CN105449274B - lithium ion battery and electrolyte thereof - Google Patents
lithium ion battery and electrolyte thereof Download PDFInfo
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- CN105449274B CN105449274B CN201410505635.7A CN201410505635A CN105449274B CN 105449274 B CN105449274 B CN 105449274B CN 201410505635 A CN201410505635 A CN 201410505635A CN 105449274 B CN105449274 B CN 105449274B
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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
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- 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 and electrolyte thereof. The electrolyte of the lithium ion battery comprises: a non-aqueous organic solvent; a lithium salt dissolved in a non-aqueous organic solvent; and an additive. The additives include fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), and cyano-containing titanate. The lithium ion battery comprises the electrolyte of the lithium ion battery. The lithium ion battery has excellent storage performance and cycle performance at high temperature and high pressure.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of lithium ion battery and its electrolyte.
Background technology
Lithium ion battery has the advantages that high-energy-density, long circulation life, wide operating temperature range and green,
Turn into the main energy sources of mobile electronic device at present.But mobile electronic device, particularly smart mobile phone are frivolous in recent years
The rapid development of change, higher demand is proposed to the energy density of lithium ion battery.
In order to improve the energy density of lithium ion battery, usually using the positive-active material with more high charge blanking voltage
Material is a kind of very effective method.But these have the positive electrode active materials of high charge blanking voltage at high temperature under high pressure
Due to strong oxidizing property so that electrolyte is easily oxidized decomposition, so as to produce substantial amounts of gas, in turn results in lithium ion
Battery failure.In addition, lithium ion battery in cyclic process as the oxidation Decomposition and positive electrode active materials of electrolyte
The side reaction (precipitation of such as oxygen, the dissolution of transition metal ions) of itself causes its cycle performance to deteriorate.
Therefore, it is to improve lithium ion battery to the oxidation Decomposition of electrolyte effectively to suppress positive electrode active materials under HTHP
The key of storage performance and cycle performance under HTHP.In lithium ion battery, frequently with fluorinated ethylene carbonate (FEC)
As additive improve lithium ion battery cycle performance, using PS (PS) as additive come improve lithium from
The high-temperature storage performance of sub- battery.Fig. 1, which provides to be used as using fluorinated ethylene carbonate (FEC) and 1,3- propane sultones (PS), to be added
Add the lithium ion battery of agent stored 30 days at 60 DEG C after thickness swelling.Fig. 2 is provided using fluorinated ethylene carbonate (FEC)
Capability retention after being circulated with 1,3- propane sultones (PS) as the lithium ion battery of additive at 45 DEG C.Can from Fig. 1
To find out, under 4.4V charge cutoff voltages, using the lithium of fluorinated ethylene carbonate (FEC) and PS (PS) from
Sub- battery has good storage performance, but when voltage is 4.45V, the storage performance of lithium ion battery substantially deteriorates.From Fig. 2
As can be seen that the cycle performance of the lithium ion battery under the conditions of 4.45V is substantially not so good as the cyclicity of the lithium ion battery under 4.4V
Energy.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of lithium ion battery and its electrolysis
Liquid, the lithium ion battery have excellent storage performance and cycle performance at high temperature under high pressure.
To achieve these goals, in the first aspect of the present invention, the invention provides a kind of electrolysis of lithium ion battery
Liquid, it includes：Non-aqueous organic solvent；Lithium salts, it is dissolved in non-aqueous organic solvent；And additive.The additive includes fluorine
For the titanate esters of ethylene carbonate (FEC), 1,3- propane sultones (PS) and cyano-containing.
In the second aspect of the present invention, the invention provides a kind of lithium ion battery, and it includes：Positive plate, including positive pole
Collector and be arranged on plus plate current-collecting body and comprising positive electrode active materials, conductive agent, binding agent positive pole diaphragm；Negative plate,
Including negative current collector and be arranged on negative current collector and comprising negative active core-shell material, conductive agent, binding agent cathode membrane；
Barrier film, it is interval between positive plate and negative plate；And electrolyte.Wherein, the electrolyte is according to first party of the present invention
The electrolyte of the lithium ion battery in face.
