CN105244538B - Lithium ion secondary battery and electrolyte thereof - Google Patents
Lithium ion secondary battery and electrolyte thereof Download PDFInfo
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- CN105244538B CN105244538B CN201410322843.3A CN201410322843A CN105244538B CN 105244538 B CN105244538 B CN 105244538B CN 201410322843 A CN201410322843 A CN 201410322843A CN 105244538 B CN105244538 B CN 105244538B
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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 secondary battery and an electrolyte thereof. The electrolyte of the lithium ion secondary battery includes: a lithium salt; a non-aqueous organic solvent; and an additive. The additive comprises a diisocyanate compound containing ether bond having the structure of formula 1 and/or formula 2; in the formula 1, m, n and p are integers of 1-4 respectively; in the formula 2, x and y are integers of 1-4 respectively; the mass percentage of the diisocyanate compound containing ether bond and having the structure of formula 1 and/or formula 2 in the electrolyte of the lithium ion secondary battery is 0.1-2.5%. The lithium ion secondary battery includes: a positive plate; a negative plate; the isolation film is spaced between the positive plate and the negative plate; and the above-mentioned electrolyte. The lithium ion secondary battery has good high-temperature storage performance, normal-temperature cycle performance and high-temperature cycle performance under high voltage.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of lithium rechargeable battery and its electrolyte.
Background technology
Lithium rechargeable battery has the advantages that high operating voltage, long lifespan and charging rate are fast, but with technology
Continue to develop, people require that lithium rechargeable battery has higher energy density.Currently in order to further improving lithium ion two
The energy density of primary cell, mainly improves the charge cutoff voltage of lithium rechargeable battery, makes positive pole abjection higher proportion of
Lithium ion reaches the purpose for improving energy density so as to obtain higher capacity.But identical positive active material is charged to
During higher blanking voltage, the oxidability of positive pole can be also improved, so that the problem of oxidation of electrolyte is even more serious.Especially
It is that under high voltage fully charged state, the negative pole of lithium rechargeable battery has high reproducibility, just has high oxidative.
In actual use, the lasting of electronic product may all make lithium ion using factors such as heating, environment temperature rises
Secondary cell is under the condition of high temperature.At high temperature, the positive pole of lithium rechargeable battery and the reactivity of negative pole further increase
By force, reacted between the positive pole, negative pole and electrolyte that cause lithium rechargeable battery, gas is produced, so as to cause lithium ion
Secondary cell expands.This does not only result in the damage of lithium rechargeable battery, and the lithium rechargeable battery is used while also resulting in
Equipment damage, when serious due to lithium rechargeable battery dilatancy cause inside battery occur short circuit or battery
Packaging, which is burst, causes flammable electrolyte to be revealed, and has the risk for causing the security incidents such as fire.It would therefore be desirable to have the technology of effect
The problem of decomposition and lithium rechargeable battery flatulence to solve electrolyte.
In lithium rechargeable battery, cyclic carbonate and linear carbonate typically are used as non-aqueous organic solvent, but
It is that under high voltage high temperature storage, the non-aqueous organic solvent of lithium rechargeable battery easily aoxidizes aerogenesis by positive pole.2013 10
The Chinese patent application publication No. that the moon 30 was announced discloses one kind for CN103380530A patent and adds six in the electrolytic solution
Methylene diisocyanate (HDI) as additive in the method for the high-temperature storage performance for improving lithium rechargeable battery, still
Hexamethylene diisocyanate (HDI) can cause the cycle performance of lithium rechargeable battery to be deteriorated.
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 rechargeable battery and its electricity
Liquid is solved, the lithium rechargeable battery has good high-temperature storage performance, normal-temperature circulating performance and high temperature under high voltages
Cycle performance.
In order to realize foregoing invention purpose, in the first aspect of the present invention, the invention provides a kind of lithium ion secondary electricity
The electrolyte in pond, it includes：Lithium salts；Non-aqueous organic solvent；And additive.The additive includes having formula 1 and/or formula 2
The diisocyanate cpd of the ether-containing key of structure；In formula 1, m, n, p are respectively 1~4 integer；In formula 2, x, y difference
For 1~4 integer；
Electricity of the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 in lithium rechargeable battery
It is 0.1%~2.5% to solve the weight/mass percentage composition in liquid.
In the second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, it includes：Positive plate, including
Plus plate current-collecting body and the positive pole diaphragm containing positive active material being arranged on plus plate current-collecting body；Negative plate, including negative pole
Collector and the cathode membrane containing negative electrode active material being arranged on negative current collector；Barrier film, is interval in positive plate
Between negative plate；And electrolyte.Wherein, the electrolyte is the lithium rechargeable battery according to first aspect present invention
Electrolyte.
Beneficial effects of the present invention are as follows：
1. the electrolyte of the lithium rechargeable battery of the present invention contains the two different of the ether-containing key with formula 1 and/or the structure of formula 2
Cyanate esters, it can form one layer of passivating film in the pole piece of lithium rechargeable battery, even under high voltages,
The side reaction between pole piece and electrolyte can be effectively prevented, so as to improve the high-temperature storage performance of lithium rechargeable battery.
2. two of the ether-containing key with formula 1 and/or the structure of formula 2 in the electrolyte of the lithium rechargeable battery of the present invention are different
The passivating film of cyanate esters formation contains more oxygen atom, so as to reduce lithium ion through resistance during passivating film,
Improve the interface performance between electrolyte and pole piece, and then improve the normal-temperature circulating performance and high temperature circulation of lithium rechargeable battery
Performance.
Embodiment
The following detailed description of the lithium rechargeable battery according to the present invention and its electrolyte and embodiment, comparative example and survey
Test result.
Illustrate the electrolyte of lithium rechargeable battery according to a first aspect of the present invention first.
The electrolyte of lithium rechargeable battery according to a first aspect of the present invention, including：Lithium salts；Non-aqueous organic solvent；With
And additive.The additive includes the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2；In formula 1,
M, n, p are respectively 1~4 integer；In formula 2, x, y are respectively 1~4 integer；
Electricity of the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 in lithium rechargeable battery
It is 0.1%~2.5% to solve the weight/mass percentage composition in liquid.
The implication of explanation "and/or", two isocyanides of the ether-containing key with formula 1 and/or the structure of formula 2 are required supplementation with herein
Weight/mass percentage composition of the ester compound in the electrolyte of lithium rechargeable battery refers to the diisocyanate of ether-containing key
Weight/mass percentage composition of the compound total amount in the electrolyte of lithium rechargeable battery；In other words, if the two of the ether-containing key
Isocyanate compound is only the diisocyanate cpd of the ether-containing key with the structure of formula 1, the then ether-containing key with the structure of formula 1
Weight/mass percentage composition of the diisocyanate cpd in the electrolyte of lithium rechargeable battery be 0.1%~2.5%；If
The diisocyanate cpd of the ether-containing key is only the diisocyanate cpd of the ether-containing key with the structure of formula 2, then has
Weight/mass percentage composition of the diisocyanate cpd of the ether-containing key of the structure of formula 2 in the electrolyte of lithium rechargeable battery be
0.1%~2.5%；If the diisocyanate cpd of the ether-containing key is the ether-containing key with the structure of formula 1 and the structure of formula 2
Diisocyanate cpd, the then diisocyanate cpd of the ether-containing key with the structure of formula 1 and the ether-containing key with the structure of formula 2
Diisocyanate cpd weight/mass percentage composition of the summation in the electrolyte of lithium rechargeable battery for 0.1%~
2.5%.
