CN108242565A - A kind of electrolyte, cathode and a kind of lithium ion battery - Google Patents
A kind of electrolyte, cathode and a kind of lithium ion battery Download PDFInfo
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- CN108242565A CN108242565A CN201611217728.5A CN201611217728A CN108242565A CN 108242565 A CN108242565 A CN 108242565A CN 201611217728 A CN201611217728 A CN 201611217728A CN 108242565 A CN108242565 A CN 108242565A
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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
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
The present invention provides electrolyte, cathode and battery; the electrolyte includes lithium salts, electrolyte solvent and additive; wherein; the additive of addition is the sulfuric acid ester compound of herein described structure; the film of additive generation that the application provides leads lithium performance with excellent, so as to reduce the activation polarization of battery, improves the cryogenic property of battery; electrolyte is hindered to be not consumed, cathode is protected to be not compromised, improves the service life of battery.
Description
Technical field
The invention belongs to a kind of field of lithium ion battery more particularly to electrolyte, a kind of cathode and lithium ion batteries.
Background technology
Lithium ion battery can form one layer of solid electrolyte interface film, abbreviation SEI in charge and discharge process in negative terminal surface
Film.Excellent SEI films have even compact, and thermal stability is good, and are the insulators of electronics, the excellence conductor of ion.
Excellent SEI films are to the performance of battery, and especially battery high/low temperature cycle performance is with important influence.
Current technology is difficult to take into account the high temperature performance of battery.Main cause is lithium ion transport speed under cryogenic conditions
Rate becomes the principal element for influencing battery performance.And the factor for influencing lithium ion transport rate mainly has：1st, the ingredient of SEI films；
2nd, electrolyte viscosity.
The prior art is to add film for additive in the electrolytic solution to this main solution, to form excellent SEI
Film, most common film for additive are vinylene carbonate (abbreviation VC).It is raw after adding film for additive vinylene carbonate
Into the main components of SEI films be organic polymer, the advantages of SEI films are also referred to as organic polymer films, organic polymer films
It is even compact, thermal stability is good, but the drawback is that lead that lithium is poor, and transmission rate of the lithium ion on SEI films is caused to reduce.
Under cryogenic, the principal element for influencing battery performance is the quantity and transmission rate of lithium ion, and transmits speed
Transmission rate of the lithium ion on SEI films influences especially notable in rate.The reduction of lithium ion transmission rate on SEI films will increase
Battery polarization reduces so as to cause the cycle performance of battery at low temperature.
Invention content
To solve the technical issues of at least one in the prior art, the present invention provides a kind of electrolyte, including lithium salts, electricity
Liquid solvent and additive are solved, wherein, the additive is formula (1) or the sulfuric acid ester compound of formula (2) described structure：
In formula (2), n is the positive integer more than or equal to 1.
A kind of cathode provided by the invention, the negative electrode material layer including negative current collector, positioned at negative current collector surface, also
The film that electrochemical reaction generation occurs by the additive including being located at negative material layer surface；The additive is formula (1)
Or the sulfuric acid ester compound of structure shown in formula (2)：
In formula (2), n is the positive integer more than or equal to 1.
The present invention provides a kind of lithium ion battery, including housing and the battery core being contained in housing, electrolyte, battery core packet
Anode, cathode and the diaphragm between positive electrode and negative electrode are included, the electrolyte is electrolyte described herein.
The present invention provides a kind of lithium ion battery, including housing and the battery core being contained in housing, electrolyte, battery core packet
Anode, cathode and the diaphragm between positive electrode and negative electrode are included, the cathode is cathode of the present invention.
For the present invention by adding the additive of structure of the present invention in the electrolytic solution, the additive of the structure can be negative
Electrochemical reaction occurs for the surface of pole material layer, and generation has the excellent film for leading lithium performance, lithium ion is effectively increased in film
Transmission rate, the cryogenic property of battery can be improved；It can effectively block electrolyte that side reaction occurs in negative terminal surface simultaneously, it can
Cathode to be protected not to be damaged, the not oxidized decomposition of electrolyte solvent is protected, extends the service life of battery.
