CN109768326A - Electrolyte and electrochemical energy storage device - Google Patents
Electrolyte and electrochemical energy storage device Download PDFInfo
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- CN109768326A CN109768326A CN201711097835.3A CN201711097835A CN109768326A CN 109768326 A CN109768326 A CN 109768326A CN 201711097835 A CN201711097835 A CN 201711097835A CN 109768326 A CN109768326 A CN 109768326A
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Abstract
The application provides an electrolyte and an electrochemical energy storage device. The electrolyte comprises a cyclic sulfate compound additive, a cyclic sulfonate compound additive, a dinitrile compound additive, and a silicon-based phosphate compound additive or a silicon-based borate compound additive or a mixture of the two. The electrolyte can effectively inhibit the transition metal ions from dissolving out, protects the positive and negative electrode interfaces, remarkably reduces the interface impedance between the electrode and the electrolyte, improves the low-temperature discharge performance of the electrochemical energy storage device, and can also remarkably improve the cycle performance and the storage performance of the electrochemical energy storage device.
Description
Technical field
This application involves energy storage device field more particularly to a kind of electrolyte and electrochemical energy storage device.
Background technique
In recent years, as people are to the growing interest of environmental problem, the gasoline vehicle using fossil fuel, bavin be can replace
Electric vehicle (EV), the hybrid electric vehicle (HEV) of oily vehicle have obtained the great attention of research staff, especially to energy
The positive progress of research of the new energy of power is provided for EV, HEV.In terms of considering the problems of environment, people couple
It is more deep that the requirement of high-energy density, high security new energy also forces research staff to carry out existing new energy
Research.Wherein, lithium ion battery due to having the characteristics that specific energy is high, have extended cycle life, self discharge is few, has a safety feature and standby
Concerned, the application of lithium ion battery at present has been deep into the every aspect in daily life, such as camera, notebook electricity
Brain, electric car etc..
During first charge-discharge, in cathode interface reduction decomposition can occur lithium ion battery for electrolyte, decomposition
Product deposition forms thin film in negative terminal surface, which is commonly known as solid electrolyte interface film (Solid
Electrolyte Interface, SEI film).Excellent SEI film can effectively prevent solvent molecule lasting in negative terminal surface
Reduction reaction prevents solvation lithium ion to be embedded in graphite layers, so as to protect cathode.And it is added in the electrolytic solution suitably
Additive then can help to form good SEI film in negative terminal surface.
Therefore, need to develop a kind of additive that can improve lithium ion battery comprehensive performance or additive combination now,
Can lithium ion battery positive and negative anodes interface forming properties are good and the lower passivating film of impedance, make lithium ion battery have compared with
Good cycle performance and storage performance.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of electrolyte and electrochemical energy storage dress
It sets, the electrolyte effectively can inhibit transition metal ions to dissolve out, and protect positive and negative anodes interface, not only significantly reduce electrode and electricity
The interface impedance between liquid is solved, improves low temperature performance, moreover it is possible to significantly improve cycle performance and storage performance.
In order to achieve the above object, in the one side of the application, this application provides a kind of electrolyte comprising additive
A, additive B, addition of C and additive D.Wherein, additive A is selected from one or more of 1 compound represented of formula, adds
Agent B is added to be selected from one or more of 2 compound represented of formula, addition of C is selected from one of 3 compound represented of formula or several
Kind, additive D is selected from one or more of 4 compound represented of formula, 5 compound represented of formula.In formula 1, R11Selected from H,
The alkenyl or halogenated alkenyl of halogen atom, the alkyl of C1~C6 or halogenated alkyl, C2~C6, in formula 2, m be 2~10 it is whole
Number, R21Selected from H, halogen atom, C1~C6 alkyl or halogenated alkyl, in formula 3, the integer that n is 1~10, in formula 4, R31、
R32、R33、R34、R35、R36、R37、R38、R39It is each independently selected from the alkyl or halogenated alkyl of C1~C10, in formula 5, R41、
R42、R43、R44、R45、R46、R47、R48、R49It is each independently selected from the alkyl or halogenated alkyl of C1~C10.
