CN110534805A - A kind of lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte - Google Patents
A kind of lithium-ion battery electrolytes and the lithium ion battery comprising the electrolyte Download PDFInfo
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- CN110534805A CN110534805A CN201910706224.7A CN201910706224A CN110534805A CN 110534805 A CN110534805 A CN 110534805A CN 201910706224 A CN201910706224 A CN 201910706224A CN 110534805 A CN110534805 A CN 110534805A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of lithium-ion battery electrolytes, which includes non-aqueous organic solvent, lithium salts and the first additive, wherein first additive is selected from least one of silicon nitrile compounds shown in formula I and formula II,
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of lithium-ion battery electrolytes and one kind comprising being somebody's turn to do
The lithium ion battery of electrolyte.
Background technique
Lithium ion battery has the characteristics that energy density height, output power, good cycle, memory-less effect, extensively
Applied to consumer electronics product and electric car.Currently, the fast development of new-energy automobile is close to the energy of lithium ion battery
More stringent requirements are proposed for degree.In order to promote the energy density of battery, the operating voltage of battery, another party on the one hand can be improved
Face can improve battery capacity by nickelic anode collocation silicon-based anode.But under high temperature high voltage, traditional LiPF6/
The electrolyte meeting continued oxidation of carbonic ester system decomposes, and produces gas and obviously increases, leads to battery high-temperature storage performance and security performance
It is deteriorated；Under low temperature, the viscosity of traditional electrolyte increases, and conductivity reduces, the serious migration for hindering lithium ion and electrolyte
Decomposition product is deposited on electrode surface, and interface membrane impedance increases, and battery polarization obviously increases, impaired low temperature performance.In addition to this,
The dissolution of the oxygen release and transition metal ions of nickelic anode and silicon-based anode electric conductivity is poor and bulk effect, can all lead to electricity
Pond performance degradation.
Summary of the invention
For above-mentioned the technical problems existing in the prior art, the purpose of the present invention is to provide a kind of lithium ion battery batteries
Liquid is solved, high temperature performance and cycle performance can be taken into account using the lithium ion battery of the electrolyte.
Therefore, in one aspect, the present invention provides a kind of lithium-ion battery electrolytes, which includes non-aqueous organic molten
Agent, lithium salts and the first additive, wherein at least one in first additive silicon nitrile compounds shown in the formula I and formula II
Kind,
Wherein R1、R2、R3、R4、R5、R6It is independently selected from the group without-O- or the group containing-O- ,-O- should be free of
Group be selected from hydrogen, halogen, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substitution do not take
The C in generation2-C10Alkynyl, substituted or unsubstituted C6-C16Aryl, substituted or unsubstituted C1-C10Alkane sulfonyl replaces or does not take
The C in generation6-C16Arylsulfonyl, the group for containing-O- are selected from substituted or unsubstituted C1-C10It is alkoxy, substituted or unsubstituted
C2-C10Alkenyloxy group, substituted or unsubstituted C2-C10Alkynyloxy group, substituted or unsubstituted C6-C16Aryloxy group；
Wherein X1And X2It is independently selected from substituted or unsubstituted C1-C15Alkylidene, R7- COO- group, wherein R7Solely
On the spot it is selected from substituted or unsubstituted C1-C6Alkylidene, substituted or unsubstituted C2-C15Alkenylene, substituted or unsubstituted C6-
C16Arlydene, substituted or unsubstituted C5-C15Sub- heterocyclic base, R8-O-R9Group, wherein R8And R9Independently selected from substitution or not
Substituted C1-C6Alkylidene.
Preferably, silicon nitrile compounds shown in formula I and formula II are selected from least one of compound as shown in table 1 below:
Table 1
It preferably, is in terms of 100% by the gross mass of the lithium-ion battery electrolytes, the quality percentage of first additive contains
Amount is 0.05-2%.
Preferably, which also includes Second addition as film for additive, the Second addition
Including in fluorinated ethylene carbonate, vinylene carbonate, 1,3- propane sultone, 1,4- butane sultone, 1,3- propene sulfonic acid
At least one of ester, sulfuric acid vinyl ester, sulfuric acid acrylic ester.
It preferably, is in terms of 100% by the gross mass of the lithium-ion battery electrolytes, the quality percentage of the Second addition contains
Amount is 15% or less.