Inventor has found by many experiments, using the additive of structure of the present invention, charge and discharge process at normal temperatures
Middle generation electrochemical reaction, and deposit to form one layer of fine and close film in negative terminal surface, which leads lithium performance with excellent, so as to
The activation polarization of battery can be reduced, improves the cryogenic property of battery.In addition the SEI film even compacts have oxidative resistance, together
When the active site of negative terminal surface can be covered, can effectively hinder electrolyte subsequent charge and discharge process relaying supervention life electrification
Reaction is learned, electrolyte is protected not consumed excessively, can also cathode be protected not to be damaged, while also protects electrolyte solvent not by oxygen
Change and decompose, the service life of battery is improved with this.It is provided by the invention that there is the excellent film for leading lithium performance to solve prior art use
VC leads that lithium is poor as the film that film for additive generates, and the transmission rate of lithium ion is caused to reduce, so as to increase battery polarization, most
Lead to the technical issues of cycle performance reduces under battery cryogenic conditions eventually.
By electrolyte provided by the invention in battery, in the charge and discharge process of battery, the additive in electrolyte to exist
Under room temperature, electrochemical reaction occurs on negative material surface, being formed has the excellent film for leading lithium performance, can greatly improve battery
Cryogenic property, meanwhile, additive of the present invention does not form influence to other functions of battery system.
Description of the drawings
Fig. 1 is the SEM figures that negative material enlargement ratio is 2000 in the embodiment of the present invention 1.
Fig. 2 is the SEM figures that negative material enlargement ratio is 5000 in the embodiment of the present invention 1.
Fig. 3 is the SEM figures that negative material enlargement ratio is 2000 in the embodiment of the present invention 3.
Fig. 4 is the SEM figures that negative material enlargement ratio is 5000 in the embodiment of the present invention 3.
Fig. 5 is the SEM figures that enlargement ratio is 2000 after negative electrode material layer Surface Creation SEI films in the embodiment of the present invention 3.
Fig. 6 is the SEM figures that enlargement ratio is 5000 after negative electrode material layer Surface Creation SEI films in the embodiment of the present invention 3.
Fig. 7 is the SEM figures that the enlargement ratio of the negative material in comparative example 1 of the present invention is 2000.
Fig. 8 is the SEM figures that the enlargement ratio of the negative material in comparative example 1 of the present invention is 5000.
Fig. 9 is the low temperature electrochemical testing impedance of the embodiment of the present invention, comparative example.
Specific embodiment
In order to which technical problem solved by the invention, technical solution and advantageous effect is more clearly understood, below to this
Invention is further elaborated.
The present invention provides a kind of electrolyte, and including lithium salts, electrolyte solvent and additive, the additive is formula (1)
And/or the sulfuric acid ester compound of formula (2) described structure.
In electrolyte provided by the invention, by using the sulfuric acid ester compound of herein described structure as the present invention
In room temperature charge and discharge process electrochemical reaction occurs for the additive of the electrolyte, the additive, and one is formed in negative terminal surface
Layer it is fine and close and with the excellent film for leading lithium performance, effectively increase transmission rate of the lithium ion in film, significantly improve battery
Cryogenic property；There is oxidative resistance simultaneously, the active site of negative terminal surface can be covered, can effectively block electrolyte follow-up
Charge and discharge process relaying supervention life electrochemical reaction, cathode can be protected not to be damaged, electrolyte solvent is protected not disappeared
Consumption extends the service life of battery.Compared with common additives, additive of the present invention has significant superiority.
In the present invention, used additive is formula (1) and/or the sulfuric acid ester compound of formula (2) described structure：
In formula (2), n is the positive integer more than or equal to 1.
It is preferred that the additive is selected from cyclic annular bis- (dimethyl siloxane) di-sulfates, cyclic annular three (dimethyl siloxanes)
One or more of three sulfuric esters, cyclic annular four (dimethyl siloxane) four sulfuric esters.Concrete structure is as follows：
Cyclic annular bis- (dimethyl siloxane) di-sulfates
Cyclic annular three (dimethyl siloxane) three sulfuric esters, i.e. n=1 in formula (2)：
Cyclic annular four (dimethyl siloxane) four sulfuric esters, i.e. n=2 in formula (2)：
It is preferred that on the basis of electrolyte gross mass, the content of the additive is 0.5~5wt%, further preferred content
For 1~3wt%, most preferably 2wt%.Additive can either form film that is one layer thin and having enough coverages in negative terminal surface
Layer, while there will not be extra additive and system is impacted.
