CN108242566A - Electrolyte solution and secondary battery - Google Patents
Electrolyte solution and secondary battery Download PDFInfo
- Publication number
- CN108242566A CN108242566A CN201611218760.5A CN201611218760A CN108242566A CN 108242566 A CN108242566 A CN 108242566A CN 201611218760 A CN201611218760 A CN 201611218760A CN 108242566 A CN108242566 A CN 108242566A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- chlorine
- alkyl
- chloro
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an electrolyte and a secondary battery. The electrolyte includes an electrolyte salt, an organic solvent, and an additive. The organic solvent includes a carboxylic acid ester compound. The additive comprises cyclic sulfate and triphenyl phosphite. After the electrolyte is applied to a secondary battery, the rate capability, the cycle performance and the storage performance of the secondary battery under high temperature and high voltage can be simultaneously improved under the synergistic effect of the electrolyte, the secondary battery and the electrolyte.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of electrolyte and secondary cell.
Background technology
In the information age of rapid development, the demand to electronic products such as mobile phone, notebook, cameras increases year by year.Two
Working power of the primary cell especially lithium rechargeable battery as electronic product has energy density height, memory-less effect, work
Make the features such as voltage is high, just gradually replace traditional Ni-Cd, MH-Ni battery.However as the expansion of electronics market demand
And the development of power, energy storage device, requirement of the people to lithium rechargeable battery are continuously improved, exploitation have high-energy density and
Meeting the lithium rechargeable battery of fast charging and discharging becomes the task of top priority.At present, effective method is to improve the electricity of electrode material
Pressure, compacted density and the suitable electrolyte of selection.
At present, the widely applied electrolyte of lithium rechargeable battery includes the lithium hexafluoro phosphate as electric conducting lithium salt and conduct
The cyclic carbonate of organic solvent and the mixture of linear carbonate, however above-mentioned electrolyte is there are still many deficiencies, especially
Be the poor-performing of lithium rechargeable battery under high voltages, such as high temperature cyclic performance is poor, high-temperature storage performance difference and
High rate performance is poor.
Invention content
In view of the problem of background technology, the purpose of the present invention is to provide a kind of electrolyte and secondary cell, when
After the electrolyte is applied in secondary cell, high rate performance of the secondary cell under high temperature high voltage, cycle can be improved simultaneously
Performance and storage performance.
In order to achieve the above object, in one aspect of the invention, the present invention provides a kind of electrolyte, including electrolyte
Salt, organic solvent and additive.The organic solvent includes carboxylate compound.The additive include cyclic sulfates with
And triphenyl phosphite.
In another aspect of this invention, the present invention provides a kind of secondary cell, including institute according to an aspect of the present invention
The electrolyte stated.
Relative to the prior art, beneficial effects of the present invention include, but are not limited to：
The electrolyte of the present invention is simultaneously including carboxylate compound, cyclic sulfates and triphenyl phosphite, when it should
After using in secondary cell, under the synergistic effect of three, multiplying power of the secondary cell under high temperature high voltage can be improved simultaneously
Performance, cycle performance and storage performance.
Specific embodiment
The following detailed description of electrolyte according to the present invention and secondary cell.
Illustrate electrolyte according to a first aspect of the present invention first.
Electrolyte according to a first aspect of the present invention includes：Electrolytic salt, organic solvent and additive.It is described organic molten
Agent includes carboxylate compound.The additive includes cyclic sulfates and triphenyl phosphite.
In the electrolyte described according to a first aspect of the present invention, the carboxylate compound is used to improve secondary cell
High rate performance, but when carboxylate compound is applied to the secondary cell of high voltage system, is oxidized easily decomposition, in addition uses
The secondary cell of carboxylate compound under high temperature environment in use, secondary cell repeatedly cycle after capacitance loss it is serious, and
The high-temperature storage performance deterioration of secondary cell is serious.Cyclic sulfates have higher reduction potential, can be preferentially in negative terminal surface
Film forming, inhibits the reduction of carboxylate compound, so as to improve the cycle performance of secondary cell.Triphenyl phosphite can occur with HF
Reaction is played the role of reducing HF, so as to improve the high-temperature storage performance of secondary cell.When in electrolyte while including three kinds of objects
During matter, under the synergistic effect of three, high rate performance, cycle performance of the secondary cell under high temperature high voltage can be improved simultaneously
And storage performance.