Relative to prior art, beneficial effects of the present invention are：
The lithium ion battery of the present invention has excellent storage performance and cycle performance at high temperature under high pressure.
Brief description of the drawings
Fig. 1 is using the lithium-ion electric of fluorinated ethylene carbonate (FEC) and 1,3- propane sultones (PS) as additive
Pond stored 30 days at 60 DEG C after thickness swelling；
Fig. 2 is using the lithium-ion electric of fluorinated ethylene carbonate (FEC) and 1,3- propane sultones (PS) as additive
Pond circulated at 45 DEG C after capability retention.
Embodiment
Tied the following detailed description of the lithium ion battery according to the present invention and its electrolyte and comparative example, embodiment and test
Fruit.
Illustrate the electrolyte of lithium ion battery according to a first aspect of the present invention first.
The electrolyte of lithium ion battery according to a first aspect of the present invention, including：Non-aqueous organic solvent；Lithium salts, it is dissolved in
In non-aqueous organic solvent；And additive.The additive includes fluorinated ethylene carbonate (FEC), 1,3- propane sultones
(PS) and cyano-containing titanate esters.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the titanate esters chemical combination of the cyano-containing
Contain titanate-based and cyano group in the molecular structure of thing simultaneously, titanate-based can be in lithium ion battery initial charge (chemical conversion) mistake
Aoxidize to form positive pole passivating film in positive electrode surface in journey, and the strong electrophilic inductive effect of cyano group can promote titanate-based into
Film effect further enhance, can so be obtained in the case where not increasing the dosage of titanate esters of cyano-containing densification, stably
Positive pole passivating film, so as to avoid because cyano-containing titanate esters dosage it is excessive caused by lithium ion battery cycle performance dislike
Change, and the dosage increase of the titanate esters of cyano-containing can be improved the storage performance of lithium ion battery.The positive pole generated is blunt
The transition metal ions changed in the cyano group and positive electrode active materials contained in film has very strong complexing so that is generated
Positive pole passivating film not only has good heat endurance, and has very strong adhesion with positive electrode active materials, so as to have
Effect suppresses the electrolyte particularly non-aqueous organic solvent oxidation Decomposition at high temperature under high pressure of lithium ion battery, so as to avoid lithium from
Sub- battery producing gas, and then improve the cycle performance of lithium ion battery at high temperature under high pressure.The positive pole passivating film generated may be used also
Suppress fluorinated ethylene carbonate (FEC) and HF, while the oxygen in the titanate compound of cyano-containing are formed during cathode film formation
(- O-) can and HF, PF5 in electrolyte form hydrogen bond, so as to improve the storage performance of lithium ion battery at high temperature under high pressure and
Cycle performance.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the titanate esters of the cyano-containing are optional
One or more from the compound with formula (1), formula (2), formula (3), formula (4) and formula (5) structure；
In formula (1)-(5), n is selected from the integer in 1~4, R1、R2、R3Straight chained alkyl independently selected from C1~C8,
One kind in C1~C8 branched alkyl, C1~C8 alkenyl and aromatic radical containing 6~12 carbon atoms, the straight chain alkane
Base, branched alkyl, alkenyl, the hydrogen atom on aromatic radical are completely or partially replaced by fluorine atoms.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the titanate esters of the cyano-containing are optional
From the compound with formula (5) structure；
In formula (5), n is selected from the integer in 1~4.