Under preferable case, in electrolyte provided by the invention, on the basis of electrolyte gross mass, the content of lithium salts for 8~
20wt%, further preferred content are 15~20wt%, a concentration of 0.3~2mol/L of lithium salts.The lithium salts is this field skill
The common various lithium salts of art personnel, for example, can be selected from LiPF6, LiClO4, LiBF4, LiAsF6, LiSiF6, LiAlCl4,
LiBOB、LiODFB、LiCl、LiBr、Lii、LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、Li
(SO2C2F5) one or more in 2N, Li (SO3CF3) 2N, LiB (C2O4) 2 are used in mixed way.Further preferred scheme, this
Invention is using LiPF6 as main lithium salts.
The present invention is using the common various electrolyte solvents of those skilled in the art, such as can be selected from ethylene carbonate
Ester (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), formic acid first
Ester (MF), methyl acetate (MA), methyl propionate (MP), ethyl acetate (EP), 1,3- propane sultones (1,3-PS), sulfuric acid second
Enester (DTD), sulfuric acid acrylic ester, ethylene sulfite (ES), propylene sulfite (PS), adiponitrile (ADN), succinonitrile
(SN), one or more of sulfurous acid diethyl ester (DES), gamma-butyrolacton (BL), dimethyl sulfoxide (DMSO) (DMSO).It is preferred that carbonic acid
In vinyl acetate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC)
One or more, on the basis of electrolyte gross mass, the content of the electrolyte solvent is 75~91.5wt%.Inventor is grinding
Study carefully middle discovery carbonic ester system electrolyte solvent in the prior art, it is big to deposit the internal resistance of cell under cryogenic, leads to battery life
The shortcomings that reduction.And it adds herein described additive in carbonic ester system electrolyte solvent and assists in application, electrolyte can be made molten
Agent negative terminal surface generate one layer it is fine and close and with the excellent film for leading lithium performance, there is significantly effect compared with prior art
Fruit, while electrolyte system is more stable, is widely used, lithium salts degree of dissociation is high, and additive solubility is more preferable, additive reaction process
The advantages that will not being influenced by electrolyte solvent.
It is preferred that EC:DMC:DEC:The mass ratio of EMC is 4:1:1:5.It is such setting have make what lithium salts fully dissociated
The effect for increasing lithium ion number is played in effect, is conducive to improve the rate charge-discharge performance of battery.
A kind of cathode of present invention offer, the negative electrode material layer including negative current collector, positioned at negative current collector surface,
In, further include the film that electrochemical reaction generation occurs by the additive positioned at negative material layer surface；The additive is
The sulfuric acid ester compound of structure shown in formula (1) and/or formula (2)：
In formula (2), n is the positive integer more than or equal to 1.
It is preferred that containing negative electrode active material in negative electrode material layer, which includes core body and clad, core
Heart body is graphite particle, and clad is polymer film；Preferred polymers film is weaker zone, and further preferably, clad is not complete
Full cladding.Additive in the electrolyte of the present invention can preferably be applied to such negative electrode active material, in first charge-discharge mistake
Cheng Zhong, the electrolyte and cathode contact, the additive in electrolyte are uncoated in loose polymer film and polymer film
It is deposited in graphite particle, obtain one layer of densification and leads the film that lithium is had excellent performance.The film can improve herein described negative electrode active material
The shortcomings that material can not take into account battery cryogenic property.
It is preferred that the material of polymer film is poly- (styrene sulfonic acid) lithium salts of structure shown in formula (3)：
In formula (3), R1, R2, R3, R4 each are selected from one kind in H or active group, and the active group is cyano or halogen
Element.
Preferably, the negative material layer surface has film, and the composition of the film is additive of the present invention generation
Film.Polymer film in negative material has certain retractility, will not be broken in battery charging and discharging cyclic process, together
When polymer film have good thermal stability, help to improve the high-temperature behavior of battery, but do not take into account cryogenic property.To this
Present inventor uses herein described additive, i.e., generates cause doped with by additive of the present invention in polymer film
It is close and with the excellent film for leading lithium performance, be conducive to improve the cryogenic property led lithium, improve battery of battery low temperature lower film.