In the electrolyte described according to a first aspect of the present invention, the carboxylate compound is selected from the chemical combination shown in formula I
One or more of object.Wherein, R1、R2Be each independently selected from the alkyl, carbon atom number that carbon atom number is 1~10 be 1~
One kind in 10 alkyl halide alkyl；Halogen atom in alkyl halide alkyl is selected from one or more of F, Cl, Br, I.
In the electrolyte described according to a first aspect of the present invention, the alkyl that the carbon atom number is 1~10 can be chain
Shape alkyl or cyclic alkane base.Wherein, chain alkyl includes linear paraffin base and branched alkane alkyl again.In addition, ring
Can substituent group can not also be contained with substituted base on shape alkyl.In the alkyl, the preferred lower limit of carbon atom number
Value can be 1,2,3, and the preferred upper limit value of carbon atom number can be 4,5,6,7,8,10.Preferably, R1、R2It is each independently selected from
The cyclic alkane base that the chain alkyl or carbon atom number that carbon atom number is 1~6 are 3~8.It is further preferred that R1、R2Respectively
The cyclic alkane base for being 5~7 from the chain alkyl or carbon atom number that are 1~4 independently selected from carbon atom number.
Specifically, the alkyl that carbon atom number is 1~10 may be selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, just
Butyl, isobutyl group, sec-butyl, tertiary butyl, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2 dimethyl
Propyl, 1- ethyl propyls, 1- methyl butyls, 2- methyl butyls, n-hexyl, isohesyl, 2- hexyls, 3- hexyls, cyclohexyl, 2- first
Base amyl, 3- methyl amyls, 1,1,2- thmethylpropyls, 3,3- dimethylbutyls, n-heptyl, 2- heptyl, 3- heptyl, 2- methyl
One kind in hexyl, 3- methylhexyls, 4- methylhexyls, different heptyl, suberyl, n-octyl, cyclooctyl, nonyl, decyl.
In the electrolyte described according to a first aspect of the present invention, the carbon atom number is in 1~10 alkyl halide alkyl
The substitution number and its position of substitution of halogen atom are not particularly limited, and can be selected according to actual demand.Specifically, halogen
The number of atom can be 1,2,3 or 4.When the number of halogen atom is 2 or more, the type of halogen atom can phase
Together, can also be entirely different, can also part it is identical.Alkyl halide alkyl can be that chain alkyl halide alkyl is alternatively cyclic halo alkane
Alkyl.Chain alkyl halide alkyl includes straight chain alkyl halide alkyl and branch alkyl halide alkyl again.It can be on cyclic halo alkyl
Substituted base can not also contain substituent group.In the alkyl halide alkyl, the preferred lower limiting value of carbon atom number can be 1,2,
3, the preferred upper limit value of carbon atom number can be 4,5,6,7,8,10.Preferably, R1、R2It is 1 to be each independently selected from carbon atom number
~6 chain alkyl halide alkyl or carbon atom number is 3~8 cyclic halo alkyl.It is further preferred that R1、R2Respectively solely
On the spot it is selected from the chain alkyl halide alkyl that carbon atom number is 1~4 or the cyclic halo alkyl that carbon atom number is 5~7.
Specifically, the alkyl halide alkyl that carbon atom number is 1~10 is selected from chloromethyl, dichloromethyl, trichloromethyl, 1- chloroethenes
Base, 1,2- Dichloroethyls, 2- chlorine n-propyl, bis- chloro- n-propyls of 2,2-, 1- chloro isopropyls, a chlorine cyclopropyl, 1- chloro-n-butyls,
2- chlorine isobutyl group, a chlorine cyclobutyl, 1- chlorine n-pentyl, 2- chlorine n-pentyl, 1- chlorine isopentyl, 2,2- dichloromethyls propyl, a chlorine
The chloro- 2,2- dimethyl propyls of cyclopenta, 3-, the chloro- 1- ethyl propyls of 1-, the chloro- 1- methyl butyls of 1-, 2- chloro-2-methyls butyl, 2-
Chlorine n-hexyl, a chlorine cyclohexyl, 2- chloromethyls amyl, the chloro- 3- methyl amyls of 3-, the chloro- 1,1,2- thmethylpropyls of 2-, 4- are chloro-
One kind in 3,3- dimethylbutyls, 2- chlorine n-heptyls.In above-mentioned group, Cl atoms in alkyl halide alkyl can also by F,
The substitution of one or more of Br, I part or all substitution.
