CN102593508B - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN102593508B CN102593508B CN201210041031.2A CN201210041031A CN102593508B CN 102593508 B CN102593508 B CN 102593508B CN 201210041031 A CN201210041031 A CN 201210041031A CN 102593508 B CN102593508 B CN 102593508B
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- electrolyte
- lithium ion
- ion battery
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- acid ester
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- 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 present invention provides a kind of lithium ion battery, and described lithium ion battery has excellent cycle life characteristics and high-temperature storage performance.Comprising: comprise the negative electrode of cathode active material；Comprise the anode of anode active material；The dividing plate being placed between negative electrode and anode；And electrolyte, it contains: lithium salts, organic solvent, halogenated cyclic carbonic ester, cyclic disulfonic acid ester compounds；Described cathode active material is: inner LiNixCoyM1‑X‑YO2, wherein one or more in Mn, Al, Ti, Zn of M, 0.5≤x≤1,0≤y≤0.5, simultaneously 1 x y >=0.
Description
Technical field
The present invention relates to electrochemical field, particularly relate to field of lithium ion secondary.
Background technology
In recent years, portable type electronic product, such as photographing unit, DV, mobile phone, notebook computer etc. is people
Daily life in be widely used, and have strong request towards reducing size, weight is lighter, more long-life trend
Development.It is therefore desirable to the portable power source that exploitation matches with portable type electronic product, high-energy-density especially can be provided
Lightweight secondary cell.With lead-acid battery, nickel-cadmium cell, Ni-MH battery compares, and lithium ion battery is because its energy density is big, work
The features such as voltage height, life-span length, environmental protection, are widely used in above-mentioned portable battery product.
Lithium ion battery is mainly made up of positive and negative electrode, electrolyte and barrier film.Positive pole is mainly the metal-oxide of lithium, negative
Pole is mainly Carbon Materials.Owing to the average discharge volt of lithium ion battery is about 3.6-3.7V, need the charging/put at 0-4.2V
Electrolyte component stable in piezoelectric voltage.To this end, electrolyte used by lithium ion battery must be nonaqueous electrolytic solution, the most generally make
With comprising cyclic carbonate solvents (such as ethylene carbonate) and linear carbonates solvent (such as dimethyl carbonate, diethyl carbonate, carbon
Acid methyl ethyl ester) mixture as electrolyte.
Lithium ion battery is during initial charge, and lithium ion deintercalation from the lithium metal oxide of cathode active material goes out
Come, migrate to anode carbon electrode under the driving of voltage, then slip in material with carbon element.In this process, electrolyte and carbon sun
Surface, pole reacts, and produces Li2CO3, Li2The materials such as O, LiOH, thus form one layer of passivating film at carbon anode surface, this is blunt
Change film and be 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 (such as cycle performance, high-temperature behavior, high rate performance) of battery.
After SEI film is formed during first charge-discharge, it is possible to the decomposition of prevention electrolyte solvent molecule further, and
Charge and discharge cycles subsequently is formed ion channel.But, along with the carrying out of discharge and recharge, expansion that electrode repeats and contraction,
In this case, SEI film is it may happen that rupture or gradually dissolve, and the anode exposed therewith continues to react with electrolyte, with
Time produce gas, thus increase the intrinsic pressure of battery and be substantially reduced the cycle life characteristics of battery.The carbon used according to electrolyte
The kind of acid esters and the type of anode active material, the gas of generation mainly includes CO, CO2, CH4, C2H6Deng.
Owing to electrode surface film has influence on the first charge-discharge efficiency of lithium ion battery, cycle life and safety, therefore
The formation controlling electrode surface film is necessary for realizing high performance lithium ion battery.By adding some in electrolyte
Additive can realize the regulation and control to electrode surface film, exists owing to these additive molecules can have precedence over electrolyte solvent molecule
Anode surface is reduced formation passivating film, and this passivating film can stop electrolyte solvent molecule to continue to divide at anode surface further
Solve and the common embedding of solvent molecule, simultaneously can stable existence in circulation subsequently.During initial charge, FEC can
Have precedence over solvent in negative terminal surface generation reduction reaction, the further decomposition of suppression solvent, improve stablizing of SEI film simultaneously
Property, thus improve the cycle performance of battery.