In the another aspect of the application, this application provides a kind of electrochemical energy storage devices comprising the application is on the one hand
Electrolyte.
Compared with the existing technology, the application include at least it is following the utility model has the advantages that
The electrolyte of the application effectively can inhibit transition metal ions to dissolve out, and protect positive and negative anodes interface, not only significant drop
Interface impedance between low electrode and electrolyte improves low temperature performance, moreover it is possible to significantly improve cycle performance and storage performance.
Specific embodiment
The following detailed description of the electrolyte and electrochemical energy storage device according to the application.
Illustrate the electrolyte according to the application first aspect first.
Electrolyte according to the application first aspect includes additive A, additive B, addition of C and additive D.
In the electrolyte according to the application first aspect, additive A is cyclic sulfates compound, specific optional
From one or more of 1 compound represented of formula.In formula 1, R11Selected from H, halogen atom, C1~C6 alkyl or alkyl halide
The alkenyl or halogenated alkenyl of base, C2~C6.Preferably, R11Selected from H, F, methyl, ethyl, propyl, butyl or vinyl.
In the electrolyte according to the application first aspect, additive B is cyclic sulfonic acid ester compound, specific optional
From one or more of 2 compound represented of formula.In formula 2, the integer that m is 2~10, R21Selected from H, halogen atom, C1~
C6 alkyl or halogenated alkyl.Preferably, m is 3 or 4, R21Selected from H or methyl.
In the electrolyte according to the application first aspect, addition of C is dinitrile compound, specifically can be selected from formula 3
One or more of compound represented.In formula 3, n be 1~10 integer.Preferably, 4,5 or 6 n.
In the electrolyte according to the application first aspect, additive D is silicon substrate phosphate compound, silicon substrate boric acid
The mixture of ester compounds or both specifically can be selected from one of 4 compound represented of formula, 5 compound represented of formula or several
Kind.In formula 4, R31、R32、R33、R34、R35、R36、R37、R38、R39It is each independently selected from the alkyl or alkyl halide of C1~C10
Base.In formula 5, R41、R42、R43、R44、R45、R46、R47、R48、R49It is each independently selected from the alkyl or alkyl halide of C1~C10
Base.
In the electrolyte according to the application first aspect, cyclic sulfates compound can be filled in electrochemical energy storage
It sets in chemical conversion and circulation storing process and participates in positive and negative anodes interface film forming, the main component to form a film on positive interface is alkyl
Lithium sulfate class organo-lithium compound, the main component to form a film on cathode interface be lithium sulfite and be similar to polyethylene glycol oxide
(PEO) polymer, thus can reduce positive and negative anodes interface at membrane impedance, reduce migration of the ion at positive and negative anodes interface and hinder
Power, while electrolyte can also be reduced, the probability of side reaction, but its quality for forming a film at positive interface occurs at positive and negative anodes interface
It is usually poor, electrolyte can not be effectively inhibited in the side reaction at positive interface, the furthermore thermostabilization of cyclic sulfates compound
Property is poor, easily decomposes at high temperature, decomposition product is deposited on positive and negative anodes interface, can destroy the film forming at positive and negative anodes interface.Ring
Shape sulfonate compound, which is melted into and is recycled in storing process in electrochemical energy storage device, may also participate in positive and negative anodes interface film forming, and
Its quality of forming film is preferable, can effectively inhibit electrolyte in the side reaction at positive and negative anodes interface, but the passivation membrane impedance of its formation
It is larger.Cyano (- CN) in dinitrile compound structure has negative electrical charge, can be with the transition metal ions in positive electrode active materials
It is complexed, inhibits the dissolution of transition metal ions in electrochemical energy storage device circulation storing process, stablize positive-active material
The structure of material, reduces oxygenolysis of the electrolyte anode at, and reduction recycles the gas production in storing process, but it is in cathode
Side reaction easily occurs and destroys cathode interface, and when content is more can significantly deteriorate the interface impedance of anode.Silicon substrate Phosphation
Conjunction object, silicon substrate boric acid ester compound equally can be at positive interfaces in electrochemical energy storage device chemical conversion and circulation storing process
Film forming is participated in, oxygenolysis of the electrolyte at anode is reduced, significantly reduces positive interface impedance, and reduce impedance with other and add
Agent is added to compare, it is bigger to positive interface impedance reduction amplitude, other chemical properties will not be caused significantly to deteriorate；This
Outside, during discharge, especially during low temperature discharge, positive interface impedance becomes restriction electrochemical energy storage device performance and mentions
High principal element, positive interface impedance reduction are conducive to ion and quickly deviate from from positive electrode active materials, can be from source
Upper quick release ion, therefore silicon substrate phosphate compound, silicon substrate boric acid ester compound can significantly improve electrochemical energy storage device
Low temperature performance.