In the electrolyte described according to a first aspect of the present invention, the carboxylate compound may be selected from methyl formate, first
Acetoacetic ester, ethyl acetate, ethyl propionate, ethyl valerate, ethyl isovalerate, propyl propionate, butyl propionate, isobutyl propionate, fourth
Acid butyl ester, butyl isobutyrate, amyl butyrate, isoamyl butyrate, amyl propionate, isoamyl propionate, isopropyl acetoacetic ester, butyric acid second
Ester, ethyl isobutyrate, propyl valerate, propyl isovalerate, ethyl isovalerate and aforementioned specific carboxylate compound by F, Cl,
One or more of compound that one or more of Br, I partly replace or all replace.
In the electrolyte described according to a first aspect of the present invention, the cyclic sulfates are selected from II compound represented of formula
One or more of.Wherein, n is the integer in 1~3；R3、R4、R5、R6It is former to be each independently selected from H, F, Cl, Br, I, carbon
One kind in the alkoxy that alkyl that subnumber is 1~10, carbon atom number are 1~10, wherein, the H on alkyl, alkoxy can also quilt
F, one or more of Cl, Br, I substitution.
In the electrolyte described according to a first aspect of the present invention, specifically, the cyclic sulfates are selected from following chemical combination
One or more of object；
In the electrolyte described according to a first aspect of the present invention, the triphenyl phosphite structure is as follows：
In the electrolyte described according to a first aspect of the present invention, the volume of the carboxylate compound is described organic molten
The 5%~50% of the total volume of agent.Preferably, the volume of the carboxylate compound is the total volume of the organic solvent
10%~40%.It is further preferred that the volume of the carboxylate compound for the organic solvent total volume 20%~
35%.
In the electrolyte described according to a first aspect of the present invention, the content of the cyclic sulfates is the electrolyte
The 0.5%~10% of total weight.Preferably, the content of the cyclic sulfates for the electrolyte total weight 1%~
5%.
In the electrolyte described according to a first aspect of the present invention, the content of the triphenyl phosphite is the electrolyte
Total weight 0.03%~1%.Preferably, the content of the triphenyl phosphite is the total weight of the electrolyte
0.1%~0.3%.
In the electrolyte described according to a first aspect of the present invention, there is no special for the specific type of the organic solvent
Limitation, can be selected according to actual demand.Preferably, using non-aqueous organic solvent.The organic solvent may also include arbitrarily
The carbonic ester of type and the halogenated compound of carbonic ester.The carbonic ester includes cyclic carbonate and linear carbonate.Specifically,
The organic solvent may also include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, pentylene, fluoro
Ethylene carbonate, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, tetrahydrochysene furan
One or more of mutter.
In the electrolyte described according to a first aspect of the present invention, the electrolytic salt may be selected from lithium salts, sodium salt or zinc salt,
It is different according to the difference of secondary cell that the electrolyte is applied.
In the electrolyte described according to a first aspect of the present invention, the content of the electrolytic salt is the total of the electrolyte
The 6.2%~25% of weight.Preferably, the content of the electrolytic salt for the electrolyte total weight 6.25%~
18.8%.It is further preferred that the content of the electrolytic salt is the 10%~15% of the total weight of the electrolyte.
Electrolyte is prepared using conventional method in the application, i.e., is uniformly mixed each material in electrolyte i.e.
It can.
Secondly the secondary cell of explanation according to a second aspect of the present invention.
Secondary cell according to a second aspect of the present invention includes the electrolyte described according to a first aspect of the present invention.
In the secondary cell described according to a second aspect of the present invention, the secondary cell further include positive plate, negative plate,
Isolation film.