Relative to formula (1)~(4) represent compound, using formula (5) represent compound when its film-formation result more
Well, the reason for possible is the compound with formula (5) structure with good symmetry so that four titaniums in formula (5)
Chemical environment residing for perester radical is close, so as to which simultaneous oxidation forms positive pole during lithium ion battery initial charge (chemical conversion)
Passivating film, and then improve film forming efficiency.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the titanate esters of the cyano-containing are optional
One or more from tetrem cyano group titanate esters, 4 third cyano group titanate esters, four fourth cyano group titanate esters, 4 penta cyano group titanate esters.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the titanate esters of the cyano-containing are in lithium
Weight/mass percentage composition in the electrolyte of ion battery can be 0.1%~10%.Preferably, the titanate esters of the cyano-containing are in lithium
Weight/mass percentage composition in the electrolyte of ion battery can be 0.5%~3%.When the titanate esters of cyano-containing are in lithium ion battery
When weight/mass percentage composition in electrolyte is less than 0.1%, it can not form the positive pole passivation of densification in surface of positive electrode active material
Film, and then the storage performance of lithium ion battery at high temperature under high pressure cannot significantly improve；When cyano-containing titanate esters lithium from
When weight/mass percentage composition in the electrolyte of sub- battery is higher than 10%, thicker positive pole passivating film can be formed, significantly increases positive pole
The impedance at interface, make polarization increase of the lithium ion battery under HTHP in cyclic process, so as to deteriorate lithium ion battery
Cycle performance.
In the electrolyte of lithium ion battery according to a first aspect of the present invention, the fluorinated ethylene carbonate (FEC) exists
Weight/mass percentage composition in the electrolyte of lithium ion battery can be 1%~10%.Preferably, the fluorinated ethylene carbonate
(FEC) weight/mass percentage composition in the electrolyte of lithium ion battery can be 2%~6%.When fluorinated ethylene carbonate (FEC) exists
When weight/mass percentage composition in the electrolyte of lithium ion battery is less than 1%, the lithium ion battery length under HTHP can not be met
The use demand of cycle life, and the cycle performance of lithium ion battery is acutely failed；When fluorinated ethylene carbonate (FEC) exists
When weight/mass percentage composition in the electrolyte of lithium ion battery is higher than 10%, the storage performance of lithium ion battery at high temperature under high pressure
And cycle performance can deteriorate.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the PS (PS)
Weight/mass percentage composition in the electrolyte of lithium ion battery can be 0.5%~10%, it is preferable that the PS
(PS) weight/mass percentage composition in the electrolyte of lithium ion battery can be 3%~5%.When 1,3- propane sultones (PS) are in lithium
When weight/mass percentage composition in the electrolyte of ion battery is less than 0.5%, the storage performance of lithium ion battery at high temperature under high pressure
It cannot be effectively improved；When weight/mass percentage composition of the 1,3- propane sultones (PS) in the electrolyte of lithium ion battery is higher than
When 10%, the capacity of lithium ion battery can significantly reduce, and the cycle performance of lithium ion battery at high temperature under high pressure can also occur
Deteriorate.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the lithium salts may include LiPF6、
LiBF4, one or more in LiBOB, LiDFOB, LiTFSI.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the concentration of the lithium salts can be 0.9M
~1.2M.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the non-aqueous organic solvent may be selected from
Propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethyl acetate (EA), third
One or more in acetoacetic ester (EP), propyl propionate (PP), gamma-butyrolacton (GBL).
Secondly the lithium ion battery of explanation according to a second aspect of the present invention.
Lithium ion battery according to a second aspect of the present invention includes：Positive plate, including plus plate current-collecting body and it is arranged at positive pole
On collector and comprising positive electrode active materials, conductive agent, binding agent positive pole diaphragm；Negative plate, including negative current collector and set
Be placed on negative current collector and comprising negative active core-shell material, conductive agent, binding agent cathode membrane；Barrier film, it is interval in positive pole
Between piece and negative plate；And electrolyte.Wherein, the electrolyte is the electricity according to the lithium ion battery of first aspect present invention
Solve liquid.
In lithium ion battery described according to a second aspect of the present invention, the charge cutoff voltage of the lithium ion battery can
More than or equal to 4.45V.
In lithium ion battery described according to a second aspect of the present invention, the positive electrode active materials may include lithium cobalt oxidation
Thing, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, one kind in lithium nickel cobalt aluminum oxide or
It is several.
In lithium ion battery described according to a second aspect of the present invention, the negative active core-shell material may include soft carbon, hard
One or more in carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate.
