CN102593508A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN102593508A CN102593508A CN2012100410312A CN201210041031A CN102593508A CN 102593508 A CN102593508 A CN 102593508A CN 2012100410312 A CN2012100410312 A CN 2012100410312A CN 201210041031 A CN201210041031 A CN 201210041031A CN 102593508 A CN102593508 A CN 102593508A
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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 invention provides a lithium ion battery which has an excellent cycling life characteristic and a high-temperature storage property. The lithium ion battery comprises: a cathode containing a cathode active material; an anode containing an anode active material; a clapboard positioned between the cathode and the anode; and an electrolyte solution containing lithium salt, an organic solvent, halogenated cyclic carbamate and a cyclic di-sulphonate compound. The cathode active material refers to LiNixCoyM1-X-YO2, wherein M refers to one or more selected from Mn, Al, Ti and Zn, x is greater than or equal to 0.5 and smaller than or equal to 0.5 and the difference of 1 minus x minus y is greater than or equal to 0.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to field of lithium ion secondary.
Background technology
In recent years, portable type electronic product, camera for example, DV, mobile phone, notebook computers etc. are widely used in daily life, and strong request are arranged towards reducing size, and weight is lighter, more long-life trend development.Therefore, require to develop the portable power source that matches with portable type electronic product, the lightweight secondary cell of high-energy-density especially can be provided.With lead-acid battery, nickel-cadmium cell, Ni-MH battery is compared, and characteristics such as lithium ion battery is big because of its energy density, operating voltage is high, the life-span is long, environmental protection are widely used in the above-mentioned portable battery product.
Lithium ion battery mainly is made up of positive and negative electrode, electrolyte and barrier film.Positive pole mainly is the metal oxide of lithium, and negative pole mainly is the raw material of wood-charcoal material.Because the average discharge volt of lithium ion battery is about 3.6-3.7V, need be in the charging of 0-4.2V stable electrolyte component.For this reason; The used electrolyte of lithium ion battery must be non-aqueous solution electrolysis liquid, for example uses the mixture that comprises cyclic carbonate ester solvent (like ethylene carbonate) and linear carbonates solvent (like dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate) as electrolyte usually.
Lithium ion battery is in the initial charge process, and lithium ion takes off embedding and comes out from the lithium metal oxide of cathode active material, and the migration of anode carbon electrode is slipped in the material with carbon element then under the driving of voltage.In this process, electrolyte and carbon anode surface react, and produce Li
2CO
3, Li
2O, materials such as LiOH, thus forming one deck passivating film on the carbon anode surface, this passivating film is referred to as solid electrolyte interface (SEI) film.Because no matter be charging or discharge, lithium ion must pass through this layer SEI film, so the performance of SEI film has determined many performances (like cycle performance, high-temperature behavior, high rate performance) of battery.
The SEI film can further stop the decomposition of electrolyte solvent molecule after in the first charge-discharge process, forming, and in charge and discharge cycles subsequently, forms ion channel.Yet; Along with the carrying out that discharges and recharges, expansion and contraction that electrode repeats, in this case; The SEI film possibly break or dissolving gradually; Exposed anode continues to react with electrolyte thereupon, produces gas simultaneously, thereby the interior pressure of increase battery also reduces the cycle life characteristics of battery greatly.The kind of the carbonic ester that uses according to electrolyte and the type of anode active material, the gas of generation mainly comprises CO, CO
2, CH
4, C
2H
6Deng.
Because the electrode surface film has influence on first charge-discharge efficiency, cycle life and the fail safe of lithium ion battery, so the formation of control electrode skin covering of the surface is necessary for what realize high performance lithium ion battery.Can realize regulation and control through in electrolyte, adding some additive to the electrode surface film; Because these additive molecules can have precedence over the electrolyte solvent molecule and be reduced the formation passivating film at anode surface; This passivating film can stop the electrolyte solvent molecule further to continue the common embedding of decomposition and solvent molecule at anode surface, and the while can stable existence in circulation subsequently.In the initial charge process, FEC can have precedence over solvent in negative terminal surface generation reduction reaction, suppresses the further decomposition of solvent, has improved the stability of SEI film simultaneously, thereby has improved the cycle performance of battery.