In the secondary cell described according to a second aspect of the present invention, the positive plate includes plus plate current-collecting body and positioned at institute
The positive-active pulp layer on plus plate current-collecting body is stated, wherein, the positive-active pulp layer includes positive electrode active materials.Wherein,
The specific type of the positive electrode active materials is not limited specifically, can be selected according to demand.
In the secondary cell described according to a second aspect of the present invention, the negative plate includes negative current collector and positioned at institute
State the negative electrode active pulp layer on negative current collector.The negative electrode active pulp layer includes negative electrode active material.Wherein, it is described negative
The specific type of pole active material is not limited specifically, can be selected according to demand.
In the secondary cell described according to a second aspect of the present invention, the specific type of isolation film is not exposed to specific limit
System, can be any barrier material used in existing secondary cell, for example, polyethylene, polypropylene, Kynoar and
Their multilayer complex films, but it is not limited only to these.
In the secondary cell described according to a second aspect of the present invention, the secondary cell can be lithium rechargeable battery,
Sodium ion secondary battery or zinc ion secondary cell.
When secondary cell is lithium rechargeable battery, it is preferable that the positive electrode active materials are selected from cobalt acid lithium
(LiCoO2), lithium nickelate (LiNiO2), the LiFePO4 (LiFePO of olivine-type4), the LiMPO of olivine-type4, spinel-type
LiMn2O4, tertiary cathode material LiNixAyB(1-x-y)O2And Li1-x’(A’y’B’z’C1-y’-z’)O2One or more of.Its
In, M is selected from one or more of Co, Ni, Fe, Mn, V；A, B is each independently selected from one kind in Co, Al, Mn, and A and B
It differs；0<x<1,0<y<1 and x+y<1；0≤x’<1,0≤y '<1,0≤z '<1 and y '+z '<1；A ', B ', C are each independently
One kind in Co, Ni, Fe, Mn, and A ', B ', C are differed.The negative electrode active material can be selected from lithium metal, described negative
Pole active material can also be selected from relative to Li/Li+The material of lithium can be embedded in during the electrode potential ＜ 2V of equilibrium potential.Specifically
Ground, the negative electrode active material be selected from native graphite, Delanium, the micro- carbon ball of interphase (referred to as MCMB), hard carbon, soft carbon,
Silicon, silico-carbo compound, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO2, spinel structure lithiumation TiO2-
Li4Ti5O12, one or more of Li-Al alloys.The electrolytic salt can be lithium salts, and the lithium salts may be selected from LiPF6、
LiBF4、LiN(SO2F)2(being abbreviated as LiFSi), LiN (CF3SO2)2(being abbreviated as LiTFSi), LiClO4、LiAsF6、LiB(C2O4)2
(being abbreviated as LiBOB), LiBF2C2O4(being abbreviated as LiDFOB), LiPO2F2One or more of.
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The situation that secondary cell is lithium rechargeable battery, but the present invention are only shown in embodiment
It is without being limited thereto.
In the following embodiments, reagent, material and the instrument used is commercially available to obtain such as without special explanation
.
Lithium rechargeable battery in embodiment 1-11 and comparative example 1-7 is prepared by the following method.
(1) prepared by positive plate
By positive electrode active materials cobalt acid lithium (LiCoO2), binding agent Kynoar, conductive agent acetylene black is according to weight ratio
98:1:1 is mixed, and adds in N-Methyl pyrrolidone (NMP), and stirring is to system into transparent and homogeneous under de-airing mixer effect
Shape obtains anode sizing agent；Anode sizing agent is evenly applied on the plus plate current-collecting body aluminium foil that thickness is 12 μm；By aluminium foil in room temperature
120 DEG C of oven drying 1h are transferred to after drying, then obtain positive plate by cold pressing, cutting.
(2) prepared by negative plate
By negative electrode active material Delanium, thickener sodium carboxymethylcellulose (CMC), binding agent butadiene-styrene rubber according to weight
Measure ratio 98:1:1 is mixed, and adds in deionized water, and negative electrode slurry is obtained under de-airing mixer effect；Negative electrode slurry is uniform
On the negative current collector copper foil for being 8 μm coated in thickness；Copper foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, so
Afterwards negative plate is obtained by being cold-pressed, cutting.