In the present invention, by the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 be added to lithium from
In the electrolyte of sub- secondary cell, it may be such that lithium rechargeable battery has good high-temperature storage performance, normal-temperature circulating performance
And high temperature cyclic performance.This be due to the ether-containing key with formula 1 and/or the structure of formula 2 diisocyanate cpd easily exist
Pole piece one layer of relatively stable passivating film of formation, even under high voltages, also can effectively prevent pole piece and electrolyte it
Between side reaction, so as to improve the high-temperature storage performance of lithium rechargeable battery；In addition, containing with formula 1 and/or the structure of formula 2
The passivating film of the diisocyanate cpd formation of ehter bond contains more oxygen atom, so as to reduce lithium ion through passivating film
When resistance, improve the interface performance between electrolyte and pole piece, and then improve the normal-temperature circulating performance of lithium rechargeable battery
And high temperature cyclic performance.
If the quality percentage in electrolyte with the diisocyanate cpd of the ether-containing key of formula 1 and/or the structure of formula 2 contains
Amount it is excessive (>2.5%), then the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 is formed in pole piece
Passivating film is blocked up so that the impedance increase of pole piece, deteriorates the interface performance between pole piece and electrolyte, reduction lithium ion is in pole piece
With the conductibility at the interface of electrolyte, so as to deteriorate the normal-temperature circulating performance and high temperature cyclic performance of lithium rechargeable battery.Such as
The weight/mass percentage composition in fruit electrolyte with the diisocyanate cpd of the ether-containing key of formula 1 and/or the structure of formula 2 it is very few (<
0.1%) passivating film that, then the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 is formed in pole piece
It is excessively thin, it is impossible to the side reaction between electrolyte and pole piece effectively to be prevented, so as to can not effectively improve lithium rechargeable battery
High-temperature storage performance, normal-temperature circulating performance and high temperature cyclic performance.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the lithium salts may be selected from LiN
(CaF2a+1SO2)(CbF2b+1SO2)、LiPF6、LiBF4、LiBOB、LiAsF6、Li(CF3SO2)2N、LiCF3SO3And LiClO4In
At least one, wherein, a, b be natural number.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the concentration of the lithium salts can be
0.5M~2M.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the non-aqueous organic solvent can
Combination including cyclic carbonate and linear carbonate.The cyclic carbonate has higher dielectric constant, can very well and lithium
Ion formation solvation lithium ion molecule；The linear carbonate has relatively low viscosity, so as to be conducive to the conduction of lithium ion.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the cyclic carbonate is optional
From at least one of ethylene carbonate (EC), propene carbonate (PC) and butylene (BC)；The linear carbonate
It may be selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), carbonic acid first
At least one of propyl ester (MPC) and ethyl propyl carbonic acid ester (EPC).
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the cyclic carbonate is in lithium
Weight/mass percentage composition in the electrolyte of ion secondary battery can be 10%~70%；The linear carbonate is in lithium ion secondary
Weight/mass percentage composition in the electrolyte of battery can be 15%~80%.
It is described with the structure of formula 1 in the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention
The diisocyanate cpd of ether-containing key may be selected from the compound with molecular formula 1-1 structures to molecular formula 1-20 structures extremely
Few one kind,
It is described with the structure of formula 2 in the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention
The diisocyanate cpd of ether-containing key may be selected from the compound with molecular formula 2-1 structures to molecular formula 2-6 structures extremely
Few one kind,
It is described that there is formula 1 and/or formula in the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention
Weight/mass percentage composition of the diisocyanate cpd of the ether-containing key of 2 structures in the electrolyte of lithium rechargeable battery can be
0.2%~2%.That is, if the diisocyanate cpd of described ether-containing key is only two isocyanides of the ether-containing key with the structure of formula 1
Ester compound, then the diisocyanate cpd of the ether-containing key with the structure of formula 1 is in the electrolyte of lithium rechargeable battery
Weight/mass percentage composition be 0.2%~2%；If the diisocyanate cpd of the ether-containing key is only with the structure of formula 2
The diisocyanate cpd of ether-containing key, then the diisocyanate cpd of the ether-containing key with the structure of formula 2 is in lithium ion secondary
Weight/mass percentage composition in the electrolyte of battery is 0.2%~2%；If the diisocyanate cpd of the ether-containing key is tool
There is the diisocyanate cpd of the ether-containing key of the structure of formula 1 and the structure of formula 2, then two isocyanic acids of the ether-containing key with the structure of formula 1
Electrolyte of the summation of the diisocyanate cpd of ester compounds and ether-containing key with the structure of formula 2 in lithium rechargeable battery
In weight/mass percentage composition be 0.2%~2%.
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, in addition to：1,3- propane sulphurs
Lactone (PS).
In the electrolyte of lithium rechargeable battery described according to a first aspect of the present invention, the PS
Weight/mass percentage composition in the electrolyte of lithium rechargeable battery can be 0.1%~5%.
Secondly lithium rechargeable battery according to a second aspect of the present invention is illustrated.
Lithium rechargeable battery according to a second aspect of the present invention, including：Positive plate, including plus plate current-collecting body and setting
In the positive pole diaphragm containing positive active material on plus plate current-collecting body；Negative plate, including negative current collector and be arranged at negative
The cathode membrane containing negative electrode active material on the collector of pole；Barrier film, is interval between positive plate and negative plate；And electricity
Solve liquid.Wherein, the electrolyte is the electrolyte of the lithium rechargeable battery according to first aspect present invention.
In lithium rechargeable battery described according to a second aspect of the present invention, the charging of the lithium rechargeable battery is cut
Can be 4.35V~4.9V to voltage.
In lithium rechargeable battery described according to a second aspect of the present invention, the positive active material may be selected from
LixCoyM1-yA2、LiMnzN2-zO4At least one of, wherein, 0.97≤x≤1.06,0≤y≤1,0≤z≤2, M be selected from Ni,
At least one of Fe, Mg, Al, Ti, V, Ge, Zr, Mn, Cr, A are selected from least one of O, F, S, P, and N is selected from Co, Ni, Fe
At least one of.The diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 of the present invention is easily in pole piece
Surface forms one layer of relatively stable passivating film, while the molten of transition metal in positive active material (Mn, Co, Ni etc.) can be prevented
Go out, so as to more effectively improve the high-temperature storage performance of lithium rechargeable battery.
Next explanation is according to the lithium rechargeable battery of the present invention and its embodiment and comparative example of electrolyte.
Embodiment 1
(1) preparation of the positive plate of lithium rechargeable battery
By positive active material cobalt acid lithium LiCoO2, conductive agent Super-P, bonding agent PVDF in mass ratio 96:2:2 add
It is well mixed into solvent N-methyl pyrilidone (NMP) and anode sizing agent is made, anode sizing agent is coated in current collector aluminum foil,
Afterwards by cold pressing, drying (forming positive pole diaphragm), soldering polar ear, the positive plate of lithium rechargeable battery is made.