But, although FEC can improve the cycle performance of battery, but reducing the high-temperature behavior of battery, battery is at height
When temperature storage or high temperature circulation, battery produces flatulence, has had a strong impact on the security performance of battery.It is especially nickeliferous when cathode material
Composite oxides time, high-temperature behavior is worse.This is because the phase surface activity after charging Han ni compound oxide cathode material
Higher and the biggest with nickel content, its surface activity is the highest, and solvent molecule is decomposed on its surface reaction, so that battery
Produce tympanites.
Therefore field of lithium ion battery technical staff actively finds suitable additive for improving the performance of lithium battery, example
Such as Publication No.: CN 101978548A, entitled " for the non-aqueous electrolytic solution of lithium secondary battery and the lithium two comprising it
Primary cell " Chinese patent application in disclose and add the such as technical scheme of sulfonic fluoropolymer ester compounds in the electrolytic solution, to reach
Produce the generation of gaseous phenomena to suppression inside battery, and then reach to improve the purpose of battery performance.
But, add merely sulfonates compounds, gratifying technique effect can't be reached.
Summary of the invention
It is an object of the invention to provide a kind of lithium ion battery, it is special that described lithium ion battery has excellent cycle life
Property and high-temperature storage performance.
For achieving the above object, the invention provides a kind of lithium ion battery, comprising:
Comprise the negative electrode of cathode active material；
Comprise the anode of anode active material；
The dividing plate being placed between negative electrode and anode；
And electrolyte, it contains: lithium salts, organic solvent, halogenated cyclic carbonic ester, cyclic disulfonic acid ester compounds；
Described cyclic disulfonic acid ester compound chemical structure is as shown in structural formula I:
Wherein, A is the straight chain selected from 1-5 carbon atom or the alkylidene with side chain, straight chain or the halo with side chain
Alkylidene；B is selected from one of sulfinyl, carbonyl or following group: the alkylidene containing 1-5 carbon atom, halogeno alkylen；
Described halogenated cyclic carbonic ester chemical constitution is as shown in formula II:
Wherein, wherein R1, R2, R3And R4Be independently from each other hydrogen atom, halogen atom, the alkyl of 1-2 carbon atom or
Haloalkyl, and R1, R2, R3And R4In at least one selected from halogen atom or haloalkyl.
Described cathode active material is: LiNixCoyM1-X-YO2, wherein one or more in Mn, Al, Ti, Zn of M,
0.5≤x≤1,0≤y≤0.5, simultaneously 1-x-y >=0.
As the preferred version of the present invention, described cyclic disulfonic acid ester compounds is selected from following molecular formula 1-molecular formula 5 institute
Show one or more in compound:
In addition to this it is possible to selected from compound:
As the preferred version of the present invention, described cyclic disulfonic acid ester compounds content in the electrolytic solution presses electrolyte
Gross weight is calculated as 0.1%-5%.
As the preferred version of the present invention, described cyclic disulfonic acid ester compounds content in the electrolytic solution presses electrolyte
Gross weight is calculated as 1%-5%.
As the preferred version of the present invention, described halogenated cyclic carbonic ester is selected from following molecular formula 6-molecular formula 10 shownization
In compound one or more:
In addition to this it is possible to selected from compound:
As the preferred version of the present invention, described halogenated cyclic carbonic ester content in the electrolytic solution presses the gross weight of electrolyte
Amount is calculated as 0.1-10 weight %.
As the preferred version of the present invention, described halogenated cyclic carbonic ester content in the electrolytic solution presses the gross weight of electrolyte
Amount is calculated as 2-5 weight %.
As the preferred version of the present invention, described cyclic disulfonic acid ester compounds content in the electrolytic solution: described halo
Cyclic carbonate content in the electrolytic solution is 1: 1-1: 5.
The lithium ion battery of the present invention is compared traditional lithium ion battery and is had excellent cycle life characteristics and high temperature storage
Sustainability energy.
Detailed description of the invention
By describing the technology contents of the present invention, structural feature in detail, being realized purpose and effect, below in conjunction with embodiment
It is explained in detail.
