CN105449274A - Lithium ion battery and electrolyte solution thereof - Google Patents
Lithium ion battery and electrolyte solution thereof Download PDFInfo
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- CN105449274A CN105449274A CN201410505635.7A CN201410505635A CN105449274A CN 105449274 A CN105449274 A CN 105449274A CN 201410505635 A CN201410505635 A CN 201410505635A CN 105449274 A CN105449274 A CN 105449274A
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Abstract
The invention provides a lithium ion battery and an electrolyte solution thereof. The electrolyte solution of the lithium ion battery includes: a non-aqueous organic solvent; a lithium salt dissolved in the non-aqueous organic solvent; and additives. The additives comprise fluoroethylene carbonate (FEC), 1, 3-propane sultone (PS) and cyano-containing titanate. The lithium ion battery comprises the electrolyte solution of the lithium ion battery. The lithium ion battery provided by the invention has excellent storage performance and cycle performance under high temperature and high pressure.
Description
Technical field
The present invention relates to cell art, particularly relate to a kind of lithium ion battery and electrolyte thereof.
Background technology
Lithium ion battery has the advantages such as high-energy-density, long circulation life, wide operating temperature range and environmental protection, has become the main energy sources of mobile electronic device at present.But the develop rapidly that mobile electronic device in recent years, particularly smart mobile phone are lightening, proposes higher demand to the energy density of lithium ion battery.
In order to improve the energy density of lithium ion battery, usually the positive electrode active materials with more high charge cut-ff voltage is used to be a kind of very effective way.But these positive electrode active materials with high charge cut-ff voltage, at high temperature under high pressure owing to having strong oxidizing property, make electrolyte be easy to oxidized decomposition, thus produce a large amount of gas, and then cause lithium ion battery to lose efficacy.In addition, lithium ion battery also can make its cycle performance worsen because of the side reaction (as the precipitation of oxygen, the stripping of transition metal ions) of the oxidation Decomposition of electrolyte and positive electrode active materials self in cyclic process.
Therefore, the oxidation Decomposition of positive electrode active materials to electrolyte under HTHP is effectively suppressed to be improve the key of memory property under high-temperature lithium ion battery high pressure and cycle performance.In lithium ion battery, often adopt fluorinated ethylene carbonate (FEC) to improve the cycle performance of lithium ion battery as additive, adopt PS (PS) to improve the high-temperature storage performance of lithium ion battery as additive.Fig. 1 provides and adopts fluorinated ethylene carbonate (FEC) and PS (PS) at 60 DEG C, to store the thickness swelling after 30 days as the lithium ion battery of additive.Fig. 2 provides the capability retention after adopting fluorinated ethylene carbonate (FEC) and PS (PS) to circulate at 45 DEG C as the lithium ion battery of additive.As can be seen from Figure 1, under 4.4V charge cutoff voltage, the lithium ion battery of fluorinated ethylene carbonate (FEC) and PS (PS) is used to have good memory property, but when voltage is 4.45V, the memory property of lithium ion battery obviously worsens.As can be seen from Figure 2, the cycle performance of the lithium ion battery under 4.45V condition is obviously not as the cycle performance of the lithium ion battery under 4.4V.
Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of lithium ion battery and electrolyte thereof, described lithium ion battery has excellent memory property and cycle performance at high temperature under high pressure.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of electrolyte of lithium ion battery, it comprises: non-aqueous organic solvent; Lithium salts, is dissolved in non-aqueous organic solvent; And additive.Described additive comprises the titanate esters of fluorinated ethylene carbonate (FEC), PS (PS) and cyano-containing.
In a second aspect of the present invention, the invention provides a kind of lithium ion battery, it comprises: positive plate, comprises plus plate current-collecting body and to be arranged on plus plate current-collecting body and to comprise the positive pole diaphragm of positive electrode active materials, conductive agent, binding agent; Negative plate, comprises negative current collector and to be arranged on negative current collector and to comprise the cathode membrane of negative active core-shell material, conductive agent, binding agent; Barrier film, is interval between positive plate and negative plate; And electrolyte.Wherein, described electrolyte is the electrolyte of lithium ion battery according to a first aspect of the present invention.