Preferably, which includes lithium hexafluoro phosphate, lithium perchlorate, LiBF4, di-oxalate lithium borate, double fluorine oxalic acid
At least one of lithium borate, bis- (trimethyl fluoride sulfonyl) imine lithiums and double fluorine sulfimide lithiums.
It preferably, is in terms of 100% by the gross mass of the lithium-ion battery electrolytes, the mass percentage of the lithium salts is
10-18%.
Preferably, the non-aqueous organic solvent include ethylene carbonate, propene carbonate, butylene, dimethyl carbonate,
Diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, propionic acid second
Ester, propyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolacton, γ-valerolactone, δ-valerolactone, in 6-caprolactone at least
It is a kind of.
On the other hand, the present invention provides a kind of lithium ion battery, the lithium ion battery include anode, cathode, diaphragm and
Electrolyte, the electrolyte are the lithium-ion battery electrolytes of first aspect.
Preferably, the active material of the anode is transition metal oxide.
Preferably, which is LiNixCoyMnzL(1-x-y-z)O2, wherein L Al, Sr, Mg, Ti, Ca,
The value of one of Zr, Zn, Si and Fe, x, y, z meet: 0≤x <, 1,0 < y≤1,0≤z < 1, and 0 x+y+z≤1 <.
Preferably, the active material of the cathode is graphite, composite material or lithium titanate containing Si.
At least one in silicon nitrile compounds shown in lithium-ion battery electrolytes selecting type I provided by the invention and formula II
Kind is used as additive, is mainly used for improving battery filming performance in first charge-discharge, to improve the performance of lithium ion battery.One
With the transition metal ions in positive electrode active materials complexing can occur for aspect, the itrile group in silicon nitrile compounds, can be just
Pole surface forms stable high temperature resistant passivating film, and the oxygenolysis of electrolyte is effectively inhibited to produce the oxygen release of gas, positive electrode active materials
With the dissolution of positive transition metal ions.On the other hand, the silane in silicon nitrile compounds can be on negative electrode active material surface
Fine and close, stable, flexible SEI film is formed, the change of volume of the negative electrode active material in charge and discharge process can be better adapted to
Change, improves the electrode/electrolyte interface of high-voltage lithium ion batteries, slow down the hair of positive and negative anodes interface side reaction in cyclic process
It is raw；Moreover, the silane structure is a kind of lewis base, it can be with HF, the H of the hydrogen containing active proton in electrolyte2O is hydrolyzed
Or polymerization reaction, reach removal H2O, inhibit the purpose of HF, and then promote LiPF6Thermal stability, improve battery high-temperature
Energy；And, the Si in the silane structure can also react with F again, reduce the LiF of electrode surface, reduce interface impedance, improve
The cryogenic property of lithium ion battery.Therefore, had using the lithium ion battery of lithium-ion battery electrolytes of the invention excellent
Normal-temperature circulating performance, high temperature cyclic performance, high-temperature storage performance and low temperature performance.
Specific embodiment
In order to keep the technical problem to be solved in the present invention, used technical solution and acquired beneficial effect more clear
Chu Mingbai, the present invention will be described in further detail with reference to embodiments.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
I. lithium-ion battery electrolytes
The present invention provides a kind of lithium-ion battery electrolytes, which adds comprising non-aqueous organic solvent, lithium salts and first
Add agent, can also include Second addition.
1. the first additive
First additive is selected from least one of silicon nitrile compounds shown in formula I and formula II,
Wherein R1、R2、R3、R4、R5、R6It is independently selected from the group without-O- or the group containing-O- ,-O- should be free of
Group be selected from hydrogen, halogen, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10Alkenyl, substitution do not take
The C in generation2-C10Alkynyl, substituted or unsubstituted C6-C16Aryl, substituted or unsubstituted C1-C10Alkane sulfonyl replaces or does not take
The C in generation6-C16Arylsulfonyl, the group for containing-O- are selected from substituted or unsubstituted C1-C10It is alkoxy, substituted or unsubstituted
C2-C10Alkenyloxy group, substituted or unsubstituted C2-C10Alkynyloxy group, substituted or unsubstituted C6-C16Aryloxy group；
Wherein X1And X2It is independently selected from substituted or unsubstituted C1-C15Alkylidene, R7- COO- group, wherein R7Solely
On the spot it is selected from substituted or unsubstituted C1-C6Alkylidene, substituted or unsubstituted C2-C15Alkenylene, substituted or unsubstituted C6-
C16Arlydene, substituted or unsubstituted C5-C15Sub- heterocyclic base, R8-O-R9Group, wherein R8And R9Independently selected from substitution or not
Substituted C1-C6Alkylidene.