(2) preparation of the negative plate of lithium rechargeable battery
By negative electrode active material graphite, conductive agent Super-P, thickener CMC, bonding agent SBR in mass ratio 96.5:1.0:
1.0:1.5 be added in solvent deionized water be well mixed cathode size is made, cathode size is coated on copper foil of affluxion body,
Afterwards by cold pressing, drying (formation cathode membrane), soldering polar ear, the negative plate of lithium rechargeable battery is made.
(3) preparation of the electrolyte of lithium rechargeable battery
The electrolyte of lithium rechargeable battery is using concentration as 1M lithium hexafluoro phosphates (LiPF6) it is lithium salts, with ethylene carbonate
(EC), the mixture of propene carbonate (PC) and diethyl carbonate (DEC) is non-aqueous organic solvent, wherein the matter of each carbonic ester
Amount is than being EC:PC:DEC=30:30:40.In addition, also containing additive in electrolyte, additive is in lithium rechargeable battery
Electrolyte in weight/mass percentage composition be 0.1% the compound with molecular formula 1-2 structures.
(4) preparation of lithium rechargeable battery
By the positive plate, negative plate and barrier film (polyethylene, PE) of the lithium rechargeable battery of preparation by winding work
Skill is fabricated to injection electrolyte after battery core, vacuum bakeout, stands 24 hours, afterwards with 0.1C constant current charge to 4.4V
(charge cutoff voltage), then drops to 0.05C with 4.4V constant-voltage charges to electric current；Then it is discharged to 0.5C constant current
3.0V, is repeated 2 times discharge and recharge, finally completes the preparation of lithium rechargeable battery again with 0.5C constant current charge to 3.9V.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.2% to have
The compound of molecular formula 1-2 structures.
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures.
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0% to have
The compound of molecular formula 1-2 structures.
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.5% to have
The compound of molecular formula 1-2 structures.
Embodiment 6
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 2.0% to have
The compound of molecular formula 1-2 structures.
Embodiment 7
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 2.5% to have
The compound of molecular formula 1-2 structures.
Embodiment 8
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0% to have
The compound of molecular formula 2-1 structures.
Embodiment 9
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0% to have
The compound of molecular formula 2-6 structures.
Embodiment 10
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0% to have
The compound of molecular formula 1-7 structures.
Embodiment 11
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0% to have
The compound of molecular formula 1-9 structures.
Embodiment 12
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0% to have
The compound of molecular formula 1-16 structures.
Embodiment 13
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the weight/mass percentage composition in the electrolyte of lithium rechargeable battery have for 0.5%
The compound of molecular formula 2-1 structures.
Embodiment 14
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the weight/mass percentage composition in the electrolyte of lithium rechargeable battery have for 0.5%
The compound of molecular formula 2-6 structures.
Embodiment 15
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the weight/mass percentage composition in the electrolyte of lithium rechargeable battery have for 0.5%
The compound of molecular formula 1-7 structures.
Embodiment 16
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the weight/mass percentage composition in the electrolyte of lithium rechargeable battery have for 0.5%
The compound of molecular formula 1-9 structures.
Embodiment 17
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the weight/mass percentage composition in the electrolyte of lithium rechargeable battery have for 0.5%
The compound of molecular formula 1-16 structures.
Embodiment 18
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 19
Method according to embodiment 2 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 20
Method according to embodiment 3 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 21
Method according to embodiment 4 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 22
Method according to embodiment 5 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 23
Method according to embodiment 6 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 24
Method according to embodiment 7 prepares lithium rechargeable battery, simply lithium rechargeable battery electrolyte just
In the preparation (i.e. step (1)) of pole piece, positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 25
Method according to embodiment 8 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 26
Method according to embodiment 9 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 27
Method according to embodiment 10 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 28
Method according to embodiment 11 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 29
Method according to embodiment 12 prepares lithium rechargeable battery, is the system in the positive plate of lithium rechargeable battery
In standby (i.e. step (1)), positive active material is LiNi1/3Co1/3Mn1/3O2。
Embodiment 30
Method according to embodiment 3 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the electrolyte of lithium rechargeable battery is with ethylene carbonate (EC), propene carbonate (PC), carbonic acid two
The mixture of ethyl ester (DEC) and methyl ethyl carbonate (EMC) is non-aqueous organic solvent, wherein the mass ratio of each carbonic ester is EC:
PC:DEC:EMC=20:20:20:40.
Embodiment 31
Method according to embodiment 4 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the electrolyte of lithium rechargeable battery is with ethylene carbonate (EC), propene carbonate (PC), carbonic acid two
The mixture of ethyl ester (DEC) and methyl ethyl carbonate (EMC) is non-aqueous organic solvent, wherein the mass ratio of each carbonic ester is EC:
PC:DEC:EMC=20:20:20:40.
Embodiment 32
Method according to embodiment 5 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the electrolyte of lithium rechargeable battery is with ethylene carbonate (EC), propene carbonate (PC), carbonic acid two
The mixture of ethyl ester (DEC) and methyl ethyl carbonate (EMC) is non-aqueous organic solvent, wherein the mass ratio of each carbonic ester is EC:
PC:DEC:EMC=20:20:20:40.
Embodiment 33
Method according to embodiment 6 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the electrolyte of lithium rechargeable battery is with ethylene carbonate (EC), propene carbonate (PC), carbonic acid two
The mixture of ethyl ester (DEC) and methyl ethyl carbonate (EMC) is non-aqueous organic solvent, wherein the mass ratio of each carbonic ester is EC:
PC:DEC:EMC=20:20:20:40.
Embodiment 34
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the PS that the weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.1%.
Embodiment 35
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the PS that the weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0%.
Embodiment 36
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the PS that the weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 3.0%.
Embodiment 37
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.5% to have
The compound of molecular formula 1-2 structures and the PS that the weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 5.0%.
Embodiment 38
Method according to embodiment 21 prepares lithium rechargeable battery, except following difference：
In the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, the mass ratio of each carbonic ester is EC:PC:
DEC=20:20:60；
In the preparation (i.e. step (4)) of lithium rechargeable battery, the charge cutoff voltage of lithium rechargeable battery is
4.35V。
Embodiment 39
Method according to embodiment 38 prepares lithium rechargeable battery, simply (is walked in the preparation of lithium rechargeable battery
Suddenly in (4)), the charge cutoff voltage of lithium rechargeable battery is 4.4V.
Embodiment 40
Method according to embodiment 38 prepares lithium rechargeable battery, simply (is walked in the preparation of lithium rechargeable battery
Suddenly in (4)), the charge cutoff voltage of lithium rechargeable battery is 4.5V.
Embodiment 41
Method according to embodiment 38 prepares lithium rechargeable battery, simply (is walked in the preparation of lithium rechargeable battery
Suddenly in (4)), the charge cutoff voltage of lithium rechargeable battery is 4.6V.