The present invention also provides a kind of lithium ion battery, including housing and the battery core being contained in housing, electrolyte, battery core
Including anode, cathode and the diaphragm between positive electrode and negative electrode, wherein, the electrolyte is electrolyte as described above.
The present invention also provides a kind of lithium ion battery, including housing and the battery core being contained in housing, electrolyte, battery core
Including anode, cathode and the diaphragm between positive electrode and negative electrode, wherein, the cathode is cathode provided by the invention.Its
Middle anode includes plus plate current-collecting body and positive electrode, and positive electrode includes positive active material, conductive agent, positive electrode binder, institute
It can be conductive agent commonly used in the art, positive electrode binder to state conductive agent, positive electrode binder；Cathode includes negative current collector
And negative material, negative material include negative electrode active material, negative electrode binder, the packet of the being also an option that property of negative material
Conductive agent is included, which is conventional conductive agent, can be identical or different with the conductive agent in positive electrode material layer, and the cathode glues
It can be negative electrode binder commonly used in the art to tie agent.
Due to the preparation process of negative plate, positive plate, diaphragm technology well known in the art, and the assembling of battery is also
Technology known in the field, details are not described herein again.
A kind of lithium ion battery, additive can finally be totally consumed and form one layer of densification in negative terminal surface in electrolyte
And with the excellent film for leading lithium performance, it is also possible to there is part in the electrolytic solution and remain.
The preparation of battery in the present invention can be the electrolysis for providing the anode, cathode and the application of this field routine
Liquid, which is packaged, is prepared battery, the additive described herein added in electrolyte, under normal temperature condition for the first time and/or
Can occur electrochemical reaction in secondary charge and discharge process, and negative terminal surface deposit to be formed one layer it is fine and close, and with excellent
The film for leading lithium performance.
Can also be that negative material layer surface is prepared is fine and close and with excellent with one layer in the present invention simultaneously
After the cathode for leading the film of lithium performance, which is used to prepare to obtain battery；The preparation method of cathode is not particularly limited at this time,
As long as additive described herein is enabled to electrochemical reaction to occur and in negative terminal surface deposition compact, and with excellent
The film for leading lithium performance, reaction condition is room temperature.
Other constructions of battery and specific preparation method are known to the skilled person, and therefore not to repeat here.
Make below in conjunction with lithium ion battery of the specific embodiment to the electrolyte of the present invention and containing the electrolyte further
Explanation.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.It is real
Raw material employed in example and comparative example is applied to be commercially available.
Embodiment 1
Step 1: the preparation of negative material：
1st, 200ml N-Methyl pyrrolidones (NMP) are weighed in 500ml beakers, are stirred；
2nd, it is poly- (styrene sulfonic acid) that 100g is added in into above-mentioned beaker, stirs 30min；
3rd, 50g lithium carbonates are weighed to be slowly added in above-mentioned beaker, stir 1h；
4th, 50g graphite is added in, continues to stir 2h；
5th, enough hydrochloric acid is added dropwise, until no longer effervescent in beaker；
6th, stop stirring, filter, and be washed with deionized, then dry, surface is made and coats poly- (styrene sulfonic acid)
The graphite of lithium salts, wherein R1-R4 are F elements；
7th, surface obtained above is coated to the graphite and conductive black, butadiene-styrene rubber, carboxylic of poly- (styrene sulfonic acid) lithium salts
Methylcellulose is 95 by weight:1:1.7:2.3 dispersions obtain negative electrode slurry in deionized water；
8th, on the copper foil two sides for being 10 μm coated in thickness by the negative electrode slurry after stirring evenly, and at 110 DEG C ± 5 DEG C
Baking then by calendering, vacuum drying, forms the material layer that thickness is 100 μm ± 5 μm, obtains negative material.
Step 2: the preparation of electrolyte：
By ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid first in argon gas glove box
Ethyl ester (EMC) is according to EC:DMC:DEC:The mass ratio of EMC is 4:1:1:5 mass ratio mixing, while add in 0.5% weight
Part bis- (dimethyl siloxane) di-sulfates of ring-type to get to non-aqueous organic solvent, then be charged with 8% parts by weight
LiPF6Non-aqueous organic electrolyte is obtained, is denoted as C1.