As a result, in the electrolyte of the application, it can be formed at positive and negative anodes interface using cyclic sulfonic acid ester compound good
Interface passivation film inhibits electrolyte that side reaction occurs at positive and negative anodes interface, utilizes cyclic sulfates compound and silicon substrate phosphate
Compound, silicon substrate boric acid ester compound inhibit the cyclic sulfonic acid ester compound at the raising of membrane impedance, using dinitrile compound come
Stablize anode interfacial structure, while cyclic sulfates compound and cyclic sulfonic acid ester compound can protect cathode interface, avoid
Deterioration of the dinitrile compound to cathode interface, inhibits two nitrilations using silicon substrate phosphate compound, silicon substrate boric acid ester compound
Close deterioration of the object to positive interface impedance.Under the collective effect of above-mentioned substance, not only can electrochemical energy storage device just
Cathode interface forms that impedance is lower and the second best in quality passivating film, can also effectively inhibit transition metal in positive electrode active materials
Positive and negative anodes interface is protected in the dissolution of ion, is not only significantly reduced the interface impedance between electrode and electrolyte, is improved low temperature discharge property
It can, moreover it is possible to significantly improve the cycle performance and storage under cycle performance and storage performance, especially high temperature and high pressure environment
Energy.
It does not include halogenated cyclic carbonation in the electrolyte in the electrolyte according to the application first aspect
Object is closed, such as fluorinated ethylene carbonate (FEC).This is because side reaction occurs in the electrolytic solution for such additive can generate fluorination
Hydrogen, hydrogen fluoride can corrode positive interface, especially in nickelic ternary positive electrode active material system, influence on high-temperature storage performance
It is very big, and hydrogen fluoride also reacts with the organic solvent in electrolyte, so that electrolyte composition is greatly destroyed.
Therefore in the electrolyte of the application, using cyclic sulfonic acid ester compound and cyclic sulfates compound combination using substituting halogen
For the filming function of cyclic carbonate (such as FEC).