Relative to prior art, beneficial effect of the present invention is:
Lithium ion battery of the present invention has excellent memory property and cycle performance at high temperature under high pressure.
Accompanying drawing explanation
Fig. 1 stores the thickness swelling after 30 days for adopting fluorinated ethylene carbonate (FEC) and PS (PS) as the lithium ion battery of additive at 60 DEG C;
Fig. 2 is the capability retention after adopting fluorinated ethylene carbonate (FEC) and PS (PS) to circulate at 45 DEG C as the lithium ion battery of additive.
Embodiment
The following detailed description of lithium ion battery according to the present invention and electrolyte thereof and comparative example, embodiment and test result.
First the electrolyte of lithium ion battery is according to a first aspect of the present invention described.
The electrolyte of lithium ion battery according to a first aspect of the present invention, comprising: non-aqueous organic solvent; Lithium salts, is dissolved in non-aqueous organic solvent; And additive.Described additive comprises the titanate esters of fluorinated ethylene carbonate (FEC), PS (PS) and cyano-containing.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, simultaneously containing titanate-based and cyano group in the molecular structure of the titanate compound of described cyano-containing, titanate-based can form positive pole passivating film in positive electrode surface oxidation in lithium ion battery initial charge (changing into) process, and the strong electrophilic inductive effect of cyano group can promote that the filming function of titanate-based strengthens further, can obtain fine and close like this when not increasing the consumption of titanate esters of cyano-containing, stable positive pole passivating film, thus avoid because the cycle performance of the excessive lithium ion battery caused of titanate esters consumption of cyano-containing worsens, and the consumption increase of the titanate esters of cyano-containing can make the memory property of lithium ion battery improve.Transition metal ions in the cyano group contained in the positive pole passivating film generated and positive electrode active materials has very strong complexing, generated positive pole passivating film is made not only to have good thermal stability, and with positive electrode active materials, there is very strong adhesion, thus effectively can suppress the electrolyte particularly non-aqueous organic solvent oxidation Decomposition at high temperature under high pressure of lithium ion battery, thus avoid lithium ion battery aerogenesis, and then improve lithium ion battery cycle performance at high temperature under high pressure.The positive pole passivating film generated also can suppress fluorinated ethylene carbonate (FEC) to form HF in cathode film formation process, oxygen (-O-) in the titanate compound of simultaneously cyano-containing can form hydrogen bond with HF, the PF5 in electrolyte, thus raising lithium ion battery memory property 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 described cyano-containing can be selected from one or more in the compound with general formula (1), general formula (2), general formula (3), general formula (4) and general formula (5) structure;
In general formula (1)-(5), n is selected from the integer in 1 ~ 4, R
1, R
2, R
3independently selected from the straight chained alkyl of C1 ~ C8, the branched alkyl of C1 ~ C8, the thiazolinyl of C1 ~ C8 and containing the one in the aromatic radical of 6 ~ 12 carbon atoms, the hydrogen atom on described straight chained alkyl, branched alkyl, thiazolinyl, aromatic radical is all or part of to be 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 described cyano-containing can be selected from the compound with general formula (5) structure;
In general formula (5), n is selected from the integer in 1 ~ 4.
Relative to the compound that general formula (1) ~ (4) represent, during the compound using general formula (5) to represent, its film-formation result is better, possible reason is that the compound with general formula (5) structure has good symmetry, make the chemical environment residing for four titanate-based in general formula (5) close, thus simultaneous oxidation forms positive pole passivating film in lithium ion battery initial charge (changing into) process, 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 described cyano-containing can be 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.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, the mass percentage of titanate esters in the electrolyte of lithium ion battery of described cyano-containing can be 0.1% ~ 10%.Preferably, the mass percentage of titanate esters in the electrolyte of lithium ion battery of described cyano-containing can be 0.5% ~ 3%.When the mass percentage in electrolyte at lithium ion battery of the titanate esters of cyano-containing lower than 0.1% time, it cannot form fine and close positive pole passivating film at surface of positive electrode active material, and then lithium ion battery memory property at high temperature under high pressure can not get remarkable improvement; When the mass percentage in electrolyte at lithium ion battery of the titanate esters of cyano-containing higher than 10% time, thicker positive pole passivating film can be formed, enlarge markedly the impedance at positive pole interface, the polarization of lithium ion battery under HTHP in cyclic process is increased, thus worsens the cycle performance of lithium ion battery.