(3) prepared by electrolyte
In water content<In the argon gas atmosphere glove box of 10ppm, by EC, PC, DEC according to volume ratio be EC:PC:DEC=1:
1:1 is mixed, then by fully dry lithium salts LiPF6It is dissolved in mixed organic solvents, adds in carboxylate chemical combination later
Object, cyclic sulfates and triphenyl phosphite, obtain electrolyte after mixing.Wherein, LiPF6Content for electrolyte
The 12.5% of total weight.Used carboxylate compound in electrolyte, cyclic sulfates and triphenyl phosphite it is specific
Type and content are as shown in table 1.In table 1, the content of carboxylate compound is calculated for the total volume based on organic solvent
What the content of the percentage by volume arrived, cyclic sulfates and triphenyl phosphite was calculated for the total weight based on electrolyte
Weight percent.
(4) preparation of isolation film
Select the polypropylene isolation film of 16 μ m-thicks (model A273 is provided by Celgard companies).
(5) preparation of lithium rechargeable battery
Positive plate, isolation film, negative plate are folded in order, isolation film is made to play isolation between being in positive and negative plate
Then effect winds and obtains naked battery core；Naked battery core is placed in outer packing foil, the above-mentioned electrolyte prepared is injected into drying
In naked battery core afterwards, by processes such as Vacuum Package, standing, chemical conversion, shapings, lithium rechargeable battery is obtained.
The test process of lithium rechargeable battery will be illustrated next.
(1) the high rate performance test of lithium rechargeable battery
At 25 DEG C, by lithium rechargeable battery using 1C (nominal capacity) constant-current charges to voltage as 4.4V, then with
4.4V constant-voltage charge to electric current is less than or equal to 0.05C, after shelving 5min, with 0.2C constant-current discharges to by voltage 3V, at this time
Discharge capacity is denoted as D0.
Then by lithium rechargeable battery using 1C constant-current charges to voltage as 4.4V, then it is small to electric current with 4.4V constant-voltage charges
In equal to 0.05C, after shelving 5min, with 2C constant-current discharges to by voltage 3V, discharge capacity at this time is denoted as D1.
Lithium rechargeable battery 2C/0.2C high rate performances=D1/D0 × 100%.
(2) the high temperature cyclic performance test of lithium rechargeable battery
At 45 DEG C, by lithium rechargeable battery first using 1C constant-current charges to voltage as 4.4V, further with 4.4V constant pressures
Electric current is charged to as 0.05C, then using 1C constant-current discharges to voltage as 3.0V, this is a charge and discharge cycles process, this
Discharge capacity is the discharge capacity recycled for the first time.Lithium rechargeable battery is carried out to 300 cycle chargings/put according to the method described above
Electrical testing, detection obtain the discharge capacity of the 300th cycle.
Lithium rechargeable battery recycle 300 times after capacity retention ratio (%)=(lithium rechargeable battery recycles 300 times
The discharge capacity that discharge capacity/lithium rechargeable battery recycles for the first time) × 100%.
(3) the high-temperature storage performance test of lithium rechargeable battery
At 85 DEG C, by lithium rechargeable battery using 0.5C constant-current charges to voltage as 4.4V, then filled with 4.4V constant pressures
Electricity to electric current is 0.05C, tests the thickness of lithium rechargeable battery at this time and is denoted as h0；Lithium rechargeable battery is put into later
85 DEG C of insulating box, storage are taken out afterwards for 24 hours, are tested the thickness of lithium rechargeable battery at this time and are denoted as h1。
Thickness swelling (%)=[(h after lithium rechargeable battery storage for 24 hours1-h0)/h0] × 100%.
Table 1 provides the parameter and the performance test results of embodiment 1-11 and comparative example 1-7.