In lithium ion battery described according to a second aspect of the present invention, it is porous that the barrier film may be selected from polyethylene (PE)
The treated porous polymer of thin polymer film, polyethylene/polypropylene (PE/PP) MULTILAYER COMPOSITE porous polymer film, ceramics
One kind in film.
Next explanation is according to the lithium ion battery of the present invention and its comparative example, the embodiment of electrolyte.
Comparative example 1
(1) electrolyte of lithium ion battery is prepared
LiPF6 of the electrolyte of lithium ion battery using concentration as 1.15M is lithium salts, with ethylene carbonate (EC), carbonic acid third
Mixture (the mass ratio 30 of alkene ester (PC) and diethyl carbonate (DEC):30:40) it is non-aqueous organic solvent.In addition lithium ion
Also contain additive in the electrolyte of battery, additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
Fluorinated ethylene carbonate (FEC) and sulphurs of 1,3- third that weight/mass percentage composition in the electrolyte of lithium ion battery is 4%
Acid lactone (PS).
(2) positive plate of lithium ion battery is prepared
By positive electrode active materials cobalt acid lithium (LiCoO2), conductive agent Super-P, binding agent polyvinylidene fluoride (PVDF) press
Mass ratio 97:1.4:1.6 are well mixed with solvent N-methyl pyrilidone (NMP) anode sizing agent are made, afterwards by anode sizing agent
It is uniformly coated on plus plate current-collecting body aluminium foil, is cold-pressed after being dried afterwards at 85 DEG C, then carries out trimming, cut-parts, slitting,
And 4h is dried under 85 DEG C of vacuum condition, positive pole ear is welded, the positive plate of lithium ion battery is made.
(3) negative plate of lithium ion battery is prepared
By negative active core-shell material Delanium, conductive agent Super-P, thickener sodium carboxymethylcellulose (CMC), bonding agent
Butadiene-styrene rubber (SBR) in mass ratio 97:1.0:1.0:1.5 are well mixed with solvent deionized water cathode size are made, and afterwards will
Cathode size is uniformly coated on negative current collector copper foil, and is dried at 85 DEG C, then progress trimming, cut-parts, slitting, and
4h is dried under 110 DEG C of vacuum condition, welds negative lug, the negative plate of lithium ion battery is made.
(4) lithium ion battery is prepared
Obtained positive plate, barrier film (PE porous polymer films), negative plate are folded in order, are in barrier film
Between positive plate and negative plate, winding obtains naked battery core, naked battery core is placed in battery outer packing afterwards, by the electricity of above-mentioned preparation
Solution liquid is injected into dried battery core, by encapsulating, standing, be melted into (with 0.02C constant-current charges to 3.4V, then with 0.1C perseverances
Current charge is to 3.85V), shaping, after the process such as capacity, complete the preparation of lithium ion battery, wherein, the thickness of lithium ion battery is
4.2mm, width 32mm, length 82mm.
Comparative example 2
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 7% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC) the 1,3- propane sultones (PS) that the weight/mass percentage composition and in the electrolyte of lithium ion battery is 4%.
Embodiment 1
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 2
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The 4 third cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 3
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The four fourth cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 4
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The 4 penta cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 5
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.1%.
Embodiment 6
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 10%.
Embodiment 7
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.3%.
Embodiment 8
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 1%.
Embodiment 9
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 3%.
Embodiment 10
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 5%.
Embodiment 11
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 7%.
Embodiment 12
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 1% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 13
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 7% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 14
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 10% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 4% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 15
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 0.5% 1,3- propane sultones (PS) and in lithium
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of ion battery is 0.5%.
Embodiment 16
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 6% 1,3- propane sultones (PS) and lithium from
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of sub- battery is 0.5%.
Embodiment 17
Method according to comparative example 1 prepares lithium ion battery, simply prepare the electrolyte of lithium ion battery the step of (i.e.