Embodiment 42
Method according to embodiment 38 prepares lithium rechargeable battery, except following difference：
In the preparation (i.e. step (1)) of the positive plate of lithium rechargeable battery, positive active material is
LiNi0.5Mn1.5O4；
In the preparation (i.e. step (4)) of lithium rechargeable battery, the charge cutoff voltage of lithium rechargeable battery is
4.7V。
Embodiment 43
Method according to embodiment 42 prepares lithium rechargeable battery, simply (is walked in the preparation of lithium rechargeable battery
Suddenly in (4)), the charge cutoff voltage of lithium rechargeable battery is 4.8V.
Embodiment 44
Method according to embodiment 42 prepares lithium rechargeable battery, simply (is walked in the preparation of lithium rechargeable battery
Suddenly in (4)), the charge cutoff voltage of lithium rechargeable battery is 4.9V.
Comparative example 1
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), without any additive.
Comparative example 2
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the tool that additive is 0.01% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery
There is the compound of molecular formula 1-2 structures.
Comparative example 3
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 5.0% to have
The compound of molecular formula 1-2 structures.
Comparative example 4
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is six Asias that the weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0%
Methyl diisocyanate (HDI).
Comparative example 5
Method according to embodiment 18 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), without any additive.
Comparative example 6
Method according to embodiment 18 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the tool that additive is 0.01% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery
There is the compound of molecular formula 1-2 structures.
Comparative example 7
Method according to embodiment 18 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is that weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 5.0% to have
The compound of molecular formula 1-2 structures.
Comparative example 8
Method according to embodiment 18 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), additive is six Asias that the weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 1.0%
Methyl diisocyanate (HDI).
Comparative example 9
Method according to embodiment 1 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the PS that additive is 1.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Comparative example 10
Method according to embodiment 38 prepares lithium rechargeable battery, in the preparation of the electrolyte of lithium rechargeable battery
In (i.e. step (3)), the PS that additive is 2.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Comparative example 11
Method according to embodiment 39 prepares lithium rechargeable battery, except following difference：
In the preparation (i.e. step (3)) of the electrolyte of lithium rechargeable battery, additive is in lithium rechargeable battery
Electrolyte in weight/mass percentage composition be 2.0% PS.
Comparative example 12
Method according to embodiment 40 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the PS that additive is 2.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Comparative example 13
Method according to embodiment 41 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the PS that additive is 2.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Comparative example 14
Method according to embodiment 42 prepares lithium rechargeable battery, is the system in the electrolyte of lithium rechargeable battery
In standby (i.e. step (3)), the PS that additive is 2.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Comparative example 15
Method according to embodiment 43 prepares lithium rechargeable battery, in the preparation of the electrolyte of lithium rechargeable battery
In (i.e. step (3)), the PS that additive is 2.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Comparative example 16
Method according to embodiment 44 prepares lithium rechargeable battery, in the preparation of the electrolyte of lithium rechargeable battery
In (i.e. step (3)), the PS that additive is 2.0% for the weight/mass percentage composition in the electrolyte of lithium rechargeable battery.
Finally provide the performance test of embodiment 1-44 and comparative example 1-16 lithium rechargeable battery and its electrolyte
Journey and test result.
(1) the high-temperature storage performance test of lithium rechargeable battery
At 25 DEG C, its respective charge cutoff electricity is first charged to lithium rechargeable battery with 0.5C constant current
Pressure, further under its respective charge cutoff voltage constant-voltage charge to electric current be less than 0.05C, test its thickness, be designated as lithium from
Thickness before sub- secondary cell high temperature storage, then in 85 DEG C of environment store 24 hours, its thickness is tested again, be designated as lithium from
Thickness after sub- secondary cell high temperature storage.
Thickness swelling (%)=[(before thickness-storage after storage after 85 DEG C/24h of lithium rechargeable battery storages
Thickness)/storage before thickness] × 100%.
At 25 DEG C, its respective charge cutoff electricity is first charged to lithium rechargeable battery with 0.5C constant current
Pressure, further under its respective charge cutoff voltage constant-voltage charge to electric current be less than 0.05C, test its thickness, be designated as lithium from
Thickness before sub- secondary cell high temperature storage, then stores 15 days in 60 DEG C of environment, its thickness is tested again, lithium ion is designated as
Thickness after secondary cell high temperature storage.
Thickness swelling (%)=[(before thickness-storage after storage after 60 DEG C/15day of lithium rechargeable battery storages
Thickness)/storage before thickness] × 100%.
(2) the cycle performance test of lithium rechargeable battery
Under the conditions of 25 DEG C and 45 DEG C, its is charged to lithium rechargeable battery with 0.5C constant current respectively respective
Charge cutoff voltage, further constant-voltage charge to electric current is less than 0.05C under its respective charge cutoff voltage, then with 0.5C
Constant current be discharged to 3.0V to lithium rechargeable battery, current discharge capacity is designated as lithium rechargeable battery and followed for the first time
The discharge capacity of ring；Carry out cycle charge discharge electrical testing in a manner described to lithium rechargeable battery, record putting for the 300th circulation
Capacitance.
Capability retention=(discharge capacity/first time of the 300th circulation after 300 circulations of lithium rechargeable battery
The discharge capacity of circulation) × 100%.
Table 1 provides embodiment 1-44 and comparative example 1-16 relevant parameter and the performance test results.
Next the performance test results to lithium rechargeable battery are analyzed.
(1) test result analysis of the high-temperature storage performance of lithium rechargeable battery
From embodiment 1-17 and comparative example 1 (any additive, the thickness swelling after 4.4V/85 DEG C/24h storages are not added
Rate be the thickness swelling after 92%, 4.4V/60 DEG C/15day storages in contrast 140%) as can be seen that in lithium ion two
The lithium ion two of the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 is with the addition of in the electrolyte of primary cell
Primary cell has relatively low thickness swelling.This is due to without adding under any additive, high-voltage state in comparative example 1
Just having the non-aqueous organic solvent in very strong oxidisability, meeting oxidation electrolyte, causing lithium rechargeable battery aerogenesis, and then
Thickness swelling after lithium rechargeable battery storage is too high.And two isocyanic acids of the ether-containing key with formula 1 and/or the structure of formula 2
Ester compounds can prevent the pair between the active material and electrolyte in pole piece in pole piece one layer of fine and close passivating film of formation
Reaction, reduces aerogenesis, so that lithium rechargeable battery has relatively low thickness swelling；And with formula 1 and/or the knot of formula 2
The diisocyanate cpd of the ether-containing key of structure can also react with the water in electrolyte, HF, so as to reduce water, HF and electrolysis
Side reaction between liquid, and then aerogenesis is reduced, therefore lithium rechargeable battery has relatively low thickness swelling.