From the Correlative data analysis of table 1 it is found that in comparative example 1 without add in carboxylate compound, annular phosphate and
Triphenyl phosphite, the high rate performance of lithium rechargeable battery, high temperature cyclic performance and high-temperature storage performance are poor；Work as electrolysis
When only containing carboxylate compound (comparative example 2) in liquid, the high rate performance of lithium rechargeable battery is improved, but high temperature
Cycle performance and high-temperature storage performance deteriorate；When only containing cyclic sulfates (comparative example 3) in electrolyte, lithium ion secondary
The high temperature cyclic performance of battery is improved, and high rate performance and high-temperature storage performance are then without significant change；When in electrolyte
When only containing triphenyl phosphite (comparative example 4), the high-temperature storage performance of lithium rechargeable battery is improved, but multiplying power
Penalty；When adding in carboxylate compound and cyclic sulfates (comparative example 5) simultaneously in electrolyte, can improve forthright again
Can while improve high temperature cyclic performance, but high-temperature storage performance severe exacerbation.When in electrolyte simultaneously add in carboxylic esterification
It closes object and during triphenyl phosphite (comparative example 6), can take into account high rate performance and high-temperature storage performance, but high temperature cyclic performance
It is deteriorated；When adding in cyclic sulfates and triphenyl phosphite (comparative example 7) simultaneously in electrolyte, high temperature circulation can be improved
Energy and high-temperature storage performance, but high rate performance deteriorates.
When containing carboxylate compound, annular phosphate and triphenyl phosphite simultaneously in electrolyte, lithium ion two
Primary cell has preferable high rate performance while has both preferable high temperature cyclic performance and high-temperature storage performance.
The announcement of book according to the above description, the application those skilled in the art can also carry out the above embodiment
Appropriate change and modification.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection domain of claims hereof.
Claims (10)
1. a kind of electrolyte, including：
Electrolytic salt；
Organic solvent；And
Additive；
It is characterized in that,
The organic solvent includes carboxylate compound；
The additive includes cyclic sulfates and triphenyl phosphite.
2. electrolyte according to claim 1, which is characterized in that the carboxylate compound is selected from the chemical combination shown in formula I
One or more of object；
Wherein,
R1、R2It is each independently selected from the alkyl halide alkyl that alkyl, carbon atom number that carbon atom number is 1~10 are 1~10
It is a kind of；
Halogen atom in alkyl halide alkyl is selected from one or more of F, Cl, Br, I.
3. electrolyte according to claim 2, which is characterized in that
The alkyl that the carbon atom number is 1~10 is selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl
Base, sec-butyl, tertiary butyl, cyclobutyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, cyclopenta, 2,2 dimethyl propyls, 1- second
Base propyl, 1- methyl butyls, 2- methyl butyls, n-hexyl, isohesyl, 2- hexyls, 3- hexyls, cyclohexyl, 2- methyl amyls, 3-
Methyl amyl, 1,1,2- thmethylpropyls, 3,3- dimethylbutyls, n-heptyl, 2- heptyl, 3- heptyl, 2- methylhexyls, 3- first
One kind in base hexyl, 4- methylhexyls, different heptyl, suberyl, n-octyl, cyclooctyl, nonyl, decyl；
The alkyl halide alkyl that the carbon atom number is 1~10 is selected from chloromethyl, dichloromethyl, trichloromethyl, 1- chloroethyls, 1,2-
Dichloroethyl, 2- chlorine n-propyl, bis- chloro- n-propyls of 2,2-, 1- chloro isopropyls, a chlorine cyclopropyl, 1- chloro-n-butyls, 2- chlorine isobutyls
Base, a chlorine cyclobutyl, 1- chlorine n-pentyl, 2- chlorine n-pentyl, 1- chlorine isopentyl, 2,2- dichloromethyls propyl, a chlorine cyclopenta, 3-
The chloro- 1- ethyl propyls of chloro- 2,2- dimethyl propyls, 1-, the chloro- 1- methyl butyls of 1-, 2- chloro-2-methyls butyl, 2- chlorine n-hexyl,
One chlorine cyclohexyl, 2- chloromethyls amyl, the chloro- 3- methyl amyls of 3-, the chloro- 1,1,2- thmethylpropyls of 2-, the chloro- 3,3- dimethyl of 4-
One kind in butyl, 2- chlorine n-heptyls, wherein the Cl atoms in alkyl halide alkyl can also be by one or more of F, Br, I portions
Divide substitution or all substitution.