Yet, though FEC can improve the cycle performance of battery, having reduced the high-temperature behavior of battery, battery is when high-temperature storage or high temperature circulation, and battery produces inflatable, has had a strong impact on the security performance of battery.Especially when cathode material was nickeliferous composite oxides, high-temperature behavior was poorer.This is higher in charging later stage surface activity because contain the ni compound oxide cathode material, and big more with nickel content, and its surface activity is also higher, and solvent molecule on its surface decomposition reaction takes place, thereby makes battery produce bulging.
Therefore the lithium ion battery those skilled in the art actively seek the performance that suitable additive is used to improve lithium battery; For example publication number is: CN 101978548A; The one Chinese patent application that name is called " non-aqueous electrolytic solution and the lithium secondary battery that comprises it that are used for lithium secondary battery " discloses the technical scheme of in electrolyte, adding like the sulfonic fluoropolymer ester compounds; Suppress the generation that inside battery produces gaseous phenomena to reach, and then reach the purpose of improving battery performance.
But, add sulfonates compounds merely, can't reach gratifying technique effect.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery, said lithium ion battery has good cycle life characteristics and high-temperature storage performance.
For realizing the foregoing invention purpose, the invention provides a kind of lithium ion battery, it comprises:
The negative electrode that comprises cathode active material;
The anode that comprises anode active material;
Place the dividing plate between negative electrode and the anode;
And electrolyte, it contains: lithium salts, organic solvent, halogenated cyclic carbonic ester, cyclic disulfonic acid ester compounds;
Said cyclic disulfonic acid ester compound chemical structure is shown in structural formula I:
Wherein, A is selected from the straight chain of 1-5 carbon atom or has alkylidene, the straight chain of side chain or have the halo alkylidene of side chain; B is selected from one of sulfinyl, carbonyl or following group: the alkylidene, the halo alkylidene that contain 1-5 carbon atom;
Said halogenated cyclic carbonic ester chemical constitution is shown in structural formula II:
Wherein, R wherein
1, R
2, R
3And R
4Be independently from each other the alkyl or the haloalkyl of hydrogen atom, halogen atom, a 1-2 carbon atom, and R
1, R
2, R
3And R
4In at least one is selected from halogen atom or haloalkyl.
Said cathode active material is: LiNi
xCo
yM
1-X-YO
2, wherein M is selected from one or more among Mn, Al, Ti, the Zn, 0.5≤x≤1,0≤y≤0.5,1-x-y>=0 simultaneously.
As preferred version of the present invention, said cyclic disulfonic acid ester compounds is selected from shown in the following molecular formula 1-molecular formula 5 in the compound one or more:
In addition, can also be selected from compound:
As preferred version of the present invention, the content of said cyclic disulfonic acid ester compounds in electrolyte is counted 0.1%-5% by the total weight of electrolyte.
As preferred version of the present invention, the content of said cyclic disulfonic acid ester compounds in electrolyte is counted 1%-5% by the total weight of electrolyte.
As preferred version of the present invention, said halogenated cyclic carbonic ester is selected from shown in the following molecular formula 6-molecular formula 10 in the compound one or more:
In addition, can also be selected from compound:
As preferred version of the present invention, the content of said halogenated cyclic carbonic ester in electrolyte is counted 0.1-10 weight % by the total weight of electrolyte.
As preferred version of the present invention, the content of said halogenated cyclic carbonic ester in electrolyte is counted 2-5 weight % by the total weight of electrolyte.
As preferred version of the present invention, the content of said cyclic disulfonic acid ester compounds in electrolyte: the content of said halogenated cyclic carbonic ester in electrolyte is 1: 1-1: 5.
Lithium ion battery of the present invention is compared traditional lithium ion battery and is had good cycle life characteristics and high-temperature storage performance.