From embodiment 1-7 contrast as can be seen that in the electrolyte of lithium rechargeable battery add 0.1%~
2.5% compound with molecular formula 1-2 structures, can be prevented in pole piece in pole piece one layer of fine and close passivating film of formation
Active material and electrolyte between side reaction, therefore lithium rechargeable battery has a relatively low thickness swelling, and with
The weight/mass percentage composition increase of compound with molecular formula 1-2 structures, after 4.4V/85 DEG C of lithium rechargeable battery/24h storages
Thickness swelling and 4.4V/60 DEG C/15day storage after thickness swelling first reduce after slightly increase.But, work as tool
When having the weight/mass percentage composition of the compound of molecular formula 1-2 structures too small (comparative example 2), although lithium rechargeable battery can be improved
High-temperature storage performance, but do not reach preferable effect also, this is probably due to the compound with molecular formula 1-2 structures
Weight/mass percentage composition very little, causes formed passivating film not fine and close enough, it is impossible to effectively prevent active material and electrolysis in pole piece
Thickness swelling after side reaction between liquid, and then lithium rechargeable battery high temperature storage is still higher.When with molecular formula 1-2
When the weight/mass percentage composition of the compound of structure is too high (comparative example 3), the high-temperature storage performance of lithium rechargeable battery deteriorates, this
It is probably, because the excessive compound with molecular formula 1-2 structures causes the passivating film in pole piece formation blocked up, to cause
Interface impedance is excessive, it is impossible to effectively prevents the side reaction between the active material and electrolyte in pole piece, causes lithium ion secondary
Thickness swelling after battery high-temperature storage is higher.
Added from embodiment 4 and embodiment 8-12 contrast as can be seen that in the electrolyte of lithium rechargeable battery
The diisocyanate cpd of 1% ether-containing key with formula 1 or the structure of formula 2, due to foring the passivating film of densification, is prevented
The side reaction between active material and electrolyte in pole piece, therefore lithium rechargeable battery has relatively low thickness swelling,
Thickness swelling after 4.4V/85 DEG C/24h storages is below 26%, and the thickness swelling after 4.4V/60 DEG C/15day storages exists
Less than 32%.
Addition 1% has from embodiment 13-17 contrast as can be seen that in the electrolyte of lithium rechargeable battery
The mixture of the diisocyanate cpd of the ether-containing key of formula 1 and the structure of formula 2, due to foring the passivating film of densification, is prevented
The side reaction between active material and electrolyte in pole piece, therefore lithium rechargeable battery has relatively low thickness swelling,
Thickness swelling after 4.4V/85 DEG C/24h storages is below 25%, and the thickness swelling after 4.4V/60 DEG C/15day storages exists
Less than 31%.
From embodiment 18-29 and comparative example 5 (any additive, the thickness swelling after 4.4V/85 DEG C/24h storages are not added
Rate be the thickness swelling after 142%, 4.4V/60 DEG C/15day storages in contrast 98%) as can be seen that in lithium ion two
The lithium ion secondary electricity of the diisocyanate cpd of the ether-containing key with formula 1 or the structure of formula 2 is added in the electrolyte of primary cell
Pond has relatively low thickness swelling.This is due to no positive pole added under any additive, high-voltage state in comparative example 5
With very strong oxidisability, non-aqueous organic solvent that can be in oxidation electrolyte causes lithium rechargeable battery aerogenesis, so lithium from
Thickness swelling after sub- secondary cell storage is too high.And the diisocyanate cpd of the ether-containing key with formula 1 or the structure of formula 2
It can prevent the side reaction between the active material and electrolyte in pole piece at pole piece one layer of fine and close passivating film of formation, subtract
Few aerogenesis, so that lithium rechargeable battery has relatively low thickness swelling；Ether-containing key with formula 1 or the structure of formula 2
Diisocyanate cpd can also effectively prevent transition metal (Mn, Co, Ni etc.) dissolution in the passivating film that pole piece is formed,
Also it can make lithium rechargeable battery that there is relatively low thickness swelling；The diisocyanate of ether-containing key with formula 1 or the structure of formula 2
Compound can also react with the water in electrolyte, HF, so as to reduce the side reaction between water, HF and electrolyte, reduce production
Gas, also can make lithium rechargeable battery have relatively low thickness swelling；Two of ether-containing key with formula 1 and/or the structure of formula 2 are different
After cyanate esters react with HF, moreover it is possible to reduce the side reaction between HF and pole piece, reduction transition metal (Mn, Co, Ni
Deng) dissolution so that lithium rechargeable battery has relatively low thickness swelling.
From embodiment 18-24 contrast as can be seen that in the electrolyte of lithium rechargeable battery add 0.1%~
2.5% compound with molecular formula 1-2 structures, can be prevented in pole piece in pole piece one layer of fine and close passivating film of formation
Active material and electrolyte between side reaction, therefore lithium rechargeable battery has a relatively low thickness swelling, and with
The weight/mass percentage composition increase of compound with molecular formula 1-2 structures, after 4.4V/85 DEG C of lithium rechargeable battery/24h storages
Thickness swelling and 4.4V/60 DEG C/15day storage after thickness swelling first reduce after slightly increase.But, work as tool
When having the weight/mass percentage composition of the compound of molecular formula 1-2 structures too small (comparative example 6), although lithium rechargeable battery can be improved
High-temperature storage performance, but do not reach preferable effect also, this is probably due to the compound with molecular formula 1-2 structures
Weight/mass percentage composition very little, causes formed passivating film not fine and close enough, it is impossible to effectively prevent the active material and electricity in pole piece
The side reaction between liquid is solved, and because passivating film is not fine and close enough, it is impossible to effectively prevent the molten of transition metal (Mn, Co, Ni etc.)
Go out, and then the thickness swelling after lithium rechargeable battery high temperature storage is higher.When the compound with molecular formula 1-2 structures
When weight/mass percentage composition is too high (comparative example 7), the high-temperature storage performance of lithium rechargeable battery deteriorates, and this is probably due to excessive
The compound with molecular formula 1-2 structures cause pole piece formation passivating film it is blocked up, cause interface impedance excessive, no
The side reaction between the active material in pole piece and electrolyte can be effectively prevented, is caused after lithium rechargeable battery high temperature storage
Thickness swelling is higher.
Add from embodiment 21 and embodiment 25-29 contrast as can be seen that in the electrolyte of lithium rechargeable battery
Enter the diisocyanate cpd of 1% ether-containing key with formula 1 or the structure of formula 2, due to foring the passivating film of densification, prevent
The side reaction between active material and electrolyte in pole piece, therefore lithium rechargeable battery has relatively low thickness swelling
Rate, the thickness swelling after 4.4V/85 DEG C/24h storages is below 30%, the thickness swelling after 4.4V/60 DEG C/15day storages
Rate is below 25%.
From embodiment 30 and embodiment 3, embodiment 31 and embodiment 4, embodiment 32 and embodiment 5, embodiment 33 with it is real
Apply in the contrast of example 6 as can be seen that the thickness swelling after embodiment 30-33 lithium rechargeable battery high temperature storage is relatively low.
This is probably that, due to adding EMC in embodiment 30-33 electrolyte, it has preferably steady under high temperature high voltage condition
It is qualitative, and EC, PC and DEC easy oxidation Decomposition under high temperature high voltage condition, can so substituting part EC, PC and DEC with EMC
To improve the high-temperature storage performance of lithium rechargeable battery to a certain extent.