In the silicon nitrile compounds shown in formula I and formula II, R1、R2、R3Or R4、R5、R6It is to connect on the silicon atoms, carbon
Chain length is suitable for that molecular structure size is suitable, has preferable compatibility with non-aqueous organic solvent, is had with positive and negative anodes preferable
Reactivity is conducive to form low-impedance SEI film in positive and negative anodes, improves the low-temperature characteristics and power characteristic of lithium ion battery, suppression
Electrolyte processed improves the high-temperature storage performance of lithium ion battery in the oxygenolysis of anode.If R1、R2、R3、R4、R5、R6In group
Carbon atom number it is excessive, then not only reduce the solubility property of silicon nitrile compounds, but also since steric hindrance is excessive, portion can be covered
Divide reaction site, improve reaction difficulty, reduces reactivity, the formation of final influence SEI film.
In some embodiments of the silicon nitrile compounds shown in formula I and formula II, R1、R2、R3、R4、 R5、R6Group sheet
As halogen, or the C replaced for halogen1-C10The C that alkyl, halogen replace2-C10The C that alkenyl, halogen replace2-C10Alkynyl, halogen
The C that element replaces6-C16The C that aryl, halogen replace1-C10The C that alkane sulfonyl, halogen replace6-C16Arylsulfonyl, halogen replace
C1-C10The C that alkoxy, halogen replace2-C10The C that alkenyloxy group, halogen replace2-C10The C that alkynyloxy group, halogen replace6-C16Fragrant oxygen
Base, wherein halogen atom is F, Cl, Br, preferably F and Cl.Since halogen atom has biggish electronegativity, halogen replaces
R1、 R2、R3、R4、R5、R6Group is conducive to the dispersion of electron cloud, thus improve central atom electronic capability, can compared with
Preferentially reduction forms SEI protective film under the high current potential of solvent reduction current potential, to improve the electrochemical stability of electrolyte and resistance to
High-temperature behavior.
In some embodiments of the silicon nitrile compounds shown in formula I and formula II, X1、X2Group is the C that halogen replaces1-
C15The R that alkylidene, halogen replace7- COO- group, wherein R7The C replaced independently selected from halogen1-C6Alkylidene, halogen replace
C2-C15The C that alkenylene, halogen replace6-C16The C that arlydene, halogen replace5-C15The R that sub- heterocyclic base, halogen replace8-O-R9
Group, wherein R8And R9The C replaced independently selected from halogen1-C6Alkylidene, wherein halogen atom be F, Cl, Br, preferably F and
Cl.Since halogen atom has biggish electronegativity, the X that halogen replaces1、X2Group is conducive to the dispersion of electron cloud, thus
That improves central atom obtains electronic capability, can preferentially restore under the current potential high compared with solvent reduction current potential and form SEI protective film,
To improve the electrochemical stability and high temperature resistance of electrolyte.
In a preferred embodiment of the invention, silicon nitrile compounds shown in formula I and formula II are selected from as shown in the following table 3
At least one of compound includes No. CAS of these preferred silicon nitrile compounds in table 3.Table 3
If specific embodiment part proves, these preferred silicon nitrile compounds adding as lithium-ion battery electrolytes
Add agent, in normal-temperature circulating performance, high temperature cyclic performance, high-temperature storage performance and the low temperature performance side for improving lithium ion battery
Face has the effect of excellent.
It is silicon nitrile shown in Formulas I and/or Formula II in terms of 100% by the gross mass of lithium-ion battery electrolytes of the invention
The mass percentage of compound is 0.05-2%.If the mass percentage of the silicon nitrile compounds is lower than 0.05%, no
Stable protective film can be formed in electrode surface, be not achieved and inhibited the side reaction of electrode and electrolyte, reduce interface impedance, synthesis
The improvement for promoting cell output, furthermore can not improve the low temperature performance of battery；If the silicon nitrile compounds
Mass percentage be higher than 2%, then its electrode surface formed SEI film it is blocked up, battery polarization increase, deteriorate it is cell performance
Energy.