In step (1))：
The fluorinated ethylene carbonate that additive is 5% for the weight/mass percentage composition in the electrolyte of lithium ion battery
(FEC), the weight/mass percentage composition in the electrolyte of lithium ion battery be 10% 1,3- propane sultones (PS) and in lithium
The tetrem cyano group titanate esters that weight/mass percentage composition in the electrolyte of ion battery is 0.5%.
Finally illustrate the performance test process and test result of the lithium ion battery according to the present invention.
(1) the cycle performance test under high-temperature lithium ion battery high pressure
At 45 DEG C, 4.45V is first charged to lithium ion battery with 0.7C constant current, it is further constant with 4.45V
It is 0.05C that voltage, which charges to electric current, is then discharged to 3.0V to lithium ion battery with 1C constant current, and this is a discharge and recharge
Cyclic process, the discharge capacity that this discharge capacity circulates for first time.Lithium ion battery is circulated in a manner described
Charge-discharge test, take the discharge capacity of the 500th circulation.Cycle performance under high-temperature lithium ion battery high pressure is kept by its capacity
Rate is evaluated.
The capability retention (%) of lithium ion battery=(electric discharge of the discharge capacity of the 500th circulation/first time circulation is held
Amount) × 100%.
(2) the storage performance test under high-temperature lithium ion battery high pressure
At 25 DEG C, 4.45V is first charged to lithium ion battery with 0.5C constant current, it is further constant with 4.45V
Voltage charges to electric current and is less than 0.05C, obtains the thickness before lithium ion battery storage；Then lithium ion battery is placed in 60 DEG C of rings
Stored 30 days in border, obtain the thickness after lithium ion battery storage.Storage performance under high-temperature lithium ion battery high pressure is deposited by it
Thickness swelling after storage is evaluated.
The thickness swelling (%) of the lithium ion battery=[thickness before (thickness before thickness-storage after storage)/storage
Degree] × 100%.
Table 1 provides comparative example 1-2 and embodiment 1-17 parameter and the performance test results.
The comparative example 1-2 of table 1 and embodiment 1-17 parameter and the performance test results
Next the performance test results of lithium ion battery are analyzed.
It was found from from comparative example 1 and embodiment 1-4 contrast, addition 0.5% contains in the electrolyte of lithium ion battery
The cycle performance and storage performance that can be effectively improved after the titanate compound of cyano group under high-temperature lithium ion battery high pressure.This be because
To contain titanate-based and cyano group in the molecular structure of the titanate compound of cyano-containing simultaneously, titanate-based can be in lithium ion
Aoxidize to form positive pole passivating film in positive electrode surface during battery initial charge (chemical conversion), and the strong electrophilic inductive effect of cyano group
The filming function of titanate-based can be promoted to further enhance, so can be in the feelings of the dosage for the titanate esters for not increasing cyano-containing
Densification, stable positive pole passivating film is obtained under condition, so as to avoid because lithium caused by the titanate esters dosage of cyano-containing is excessive from
The cycle performance of sub- battery deteriorates.Transition metal in the cyano group and positive electrode active materials that contain in the positive pole passivating film generated
Ion has very strong complexing so that the positive pole passivating film generated not only has a good heat endurance, and with just
Pole active material has very strong adhesion, so as to effectively suppress the electrolyte of lithium ion battery particularly non-aqueous organic solvent
Oxidation Decomposition at high temperature under high pressure, so as to avoid lithium ion battery aerogenesis, and then lithium ion battery is improved in HTHP
Under cycle performance.
Also known from embodiment 1-4 contrast, 0.5% tetrem cyano group titanium is added in the electrolyte of lithium ion battery
Improvement of the acid esters to the cycle performance under high-temperature lithium ion battery high pressure is most obvious.The reason for possible is the metatitanic acid with cyano-containing
The growth (i.e. n increases) of the strand of ester compounds, the viscosity increase of electrolyte, so that lithium ion battery is in cyclic process
In polarization increase.