As can be seen that containing with the structure of formula 1 from the contrast of embodiment 3, embodiment 34-37 and comparative example 9
PS is added in the electrolyte of the lithium rechargeable battery of the diisocyanate cpd of ether-containing key, lithium ion secondary electricity can be improved
The high-temperature storage performance in pond.And the high-temperature storage performance of the lithium rechargeable battery containing single PS is poor, but PS can be
Formed by the diisocyanate cpd of the ether-containing key with the structure of formula 1 and one layer of stable passivation is re-formed on the basis of passivating film
Film so that passivating film turns into composite passivation film, the composite passivation film can be such that the interface between pole piece and electrolyte more stablizes, enter
And the high-temperature storage performance of lithium rechargeable battery can be improved.It can also be seen that with addition from embodiment 34-37 contrasts
PS weight/mass percentage composition increase, thickness swelling and 4.4V/60 after 4.4V/85 DEG C of lithium rechargeable battery/24h storages
DEG C/15day storage after thickness swelling have obvious reduction.
From embodiment 38 and comparative example 10, embodiment 39 and comparative example 11, embodiment 40 and comparative example 12, embodiment 41 with
Comparative example 13, embodiment 42 and comparative example 14, embodiment 43 and comparative example 15, embodiment 44 with can be with the contrast of comparative example 16
Find out, the lithium of the diisocyanate cpd of the ether-containing key with the structure of formula 1 is added in the electrolyte of lithium rechargeable battery
Than the only lithium rechargeable battery containing PS, (4.35V~4.90V) has more preferable high temperature to ion secondary battery under high voltages
Storage performance.This is probably because the diisocyanate cpd of the ether-containing key with the structure of formula 1 can be in pole piece formation one
The fine and close passivating film of layer, prevents the side reaction between the active material and electrolyte in pole piece, aerogenesis is reduced, so lithium ion two
Primary cell has relatively low thickness swelling；And the diisocyanate cpd of the ether-containing key with the structure of formula 1 can also be with electrolysis
Water, HF in liquid react, the reaction between reduction water, HF and electrolyte, reduce aerogenesis, can also make lithium rechargeable battery
With relatively low thickness swelling.And individually PS the passivating film that pole piece is formed under high voltage condition it is not fine and close enough with
It is stable, cause the high-temperature storage performance of lithium rechargeable battery poor.
(2) test result analysis of the cycle performance of lithium rechargeable battery
From embodiment 1-17 and comparative example 1 (do not add any additive, the capability retention after 25 DEG C of circulations is 20%,
Capability retention after 45 DEG C of circulations adds to can be seen that in contrast 13%) in the electrolyte of lithium rechargeable battery
The lithium rechargeable battery with the diisocyanate cpd of the ether-containing key of formula 1 and/or formula 2 structure has higher circulation
Capability retention afterwards.This is due to no any additive of addition in comparative example 1, and non-aqueous organic solvent can occur in negative terminal surface
More side reaction, causes the capability retention after lithium rechargeable battery circulation relatively low.And with formula 1 and/or the structure of formula 2
The diisocyanate cpd of ether-containing key can form one layer of fine and close passivating film on positive plate surface, and due to formula 1 and/or
The isocyanate functional group of the diisocyanate cpd of the ether-containing key of the structure of formula 2 has high chemical reactivity, therefore its energy
With the anti-biochemical reaction of functional group on negative plate surface, so as to also form one layer of passivating film on negative plate surface, prevent in pole piece
Active material and electrolyte between side reaction, improve lithium rechargeable battery normal-temperature circulating performance and high temperature circulation
Energy；And the passivating film formed by the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 contains more oxygen
Atom, it is possible to decrease lithium ion passes through resistance during passivating film, improves the interface performance between electrolyte and pole piece, so as to improve lithium
The normal-temperature circulating performance and high temperature cyclic performance of ion secondary battery.
From embodiment 1-7 contrast as can be seen that in the electrolyte of lithium rechargeable battery add 0.1%~
2.5% compound with molecular formula 1-2 structures, can be prevented in pole piece in pole piece one layer of fine and close passivating film of formation
Active material and electrolyte between side reaction, therefore lithium rechargeable battery have higher circulation after capability retention,
And with the weight/mass percentage composition increase of the compound with molecular formula 1-2 structures, 25 DEG C and 45 DEG C of lithium rechargeable battery is followed
Capability retention after ring first raise be decreased slightly as afterwards it is low.But, when the quality percentage of the compound with molecular formula 1-2 structures contains
When measuring very few (comparative example 2), although the normal-temperature circulating performance and high temperature cyclic performance of lithium rechargeable battery can be improved, but also
Do not reach preferable effect, this be probably due to the compound with molecular formula 1-2 structures weight/mass percentage composition very little, institute's shape
Into passivating film it is not fine and close enough, it is impossible to effectively prevent pole piece in active material and electrolyte between side reaction, and then lithium from
The normal-temperature circulating performance and high temperature cyclic performance of sub- secondary cell are poor.When the quality of the compound with molecular formula 1-2 structures
When percentage composition is too high (comparative example 3), the capability retention after 25 DEG C of lithium rechargeable battery and 45 DEG C circulations significantly drops
Low, this is probably that the passivating film resulted in due to the excessive compound with molecular formula 1-2 structures is blocked up, causes interface to hinder
Anti- larger, the interface performance between pole piece and electrolyte is poor, and then the normal-temperature circulating performance and high temperature of lithium rechargeable battery
Cycle performance deteriorates.
Added from embodiment 4 and embodiment 8-12 contrast as can be seen that in the electrolyte of lithium rechargeable battery
The diisocyanate cpd of 1% ether-containing key with formula 1 or the structure of formula 2, due to foring the passivating film of densification, is prevented
The side reaction between active material and electrolyte in pole piece, therefore there is lithium rechargeable battery capacity after higher circulation to protect
Holdup, the capability retention after 25 DEG C of circulations is more than 80%, and the capability retention after 45 DEG C of circulations is more than 71%.
Addition 1% has from embodiment 13-17 contrast as can be seen that in the electrolyte of lithium rechargeable battery
The mixture of the diisocyanate cpd of the ether-containing key of formula 1 and the structure of formula 2, due to foring the passivating film of densification, is prevented
The side reaction between active material and electrolyte in pole piece, therefore there is lithium rechargeable battery capacity after higher circulation to protect
Holdup, the capability retention after 25 DEG C of circulations is more than 80%, and the capability retention after 45 DEG C of circulations is more than 72%.
Added from the contrast of embodiment 8 and comparative example 4 it can also be seen that in the electrolyte of lithium rechargeable battery
Hexamethylene diisocyanate (HDI) of the diisocyanate cpd of 1% ether-containing key with the structure of formula 1 than addition 1%
Normal-temperature circulating performance and high temperature cyclic performance it is good.This is probably due to the diisocyanate of the ether-containing key with the structure of formula 1
The passivating film of compound formation contains more oxygen atom, it is possible to decrease lithium ion passes through resistance during passivating film, shows relatively low
Impedance, improve the interface performance between electrolyte and pole piece, thus improve lithium rechargeable battery normal-temperature circulating performance and
High temperature cyclic performance.And the impedance of the passivating film formed by hexamethylene diisocyanate (HDI) is larger, pole piece and electricity can be deteriorated
The interface performance between liquid is solved, causes the normal-temperature circulating performance and high temperature cyclic performance of lithium rechargeable battery to deteriorate；And 25 DEG C
Under cycle performance deterioration than more serious, this be probably because lithium ion is relatively difficult through passivating film at 25 DEG C, and
Lithium ion is compared under the conditions of 25 DEG C easily through passivating film at 45 DEG C.