Embodiment
By specifying technology contents of the present invention, structural feature, realized purpose and effect, give explanation below in conjunction with execution mode is detailed.
Embodiment 1
Lithium ion battery is made:
The anodal making: the quality of pressing 93: 4: 3 are than blended anode active material lithium nickel cobalt manganese oxidation thing (LiNi
0.5Co
0.3Mn
0.2O
2), conductive carbon black Super-P and binding agent polyvinylidene fluoride (PVDF) are dispersed in them in the N-N-methyl-2-2-pyrrolidone N-(NMP) then, obtain anode sizing agent.Slurry is uniformly coated on the two sides of aluminium foil, through oven dry, calendering and vacuumize, and burn-ons with supersonic welder and to obtain positive plate behind the aluminum lead-out wire, the thickness of pole plate is at 120-150 μ m.
Negative pole is made: by 94: 1: 2.5: 2.5 mass ratio mixing negative active core-shell material modified natural graphite; Conductive carbon black Super-P; Binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC) are dispersed in them in the deionized water then, obtain cathode size.Slurry is coated on the two sides of Copper Foil, through oven dry, calendering and vacuumize, and burn-ons with supersonic welder and to obtain negative plate after the nickel making outlet, the thickness of pole plate is at 120-150 μ m.
The preparation of electrolyte: with ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) by weight for EC: DEC: EMC=1: mix at 1: 1; After the mixing; Adding lithium hexafluoro phosphate (LiPF6) to molar concentration then is 1mol/L, adds by the cyclic disulfonic acid ester compounds of the molecular formula 1 of the gross mass 2% of electrolyte and by the halo carbonate products of the molecular formula 6 of the gross mass 1% of electrolyte again.
Barrier film is made: adopt three layers of barrier film of polypropylene, polyethylene/polypropylene, thickness is 20 μ m.
It is that the polyethene microporous membrane of 20 μ m is as barrier film that being prepared between positive plate and the negative plate of electricity core placed thickness; The sandwich structure of then positive plate, negative plate and barrier film being formed is reeled; Put into square aluminum metal-back after again coiling body being flattened; The lead-out wire of both positive and negative polarity is welded on respectively on the relevant position of cover plate, and cover plate and metal-back is welded as a whole, obtain treating the electric core of fluid injection with laser-beam welding machine.
The fluid injection of electricity core and changing at dew point in the glove box that is controlled at below-40 ℃ is injected electric core with the electrolyte of above-mentioned preparation through liquid injection hole, and the amount of electrolyte will guarantee to be full of the space in the electric core.Change into according to the following steps then: 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min; Shaping is sealed after shelving 1hr; Then further with the electric current constant current charge of 0.2C to 4.2V, after normal temperature is shelved 24hr, with the electric current constant-current discharge of 0.2C to 3.0V.
The normal-temperature circulating performance test
With the electric current constant current charge of 1C to 4.2V then constant voltage charge to electric current drop to 0.1C, then with the electric current constant-current discharge of 1C to 3.0V, so circulated for 200 weeks, write down the discharge capacity and the discharge capacity in the 200th week in the 1st week, be calculated as follows capability retention:
The discharge capacity * 100% high-temperature storage performance test in the discharge capacity in capability retention=the 200th week/the 1st week
At room temperature with the electric current constant current charge of 1C to 4.2V then constant voltage charge to electric current drop to 0.1C; Measure the thickness of battery, place the baking oven of 85 ℃ of constant temperature to store 4h on battery then, take 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 the storage)/storage
Embodiment 2
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 2, and said halo carbonate products is a molecular formula 7.
Embodiment 3
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 3, and said halo carbonate products is a molecular formula 8.
Embodiment 4
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 4, and said halo carbonate products is a molecular formula 9.
Embodiment 5
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 5, and said halo carbonic ester is a molecular formula 10.
Comparative example 1
This comparative example is similar to embodiment 1, and difference is: the cyclic disulfonic acid ester compounds does not add in the electrolyte.
Comparative example 2
Present embodiment is similar to embodiment 1, and difference is: the halo carbonic ester does not add in the electrolyte.