Step 3: the preparation of lithium ion battery：
Respectively by above-mentioned negative material and corresponding collector, diaphragm paper and positive electrode and corresponding collector by winding,
Then battery core is put into rectangular aluminum hull, with spacer ring and cover plate for sealing, is subsequently placed into vacuum drying chamber into battery core by welding production,
12h is toasted at 95 DEG C or so, finally injects electrolyte C1, and sealed to get battery S1 with steel ball.
Embodiment 2
Negative material is prepared using step same as Example 1, the difference lies in：Poly- (the benzene used in step 1
Vinyl sulfonic acid) lithium salts, wherein R1 to R4 is H element；
Electrolyte and battery are prepared using step same as Example 1, the difference lies in：1% is used in step 2
Three sulfuric ester of ring-type three (dimethyl siloxane) of parts by weight；The LiPF of 10% parts by weight6Non-aqueous organic electrolyte is obtained, is denoted as
C2 and battery S2.
Embodiment 3
Negative material is prepared using step same as Example 1, the difference lies in：Poly- (the benzene used in step 1
Vinyl sulfonic acid) lithium salts, wherein R1-R4 is cyano；
Electrolyte and battery are prepared using step same as Example 1, the difference lies in：2% is used in step 2
Bis- (dimethyl siloxane) di-sulfates of ring-type of parts by weight；The LiPF of 12% parts by weight6Non-aqueous organic electrolyte is obtained, is denoted as
C3 and battery S3.
Embodiment 4
Negative material is prepared using step same as Example 1, the difference lies in：Poly- (the benzene used in step 1
Vinyl sulfonic acid) lithium salts, wherein R1-R4 is Cl elements；
Electrolyte and battery are prepared using step same as Example 1, the difference lies in：3% is used in step 2
Four sulfuric ester of ring-type four (dimethyl siloxane) of parts by weight；The LiPF of 15% parts by weight6Non-aqueous organic electrolyte is obtained, is denoted as
C4 and battery S4.
Embodiment 5
Negative material is prepared using step same as Example 1, the difference lies in：Poly- (the benzene used in step 1
Vinyl sulfonic acid) lithium salts, wherein R1 is H element, and R2 is F elements, and R3 is Cl elements, and R4 is Br elements；
Electrolyte and battery are prepared using step same as Example 1, the difference lies in：4% is used in step 2
Bis- (dimethyl siloxane) di-sulfates of ring-type of parts by weight；The LiPF of 18% parts by weight6Non-aqueous organic electrolyte is obtained, is denoted as
C5 and battery S5.
Embodiment 6
Negative material is prepared using step same as Example 1, the difference lies in：Poly- (the benzene used in step 1
Vinyl sulfonic acid) lithium salts, wherein R1-R4 is I elements；
Electrolyte and battery are prepared using step same as Example 1, the difference lies in：5% is used in step 2
Three sulfuric ester of ring-type three (dimethyl siloxane) of parts by weight；The LiPF of 20% parts by weight6Non-aqueous organic electrolyte is obtained,
Embodiment 7
Step 1: negative material uses the graphite without any processing；Remaining is prepared using step same as Example 1
Non-aqueous organic electrolyte is denoted as C7 and battery S7.
Comparative example 1
Step 1: negative material uses the graphite without any processing；
Electrolyte and battery are prepared using step same as Example 1, the difference lies in do not contain ring in step 2
Bis- (dimethyl siloxane) di-sulfates of shape.
Performance test
First, test equipment
Electrochemical workstation (Shanghai Chen Hua CHI660D), battery charging and discharging test cabinet (the blue strange BK6808 in Guangzhou), high/low temperature
Chamber (Wuxi southern Jiangsu GDJS-100).
2nd, test event and method
(1) first charge-discharge efficiency is tested
Method：By the rectangular cell 0.1C constant-current charges of making to 3.6V under room temperature, charging capacity is recorded, is then shelved
10min, then with 0.1C constant-current discharges to 2.0V, record discharge capacity.
First charge-discharge efficiency=(discharge capacity/charging capacity) * 100%
(2) battery low-temperature circulating is tested
Method：In -20 DEG C of low temperature, 0.2C charges to 3.6V, cut-off current 0.02C, and then 0.2C is discharged to 2.0V, follows
Ring 300 times, obtains capacity retention ratio.