2. Second addition
At least one of lithium-ion battery electrolytes of the invention silicon nitrile compounds shown in adding type I and Formula II
On the basis of additive, other additives can also be further added as film for additive, to optimize lithium-ion electric
Pond performance.Other additives may include fluorinated ethylene carbonate, vinylene carbonate, 1,3- propane sultone, 1,4- butane sulphur
At least one of lactone, 1,3- propene sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester.These other additives are not by
Saturated bond or halogen atom or the sucting electronic effect of the functional group containing S improve central atom electronic capability, can be also compared with solvent
It being restored under the high current potential of former current potential, reduzate is adsorbed in cathode such as graphite surface active site, and auxiliary forms SEI film,
Improve the cyclical stability of battery.
It is the mass percentage of other additives in terms of 100% by the gross mass of lithium-ion battery electrolytes of the invention
For 15% hereinafter, content to guarantee non-aqueous organic solvent in electrolyte, lithium salts, and then guarantee the performance of electrolyte.In this base
On plinth, it is preferable that any one other additive (fluorinated ethylene carbonate, vinylene carbonate, 1,3-propane sultone, 1,
4- butane sultone, 1,3- propene sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester) mass percentage individually account for electrolysis
The 0.1-10% of liquid gross mass.
3. lithium salts
In lithium-ion battery electrolytes of the invention, lithium salts can select the common lithium salts of lithium ion battery, including but
It is not limited to lithium hexafluoro phosphate, lithium perchlorate, LiBF4, di-oxalate lithium borate, double fluorine Lithium bis (oxalate) borates, bis- (trifluoromethyls
Sulphonyl) one of imine lithium and double fluorine sulfimide lithiums or a variety of.Further, the dosage of lithium salts accounts for lithium ion battery electrolysis
The mass percentage of liquid is 10-18%.
4. non-aqueous organic solvent
Since water has a certain impact to the formation of lithium ion battery SEI film and battery performance, it is embodied in battery appearance
Amount becomes smaller, discharge time shortens, internal resistance increase, Capacity fading, cell expansion etc., therefore lithium ion battery battery of the invention
It solves liquid and uses solvent composition of the non-aqueous organic solvent as electrolyte.
The preferred example of non-aqueous organic solvent includes ethylene carbonate, propene carbonate, butylene, carbonic acid diformazan
Ester, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, propionic acid
Ethyl ester, propyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolacton, γ-valerolactone, δ-valerolactone, in 6-caprolactone extremely
Few one kind.The addition of preferred non-aqueous organic solvent, can be improved the more excellent comprehensive performance of lithium ion secondary battery.
It is in terms of 100%, in addition to the first additive, optional second by the gross mass of lithium-ion battery electrolytes of the invention
Additive, lithium salts above-mentioned mass percentage other than, non-aqueous organic solvent accounts for remaining mass percentage.
II. lithium ion battery
The present invention also provides a kind of lithium ion battery, which includes anode, cathode, diaphragm and electrolyte, is somebody's turn to do
Electrolyte is lithium-ion battery electrolytes above-mentioned.
The anode includes positive active material.Positive active material can be any anode conventionally used for lithium ion battery
Active material, but preferably, the active material of the anode selects transition metal oxide.Particularly preferably, the oxo transition metal
Compound is LiNixCoyMnzL(1-x-y-z)O2, wherein one of L Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, x, y, z
Value meet: 0≤x <, 1,0 < y≤1,0≤z < 1, and 0 x+y+z≤1 <.
The cathode includes negative electrode active material.Negative electrode active material can be any cathode conventionally used for lithium ion battery
Active material, but preferably, the active material of the cathode is graphite, composite material or lithium titanate containing Si.
The diaphragm includes but is not limited to monolayer polyethylene (PE), single-layer polypropylene (PP), bilayer PP/PE, three layers of PP/PE/
PP or ceramic diaphragm.
The composition of the electrolyte, the selection of each constituent, content, preferred type and its selection gist are as described above,
In order to save length, details are not described herein again.
Lithium ion battery of the invention, due to contain lithium-ion battery electrolytes of the invention, can be obviously improved lithium from
The high temperature performance and cycle performance of sub- battery promote the overall output performance of lithium ion battery.
