. lithium ion battery according to claim 8 or claim 9, it is characterized in that, the charge cutoff voltage of described lithium ion battery is more than or equal to 4.35V.
CN201410534841.0A 2014-10-11 2014-10-11 Non-aqueous electrolyte of lithium ion battery and lithium ion battery Pending CN104300174A (en)

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WO2017020431A1 (en) * 2015-08-03 2017-02-09 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte of lithium-ion battery and lithium-ion battery
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CN105428715A (en) * 2015-11-04 2016-03-23 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte solution of lithium ion battery and lithium ion battery
US10530016B2 (en) 2015-12-18 2020-01-07 Shenzhen Capchem Technology Co., Ltd. Electrolyte for lithium-ion battery and lithium-ion battery
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