In the electrolyte of lithium ion battery according to a first aspect of the present invention, described fluorinated ethylene carbonate (FEC) mass percentage in the electrolyte of lithium ion battery can be 1% ~ 10%.Preferably, described fluorinated ethylene carbonate (FEC) mass percentage in the electrolyte of lithium ion battery can be 2% ~ 6%.When the mass percentage in the electrolyte of fluorinated ethylene carbonate (FEC) at lithium ion battery lower than 1% time, the user demand of the lithium ion battery long circulation life under HTHP cannot be met, and the cycle performance of lithium ion battery is acutely failed; When the mass percentage in the electrolyte of fluorinated ethylene carbonate (FEC) at lithium ion battery higher than 10% time, lithium ion battery memory property at high temperature under high pressure and cycle performance all can worsen.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, described 1,3-N-morpholinopropanesulfonic acid lactone (PS) mass percentage in the electrolyte of lithium ion battery can be 0.5% ~ 10%, preferably, described PS (PS) mass percentage in the electrolyte of lithium ion battery can be 3% ~ 5%.When the mass percentage in the electrolyte of PS (PS) at lithium ion battery lower than 0.5% time, lithium ion battery memory property at high temperature under high pressure can not get effective improvement; When the mass percentage in the electrolyte of PS (PS) at lithium ion battery higher than 10% time, the capacity of lithium ion battery can significantly reduce, and lithium ion battery cycle performance at high temperature under high pressure also can worsen.
In the electrolyte of lithium ion battery described according to a first aspect of the present invention, described lithium salts can comprise LiPF
6, LiBF
4, 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 described 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, described non-aqueous organic solvent can be selected from one or more in propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), gamma-butyrolacton (GBL).
Secondly lithium ion battery is according to a second aspect of the present invention described.
Lithium ion battery according to a second aspect of the present invention comprises: positive plate, comprises plus plate current-collecting body and to be arranged on plus plate current-collecting body and to comprise the positive pole diaphragm of positive electrode active materials, conductive agent, binding agent; Negative plate, comprises negative current collector and to be arranged on negative current collector and to comprise the cathode membrane of negative active core-shell material, conductive agent, binding agent; Barrier film, is interval between positive plate and negative plate; And electrolyte.Wherein, described electrolyte is the electrolyte of lithium ion battery according to a first aspect of the present invention.
In lithium ion battery described according to a second aspect of the present invention, the charge cutoff voltage of described lithium ion battery can be more than or equal to 4.45V.
In lithium ion battery described according to a second aspect of the present invention, described positive electrode active materials can comprise one or more in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide.
In lithium ion battery described according to a second aspect of the present invention, described negative active core-shell material can comprise one or more in soft carbon, hard 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, the optional one in polyethylene (PE) porous polymer film, polyethylene/polypropylene (PE/PP) MULTILAYER COMPOSITE porous polymer film, the ceramic porous polymer film processed of described barrier film.
Following explanation is according to comparative example, the embodiment of lithium ion battery of the present invention and electrolyte thereof.
Comparative example 1
(1) electrolyte of lithium ion battery is prepared
The electrolyte of lithium ion battery take concentration as the LiPF6 of 1.15M is lithium salts, with the mixture (mass ratio is for 30:30:40) of ethylene carbonate (EC), propene carbonate (PC) and diethyl carbonate (DEC) for non-aqueous organic solvent.Also containing additive in the electrolyte of lithium ion battery in addition, additive is the mass percentage in the electrolyte of lithium ion battery to be the fluorinated ethylene carbonate (FEC) of 5% and the mass percentage in the electrolyte of lithium ion battery be 4% PS (PS).