In the electrolyte according to the application first aspect, additive A, additive B, addition of C relationship between quality
Are as follows: 1≤additive A/additive B≤4,1≤additive A/addition of C≤4.Additive A aoxidizes at positive interface, oxidation
The product of reaction participates in forming a film at positive interface, and main component is alkylsurfuric acid lithium class organo-lithium compound, while additive A
Reduction reaction can occur in cathode interface, the product of reduction reaction participates in the formation of cathode interface SEI film, and main component is
Lithium sulfite and be similar to polyethylene glycol oxide (PEO) polymer, therefore additive A can make positive and negative anodes interface at membrane impedance
It is all relatively low, and electrolyte can be inhibited to a certain extent in the side reaction at positive and negative anodes interface, but its positive interface at
Film quality is usually poor, it is difficult to completely inhibit electrolyte in the side reaction at positive interface.The main function of additive B is to participate in just
Negative interface film forming, quality of forming film is preferable, can effectively inhibit electrolyte in anode and occur oxygenolysis, but it also can be
Reduction reaction occurs for cathode, and product deposition easily leads to cathode interface impedance increase, have not to chemical property in negative terminal surface
The influence of benefit.The mass ratio of control additive A and additive B is between 1~4, when guaranteeing that additive A content is more than additive B,
When effectively can participate in the deterioration to form a film to cathode interface impedance in cathode by suppressant additive B, but be above its 4 times, due to
The thermal stability of additive A itself is poor, easily decomposes at high temperature, and the organic polymer for decomposing generation can be deposited on positive and negative boundary
On face, original interfacial film is damaged, so that the chemical property of electrochemical energy storage device can be deteriorated.The work of addition of C
With being complexed with positive transition metal ions, protects positive electrode active materials structure not to be destroyed, inhibit electrolyte at positive interface
Oxidation, but addition of C is easily reduced in cathode, is destroyed cathode interface and then is deteriorated chemical property.And additive A can have
The participation cathode film formation of effect acts on, and protects cathode, reduction of the suppressant additive C in cathode.Additive A and addition of C
When mass ratio is between 1~4, anode structure can not only be effectively protected, inhibit positive transition metal ions dissolution, Er Qieke
Destruction to avoid addition of C to cathode, when the two mass ratio is relatively low, additive A film forming is insufficient, is not enough to protect negative polarity node
Structure, when the two mass ratio is higher, excessive additive A may be because of itself in the cyclic process of electrochemical energy storage device
Thermal stability difference and decompose, decomposition product, which is deposited on cathode, can destroy cathode interface passivating film, can not be to addition of C
Effective inhibiting effect is played in the reduction of cathode.
In the electrolyte according to the application first aspect, it is preferable that additive A can be selected from following compounds
It is one or more of:
In the electrolyte according to the application first aspect, when the content of additive A is very few, it is difficult in positive and negative anodes circle
Face forms complete passivating film, and when the content of additive A is excessive, then it can deteriorate the high-temperature behavior of electrochemical energy storage device, and
And it can largely increase the cost of electrolyte.Preferably, the content of additive A is the 0.01% of the electrolyte gross mass
~3%.
In the electrolyte according to the application first aspect, it is preferable that additive B can be selected from following compounds
It is one or more of:
In the electrolyte according to the application first aspect, when the content of additive B is very few, to optimization passivating film
Quality do not have significant improvement result, and when the content of additive B is excessive, the passivating film that positive and negative anodes interface is formed compared with
Thickness will increase the interface impedance of positive and negative anodes, be unfavorable for the performance boost of electrochemical energy storage device.Preferably, the content of additive B
It is the 0.01%~3% of the electrolyte gross mass.
In the electrolyte according to the application first aspect, it is preferable that addition of C can be selected from succinonitrile, glutaronitrile,
One or more of adiponitrile, 1,4- sebacic dinitrile.
In the electrolyte according to the application first aspect, when the content of addition of C is very few, complexed transition is not had
The effect of metal ion, so that it is unable to reach the purpose of protection positive electrode active materials, and when the content of addition of C is excessive, it can increase
The viscosity of big electrolyte and excessive itrile group are attached to positive electrode surface and will increase positive interface impedance, deteriorate electrochemical energy storage dress
The dynamic performance set.Preferably, the content of addition of C is the 0.01%~3% of the electrolyte gross mass.
In the electrolyte according to the application first aspect, additive D can be selected from three (trimethyl silane) borates,
Three (triethylsilane) borates, three (tripropyl silane) borates, three (tributyl silane) borates, two (trimethyl silanes)
Boron triethyl acid esters, three (trimethyl silane) phosphates, three (triethylsilane) phosphates, three (tripropyl silane) phosphates,
One or more of three (tributyl silane) phosphates, two (trimethyl silane) triethyl phosphates.