Embodiment 1
Lithium ion battery makes:
Positive pole makes: the quality by 93: 4: 3 is than blended anode active material lithium nickel cobalt manganese oxide
(LiNi0.5Co0.3Mn0.2O2), conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF), then disperse them in
In METHYLPYRROLIDONE (NMP), obtain anode sizing agent.Slurry is uniformly coated on the two sides of aluminium foil, through drying,
Calendering and vacuum drying, and burn-on with supersonic welder and obtain positive plate after aluminum lead-out wire, the thickness of pole plate is at 120-150 μ
m。
Negative pole makes: 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 disperse them in deionized water,
To cathode size.Slurry is coated on the two sides of Copper Foil, through drying, rolling and be vacuum dried, and welds with supersonic welder
Obtaining negative plate after upper nickel making outlet, the thickness of pole plate is in 120-150 μm.
The preparation of electrolyte: by ethylene carbonate (EC), diethyl carbonate (DEC) and Ethyl methyl carbonate (EMC) by weight
Ratio is for EC: mix at DEC: EMC=1: 1: 1, and after mixing, being subsequently adding lithium hexafluoro phosphate (LiPF6) to molar concentration is
1mol/L, adds the cyclic disulfonic acid ester compounds of the molecular formula 1 of based on the gross mass of electrolyte 2% and total by electrolyte
The halocarbonate compound of the molecular formula 6 of quality meter 1%.
Barrier film makes: using three layers of isolating membrane of polypropylene, polyethylene/polypropylene, thickness is 20 μm.
Battery core preparation between positive plate and negative plate place thickness be the polyethene microporous membrane of 20 μm as barrier film, so
After by positive plate, negative plate and barrier film form sandwich structure be wound, then by coiling body flatten after put into square aluminum
In metal-back, the lead-out wire of both positive and negative polarity is respectively welded on the relevant position of cover plate, and with laser-beam welding machine by cover plate and gold
Belong to shell to be welded as a whole, obtain treating the battery core of fluid injection.
The electrolyte of above-mentioned preparation, in the glove box that dew point controls below-40 DEG C, is led to by the fluid injection of battery core and chemical conversion
Crossing liquid injection hole and inject in battery core, the amount of electrolyte to ensure the space being full of in battery core.It is melted into the most according to the following steps:
0.05C constant-current charge 3min, 0.2C constant-current charge 5min, 0.5C constant-current charge 25min, shelves shaping sealing after 1hr, then enters
One step 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.
Normal-temperature circulating performance is tested
Dropping to 0.1C to 4.2V then constant-voltage charge to electric current with the electric current constant-current charge of 1C, then the electric current with 1C is permanent
Stream is discharged to 3.0V, so circulation 200 weeks, records the discharge capacity of the 1st week and the discharge capacity of the 200th week, is calculated as follows
Capability retention:
The discharge capacity * 100% high-temperature storage performance test of the discharge capacity of capability retention=200th week/1st week
At room temperature drop to 0.1C with electric current constant-current charge to 4.2V then constant-voltage charge to the electric current of 1C, measure battery
Thickness, then battery is placed in the baking oven of constant temperature 85 DEG C storage 4h, takes out relief battery and be cooled to room temperature, measure battery
Thickness, is calculated as follows the thickness swelling of battery:
Cell thickness * before thickness swelling=(cell thickness before cell thickness-storage after storage)/storage
100%
Embodiment 2
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 2, institute
Stating halocarbonate compound is molecular formula 7.
Embodiment 3
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 3, institute
Stating halocarbonate compound is molecular formula 8.
Embodiment 4
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 4, institute
Stating halocarbonate compound is molecular formula 9.
Embodiment 5
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 5, institute
Stating halocarbonate is molecular formula 10.
Comparative example 1
This comparative example is similar to embodiment 1, and difference is: cyclic disulfonic acid ester compounds is not added to electrolyte
In.
Comparative example 2
The present embodiment is similar to embodiment 1, and difference is: halocarbonate is not added in electrolyte.