Capacity retention ratio=(discharge capacity/first time discharge capacity after recycling 300 times) * 100%
(3) battery high-temperature loop test
Method：In 60 DEG C of high temperature, 1C charges to 3.6V, cut-off current 0.02C, and then 1C is discharged to 2.0V, cycle 500
It is secondary, obtain capacity retention ratio.
Capacity retention ratio=(discharge capacity/first time discharge capacity after recycling 500 times) * 100%
(4) 60 DEG C of storge quality tests of high temperature
Method：Battery high-temperature 60 DEG C of storages performance test in 7 days：Under the conditions of 25 DEG C of room temperature, 3.6V, cut-off electricity are charged to 1C
0.02C is flowed, 2.0V is then discharged to 1C, records the initial capacity of battery；Then 3.6V is charged under similarity condition, be put into
Insulating box stores 7 days under the conditions of 60 DEG C；2.0V is discharged to 1C after storage, records residual capacity；Finally under normal temperature condition
Charge and discharge are carried out, record the recovery capacity of battery.
Capacity surplus ratio=(residual capacity/initial capacity) × 100%
Capacity restoration rate=(restoring capacity/initial capacity) × 100%
(5) low temperature electrochemical testing impedance
Method：Negative material, electrolyte and the diaphragm prepared with above-described embodiment 1- embodiments 7,1 the method for comparative example
Paper is assembled into 2016 type button cells, wherein the negative material does anode, pour lithium slice does cathode.The button cell of assembling is existed
Under the conditions of -20 DEG C of low temperature electrochemical AC impedance test is carried out with electrochemical workstation.
3rd, test result
1st, first charge-discharge efficiency test, low-temperature circulating performance test and high temperature cyclic performance test result is as follows table 1
It is shown.
Table 1
According to the data of table 1, the S1 highests in first charge-discharge efficiency, while S1 to S7 is above comparative example 1, illustrates this
Apply for that the additive can improve the efficiency for charge-discharge of battery.
In low-temperature circulating capacity retention ratio, while S1 to S7 is significantly higher than comparative example 1, illustrates herein described additive
Be conducive to improve the cryogenic property of battery.
In high temperature circulation capacity retention ratio, S1 to S7 is above comparative example 1, illustrates that negative terminal surface coats polystyrene sulphur
Sour lithium salts can improve the high temperature cyclic performance of battery.
In summary, S1 to S7 is kept in first charge-discharge efficiency, low-temperature circulating capacity retention ratio and high temperature circulation capacity
Rate is higher than comparative example 1, illustrates that negative terminal surface coats polystyrolsulfon acid lithium salts, while it is cyclic annular that additive is added in electrolyte
Bis- (dimethyl siloxane) di-sulfates can improve the high temperature performance of battery.
2nd, test result is as follows shown in table 2 for 60 DEG C of storge qualities of high temperature.
Table 2
Polystyrolsulfon acid lithium salts is coated to negative terminal surface it can be seen from 2 data of table, while this Shen is added in electrolyte
Please the additive battery (S1 to S7) high-temperature storage performance be superior to negative terminal surface do not do it is any processing or electrolyte in not
Add the battery (comparative example 1) of herein described additive.
3rd, low temperature electrochemical testing impedance is as shown in Figure 9.
As shown in Figure 9, the Charge-transfer resistance in electrochemical AC impedance is significantly less than embodiment 1- embodiments 7, right
The Charge-transfer resistance of ratio 1, illustrating that herein described additive has reduces battery electrochemical impedance, reduces battery polarization
Effect.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of electrolyte, including lithium salts, electrolyte solvent and additive, which is characterized in that the additive for formula (1) and/
Or the sulfuric acid ester compound of formula (2) described structure：
In formula (2), n is the positive integer more than or equal to 1.
2. electrolyte according to claim 1, which is characterized in that the additive is selected from cyclic annular bis- (dimethyl siloxanes)
Di-sulfate, cyclic annular three (dimethyl siloxane) three sulfuric esters, one kind in cyclic annular four (dimethyl siloxane) four sulfuric esters or
It is several.
3. electrolyte according to claim 1, which is characterized in that on the basis of electrolyte gross mass, the additive
Content is 0.5~5wt%.
4. electrolyte according to claim 3, which is characterized in that on the basis of electrolyte gross mass, the additive
1~3wt% of content.