III. embodiment
Further illustrate is made to the present invention below by way of non-limiting embodiment.In embodiments, English letter
The Chinese paraphrase write is explained as follows:
EC: ethylene carbonate
EMC: methyl ethyl carbonate
DMC: dimethyl carbonate
LiPF6: lithium hexafluoro phosphate
FEC: fluorinated ethylene carbonate
DTD: sulfuric acid vinyl ester
PS:1,3- propane sultone
PST:1,3- propene sultone
Silicon nitrile compounds additive shown in the formula I and formula II used in embodiments see above " 1. first add
Add agent " table in a section.
Embodiment 1
The lithium ion battery of the present embodiment, including positive cathode, diaphragm and electrolyte, wherein the active material of anode is nickel
Cobalt manganic acid lithium (NCM811) material, the active material of cathode are Si-C composite material (Si/C).The lithium ion battery is prepared as follows:
Gather inclined difluoro than blended anode active material NCM811, conductive carbon black and binder by the quality of 96.8:2.0:1.2
Ethylene is dispersed in n-methyl-2-pyrrolidone, obtains anode sizing agent, and anode sizing agent is uniformly coated on the two sides of aluminium foil,
It by drying, calendering and vacuum drying, and is burn-on with supersonic welder and obtains positive plate after aluminum lead-out wire, the thickness of pole plate exists
Between 100-115 μm.
By mass ratio mixing Si-C composite material (Si/C), conductive carbon black, the binder butadiene-styrene rubber of 96:1:1.2:1.8
And carboxymethyl cellulose, dispersion in deionized water, obtain negative electrode slurry, negative electrode slurry are coated on the two sides of copper foil, pass through
Drying, calendering and vacuum drying are crossed, and is burn-on with supersonic welder and obtains negative plate after nickel lead-out wire, the thickness of pole plate exists
Between 115-135 μm.
Diaphragm coats Al using single side2O3The ceramic diaphragm of preparation.
Ethylene carbonate (EC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC) are carried out in mass ratio for 2:1:7
The lithium hexafluoro phosphate based on electrolyte gross mass 12.5% is added in mixing after mixing, the change based on electrolyte gross mass 1% is added
Object 1 is closed, electrolyte is prepared.
The negative plate of the positive plate of above-mentioned preparation, ceramic diaphragm, above-mentioned preparation is put on sutomatic winding machine, winding obtains
Naked battery core.Naked battery core is placed in cylindrical steel shell, negative lug and nut cap tab is welded, the electrolyte of above-mentioned preparation is injected
In battery core after to drying, sealing, standing, preliminary filling, aging and partial volume complete the preparation (18650-3.0Ah) of lithium ion battery.
Embodiment 2-23
Embodiment 2-23, in addition in electrolyte component it is different other than, remaining positive plate, negative plate, diaphragm, lithium ion battery
With embodiment 1, the selection of compound shown in each embodiment Chinese style I and formula II and its content are as shown in table 3 for preparation.
Embodiment 24-27
Embodiment 24-27, in order to further enhance the synthesis output performance of battery, on the basis of above-described embodiment 1-23
Upper addition film for additive, the selection of each ingredient and its content are as shown in Table 4 below.
Comparative example 1-5
In comparative example 1-5, in addition to non-aqueous organic solvent, the type of additive and content are (total based on electrolyte in electrolyte
Quality) it is different outer, the preparation of remaining positive plate, negative plate, diaphragm, lithium ion battery is non-aqueous in comparative example 1 with embodiment 1
Organic solvent, the type of additive and content are as shown in table 3, non-aqueous organic solvent in comparative example 2-4, additive type with
Content is as shown in table 4.
Embodiment 1-27, comparative example the 1-5 lithium ion battery prepared are tested for the property, test method is as follows:
1) at 25 ± 2 DEG C/45 DEG C ± 2 DEG C, the battery after partial volume cycle performance: is charged to 4.2V with 0.5C constant current constant voltage
(cut-off current 0.01C), then with 1C constant-current discharge to 2.75V.N-th circulation volume is calculated after charge/discharge n times circulation
Conservation rate, calculation formula are as follows:
N-th circulation volume conservation rate (%)=(n-th cyclic discharge capacity/1st time cyclic discharge capacity) ×
100%；
2) battery after partial volume high-temperature storage performance: is charged to 4.2V (cut-off current with 0.5C constant current constant voltage at normal temperature
For 0.01C), battery initial discharge capacity is measured, then after 60 DEG C store 7 days, 2.75V measurement battery is discharged to 0.5C
It keeps capacity and restores capacity.Calculation formula is as follows:
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%；
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
3) low temperature performance: in room temperature with 0.5C constant-current constant-voltage charging to 4.2V, 5min is shelved, 0.2C is discharged to
2.75V detects battery initial capacity.Shelve 5min, 0.5C constant-current constant-voltage charging to 4.2V (cut-off current 0.01C).It will be electric
Pond, which is put into -20 DEG C of cryogenic box, shelves 6h, and is discharged to 2.75V with this condition with 0.2C, and the electric discharge detected under low temperature is held
Amount.
