CN106876778B - A kind of lithium ion secondary battery - Google Patents

A kind of lithium ion secondary battery Download PDF

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CN106876778B
CN106876778B CN201710115842.5A CN201710115842A CN106876778B CN 106876778 B CN106876778 B CN 106876778B CN 201710115842 A CN201710115842 A CN 201710115842A CN 106876778 B CN106876778 B CN 106876778B
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lithium
lithium ion
ion secondary
secondary battery
electrode active
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CN106876778A (en
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宋以仁
敖晓凭
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Hangzhou weisibo System Technology Co.,Ltd.
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Zhangjiagang Jinsheng Lotus Energy Technology 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
    • H01M10/052—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of lithium ion secondary batteries, the battery includes anode, cathode, diaphragm and electrolyte, negative electrode active material used by the cathode of the battery includes the component of following mass fraction: 20 ~ 30% modified fluorinated carbon, 30% ~ 50% graphite, 2% ~ 5% stannide, 30% ~ 50% silico-carbo compound, wherein, the modified fluorinated carbon is obtained after ball milling by mass ratio 1:1 ~ 2:10 ~ 20 that feed intake by gallium compound, titaniferous compound, fluorocarbons.Lithium ion secondary battery of the invention has preferable low temperature performance, while also having preferable charging performance at normal temperature.

Description

A kind of lithium ion secondary battery
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion secondary battery.
Background technique
A kind of function element of the lithium ion battery as clean and environmental protection is got in more and more fields at present To be more widely applied.For example, consumer electronics sector, electric automobiles, energy-storage system field and recently it is emerging Balance car field etc..
Wherein, in electric automobiles, such as express delivery electric vehicle, in cold winter, under the conditions of subzero 20 DEG C of temperature, The battery of electric vehicle can not discharge substantially, bring big inconvenience therefore to user, how realize that electric discharge is at low temperature Those skilled in the art's urgent problem.And in order to solve the above-mentioned technical problem, application number 2016101846435(is non-aqueous Electrolyte and lithium ion battery comprising it) in propose the electrolyte of battery improved, i.e., ring is used in electrolyte Shape sulfuric acid ester compound and sodium salt are as additive, so that the high temperature cyclic performance of lithium ion battery can not only be improved, together When can also be under the conditions of -10 DEG C of temperature, 0.5C is discharged to 3.0V, and discharge capacity can reach room temperature discharge capacity 78.37%, and application number 2014103742643(lithium ion battery and its electrolyte) by improving electrolyte in, fluoro carbon is added Vinyl acetate, so that the lithium battery, under the conditions of -10 DEG C of temperature, 0.5C is discharged to 3.0V, discharge capacity can reach room temperature The 95% of discharge capacity, but it can not discharge under the conditions of lower temperature, for courier to the need of used electric vehicle It asks, which is not able to satisfy its demand still.Meanwhile courier is during using electric vehicle, it is also necessary to battery It can be realized quick charge, to improve delivery efficiency.And currently, existing lithium ion battery can't meet fast charge and low simultaneously The requirement of temperature electric discharge.
Summary of the invention
It is low at -20 DEG C the purpose of the present invention is overcoming the deficiencies of the prior art and provide a kind of lithium ion secondary battery Still there is preferable discharge performance under temperature, while also there is preferable charging performance at normal temperature.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of lithium ion secondary battery, the battery include Anode, cathode, diaphragm and electrolyte, negative electrode active material used by the cathode of the battery include the group of following mass fraction Point: 20 ~ 30% modified fluorinated carbon, 25% ~ 50% graphite, 2% ~ 5% stannide, 25% ~ 50% silico-carbo compound, wherein described changes Property fluorocarbons be obtained after ball milling by mass ratio 1:1 ~ 2:10 ~ 20 that feed intake by gallium compound, titaniferous compound, fluorocarbons.