5. electrolyte according to claim 1, which is characterized in that the lithium salts is selected from LiPF6、LiClO4、LiBF4、
LiAsF6、LiSiF6、LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、LiI、LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、Li(SO2C2F5)2N、Li(SO3CF3)2N、LiB(C2O4)2One or more of；With electrolyte gross mass
On the basis of, the content of the lithium salts is 8~20wt%.
6. electrolyte according to claim 1, which is characterized in that the electrolyte solvent include methyl ethyl carbonate (EMC),
Dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), propene carbonate (PC), butylene (BC),
Ethylene sulfite (ES), propylene sulfite (PS), sulfurous acid diethyl ester (DES), gamma-butyrolacton (BL), dimethyl sulfoxide (DMSO)
(DMSO), one or more of ethyl acetate, methyl acetate；On the basis of the gross mass of electrolyte, the electrolyte solvent
Content be 75~91.5wt%.
7. a kind of cathode, the negative electrode material layer including negative current collector and positioned at negative current collector surface, which is characterized in that also wrap
Include the film that electrochemical reaction generation occurs by the additive positioned at negative material layer surface；The additive for formula (1) and/
Or the sulfuric acid ester compound of structure shown in formula (2)：
In formula (2), n is the positive integer more than or equal to 1.
8. cathode according to claim 7, which is characterized in that contain negative electrode active material, institute in the negative electrode material layer
State negative electrode active material include core body and clad, the core body be graphite particle, the clad be polymer film, institute
Polymer film is stated as weaker zone.
9. cathode according to claim 8, which is characterized in that the clad does not coat completely.
10. cathode according to claim 8, which is characterized in that the material of the polymer film is structure shown in formula (3)
Poly- (styrene sulfonic acid) lithium salts：
In formula (3), R1, R2, R3, R4 each are selected from one kind in H or active group, and the active group is cyano or halogen.
11. a kind of lithium ion battery, including housing and the battery core being contained in housing, electrolyte, battery core include anode, cathode and
Diaphragm between positive electrode and negative electrode, which is characterized in that the electrolyte is the electrolysis described in claim 1-6 any one
Liquid.
12. a kind of lithium ion battery, including housing and the battery core being contained in housing, electrolyte, battery core include anode, cathode and
Diaphragm between positive electrode and negative electrode, which is characterized in that the cathode is the cathode that claim 7-10 any one provides.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381073A (en) * | 2021-07-27 | 2021-09-10 | 中节能万润股份有限公司 | Silicon sulfonate non-aqueous electrolyte additive and application thereof |
| CN117954690A (en) * | 2024-03-26 | 2024-04-30 | 深圳海辰储能科技有限公司 | Battery, power utilization system and energy storage system |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495959A (en) * | 2002-08-29 | 2004-05-12 | �ձ�������ʽ���� | Electrolyte for xecondary battery and secondary battery using said electrolyte |
| JP2009054287A (en) * | 2007-08-23 | 2009-03-12 | Sony Corp | Electrolyte solution and battery |
| CN101471455A (en) * | 2007-12-28 | 2009-07-01 | 张家港市国泰华荣化工新材料有限公司 | Additive for lithium ion battery non-aqueous electrolyte and non-aqueous electrolyte made by the same |
| JP2010103052A (en) * | 2008-10-27 | 2010-05-06 | Nec Tokin Corp | Nonaqueous electrolytic solution, and nonaqueous electrolytic solution secondary battery using the same |
| CN101783412A (en) * | 2009-01-15 | 2010-07-21 | 索尼公司 | Electrolyte and secondary battery |
| CN103004006A (en) * | 2011-07-07 | 2013-03-27 | 住友精化株式会社 | Additive for nonaqueous electrolyte, nonaqueous electrolyte, and electricity storage device |