(2) positive plate of lithium ion battery is prepared
By positive electrode active materials cobalt acid lithium (LiCoO
2), conductive agent Super-P, binding agent polyvinylidene fluoride (PVDF) in mass ratio 97:1.4:1.6 mix with solvent N-methyl pyrilidone (NMP) and make anode sizing agent, afterwards anode sizing agent is uniformly coated on plus plate current-collecting body aluminium foil, cold pressing after drying at 85 DEG C afterwards, then trimming, cut-parts, itemize is carried out, and 4h is dried under the vacuum condition of 85 DEG C, welding positive pole ear, makes the positive plate of lithium ion battery.
(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 to mix with solvent deionized water and make cathode size, afterwards cathode size is uniformly coated on negative current collector Copper Foil, and dry at 85 DEG C, then trimming, cut-parts, itemize is carried out, and 4h is dried under the vacuum condition of 110 DEG C, welding negative lug, makes the negative plate of lithium ion battery.
(4) lithium ion battery is prepared
By obtained positive plate, barrier film (PE porous polymer film), negative plate is folded in order, barrier film is made to be between positive plate and negative plate, winding obtains naked battery core, afterwards naked battery core is placed in battery external packing, the electrolyte of above-mentioned preparation is injected in dried battery core, through encapsulation, leave standstill, change into (with 0.02C constant current charge to 3.4V, again with 0.1C constant current charge to 3.85V), shaping, after the operations such as capacity, complete the preparation of lithium ion battery, wherein, the thickness of lithium ion battery is 4.2mm, width is 32mm, length is 82mm.
Comparative example 2
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery to be the fluorinated ethylene carbonate (FEC) of 7% and the mass percentage in the electrolyte of lithium ion battery be 4% PS (PS).
Embodiment 1
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Embodiment 2
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% 4 third cyano group titanate esters.
Embodiment 3
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% four fourth cyano group titanate esters.
Embodiment 4
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% 4 penta cyano group titanate esters.
Embodiment 5
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.1% tetrem cyano group titanate esters.
Embodiment 6
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 10% tetrem cyano group titanate esters.
Embodiment 7
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.3% tetrem cyano group titanate esters.
Embodiment 8
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 1% tetrem cyano group titanate esters.
Embodiment 9
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 3% tetrem cyano group titanate esters.
Embodiment 10
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 5% tetrem cyano group titanate esters.
Embodiment 11
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 7% tetrem cyano group titanate esters.
Embodiment 12
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 1%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Embodiment 13
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 7%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Embodiment 14
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 10%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 4% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Embodiment 15
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 0.5% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Embodiment 16
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 6% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Embodiment 17
Method according to comparative example 1 prepares lithium ion battery, is the step (namely in step (1)) at the electrolyte preparing lithium ion battery:
Additive is the mass percentage in the electrolyte of lithium ion battery is the fluorinated ethylene carbonate (FEC) of 5%, the mass percentage in the electrolyte of lithium ion battery to be the PS (PS) of 10% and the mass percentage in the electrolyte of lithium ion battery be 0.5% tetrem cyano group titanate esters.
Performance test process according to lithium ion battery of the present invention and test result are finally described.
(1) the cycle performance test under high-temperature lithium ion battery high pressure
At 45 DEG C, first with the constant current of 0.7C to lithium ion cell charging to 4.45V, further with 4.45V constant-potential charge to electric current for 0.05C, then with the constant current of 1C, 3.0V is discharged to lithium ion battery, this is a charge and discharge cycles process, and this discharge capacity is the discharge capacity of first time circulation.Lithium ion battery is carried out cycle charge discharge electrical testing in a manner described, gets the discharge capacity of the 500th circulation.Cycle performance under high-temperature lithium ion battery high pressure is evaluated by its capability retention.
Capability retention (%)=(discharge capacity of the discharge capacity/first time circulation of the 500th circulation) × 100% of lithium ion battery.