Low temperature discharge conservation rate (%)=low temperature discharge capacity/initial capacity × 100%.
Test result see the table below shown in 3, table 4.
Table 3
Embodiment 1-23 and comparative example 1 are compared and analyzed.Seen from table 3, embodiment 1-4 shows representativeization
Object 1 is closed in the content range of 0.05wt%, 0.5wt%, 1wt% and 2wt%, the normal-temperature circulating performance of lithium ion battery, height
Warm cycle performance, high-temperature storage performance and low temperature performance are significantly better than that comparative example 1, wherein the performance in 1wt% content
It is optimal.And use normal-temperature circulating performance, high temperature cyclic performance, the high-temperature storage performance of the lithium ion battery of 1 electrolyte of comparative example
It is lower with low temperature performance, high temperature performance and cycle performance cannot be taken into account.Embodiment 1 and embodiment 5-17 show table 2
Compound shown in listed formula I and formula II is under the content of 1wt%, normal-temperature circulating performance, the high temperature circulation of lithium ion battery
Energy, high-temperature storage performance and low temperature performance are closer to, and are significantly better than that comparative example 1.Embodiment 18-23 shows In
The compound 1 of 1wt%, the normal temperature circulation of lithium ion battery are added in electrolyte containing different non-aqueous organic solvent and lithium salts
Performance, high temperature cyclic performance, high-temperature storage performance and low temperature performance and embodiment 1 are closer to, and are significantly better than that pair
Ratio 1.
Table 3 the result shows that, the representative compound 1-14 of table 2 is added in electrolyte, can effectively improve lithium ion
Normal-temperature circulating performance, high temperature cyclic performance, high-temperature storage performance and the low temperature performance of battery.
Table 4
In order to further enhance the comprehensive performance of lithium ion battery, the lithium ion battery of embodiment 24-27 is electrolysed in table 4
Liquid adds film for additive fluoro carbonic ester on the basis of 1 additive of compound of the 1wt% of above-described embodiment 1 respectively
(FEC), 1,3- propane sultone (PS), 1,3- propene sultone (PST), sulfuric acid vinyl ester (DTD).Comparative example 2- in table 4
5 lithium-ion battery electrolytes contain corresponding film for additive, but are free of 1 additive of compound of 1wt%.By the knot of table 4
Fruit as it can be seen that the lithium ion battery of embodiment 24-27 normal-temperature circulating performance, high temperature cyclic performance, high-temperature storage performance and low temperature
Discharge performance is superior to the lithium ion battery of comparative example 2-5.The normal-temperature circulating performance of the lithium ion battery of comparative example 2-5, high temperature
Cycle performance, high-temperature storage performance and low temperature performance are poor, cannot take into account high temperature performance and cycle performance.By 3 He of table
Table 4 further adds film for additive fluorine as it can be seen that on the basis of lithium-ion battery electrolytes increase formula I or II compound of formula
For carbonic ester (FEC), 1,3-propane sultone (PS), 1,3- propene sultone (PST), sulfuric acid vinyl ester (DTD), Ke Yijin
The chemical property of one-step optimization lithium ion battery.
To sum up, find that the embodiment of the present invention by adding structure in the electrolytic solution by each embodiment and comparative example comparison
At least one of compound shown in formula I and formula II can form SEI protective film on positive and negative anodes, so that containing this non-aqueous solution electrolysis
The lithium ion battery of liquid obtains good normal-temperature circulating performance, high temperature cyclic performance, high-temperature storage performance and low temperature performance
Equal battery performances.Technical solution of the present invention significantly improves effect for nickelic anode collocation silicon-carbon composite cathode system.