It was found from from embodiment 1 and embodiment 5-11 contrast, the weight/mass percentage composition of the titanate compound of cyano-containing
Also the performance of lithium ion battery can be influenceed.Because when the weight/mass percentage composition of the titanate compound of cyano-containing is relatively low,
The positive pole passivating film of formation is not fine and close enough, it is impossible to fully covers positive electrode active materials；When the matter of the titanate compound of cyano-containing
When amount percentage composition is higher, thicker positive pole passivating film can be formed, causes the interface impedance of inside lithium ion cell to increase, although
Improve the storage performance of lithium ion battery, but because polarize the cycle performance of lithium ion battery can substantially be produced it is a certain degree of
Deteriorate.
It was found from from comparative example 1-2, embodiment 1 and embodiment 12-14 contrast, the matter of fluorinated ethylene carbonate (FEC)
Amount percentage composition can also impact to the performance of lithium ion battery.It was found from from comparative example 1-2 contrast, tetrem is being added without
During cyano group titanate esters, the weight/mass percentage composition of increase fluorinated ethylene carbonate (FEC) can substantially deteriorate lithium ion battery in high temperature
Storage performance and cycle performance under high pressure, this is probably because fluorinated ethylene carbonate (FEC) shape during cathode film formation
Into HF can deteriorate positive pole.And from embodiment 1 and embodiment 12-14 contrast it was found from, after tetrem cyano group titanate esters are added,
The weight/mass percentage composition of increase fluorinated ethylene carbonate (FEC) can significantly improve the storage of lithium ion battery at high temperature under high pressure
Energy and cycle performance, this is due to the positive pole passivating film that tetrem cyano group titanate esters can form densification in positive electrode surface, so as to suppress
The negative effect of fluorinated ethylene carbonate (FEC), at the same oxygen (- O-) in tetrem cyano group titanate esters can with the HF in electrolyte,
PF5 forms hydrogen bond.But the weight/mass percentage composition of fluorinated ethylene carbonate (FEC) is too high (embodiment 14), lithium ion battery
Cycle performance deteriorates on the contrary.
It was found from from embodiment 1 and embodiment 15-17 contrast, the weight/mass percentage composition of PS (PS)
The performance of lithium ion battery can be impacted.The weight/mass percentage composition of increase 1,3- propane sultones (PS) can significantly improve lithium
The cycle performance of ion battery at high temperature under high pressure.
Claims (13)
1. a kind of electrolyte of lithium ion battery, including：
Non-aqueous organic solvent；
Lithium salts, it is dissolved in non-aqueous organic solvent；And
Additive；
Characterized in that, the additive includes the titanate esters of fluorinated ethylene carbonate, PS and cyano-containing.
2. the electrolyte of lithium ion battery according to claim 1, it is characterised in that the titanate esters of the cyano-containing are selected from
One or more in compound with formula (1), formula (2), formula (3), formula (4) and formula (5) structure；
In formula (1)-(5), n is selected from the integer in 1~4, R1、R2、R3Straight chained alkyl, C1 independently selected from C1~C8~
One kind in C8 branched alkyl, C1~C8 alkenyl and aromatic radical containing 6~12 carbon atoms, the straight chained alkyl, branch
Alkyl group, alkenyl, the hydrogen atom on aromatic radical are completely or partially replaced by fluorine atoms.
3. the electrolyte of lithium ion battery according to claim 2, it is characterised in that the titanate esters of the cyano-containing are selected from
Compound with formula (5) structure；
In formula (5), n is selected from the integer in 1~4.
4. the electrolyte of lithium ion battery according to claim 3, it is characterised in that the titanate esters of the cyano-containing are selected from
One or more in tetrem cyano group titanate esters, 4 third cyano group titanate esters, four fourth cyano group titanate esters, 4 penta cyano group titanate esters.
5. the electrolyte of lithium ion battery according to claim 1, it is characterised in that the titanate esters of the cyano-containing are in lithium
Weight/mass percentage composition in the electrolyte of ion battery is 0.1%~10%.
6. the electrolyte of lithium ion battery according to claim 5, it is characterised in that the titanate esters of the cyano-containing are in lithium
Weight/mass percentage composition in the electrolyte of ion battery is 0.5%~3%.