Wherein, fluorocarbons is applied under normal conditions in the anode of battery, to form conductive path to reduce in anode Resistance, and in the present invention, using modified fluorocarbons, the low temperature performance of battery cathode can be effectively improved, passed through Gallium compound and titaniferous compound are added in fluorocarbons, can be improved the speed of lithium ion disengaging cathode, while cooperating stannide, silicon- Carbon complex, graphite, which enable to lithium ion battery of the invention at normal temperature, has preferable charging performance.
Preferably, the gallium compound is selected from least one of gallium nitride, GaAs, gallium selenide.
Preferably, the titaniferous compound is titanium dioxide.
Preferably, 5% ~ 15% germanium material is also added in the negative electrode active material.
It preferably, include the component of following mass fraction in positive electrode active materials used by the anode of the battery: 20% ~ 30% LiMn2O4,20% ~ 30% cobalt acid lithium, 30% ~ 50% nickle cobalt lithium manganate, 10% ~ 20% nickel cobalt lithium aluminate.
It is further preferred that the surface of the positive electrode active materials is also wrapped on a protective layer, the protective layer be by Account for 1% ~ 5% M of the positive electrode active materials quality oxide constitute, the oxide of the M be by copper oxide, magnesia, Yttrium oxide is mixed according to mass ratio 1:1 ~ 2:1 ~ 3.By coating protective layer on the surface of positive-active material, so that i.e. In the case where making to be mixed into foreign conducting matter inside electrode body, it also can be effectively prevented and short circuit occur between positive plate and negative plate The phenomenon that, improve the safety coefficient of the lithium ion battery.
It is further preferred that being also added with 1% ~ 5% lithium titanate in the positive electrode.
Preferably, the electrolyte of the battery includes lithium salts, solvent and additive, and the use quality of the additive is institute State the 0.1% ~ 5% of lithium salts and the solvent gross mass, the additive include propylene sulfite, 1,3- propane sultone, One of three (trimethyl silane) borates, acetonitrile, vinylene carbonate, fluorinated ethylene carbonate or a variety of combinations.1, 3- propane sultone energy and fluorinated ethylene carbonate are formed surely before negative terminal surface restores and to form HF gas in positive electrode surface Fixed positive SEI protective film, avoids positive electrode active materials by the corrosion of HF gas, while can also form stabilization in negative terminal surface Cathode SEI protective film, and improve the conductive performance of the lithium ion at cathode SEI protective film, therefore, the impedance of lithium ion battery It is significantly reduced, is effectively improved the low temperature discharge high rate performance of lithium ion battery.
It is further preferred that the solvent includes ethylene carbonate and linear carboxylate, wherein the linear carboxylate Selected from least one of ethyl acetate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate.
It is further preferred that lithium salts employed in the electrolyte of the battery is lithium hexafluoro phosphate, hexafluoroarsenate lithium, two At least one of Lithium bis (oxalate) borate, trifluoromethyl sulfonic acid lithium, lithium perchlorate, sulfonyloxy methyl imines lithium salts.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages: lithium of the invention from Sub- secondary cell, negative electrode active material use modified fluorocarbons, graphite, stannide, silico-carbo compound, can be effective Improve the low temperature performance of lithium battery, while the charging performance of battery under room temperature can also be improved, to meet the needs of users. Lithium ion secondary battery of the invention, by taking capacity is the battery of 5000mAH as an example, at normal temperature, extremely using 3C constant-current charge 4.2V, then with the constant-voltage charge of 4.2V to 0.05C, during which, when constant-current charge time 16min, charge volume can reach full capacity 83%, and entire battery filling time is no more than 43min.Meanwhile under the conditions of -10 DEG C of temperature, 1C is discharged to 2.75V, Discharge capacity is up to 95.3% or more, and under -20 DEG C of cryogenic conditions, 1C is discharged to 2.75V, discharge capacity up to 71.8% with On.