Table one:
Knowable to table one data, adding halocarbonate compound in the electrolytic solution, battery has the cycle performance of excellence,
But during high-temperature storage, battery tympanites is serious, with the addition of the battery of cyclic disulfonic acid ester compounds, although can improve the height of battery
Warm nature energy.But reduce cycle performance.When halocarbonate and cyclic disulfonic acid ester compounds are added simultaneously in electrolyte
The cycle performance that can have both kept, does not the most reduce high-temperature behavior.
Embodiment 6
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 6, its
Content presses the 5% of electrolyte gross mass, and described halocarbonate compound is molecular formula 1, and its content presses electrolyte gross mass
0.1%.
Embodiment 7
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 6, its
Content presses the 0.1% of electrolyte gross mass, and described halocarbonate compound is molecular formula 1, and its content presses electrolyte gross mass
10%.
Embodiment 8
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 6, its
Content presses the 2% of electrolyte gross mass, and described halocarbonate compound is molecular formula 1, and its content presses electrolyte gross mass
5%.
Embodiment 9
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 6, its
Content presses the 2% of electrolyte gross mass, and described halocarbonate compound is molecular formula 1, and its content presses electrolyte gross mass
2%.
Embodiment 10
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 6, its
Content presses the 1% of electrolyte gross mass, and described halocarbonate compound is molecular formula 1, and its content presses electrolyte gross mass
3%.
Embodiment 11
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 6, its
Content presses the 5% of electrolyte gross mass, and described halocarbonate compound is molecular formula 1, and its content presses electrolyte gross mass
3%.
Embodiment 12
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 2, its
Content presses the 3% of electrolyte gross mass, and described halocarbonate compound is molecular formula 7, and its content presses electrolyte gross mass
0.1%.
Embodiment 13
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 3, its
Content presses the 0.1% of electrolyte gross mass, and described halocarbonate compound is molecular formula 8, and its content presses electrolyte gross mass
5%.
Embodiment 14
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 4, its
Content presses the 3% of electrolyte gross mass, and described halocarbonate compound is molecular formula 9, and its content presses electrolyte gross mass
2%.
Embodiment 15
The present embodiment is similar to embodiment 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 5, its
Content presses the 1% of electrolyte gross mass, and described halocarbonate compound is molecular formula 10, and its content presses electrolyte gross mass
5%.
Comparative example 3
This comparative example is similar to Example 1, and difference is: described halocarbonate compound is molecular formula 6, and it contains
Amount presses the 2% of electrolyte total amount, and cyclic disulfonic acid ester compounds is not added in electrolyte.,
Comparative example 4
This comparative example is similar to Example 1, and difference is: described cyclic disulfonic acid ester compounds is molecular formula 3, its
Content presses the 1% of electrolyte total amount, and halocarbonate compound is not added in electrolyte.
Table two
From table two data it is recognised that when halocarbonate add very few time, owing to can not be formed effectively at anode surface
Passivating film, cycle performance of battery is poor；When halocarbonate adds too much, although cycle performance of battery can be improved, but
High-temperature behavior reduces, and battery tympanites is serious.When cyclic disulfonic acid ester compounds is very few, it is impossible to effectively suppression battery tympanites, but
When adding too much, although battery tympanites can be suppressed, but seriously reduce the cycle performance of battery.
Embodiment 16
The present embodiment is similar to embodiment 1, and difference is: use LiNi0.7Co0.15Mn0.15O2Replace
LiNi0.5Co0.3Mn0.2O2。
Embodiment 17
The present embodiment is similar to embodiment 1, and difference is: use LiNi0.8Co0.1Mn0.1O2Replace
LiNi0.5Co0.3Mn0.2O2。
Embodiment 18
The present embodiment is similar to embodiment 1, and difference is: use LiNi0.8Co0.2O2Replace LiNi0.5Co0.3Mn0.2O2。
Embodiment 19
The present embodiment is similar to embodiment 1, and difference is: use LiNi0.8Co0.15Al0.55O2Replace
LiNi0.5Co0.3Mn0.2O2。
Table three
From expression data it can be seen that increase with nickel content cathode material, battery high-temperature behavior reduces, and battery tympanites is more
Seriously.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every utilize this
Equivalent structure or equivalence flow process that bright description is made convert, or are directly or indirectly used in other relevant technology necks
Territory, is the most in like manner included in the scope of patent protection of the present invention.