4. electrolyte according to claim 3, which is characterized in that the carboxylate compound is selected from methyl formate, formic acid
Ethyl ester, ethyl acetate, ethyl propionate, ethyl valerate, ethyl isovalerate, propyl propionate, butyl propionate, isobutyl propionate, butyric acid
Butyl ester, butyl isobutyrate, amyl butyrate, isoamyl butyrate, amyl propionate, isoamyl propionate, isopropyl acetoacetic ester, ethyl butyrate,
Ethyl isobutyrate, propyl valerate, propyl isovalerate, ethyl isovalerate and aforementioned carboxylic acid's ester compounds are by F, Cl, Br, I
One or more of one or more of compounds for partly replacing or all replacing.
5. electrolyte according to claim 1, which is characterized in that the cyclic sulfates are selected from II compound represented of formula
One or more of；
Wherein,
N is the integer in 1~3；
R3、R4、R5、R6It is 1~10 to be each independently selected from alkyl, carbon atom number that H, F, Cl, Br, I, carbon atom number are 1~10
Alkoxy in one kind, wherein, the H on alkyl, alkoxy can also be by one or more of F, Cl, Br, I substitution.
6. electrolyte according to claim 5, which is characterized in that the cyclic sulfates in following compounds one
Kind is several；
7. electrolyte according to claim 1, which is characterized in that the volume of the carboxylate compound is described organic molten
The 5%~50% of the total volume of agent, preferably 10%~40%, further preferably 20%~35%.
8. electrolyte according to claim 1, which is characterized in that
The content of the cyclic sulfates for the electrolyte total weight 0.5%~10%, preferably 1%~5%；
The content of the triphenyl phosphite for the electrolyte total weight 0.03%~1%, preferably 0.1%~
0.3%.
9. electrolyte according to claim 1, which is characterized in that the organic solvent further includes ethylene carbonate, carbonic acid
Sub- propyl ester, butylene carbonate, pentylene, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate,
One or more of methyl ethyl carbonate, gamma-butyrolacton, tetrahydrofuran.
10. a kind of secondary cell, which is characterized in that including the electrolyte according to any one of claim 1-9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611218760.5A CN108242566A (en) | 2016-12-26 | 2016-12-26 | Electrolyte solution and secondary battery |
| PCT/CN2017/093744 WO2018120787A1 (en) | 2016-12-26 | 2017-07-20 | Electrolyte and secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611218760.5A CN108242566A (en) | 2016-12-26 | 2016-12-26 | Electrolyte solution and secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108242566A true CN108242566A (en) | 2018-07-03 |
Family
ID=62701602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611218760.5A Pending CN108242566A (en) | 2016-12-26 | 2016-12-26 | Electrolyte solution and secondary battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108242566A (en) |
| WO (1) | WO2018120787A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037779A (en) * | 2018-09-19 | 2018-12-18 | 南通海嘉智能科技有限公司 | New energy battery electrolyte cathode film formation additive |
| CN111244541A (en) * | 2020-01-20 | 2020-06-05 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using the same |
| WO2021146839A1 (en) * | 2020-01-20 | 2021-07-29 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device using same |
| CN113363584A (en) * | 2021-07-19 | 2021-09-07 | 河源市联懋新材料有限公司 | Lithium ion battery and manufacturing method of electrolyte and electrode thereof |
| CN113707941A (en) * | 2021-09-01 | 2021-11-26 | 河源市联懋新材料有限公司 | Electrolyte for improving gas production of lithium ion battery and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116435601B (en) * | 2023-06-14 | 2024-03-22 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020168576A1 (en) * | 1998-08-27 | 2002-11-14 | Ube Industries, Ltd. | Non-aqueous electrolyte and lithium secondary battery using the same |
| CN102593517A (en) * | 2012-04-09 | 2012-07-18 | 山东鸿正电池材料科技有限公司 | Non-aqueous electrolyte for lithium iron phosphate battery |
| CN103682442A (en) * | 2013-12-18 | 2014-03-26 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and application thereof |
| CN105895954A (en) * | 2016-05-05 | 2016-08-24 | 东莞市凯欣电池材料有限公司 | High-stability power battery electrolyte |