Detailed description of the invention
Attached drawing 1 is 3C charge graph under the lithium ion battery room temperature in embodiment 1；
Attached drawing 2 is lithium ion battery in embodiment 1 respectively under the conditions of -10 DEG C, -20 DEG C of temperature, and 1C is discharged to The discharging efficiency curve graph of 2.75V.
Specific embodiment
Technical solution of the present invention is further elaborated combined with specific embodiments below.
Embodiment 1
In this example, a kind of lithium ion secondary battery is provided, which includes anode, cathode, diaphragm and electrolyte, electricity Solution liquid includes lithium salts, solvent and additive, and additive uses 0.1% ~ 5% that quality is lithium salts and solvent gross mass.This example In, the usage amount of the additive is the 2% of lithium salts and solvent gross mass.
Positive electrode active materials include the component of following mass fraction: LiMn2O4 25%, cobalt acid lithium 20%, nickle cobalt lithium manganate 40%, Nickel cobalt lithium aluminate 15%.
Negative electrode active material includes the component of following mass fraction: modified fluorinated carbon 25%, graphite 40%, stannide 3%, silicon- Carbon complex 32%, wherein modified fluorinated carbon be by gallium compound, titaniferous compound and fluorocarbons according to mass ratio 1:2:15 after ball milling It is obtained.Gallium compound therein is gallium nitride, and titaniferous compound is titanium dioxide.
Electrolyte, lithium salts are lithium hexafluoro phosphate, and the solvent used includes ethylene carbonate and linear carboxylate, specifically , which is selected from least one of ethyl acetate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate.This example Employed in additive include 1,3- propane sultone, acetonitrile, fluorinated ethylene carbonate.
Here lithium salts can also be lithium hexafluoro phosphate, hexafluoroarsenate lithium, dioxalic acid lithium borate, trifluoromethyl sulfonic acid lithium, At least one of lithium perchlorate, sulfonyloxy methyl imines lithium salts.Here additive can also be propylene sulfite, 1,3- third One of sultone, three (trimethyl silane) borates, acetonitrile, vinylene carbonate, fluorinated ethylene carbonate are more The combination of kind.
Short circuit occurs between positive plate and negative plate in order to prevent, while improving the safety coefficient of lithium ion battery, in this example, It is also wrapped on a protective layer on the surface of positive electrode active materials, which is the M by accounting for the 3% of positive electrode active materials quality Oxide constitute, in this example, the oxide of M be by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1:2 mixing and At.
Embodiment 2
A kind of lithium ion secondary battery is provided in this example.
Positive electrode active materials include the component of following mass fraction: LiMn2O4 20%, cobalt acid lithium 25%, nickle cobalt lithium manganate 35%, Nickel cobalt lithium aluminate 17%, lithium titanate 3%.
The surface coated protective layer of the positive electrode active materials is by the oxygen for the M for accounting for the 2.5% of positive electrode active materials quality What compound was constituted, in this example, the oxide of M is to be mixed by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1.5:1 's.
Negative electrode active material includes the component of following mass fraction: modified fluorinated carbon 20%, graphite 33%, stannide 2%, silicon- Carbon complex 35%, germanium material 10%.Here modified fluorinated carbon is by gallium compound, titanium dioxide and fluorocarbons according to mass ratio 1: 1:10 is obtained after ball milling.Gallium compound therein is the mixture of gallium nitride and GaAs.Here germanium material is nanometer germanium.
Electrolyte, lithium salts be hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate three mixture；It is used Solvent be ethylene carbonate, ethyl acetate, diethyl carbonate, methyl propyl carbonate mixture；Used additive makes Dosage is the 1% of lithium salts and solvent gross mass, which includes propylene sulfite, three (trimethyl silane) borates and second Nitrile.
Embodiment 3
The lithium ion secondary battery provided in this example specifically:
Positive electrode active materials include the component of following mass fraction: LiMn2O4 24%, cobalt acid lithium 22%, nickle cobalt lithium manganate 37%, Nickel cobalt lithium aluminate 16%, lithium titanate 1%.