7. the electrolyte of lithium ion battery according to claim 1, it is characterised in that the fluorinated ethylene carbonate is in lithium
Weight/mass percentage composition in the electrolyte of ion battery is 1%~10%.
8. the electrolyte of lithium ion battery according to claim 7, it is characterised in that the fluorinated ethylene carbonate is in lithium
Weight/mass percentage composition in the electrolyte of ion battery is 2%~6%.
9. the electrolyte of lithium ion battery according to claim 1, it is characterised in that the PS is in lithium
Weight/mass percentage composition in the electrolyte of ion battery is 0.5%~10%.
10. the electrolyte of lithium ion battery according to claim 9, it is characterised in that the PS exists
Weight/mass percentage composition in the electrolyte of lithium ion battery is 3%~5%.
11. a kind of lithium ion battery, including：
Positive plate, including plus plate current-collecting body and be arranged on plus plate current-collecting body and comprising positive electrode active materials, conductive agent, binding agent
Positive pole diaphragm；
Negative plate, including negative current collector and be arranged on negative current collector and comprising negative active core-shell material, conductive agent, binding agent
Cathode membrane；
Barrier film, it is interval between positive plate and negative plate；And
Electrolyte；
Characterized in that,
The electrolyte is the electrolyte of the lithium ion battery according to any one of claim 1-10.
12. lithium ion battery according to claim 11, it is characterised in that the charge cutoff voltage of the lithium ion battery
More than or equal to 4.45V.
13. lithium ion battery according to claim 11, it is characterised in that
The positive electrode active materials include lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt
One or more in Mn oxide, lithium nickel cobalt aluminum oxide；
The negative active core-shell material include soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon compound,
One or more in lithium titanate.
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| KR20180093700A (en) * | 2017-02-14 | 2018-08-22 | 에스케이이노베이션 주식회사 | Electrolyte for Secondary Battery and Lithium Secondary Battery Containing the Same |
| CN108987680B (en) * | 2017-05-31 | 2020-07-03 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN111384438B (en) * | 2018-12-29 | 2022-10-18 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN112635823A (en) * | 2019-09-24 | 2021-04-09 | 东莞市杉杉电池材料有限公司 | High-voltage lithium cobalt oxide lithium ion battery electrolyte and lithium ion battery |
| CN111987358A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Titanium-containing lithium ion battery electrolyte additive and preparation method and application thereof |
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| US6255021B1 (en) * | 1997-08-04 | 2001-07-03 | Sanyo Electric Co., Ltd. | Lithium battery including storage stabilized dioxolane-containing electrolyte |
| CN101939874A (en) * | 2008-03-05 | 2011-01-05 | 株式会社杰士汤浅国际 | Non-aqueous electrolyte battery |
| CN102593512A (en) * | 2012-02-14 | 2012-07-18 | 东莞新能源科技有限公司 | Lithium ion battery and electrolyte solution thereof |
| CN103117414A (en) * | 2013-01-31 | 2013-05-22 | 中航锂电（洛阳）有限公司 | Electrolyte solution for negative lithium titanate battery, lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005011042A1 (en) * | 2003-07-28 | 2005-02-03 | Suzuki, Toshihiro | Additive for electrolyte solution of lead acid battery and lead acid battery |
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| US6255021B1 (en) * | 1997-08-04 | 2001-07-03 | Sanyo Electric Co., Ltd. | Lithium battery including storage stabilized dioxolane-containing electrolyte |
| CN101939874A (en) * | 2008-03-05 | 2011-01-05 | 株式会社杰士汤浅国际 | Non-aqueous electrolyte battery |
| CN102593512A (en) * | 2012-02-14 | 2012-07-18 | 东莞新能源科技有限公司 | Lithium ion battery and electrolyte solution thereof |
| CN103117414A (en) * | 2013-01-31 | 2013-05-22 | 中航锂电（洛阳）有限公司 | Electrolyte solution for negative lithium titanate battery, lithium ion battery and preparation method thereof |
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