From embodiment 18-29 and comparative example 5 (do not add any additive, the capability retention after 25 DEG C of circulations is 15%,
Capability retention after 45 DEG C of circulations adds to can be seen that in contrast 10%) in the electrolyte of lithium rechargeable battery
The lithium rechargeable battery of the diisocyanate cpd of ether-containing key with formula 1 or the structure of formula 2 has to be held after higher circulation
Measure conservation rate.This is due to no any additive of addition in comparative example 5, and non-aqueous organic solvent can occur more in negative terminal surface
Side reaction, cause lithium rechargeable battery circulate after capability retention it is relatively low.And the ether-containing key with formula 1 or the structure of formula 2
Diisocyanate cpd one layer of fine and close passivating film can be formed on positive plate surface, and contain ether with formula 1 or the structure of formula 2
The isocyanate functional group of the diisocyanate cpd of key has high chemical reactivity, functional group that can be with negative plate surface
Anti- biochemical reaction, so that one layer of passivating film also can be formed on negative plate surface, prevents active material and electrolyte in pole piece
Between side reaction；The passivating film of the diisocyanate cpd formation of ether-containing key with formula 1 or the structure of formula 2 can also be prevented
Metal (Mn, Co, Ni etc.) dissolution is crossed, so as to improve the normal-temperature circulating performance and high temperature cyclic performance of lithium rechargeable battery；
The passivating film of the diisocyanate cpd formation of ether-containing key with formula 1 or the structure of formula 2 contains more oxygen atom, it is possible to decrease
Lithium ion passes through resistance during passivating film, shows relatively low impedance, improves the interface performance between electrolyte and pole piece, from
And improve the normal-temperature circulating performance and high temperature cyclic performance of lithium rechargeable battery.
From embodiment 18-24 contrast as can be seen that in the electrolyte of lithium rechargeable battery add 0.1%~
2.5% compound with molecular formula 1-2 structures, can be prevented in pole piece in pole piece one layer of fine and close passivating film of formation
Active material and electrolyte between side reaction, therefore lithium rechargeable battery have higher circulation after capacity keep
Rate, and with the weight/mass percentage composition increase of the compound with molecular formula 1-2 structures, 25 DEG C and 45 DEG C of lithium rechargeable battery
Capability retention after circulation is slightly reduced after first raising).But, when the quality of the compound with molecular formula 1-2 structures
When percentage composition is very few (comparative example 6), although the normal-temperature circulating performance and high temperature cyclic performance of lithium rechargeable battery can be improved,
But do not reach preferable effect also, this be probably due to the compound with molecular formula 1-2 structures weight/mass percentage composition too
It is few, cause formed passivating film not fine and close enough, it is impossible to effectively to prevent the pair between the active material and electrolyte in pole piece anti-
Should, it can not effectively prevent transition metal (Mn, Co, Ni etc.) dissolution, therefore the normal-temperature circulating performance of lithium rechargeable battery
Preferable effect is not reached with high temperature cyclic performance.When the weight/mass percentage composition of the compound with molecular formula 1-2 structures is too high
When (comparative example 7), the capability retention after the circulation of 25 DEG C and 45 DEG C of lithium rechargeable battery is greatly reduced, this be probably due to
The passivating film that the excessive compound with molecular formula 1-2 structures is resulted in is blocked up, causes interface impedance larger, causes pole piece
Interface performance between electrolyte is poor；And the deterioration of the cycle performance at 25 DEG C, than more serious, this is probably due to 25
Lithium ion is relatively difficult through passivating film at DEG C, and lithium ion is compared under the conditions of 25 DEG C easily through passivating film at 45 DEG C.
Add from embodiment 21 and embodiment 25-29 contrast as can be seen that in the electrolyte of lithium rechargeable battery
Enter the diisocyanate cpd of 1% ether-containing key with formula 1 or the structure of formula 2, due to foring the passivating film of densification, prevent
The side reaction between active material and electrolyte in pole piece, therefore lithium rechargeable battery has capacity after higher circulation
Conservation rate, the capability retention after 25 DEG C of circulations is more than 84%, and the capability retention after 45 DEG C of circulations is more than 68%.
As can be seen that adding 1% in the electrolyte of lithium rechargeable battery from the contrast of embodiment 21 and comparative example 8
The ether-containing key with the structure of formula 1 diisocyanate cpd lithium rechargeable battery than add 1% hexa-methylene two
The normal-temperature circulating performance and high temperature cyclic performance of the lithium rechargeable battery of isocyanates (HDI) are good.This be probably due to
The passivating film of the diisocyanate cpd formation of the ether-containing key of the structure of formula 1 contains more oxygen atom, it is possible to decrease lithium ion is worn
Resistance during transpassivation film, shows relatively low impedance, improves the interface performance between electrolyte and pole piece, thus improve lithium from
The normal-temperature circulating performance and high temperature cyclic performance of sub- secondary cell.And the passivation formed by hexamethylene diisocyanate (HDI)
The impedance of film is larger, is degrading the interface performance between pole piece and electrolyte, causes the normal temperature circulation of lithium rechargeable battery
It can deteriorate with high temperature cyclic performance；And the deterioration of the cycle performance at 25 DEG C, than more serious, this is probably due to the lithium at 25 DEG C
Ion is relatively difficult through passivating film, and lithium ion is compared under the conditions of 25 DEG C easily through passivating film at 45 DEG C.
From embodiment 30 and embodiment 3, embodiment 31 and embodiment 4, embodiment 32 and embodiment 5, embodiment 33 with it is real
Apply in the contrast of example 6 as can be seen that the capability retention after 45 DEG C of circulations is in suitable level, and the capacity of 25 DEG C of circulations is protected
Holdup embodiment 30-33 result is better than embodiment 3-6.This is probably due to being added in embodiment 30-33 electrolyte
EMC, its viscosity is relatively low, favorably with the conduction of lithium ion.By the diisocyanate cpd shape of the ether-containing key with the structure of formula 1
Into passivating film still have certain impedance, and with viscosity it is relatively low EMC part replace highly viscous PC, EC and DEC, can improve
Conduction of the lithium ion between electrolyte and pole piece interface, further reduces impedance, further improves lithium rechargeable battery
Normal-temperature circulating performance and high temperature cyclic performance.But at 45 DEG C, by the diisocyanate chemical combination of the ether-containing key with the structure of formula 1
It is small at 25 DEG C of the impedance ratio of the passivating film of thing formation, so the capacity after being circulated with EMC parts substitution PC, EC and DEC to 45 DEG C
The influence of conservation rate is little.