The surface coated protective layer of the positive electrode active materials is by the oxidation for the M for accounting for the 1% of positive electrode active materials quality What object was constituted, in this example, the oxide of M is to be mixed by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1:2.
Negative electrode active material includes the component of following mass fraction: modified fluorinated carbon 30%, graphite 30%, stannide 5%, silicon- Carbon complex 30%, germanium material 5%.Wherein, modified fluorinated carbon is by gallium compound, titanium dioxide and fluorocarbons according to mass ratio 1:2: 20 is obtained after ball milling.Wherein, gallium compound here is gallium selenide.
Electrolyte, lithium salts be dioxalic acid lithium borate, trifluoromethyl sulfonic acid lithium, lithium perchlorate mixture；It is used Solvent is the mixture of ethylene carbonate, diethyl carbonate, methyl propyl carbonate；The usage amount of used additive be lithium salts with The 0.5% of solvent gross mass, the additive include 1,3- propane sultone, three (trimethyl silane) borates.
Embodiment 4
A kind of lithium ion secondary battery provided in this example specifically:
Positive electrode active materials include the component of following mass fraction: LiMn2O4 30%, cobalt acid lithium 20%, nickle cobalt lithium manganate 35%, Nickel cobalt lithium aluminate 15%.
The surface coated protective layer of the positive electrode active materials is by the oxidation for the M for accounting for the 5% of positive electrode active materials quality What object was constituted, in this example, the oxide of M is to be mixed by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1:1.
Negative electrode active material includes the component of following mass fraction: modified fluorinated carbon 22%, graphite 40%, stannide 2%, silicon- Carbon complex 30%, germanium material 6%.Wherein, modified fluorinated carbon is by gallium compound, titanium dioxide and fluorocarbons according to mass ratio 1:1: 12 is obtained after ball milling.Wherein, gallium compound here is the mixture of gallium nitride, GaAs, gallium selenide.
Electrolyte, lithium salts are the mixture of hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium；Used solvent is carbonic acid second The mixture of enester, ethyl acetate；The usage amount of used additive is the 2% of lithium salts and solvent gross mass, the additive packet Include acetonitrile, vinylene carbonate, fluorinated ethylene carbonate.
Embodiment 5
A kind of lithium ion secondary battery provided in this example is specific as follows:
Positive electrode active materials include the component of following mass fraction: LiMn2O4 22%, cobalt acid lithium 30%, nickle cobalt lithium manganate 33%, Nickel cobalt lithium aluminate 12%, lithium titanate 3%.
The surface coated protective layer of the positive electrode active materials is by the oxidation for the M for accounting for the 5% of positive electrode active materials quality What object was constituted, in this example, the oxide of M is to be mixed by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1:1.
Negative electrode active material includes the component of following mass fraction: modified fluorinated carbon 25%, graphite 33%, stannide 2%, silicon- Carbon complex 25%, germanium material 15%.Wherein, modified fluorinated carbon is by gallium compound, titanium dioxide and fluorocarbons according to mass ratio 1: 1.5:15 obtained after ball milling.Wherein, gallium compound here is the mixture of GaAs, gallium selenide.
Electrolyte, lithium salts are the mixture of dioxalic acid lithium borate, sulfonyloxy methyl imines lithium salts；Used solvent is carbon Vinyl acetate, dimethyl carbonate, diethyl carbonate mixture；The usage amount of used additive is lithium salts and the total matter of solvent The 0.1% of amount, the additive include 1,3- propane sultone, fluorinated ethylene carbonate.
Embodiment 6
A kind of lithium ion secondary battery provided in this example is specific as follows:
Positive electrode active materials include the component of following mass fraction: LiMn2O4 27%, cobalt acid lithium 22%, nickle cobalt lithium manganate 35%, Nickel cobalt lithium aluminate 12%, lithium titanate 4%.
The surface coated protective layer of the positive electrode active materials is by the oxygen for the M for accounting for the 3.5% of positive electrode active materials quality What compound was constituted, in this example, the oxide of M is to be mixed by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1.5:1 's.