(2) the memory property test under high-temperature lithium ion battery high pressure
At 25 DEG C, first with the constant current of 0.5C to lithium ion cell charging to 4.45V, be less than 0.05C with 4.45V constant-potential charge to electric current further, obtain lithium ion battery store before thickness; Then lithium ion battery is placed in 60 DEG C of environment and stores 30 days, obtain the thickness after lithium ion battery storage.Memory property under high-temperature lithium ion battery high pressure is evaluated by the thickness swelling after its storage.
Thickness swelling (%)=[thickness before (thickness before the thickness-storage after storage)/storage] × 100% of lithium ion battery.
Table 1 provides parameter and the performance test results of comparative example 1-2 and embodiment 1-17.
The parameter of table 1 comparative example 1-2 and embodiment 1-17 and the performance test results
Next the performance test results of lithium ion battery is analyzed.
Known from the contrast of comparative example 1 and embodiment 1-4, effectively can improve the cycle performance under high-temperature lithium ion battery high pressure and memory property add the titanate compound of the cyano-containing of 0.5% in the electrolyte of lithium ion battery after.This is because simultaneously containing titanate-based and cyano group in the molecular structure of the titanate compound of cyano-containing, titanate-based can form positive pole passivating film in positive electrode surface oxidation in lithium ion battery initial charge (changing into) process, and the strong electrophilic inductive effect of cyano group can promote that the filming function of titanate-based strengthens further, fine and close, stable positive pole passivating film can be obtained when not increasing the consumption of titanate esters of cyano-containing like this, thus avoid because the cycle performance of the excessive lithium ion battery caused of titanate esters consumption of cyano-containing worsens.Transition metal ions in the cyano group contained in the positive pole passivating film generated and positive electrode active materials has very strong complexing, generated positive pole passivating film is made not only to have good thermal stability, and with positive electrode active materials, there is very strong adhesion, thus effectively can suppress the electrolyte particularly non-aqueous organic solvent oxidation Decomposition at high temperature under high pressure of lithium ion battery, thus avoid lithium ion battery aerogenesis, and then improve lithium ion battery cycle performance at high temperature under high pressure.
Also known from the contrast of embodiment 1-4, in the electrolyte of lithium ion battery, the improvement of tetrem cyano group titanate esters to the cycle performance under high-temperature lithium ion battery high pressure of interpolation 0.5% is the most obvious.Possible reason is the growth (namely n increases) of the strand of titanate compound along with cyano-containing, and the viscosity of electrolyte increases, thus the polarization of lithium ion battery in cyclic process is increased.
Known from the contrast of embodiment 1 and embodiment 5-11, the mass percentage of the titanate compound of cyano-containing also can affect the performance of lithium ion battery.This is because when the mass percentage of the titanate compound of cyano-containing is lower, the positive pole passivating film of formation is fine and close not, fully can not cover positive electrode active materials; When the mass percentage of the titanate compound of cyano-containing is higher, thicker positive pole passivating film can be formed, the interface impedance of inside lithium ion cell is caused to increase, although improve the memory property of lithium ion battery, obviously can to the cycle performance generation deterioration to a certain degree of lithium ion battery because polarizing.
Known from the contrast of comparative example 1-2, embodiment 1 and embodiment 12-14, the mass percentage of fluorinated ethylene carbonate (FEC) also can impact the performance of lithium ion battery.Known from the contrast of comparative example 1-2, when not adding tetrem cyano group titanate esters, the mass percentage increasing fluorinated ethylene carbonate (FEC) obviously can worsen lithium ion battery memory property at high temperature under high pressure and cycle performance, and this may be because the HF that fluorinated ethylene carbonate (FEC) is formed in cathode film formation process can worsen positive pole.And it is known from the contrast of embodiment 1 and embodiment 12-14, when after interpolation tetrem cyano group titanate esters, the mass percentage increasing fluorinated ethylene carbonate (FEC) can significantly improve lithium ion battery memory property at high temperature under high pressure and cycle performance, this is because tetrem cyano group titanate esters can form fine and close positive pole passivating film at positive electrode surface, thus suppressing the negative effect of fluorinated ethylene carbonate (FEC), the oxygen (-O-) simultaneously in tetrem cyano group titanate esters can form hydrogen bond with HF, the PF5 in electrolyte.But the mass percentage of fluorinated ethylene carbonate (FEC) too high (embodiment 14), the cycle performance of lithium ion battery worsens on the contrary.