Table one:
Can know that from table one data in electrolyte, add the halo carbonate products, battery has excellent cycle performance, the battery bulging is serious during high-temperature storage, has added the battery of cyclic disulfonic acid ester compounds, though can improve the high-temperature behavior of battery.But reduced cycle performance.When adding halo carbonic ester and cyclic disulfonic acid ester compounds to can both keep good in the electrolyte cycle performance simultaneously, do not reduce high-temperature behavior again.
Embodiment 6
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 6, and its content is pressed 5% of electrolyte gross mass, and said halo carbonate products is a molecular formula 1, and its content is pressed 0.1% of electrolyte gross mass.
Embodiment 7
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 6, and its content is pressed 0.1% of electrolyte gross mass, and said halo carbonate products is a molecular formula 1, and its content is pressed 10% of electrolyte gross mass.
Embodiment 8
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 6, and its content is pressed 2% of electrolyte gross mass, and said halo carbonate products is a molecular formula 1, and its content is pressed 5% of electrolyte gross mass.
Embodiment 9
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 6, and its content is pressed 2% of electrolyte gross mass, and said halo carbonate products is a molecular formula 1, and its content is pressed 2% of electrolyte gross mass.
Embodiment 10
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 6, and its content is pressed 1% of electrolyte gross mass, and said halo carbonate products is a molecular formula 1, and its content is pressed 3% of electrolyte gross mass.
Embodiment 11
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 6, and its content is pressed 5% of electrolyte gross mass, and said halo carbonate products is a molecular formula 1, and its content is pressed 3% of electrolyte gross mass.
Embodiment 12
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 2, and its content is pressed 3% of electrolyte gross mass, and said halo carbonate products is a molecular formula 7, and its content is pressed 0.1% of electrolyte gross mass.
Embodiment 13
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 3, and its content is pressed 0.1% of electrolyte gross mass, and said halo carbonate products is a molecular formula 8, and its content is pressed 5% of electrolyte gross mass.
Embodiment 14
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 4, and its content is pressed 3% of electrolyte gross mass, and said halo carbonate products is a molecular formula 9, and its content is pressed 2% of electrolyte gross mass.
Embodiment 15
Present embodiment is similar to embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 5, and its content is pressed 1% of electrolyte gross mass, and said halo carbonate products is a molecular formula 10, and its content is pressed 5% of electrolyte gross mass.
Comparative example 3
This comparative example is similar with embodiment 1, and difference is: said halo carbonate products is a molecular formula 6, and its content is pressed 2% of electrolyte total amount, and the cyclic disulfonic acid ester compounds does not add in the electrolyte.，
Comparative example 4
This comparative example is similar with embodiment 1, and difference is: said cyclic disulfonic acid ester compounds is a molecular formula 3, and its content is pressed 1% of electrolyte total amount, and the halo carbonate products does not add in the electrolyte.
Table two
Can know that from table two data when the halo carbonic ester adds when very few, owing to can not form effective passivating film at anode surface, cycle performance of battery is relatively poor; When the halo carbonic ester adds when too much, though can improve cycle performance of battery, high-temperature behavior reduces, and the battery bulging is serious.When the cyclic disulfonic acid ester compounds is very few, can not effectively suppress the battery bulging, add when too much, though can suppress the battery bulging, but seriously reduced the cycle performance of battery.