Negative electrode active material includes the component of following mass fraction: modified fluorinated carbon 27%, graphite 25%, stannide 3%, silicon- Carbon complex 40%, germanium material 5%.Wherein, modified fluorinated carbon is by gallium compound, titanium dioxide and fluorocarbons according to mass ratio 1:1: 12 is obtained after ball milling.Wherein, gallium compound here is the mixture of gallium selenide.Here germanium material is germanium dioxide.
Electrolyte, lithium salts are the mixture of lithium hexafluoro phosphate, sulfonyloxy methyl imines lithium salts；Used solvent is carbonic acid Vinyl acetate, diethyl carbonate, methyl propyl carbonate mixture；The usage amount of used additive is lithium salts and solvent gross mass 1.5%, the additive include three (trimethyl silane) borates, acetonitrile.
Comparative example
A kind of lithium ion secondary battery provided in this example is specific as follows:
Positive electrode active materials are LiNi1/3Co1/3O2；
Negative electrode active material graphite；
Electrolyte, lithium salts are lithium hexafluoro phosphate；Organic solvent is ethylene carbonate, propene carbonate, methyl ethyl carbonate； Additive is the fluorinated ethylene carbonate for accounting for electrolyte quality 3% and the 1,3- dioxolane for accounting for electrolyte quality 1%.
It is that 5000mAH is detected with battery capacity, to be higher than at 25 DEG C with 0.5C multiplying power constant-current charge to voltage 4.35V is further lower than 0.05C with 4.35V constant voltage charging to electric current, stands at 25 DEG C and -10 DEG C respectively later 60min, then be discharged to voltage with 0.2C multiplying power constant current as 3.0V measures discharging efficiency at -10 DEG C up to 95%.
Capacity is carried out to the battery that embodiment 1 to 6 provides and charge-discharge test, the capacity of surveyed battery are 5000mAH。
1) the low temperature discharge high rate performance test of lithium ion battery
[measurement of 25 DEG C of discharge capacities]
At 25 DEG C, lithium ion battery is stood 10 minutes, later with 0.5C multiplying power constant-current charge to 4.2V, Zhi Hou Constant-voltage charge is to 0.05C under 4.2V, and stands 5 minutes, and later with 1C multiplying power constant-current discharge to 2.75V, this is a charge and discharge Cyclic process, measurement discharge capacity are denoted as Q1.
[measurement of low temperature discharge capacity]
At 25 DEG C, after being charged under charge condition identical with above-mentioned circulation, it is placed in -10 DEG C of thermostat 4h, then, in the environment of -10 DEG C, 1C is discharged to voltage up to 2.75V, and measurement discharge capacity is denoted as Q2.According to identical side Lithium ion battery is carried out discharge test by method under the conditions of -20 DEG C of temperature.
Discharging efficiency when finding out low temperature discharge by following formula (1).
Discharging efficiency (%)=(Q2/Q1) * 100(% when low temperature discharge)
Specific test result is shown in Table 1.
Table 1
。
It will be seen that lithium ion battery of the invention carries out 1C and be discharged under the conditions of -10 DEG C of temperature from table 1 2.75V, discharging efficiency under the conditions of -10 DEG C of temperature, are discharged to 3V up to 95.3% or more, and in comparative example with 0.2C, Its discharging efficiency also can only cannot achieve substantially electric discharge up to 95%, and under the conditions of -20 DEG C of temperature.It will thus be seen that of the invention By the improvement to negative electrode active material, the low temperature performance of battery can be effectively improved, to meet the visitor of special dimension Family demand；Meanwhile we can see that adding germanium material in negative electrode material can be improved the low temperature performance of battery.
2) lithium ion charging performance is tested
At 25 DEG C, charging modes are with the constant-current charge of 3C to 4.2V, then with the constant-voltage charge of 4.2V to 0.05C.Wherein, Charging result is shown in Table 2.