Known from the contrast of embodiment 1 and embodiment 15-17, the mass percentage of PS (PS) also can impact the performance of lithium ion battery.The mass percentage increasing PS (PS) can significantly improve lithium ion battery cycle performance at high temperature under high pressure.
Claims (10)
1. an electrolyte for lithium ion battery, comprising:
Non-aqueous organic solvent;
Lithium salts, is dissolved in non-aqueous organic solvent; And
Additive;
It is characterized in that, described additive comprises the titanate esters of fluorinated ethylene carbonate (FEC), PS (PS) and cyano-containing.
2. the electrolyte of lithium ion battery according to claim 1, it is characterized in that, the titanate esters of described cyano-containing is selected from one or more in the compound with general formula (1), general formula (2), general formula (3), general formula (4) and general formula (5) structure;
In general formula (1)-(5), n is selected from the integer in 1 ~ 4, R1, R2, R3 are independently selected from the straight chained alkyl of C1 ~ C8, the branched alkyl of C1 ~ C8, the thiazolinyl of C1 ~ C8 and containing the one in the aromatic radical of 6 ~ 12 carbon atoms, and the hydrogen atom on described straight chained alkyl, branched alkyl, thiazolinyl, aromatic radical is all or part of to be replaced by fluorine atoms.
3. lithium-ion battery electrolytes according to claim 2, is characterized in that, the titanate esters of described cyano-containing is selected from the compound with general formula (5) structure;
In general formula (5), n is selected from the integer in 1 ~ 4.
4. the electrolyte of lithium ion battery according to claim 3, is characterized in that, the titanate esters of described cyano-containing is 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, is characterized in that, the mass percentage of titanate esters in the electrolyte of lithium ion battery of described cyano-containing is 0.1% ~ 10%, is preferably 0.5% ~ 3%.
6. the electrolyte of lithium ion battery according to claim 1, is characterized in that, the mass percentage of described fluorinated ethylene carbonate (FEC) in the electrolyte of lithium ion battery is 1% ~ 10%, is preferably 2% ~ 6%.
7. the electrolyte of lithium ion battery according to claim 1, is characterized in that, the mass percentage of described PS (PS) in the electrolyte of lithium ion battery is 0.5% ~ 10%, is preferably 3% ~ 5%.
8. a lithium ion battery, comprising:
Positive plate, comprises plus plate current-collecting body and to be arranged on plus plate current-collecting body and to comprise the positive pole diaphragm of positive electrode active materials, conductive agent, binding agent;
Negative plate, comprises negative current collector and to be arranged on negative current collector and to comprise the cathode membrane of negative active core-shell material, conductive agent, binding agent;
Barrier film, is interval between positive plate and negative plate; And
Electrolyte;
It is characterized in that,
Described electrolyte is the electrolyte of the lithium ion battery according to any one of claim 1-7.
9. lithium ion battery according to claim 8, is characterized in that, the charge cutoff voltage of described lithium ion battery is more than or equal to 4.45V.
10. lithium ion battery according to claim 8, is characterized in that,
Described positive electrode active materials comprises one or more in lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide;
Described negative active core-shell material comprises one or more in soft carbon, hard carbon, Delanium, native graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate.
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| CN108428940A (en) * | 2017-02-14 | 2018-08-21 | Sk新技术株式会社 | Electrolyte for lithium secondary battery and the lithium secondary battery including it |
| CN108987680A (en) * | 2017-05-31 | 2018-12-11 | 宁德时代新能源科技股份有限公司 | Lithium ion battery |
| CN111384438A (en) * | 2018-12-29 | 2020-07-07 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous 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 |
| 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 |
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| CN105449274B (en) | 2017-11-21 |
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