Embodiment 16
Present embodiment is similar to embodiment 1, and difference is: use LiNi
0.7Co
0.15Mn
0.15O
2Replace LiNi
0.5Co
0.3Mn
0.2O
2
Embodiment 17
Present embodiment is similar to embodiment 1, and difference is: use LiNi
0.8Co
0.1Mn
0.1O
2Replace LiNi
0.5Co
0.3Mn
0.2O
2
Embodiment 18
Present embodiment is similar to embodiment 1, and difference is: use LiNi
0.8Co
0.2O
2Replace LiNi
0.5Co
0.3Mn
0.2O
2
Embodiment 19
Present embodiment is similar to embodiment 1, and difference is: use LiNi
0.8Co
0.15Al
0.55O
2Replace LiNi
0.5Co
0.3Mn
0.2O
2
Table three
Can find out that from the expression data increase with nickel content in the cathode material, battery high-temperature behavior reduces, the battery bulging is serious more.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; Or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (8)
1. lithium ion battery is characterized in that it comprises:
The negative electrode that comprises cathode active material;
The anode that comprises anode active material;
Place the dividing plate between negative electrode and the anode;
And electrolyte, it contains: lithium salts, organic solvent, halogenated cyclic carbonic ester, cyclic disulfonic acid ester compounds;
Said cyclic disulfonic acid ester compound chemical structure is shown in structural formula I:
Wherein, A is selected from the straight chain of 1-5 carbon atom or has branched alkylidene, straight chain or have side chain halo alkylidene; B is alkylidene, the halo alkylidene that is selected from sulfinyl, carbonyl or contains 1-5 carbon atom;
Said halogenated cyclic carbonic ester chemical constitution is shown in structural formula II:
Wherein, R wherein
1, R
2, R
3And R
4Be independently from each other the alkyl or the haloalkyl of hydrogen atom, halogen atom, a 1-2 carbon atom, and R
1, R
2, R
3And R
4In at least one is selected from halogen atom or haloalkyl;
Said cathode active material is: LiNi
xCo
yM
1-X-YO
2, wherein M is selected from one or more among Mn, Al, Ti, the Zn, 0.5≤x≤1,0≤y≤0.5,1-x-y>=0 simultaneously.
2. lithium ion battery according to claim 1 is characterized in that, said cyclic disulfonic acid ester compounds is selected from shown in the following molecular formula 1-molecular formula 5 in the compound one or more:
3. lithium ion battery according to claim 2 is characterized in that, the content of said cyclic disulfonic acid ester compounds in electrolyte is counted 0.1%-5% by the total weight of electrolyte.
4. lithium ion battery according to claim 3 is characterized in that, the content of said cyclic disulfonic acid ester compounds in electrolyte is counted 1%-2% by the total weight of electrolyte.
5. lithium ion battery according to claim 1 is characterized in that, said halogenated cyclic carbonic ester is selected from shown in the following molecular formula 6-molecular formula 10 in the compound one or more:
6. lithium ion battery according to claim 5 is characterized in that, the content of said halogenated cyclic carbonic ester in electrolyte is counted 0.1-10 weight % by the total weight of electrolyte.
7. lithium ion battery according to claim 6 is characterized in that, the content of said halogenated cyclic carbonic ester in electrolyte is counted 2-5 weight % by the total weight of electrolyte.
8. according to the described lithium ion battery of each claim of claim 1-7, it is characterized in that the content of said cyclic disulfonic acid ester compounds in electrolyte: the content of said halogenated cyclic carbonic ester in electrolyte is 1: 1-1: 5.
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|---|---|---|---|
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|---|---|---|---|
| CN201210041031.2A CN102593508B (en) | 2012-02-22 | 2012-02-22 | Lithium ion battery |
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| CN105895955A (en) * | 2016-06-02 | 2016-08-24 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN106025346A (en) * | 2016-07-21 | 2016-10-12 | 天津巴莫科技股份有限公司 | Composite cathode material for lithium ion batteries, preparation method of composite cathode material, and battery formed by assembling composite cathode material |
| CN107534185A (en) * | 2015-05-26 | 2018-01-02 | 三井化学株式会社 | Nonaqueous electrolyte for battery and lithium secondary battery |
| CN107799817A (en) * | 2016-09-02 | 2018-03-13 | 三星电子株式会社 | For the electrolyte of lithium secondary battery and including the lithium secondary battery of electrolyte |
| 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 |
| CN109309252A (en) * | 2017-07-27 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and electrochemical energy storage device |
| CN110692160A (en) * | 2018-03-29 | 2020-01-14 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte battery |
| CN112436189A (en) * | 2020-11-30 | 2021-03-02 | 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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