Table 2
Group 3C fills constant-current charge to 4.2V/min 3C fills constant-voltage charge to 0.05C/min 3C filling time/min
Embodiment 1 16 27 43
Embodiment 2 16.5 24.5 41
Embodiment 3 17 22 39
Embodiment 4 16 27 43
Embodiment 5 17 23 40
Embodiment 6 17 23 40
Comparative example 60
From table 2, it will be seen that lithium ion battery in the present invention its compared with comparative example, the charging time has It is more significantly shorter, while it will be seen that increase lithium titanate in positive electrode, add germanium material in negative electrode material, Compared with not increasing above-mentioned material, the charging time is shortened.
In addition, being given in Fig. 1 in embodiment 1,3C(multiplying power under room temperature) charging rate curve, we can be with from figure Find out, constant current section charge 16min, chargeable 83%, constant pressure section fills 27min, can be full of battery；Embodiment 1 is given in Fig. 2 In lithium ion battery at -10 DEG C, -20 DEG C, 1C(multiplying power) discharging efficiency curve.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of lithium ion secondary battery, the battery includes anode, cathode, diaphragm and electrolyte, which is characterized in that the electricity Negative electrode active material used by the cathode in pond includes the component of following mass fraction: 20 ~ 30% modified fluorinated carbon, 25% ~ 50% stone Ink, 2% ~ 5% stannide, 25% ~ 50% silico-carbo compound, wherein the modified fluorinated carbon is by gallium compound, titaniferous compound, fluorination Carbon is obtained after ball milling by mass ratio 1:1 ~ 2:10 ~ 20 that feed intake.
2. lithium ion secondary battery according to claim 1, which is characterized in that the gallium compound is selected from gallium nitride, arsenic Change at least one of gallium, gallium selenide.
3. lithium ion secondary battery according to claim 1 or 2, which is characterized in that the titaniferous compound is titanium dioxide.
4. lithium ion secondary battery according to claim 1, which is characterized in that be also added in the negative electrode active material 5% ~ 15% germanium material.
5. lithium ion secondary battery according to claim 1, which is characterized in that anode used by the anode of the battery It include the component of following mass fraction: 20% ~ 30% LiMn2O4,20% ~ 30% cobalt acid lithium, 30% ~ 50% nickel cobalt mangaic acid in active material Lithium, 10% ~ 20% nickel cobalt lithium aluminate.
6. lithium ion secondary battery according to claim 5, which is characterized in that also wrap on the surface of the positive electrode active materials It is covered with a protective layer, the protective layer is made of the oxide for accounting for 1% ~ 5% M of the positive electrode active materials quality, institute The oxide for stating M is to be mixed by copper oxide, magnesia, yttrium oxide according to mass ratio 1:1 ~ 2:1 ~ 3.
7. lithium ion secondary battery according to claim 5, which is characterized in that be also added in the positive electrode active materials 1% ~ 5% lithium titanate.
8. lithium ion secondary battery according to claim 1, which is characterized in that the electrolyte of the battery include lithium salts, Solvent and additive, the additive use 0.1% ~ 5% that quality is the lithium salts and the solvent gross mass, the addition Agent includes propylene sulfite, 1,3- propane sultone, three (trimethyl silane) borates, acetonitrile, vinylene carbonate, fluorine For one of ethylene carbonate or a variety of combinations.
9. lithium ion secondary battery according to claim 8, which is characterized in that the solvent includes ethylene carbonate and line Property carboxylate, wherein the linear carboxylate is in ethyl acetate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate At least one.
10. lithium ion secondary battery according to claim 8, which is characterized in that employed in the electrolyte of the battery Lithium salts be that lithium hexafluoro phosphate, hexafluoroarsenate lithium, dioxalic acid lithium borate, trifluoromethyl sulfonic acid lithium, lithium perchlorate, sulfonyloxy methyl are sub- At least one of amine lithium salts.
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