Claims (7)
1. a lithium ion battery, it is characterised in that comprising:
Comprise the negative electrode of cathode active material；
Comprise the anode of anode active material；
The dividing plate being placed between negative electrode and anode；
And electrolyte, it contains: lithium salts, organic solvent and electrolysis additive, described electrolysis additive is by halogenated cyclic
Carbonic ester and cyclic disulfonic acid ester compounds composition；
Described cyclic disulfonic acid ester compound chemical structure is as shown in structural formula I:
Wherein, A is selected from the straight chain of 1-5 carbon atom or with branched alkylidene, straight chain or with side chain halogeno alkylen；B
It is selected from sulfinyl or carbonyl；
Described halogenated cyclic carbonic ester chemical constitution is as shown in structure formula II:
Wherein, wherein R1, R2, R3And R4It is independently from each other hydrogen atom, halogen atom, the alkyl of 1-2 carbon atom or halo
Alkyl, and R1, R2, R3And R4In at least one selected from halogen atom or haloalkyl；
Described cathode active material is: LiNixCoyM1-X-YO2, wherein one or more in Al, Ti, Zn of M, 0.5≤x ＜
1,0≤y≤0.5, simultaneously 1-x-y >=0；
Described cyclic disulfonic acid ester compounds content in the electrolytic solution: described halogenated cyclic carbonic ester content in the electrolytic solution
For 1:1-1:5.
Lithium ion battery the most according to claim 1, it is characterised in that described cyclic disulfonic acid ester compounds is selected from following
In compound shown in molecular formula 4-molecular formula 5 one or more:
Lithium ion battery the most according to claim 2, it is characterised in that described cyclic disulfonic acid ester compounds is at electrolyte
In content be calculated as 0.1%-5% by the gross weight of electrolyte.
Lithium ion battery the most according to claim 3, it is characterised in that described cyclic disulfonic acid ester compounds is at electrolyte
In content be calculated as 1%-2% by the gross weight of electrolyte.
Lithium ion battery the most according to claim 1, it is characterised in that described halogenated cyclic carbonic ester is selected from following molecule
In compound shown in formula 6-molecular formula 9 one or more:
Lithium ion battery the most according to claim 5, it is characterised in that described halogenated cyclic carbonic ester is in the electrolytic solution
Content is calculated as 0.1-10 weight % by the gross weight of electrolyte.
Lithium ion battery the most according to claim 6, it is characterised in that described halogenated cyclic carbonic ester is in the electrolytic solution
Content is calculated as 2-5 weight % by the gross weight of electrolyte.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016190404A1 (en) * | 2015-05-26 | 2016-12-01 | 三井化学株式会社 | Nonaqueous electrolyte solution for batteries and lithium secondary battery |
| CN105895955A (en) * | 2016-06-02 | 2016-08-24 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN106025346B (en) * | 2016-07-21 | 2019-01-11 | 天津巴莫科技股份有限公司 | The battery of lithium ion battery composite cathode material and preparation method thereof and assembling |
| EP3291352B1 (en) * | 2016-09-02 | 2019-05-08 | Samsung Electronics Co., Ltd | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN109309252B (en) * | 2017-07-27 | 2021-05-04 | 宁德时代新能源科技股份有限公司 | Electrolyte and electrochemical energy storage device |
| WO2019189670A1 (en) * | 2018-03-29 | 2019-10-03 | 三菱ケミカル株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte battery |
| CN109037778A (en) * | 2018-08-01 | 2018-12-18 | 桑德集团有限公司 | A kind of electrolysis additive and electrolyte, lithium ion battery and equipment containing it |
| CN112436189B (en) * | 2020-11-30 | 2022-02-11 | 广州天赐高新材料股份有限公司 | Composition, electrolyte containing composition and lithium ion battery |
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| CN1757134A (en) * | 2003-12-15 | 2006-04-05 | 日本电气株式会社 | The secondary cell that is used for the electrolyte solution of secondary cell and uses this solution |
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Granted publication date: 20161012 |