| CN103493280A (en) * | 2011-04-26 | 2014-01-01 | 宇部兴产株式会社 | Non-aqueous electrolytic solution, electrical storage device utilizing same, and cyclic sulfonic acid ester compound |
| CN104247139A (en) * | 2012-04-27 | 2014-12-24 | 日本电气株式会社 | Lithium secondary battery |
| JP2015156372A (en) * | 2014-01-15 | 2015-08-27 | 旭化成株式会社 | Electrolyte for nonaqueous power storage device and lithium ion secondary battery |
| CN105074996A (en) * | 2013-04-01 | 2015-11-18 | 宇部兴产株式会社 | Nonaqueous electrolyte solution and electricity storage device using same |
| CN105186032A (en) * | 2015-10-19 | 2015-12-23 | 东莞市凯欣电池材料有限公司 | High-voltage lithium-ion battery electrolyte and lithium-ion battery using high-voltage lithium-ion battery electrolyte |
| CN105409049A (en) * | 2013-06-06 | 2016-03-16 | 株式会社杰士汤浅国际 | Non-aqueous electrolyte secondary battery and production method for non-aqueous electrolyte secondary battery |
| CN105655640A (en) * | 2016-03-28 | 2016-06-08 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium-ion battery containing same |
| JP2016134218A (en) * | 2015-01-16 | 2016-07-25 | 日本電気株式会社 | Lithium ion secondary battery |
| CN105914399A (en) * | 2016-05-04 | 2016-08-31 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion cell containing same |
-
2016
- 2016-12-26 CN CN201611217728.5A patent/CN108242565B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495959A (en) * | 2002-08-29 | 2004-05-12 | �ձ�������ʽ���� | Electrolyte for xecondary battery and secondary battery using said electrolyte |
| JP2009054287A (en) * | 2007-08-23 | 2009-03-12 | Sony Corp | Electrolyte solution and battery |
| CN101471455A (en) * | 2007-12-28 | 2009-07-01 | 张家港市国泰华荣化工新材料有限公司 | Additive for lithium ion battery non-aqueous electrolyte and non-aqueous electrolyte made by the same |
| JP2010103052A (en) * | 2008-10-27 | 2010-05-06 | Nec Tokin Corp | Nonaqueous electrolytic solution, and nonaqueous electrolytic solution secondary battery using the same |
| CN101783412A (en) * | 2009-01-15 | 2010-07-21 | 索尼公司 | Electrolyte and secondary battery |
| CN103493280A (en) * | 2011-04-26 | 2014-01-01 | 宇部兴产株式会社 | Non-aqueous electrolytic solution, electrical storage device utilizing same, and cyclic sulfonic acid ester compound |
| CN103004006A (en) * | 2011-07-07 | 2013-03-27 | 住友精化株式会社 | Additive for nonaqueous electrolyte, nonaqueous electrolyte, and electricity storage device |
| CN104247139A (en) * | 2012-04-27 | 2014-12-24 | 日本电气株式会社 | Lithium secondary battery |
| CN105074996A (en) * | 2013-04-01 | 2015-11-18 | 宇部兴产株式会社 | Nonaqueous electrolyte solution and electricity storage device using same |
| CN105409049A (en) * | 2013-06-06 | 2016-03-16 | 株式会社杰士汤浅国际 | Non-aqueous electrolyte secondary battery and production method for non-aqueous electrolyte secondary battery |
| JP2015156372A (en) * | 2014-01-15 | 2015-08-27 | 旭化成株式会社 | Electrolyte for nonaqueous power storage device and lithium ion secondary battery |
| JP2016134218A (en) * | 2015-01-16 | 2016-07-25 | 日本電気株式会社 | Lithium ion secondary battery |
| CN105186032A (en) * | 2015-10-19 | 2015-12-23 | 东莞市凯欣电池材料有限公司 | High-voltage lithium-ion battery electrolyte and lithium-ion battery using high-voltage lithium-ion battery electrolyte |
| CN105655640A (en) * | 2016-03-28 | 2016-06-08 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium-ion battery containing same |
| CN105914399A (en) * | 2016-05-04 | 2016-08-31 | 宁德新能源科技有限公司 | Electrolyte and lithium-ion cell containing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381073A (en) * | 2021-07-27 | 2021-09-10 | 中节能万润股份有限公司 | Silicon sulfonate non-aqueous electrolyte additive and application thereof |
| CN113381073B (en) * | 2021-07-27 | 2022-03-01 | 中节能万润股份有限公司 | Silicon sulfonate non-aqueous electrolyte additive and application thereof |
| CN117954690A (en) * | 2024-03-26 | 2024-04-30 | 深圳海辰储能科技有限公司 | Battery, power utilization system and energy storage system |
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