| CN106025356A (en) * | 2016-06-23 | 2016-10-12 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion battery comprising same |
| WO2016182598A1 (en) * | 2015-05-11 | 2016-11-17 | Eaglepicher Technologies, Llc | An electrolyte, a battery including the same, and methods of reducing electrolyte flammability |
-
2016
- 2016-12-26 CN CN201611218760.5A patent/CN108242566A/en active Pending
-
2017
- 2017-07-20 WO PCT/CN2017/093744 patent/WO2018120787A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020168576A1 (en) * | 1998-08-27 | 2002-11-14 | Ube Industries, Ltd. | Non-aqueous electrolyte and lithium secondary battery using the same |
| CN102593517A (en) * | 2012-04-09 | 2012-07-18 | 山东鸿正电池材料科技有限公司 | Non-aqueous electrolyte for lithium iron phosphate battery |
| CN103682442A (en) * | 2013-12-18 | 2014-03-26 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and application thereof |
| WO2016182598A1 (en) * | 2015-05-11 | 2016-11-17 | Eaglepicher Technologies, Llc | An electrolyte, a battery including the same, and methods of reducing electrolyte flammability |
| CN105895954A (en) * | 2016-05-05 | 2016-08-24 | 东莞市凯欣电池材料有限公司 | High-stability power battery electrolyte |
| CN106025356A (en) * | 2016-06-23 | 2016-10-12 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion battery comprising same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037779A (en) * | 2018-09-19 | 2018-12-18 | 南通海嘉智能科技有限公司 | New energy battery electrolyte cathode film formation additive |
| CN111244541A (en) * | 2020-01-20 | 2020-06-05 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using the same |
| WO2021146839A1 (en) * | 2020-01-20 | 2021-07-29 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device using same |
| US20210408603A1 (en) * | 2020-01-20 | 2021-12-30 | Ningde Amperex Technology Limited | Electrolytic solution, and electrochemical device using the same |
| JP7457135B2 (en) | 2020-01-20 | 2024-03-27 | 寧徳新能源科技有限公司 | Electrolyte and electrochemical device using it |
| CN111244541B (en) * | 2020-01-20 | 2024-04-05 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device using the same |
| CN113363584A (en) * | 2021-07-19 | 2021-09-07 | 河源市联懋新材料有限公司 | Lithium ion battery and manufacturing method of electrolyte and electrode thereof |
| CN113707941A (en) * | 2021-09-01 | 2021-11-26 | 河源市联懋新材料有限公司 | Electrolyte for improving gas production of lithium ion battery and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018120787A1 (en) | 2018-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108123172B (en) | Electrolyte and secondary lithium battery | |
| CN105261788B (en) | Electrolyte and the lithium ion battery including the electrolyte | |
| CN111769329B (en) | Lithium ion battery | |
| CN108242556B (en) | Electrolyte solution and secondary battery | |
| CN108242566A (en) | Electrolyte solution and secondary battery | |
| CN108242557B (en) | Electrolyte solution and secondary battery | |
| CN107293782B (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN109728340B (en) | Lithium ion battery | |
| CN108242567A (en) | Electrolyte solution and secondary battery | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| CN110611121B (en) | Electrolyte and lithium ion battery containing same | |
| US10797348B2 (en) | Electrolyte and lithium-ion battery | |
| CN108242568A (en) | Electrolyte solution and secondary battery | |
| CN109390629B (en) | Electrolyte and battery | |
| CN107403950A (en) | Electrolyte and lithium ion battery | |
| CN109309245A (en) | Electrolyte and electrochemical energy storage device | |
| CN109309255A (en) | Electrolyte and electrochemical energy storage device | |
| CN109309249B (en) | Electrolyte and electrochemical energy storage device | |
| CN109473717B (en) | Electrolyte suitable for high-voltage high-nickel power battery and high-voltage high-nickel power battery | |
| CN107403956A (en) | Electrolyte and lithium ion battery | |
| CN108232297A (en) | Electrolyte solution and secondary battery | |
| CN108400382B (en) | Electrolyte solution and secondary battery | |
| CN107293783B (en) | Electrolyte and lithium ion battery | |
| CN109309247A (en) | Electrolyte and electrochemical energy storage device | |
| CN107403957A (en) | Electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180703 |