Use above specific example is expounded the present invention, is merely used to help understand the present invention, not to
The limitation present invention.The design of those skilled in the art according to the present invention can also be made and several simply push away
It drills, deform or replaces.These are deduced, deformation or alternative are also fallen into scope of the presently claimed invention.
Claims (10)
1. a kind of lithium-ion battery electrolytes, which is characterized in that the electrolyte adds comprising non-aqueous organic solvent, lithium salts and first
Add agent, wherein first additive is selected from least one of silicon nitrile compounds shown in formula I and formula II,
Wherein R1、R2、R3、R4、R5、R6It is independently selected from the group without-O- or the group containing-O-, it is described to be free of-O-'s
Group is selected from hydrogen, halogen, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C2-C10It is alkenyl, substituted or unsubstituted
C2-C10Alkynyl, substituted or unsubstituted C6-C16Aryl, substituted or unsubstituted C1-C10It is alkane sulfonyl, substituted or unsubstituted
C6-C16Arylsulfonyl, the group containing-O- are selected from substituted or unsubstituted C1-C10It is alkoxy, substituted or unsubstituted
C2-C10Alkenyloxy group, substituted or unsubstituted C2-C10Alkynyloxy group, substituted or unsubstituted C6-C16Aryloxy group；
Wherein X1And X2It is independently selected from substituted or unsubstituted C1-C15Alkylidene, R7- COO- group, wherein R7Independently
Selected from substituted or unsubstituted C1-C6Alkylidene, substituted or unsubstituted C2-C15Alkenylene, substituted or unsubstituted C6-C16It is sub-
Aryl, substituted or unsubstituted C5-C15Sub- heterocyclic base, R8-O-R9Group, wherein R8And R9Independently selected from substituted or unsubstituted
C1-C6Alkylidene.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that silicon nitrile shown in the formula I and formula II
Class compound is selected from least one of compound as shown in the table:
3. lithium-ion battery electrolytes according to claim 1 or 2, which is characterized in that with lithium ion battery electrolysis
The gross mass of liquid is 100% meter, and the mass percentage of first additive is 0.05-2%.
4. electrolyte according to claim 1, which is characterized in that the lithium-ion battery electrolytes also include the second addition
Agent, the Second addition include fluorinated ethylene carbonate, vinylene carbonate, 1,3-propane sultone, in Isosorbide-5-Nitrae-butane sulphur
At least one of ester, 1,3- propene sultone, sulfuric acid vinyl ester, sulfuric acid acrylic ester.
5. lithium-ion battery electrolytes according to claim 4, which is characterized in that with the lithium-ion battery electrolytes
Gross mass is 100% meter, and the mass percentage of the Second addition is 15% or less.
6. lithium-ion battery electrolytes according to claim 1, which is characterized in that the lithium salts include lithium hexafluoro phosphate,
Lithium perchlorate, LiBF4, di-oxalate lithium borate, double fluorine Lithium bis (oxalate) borates, bis- (trimethyl fluoride sulfonyl) imine lithiums and double fluorine
At least one of sulfimide lithium.
7. lithium-ion battery electrolytes according to claim 6, which is characterized in that with the lithium-ion battery electrolytes
Gross mass is 100% meter, and the mass percentage of the lithium salts is 10-18%.
8. lithium-ion battery electrolytes according to claim 1, which is characterized in that the non-aqueous organic solvent includes carbonic acid
Vinyl acetate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, acetic acid
Methyl esters, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, γ-Ding Nei
At least one of ester, gamma-valerolactone, δ-valerolactone, 6-caprolactone.
9. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode, cathode, diaphragm and electrolyte, described
Electrolyte is according to lithium-ion battery electrolytes of any of claims 1-8.
10. lithium ion battery according to claim 9, which is characterized in that the active material of the anode is transition metal
Oxide, the active material of the cathode are graphite, composite material or lithium titanate containing Si；Preferably, the transition metal
Oxide is LiNixCoyMnzL(1-x-y-z)O2, wherein one of L Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, x, y, z
Value meet: 0≤x <, 1,0 < y≤1,0≤z < 1, and 0 x+y+z≤1 <.
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| CN113948769A (en) * | 2021-10-11 | 2022-01-18 | 苏州润能动力科技有限公司 | Low-temperature lithium ion battery electrolyte and application thereof |
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