As can be seen that containing with the structure of formula 1 from the contrast of embodiment 3, embodiment 34-37 and comparative example 9
PS is added in the electrolyte of the lithium rechargeable battery of the diisocyanate cpd of ether-containing key, lithium ion secondary electricity can be improved
The normal-temperature circulating performance and high temperature cyclic performance in pond.The normal-temperature circulating performance and height of lithium rechargeable battery containing single PS
Warm cycle performance is poor, but the passivation that PS can be formed in the diisocyanate cpd by the ether-containing key with the structure of formula 1
One layer of stable passivating film is re-formed on the basis of film, passivating film is turned into composite passivation film, the composite passivation film can make pole piece
Interface between electrolyte is more stablized, and then improves the normal-temperature circulating performance and high temperature circulation of lithium rechargeable battery
Energy.It can also be seen that the increase of the PS contents with addition, 25 DEG C of lithium rechargeable battery from embodiment 34-37 contrasts
First increase with the capability retention after 45 DEG C of circulations reduces afterwards, and normal-temperature circulating performance variation is more apparent.This be probably due to
When excessive PS and the ether-containing key with the structure of formula 1 diisocyanate cpd are used in mixed way, what is resulted in is composite passivated
The impedance of film is larger, and the conduction of lithium ion at normal temperatures is sensitive to impedance comparison, and the increase of impedance is degrading the dynamic of lithium ion
Mechanical property, while being degrading the interface performance between pole piece and electrolyte；And at 45 DEG C, appearance is compared in the conduction of lithium ion
Easily, influence of the increase of impedance to the dynamic performance of lithium ion is smaller, so the shadow of the capability retention after being circulated to 45 DEG C
Sound is also smaller.
From embodiment 38 and comparative example 10, embodiment 39 and comparative example 11, embodiment 40 and comparative example 12, embodiment 41 with
Comparative example 13, embodiment 42 and comparative example 14, embodiment 43 and comparative example 15, embodiment 44 with can be with the contrast of comparative example 16
Find out, the lithium of the diisocyanate cpd of the ether-containing key with the structure of formula 1 is added in the electrolyte of lithium rechargeable battery
Than the only lithium rechargeable battery containing PS, (4.35V~4.90V) has more preferable normal temperature to ion secondary battery under high voltages
Cycle performance and high temperature cyclic performance.This is probably because the diisocyanate cpd of the ether-containing key with the structure of formula 1 can be
Positive plate surface forms one layer of fine and close passivating film, and the isocyanide of the diisocyanate cpd of the ether-containing key with the structure of formula 1
Acid ester functionality has high chemical reactivity, can be with the anti-biochemical reaction of the functional group on negative plate surface, so as to can also bear
Pole piece formation one layer of passivating film, prevent pole piece in active material and electrolyte between side reaction so that improve lithium from
The normal-temperature circulating performance and high temperature cyclic performance of sub- secondary cell；And by the diisocyanate of the ether-containing key with the structure of formula 1
The passivating film of compound formation contains more oxygen atom, it is possible to decrease lithium ion passes through resistance during passivating film, shows relatively low
Impedance, improves the interface performance between electrolyte and pole piece, so as to improve the normal-temperature circulating performance and height of lithium rechargeable battery
Warm cycle performance.And the passivating film that individually PS is formed in pole piece is in high voltage condition not enough densification and stably, therefore lithium
The normal-temperature circulating performance and high temperature cyclic performance of ion secondary battery are poor.
To sum up, the lithium of the of the invention diisocyanate cpd for containing the ether-containing key with formula 1 and/or the structure of formula 2 from
Sub- secondary cell has good high-temperature storage performance, normal-temperature circulating performance and high temperature cyclic performance under high voltages.
Claims (10)
1. a kind of electrolyte of lithium rechargeable battery, including：
Lithium salts；
Non-aqueous organic solvent；And
Additive；
Characterized in that,
The additive includes the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2；In formula 1, m, n, p
Respectively 1~4 integer；In formula 2, x, y are respectively 1~4 integer；
Electrolyte of the diisocyanate cpd of the ether-containing key with formula 1 and/or the structure of formula 2 in lithium rechargeable battery
In weight/mass percentage composition be 0.1%~2.5%.
2. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that
The non-aqueous organic solvent includes the combination of cyclic carbonate and linear carbonate；
The cyclic carbonate is selected from least one of ethylene carbonate, propene carbonate and butylene；
The linear carbonate is selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate
At least one of and ethyl propyl carbonic acid ester.
3. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that described with the structure of formula 1
The diisocyanate cpd of ether-containing key in the compound with molecular formula 1-1 structures to molecular formula 1-20 structures at least
One kind,
4. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that described with the structure of formula 2
The diisocyanate cpd of ether-containing key in the compound with molecular formula 2-1 structures to molecular formula 2-6 structures at least
One kind,
5. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that described that there is formula 1 and/or formula
Weight/mass percentage composition of the diisocyanate cpd of the ether-containing key of 2 structures in the electrolyte of lithium rechargeable battery be
0.2%~2%.
6. the electrolyte of lithium rechargeable battery according to claim 1, it is characterised in that the additive also includes 1,
3- propane sultones.
7. the electrolyte of lithium rechargeable battery according to claim 6, it is characterised in that the PS
Weight/mass percentage composition in the electrolyte of lithium rechargeable battery is 0.1%~5%.
8. a kind of lithium rechargeable battery, including：
Positive plate, including plus plate current-collecting body and the positive pole diaphragm containing positive active material that is arranged on plus plate current-collecting body；
Negative plate, including negative current collector and the cathode membrane containing negative electrode active material that is arranged on negative current collector；
Barrier film, is interval between positive plate and negative plate；And
Electrolyte；
Characterized in that,
The electrolyte is the electrolyte of the lithium rechargeable battery according to any one of claim 1-7.
9. lithium rechargeable battery according to claim 8, it is characterised in that the charging of the lithium rechargeable battery is cut
It is 4.35V~4.9V to voltage.
10. lithium rechargeable battery according to claim 8, it is characterised in that the positive active material is selected from
LixCoyM1-yA2、LiMnzN2-zO4At least one of, wherein, 0.97≤x≤1.06,0≤y≤1,0≤z≤2, M be selected from Ni,
At least one of Fe, Mg, Al, Ti, V, Ge, Zr, Mn, Cr, A are selected from least one of O, F, S, P, and N is selected from Co, Ni, Fe
At least one of.
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| CN107181001B (en) * | 2017-06-22 | 2020-08-04 | 上海大学 | Lithium ion secondary battery electrolyte additive, electrolyte and application thereof |
| CN108878956B (en) * | 2018-07-04 | 2019-06-11 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
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| CN101009392A (en) * | 2006-01-26 | 2007-08-01 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell and method for producing same |
| CN103891033A (en) * | 2011-10-17 | 2014-06-25 | 宇部兴产株式会社 | Non-aqueous electrolyte solution and electricity-storage device using same |
| CN103904364A (en) * | 2014-03-28 | 2014-07-02 | 宁德新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
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| JP6031868B2 (en) * | 2011-07-29 | 2016-11-24 | 三菱化学株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte battery using the same |
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| CN103891033A (en) * | 2011-10-17 | 2014-06-25 | 宇部兴产株式会社 | Non-aqueous electrolyte solution and electricity-storage device using same |
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