In the electrolyte according to the application first aspect, when the content of additive D is very few, it is unable to reach reduction
The effect of positive interface impedance, and when the content of additive D is excessive, it is thicker in the passivating film that positive and negative anodes interface is formed, instead can
The interface impedance for increasing positive and negative anodes, is unfavorable for the performance boost of electrochemical energy storage device.Preferably, the content of additive D is institute
State the 0.01%~3% of electrolyte gross mass.
In the electrolyte according to the application first aspect, the electrolyte may also include vinylethylene carbonate,
One or more of double LiODFBs, bis- (fluorine sulfimide) lithiums.
In the electrolyte according to the application first aspect, the electrolyte further includes organic solvent, described organic
The type of solvent does not limit specifically, can be selected according to actual needs.Preferably, selection is in higher temperature and higher electricity
Depress the non-aqueous organic solvent with good thermal stability and electrochemical stability.Specifically, the organic solvent can be selected from
Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethylene carbonate,
Propene carbonate, butylene, gamma-butyrolacton, methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate,
One or more of tetrahydrofuran.Above-mentioned organic solvent generally can be 4.2V and the electrochemical energy storage device of the above high voltage mentions
For stable electrochemical environment.
In the electrolyte according to the application first aspect, the content of the organic solvent is not limited specifically,
It can be selected according to actual needs.Preferably, the content of the organic solvent be the electrolyte gross mass 65%~
85%.
In the electrolyte according to the application first aspect, the electrolyte further includes electrolytic salt, the electrolysis
The type of matter salt does not limit specifically, can be selected according to actual needs.
In the electrolyte according to the application first aspect, the concentration of the electrolytic salt is not limited specifically,
It can be selected according to actual needs.Preferably, the concentration of the electrolytic salt is 0.5M~1.5M, it is further preferred that institute
The concentration for stating electrolytic salt is 0.8M~1.2M.
Secondly illustrate the electrochemical energy storage device according to the application second aspect.
It include the electricity according to the application first aspect according to electrochemical energy storage device described in the application second aspect
Solve liquid.
In the electrochemical energy storage device according to the application second aspect, the electrochemical energy storage device further includes just
Pole piece, negative electrode tab, isolation film and pack case etc..
In the electrochemical energy storage device according to the application second aspect, it should be noted that the electrochemistry storage
Energy device can be lithium ion battery, sodium-ion battery, Zinc ion battery, lithium metal battery, solid lithium battery or all solid state sodium
Battery.In embodiments herein, the embodiment that electrochemical energy storage device is lithium ion battery is only shown, but the application is unlimited
In this.
In lithium ion battery, positive plate includes plus plate current-collecting body and the positive electrode active materials that are set on plus plate current-collecting body
Layer.The not specific limitation of the type of the positive electrode active materials, can be selected according to actual needs.Preferably, the anode
Active material can be selected from cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), one or more of cobalt nickel lithium manganate ternary material.
It is further preferred that the positive electrode active materials can be selected from the cobalt nickel lithium manganate ternary material that nickel content is higher than 60%.It is described just
Pole piece may also include conductive agent and binder.The not specific limitation of the type of the conductive agent and binder, can be according to practical need
It asks and is selected.
In lithium ion battery, negative electrode tab includes negative current collector and the negative electrode active material that is set on negative current collector
Layer.The not specific limitation of the type of the negative electrode active material, can be selected according to actual needs.Preferably, the cathode
Active material can be selected from natural graphite, artificial graphite, carbonaceous mesophase spherules (referred to as MCMB), hard carbon, soft carbon, silicon, silicon oxidation
Object, silico-carbo compound, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2, spinel structure lithiumation TiO2-
Li4Ti5O12, one or more of Li-Al alloy.Wherein, silicon can be selected from nano silicon particles, silicon nanowires, nano-tube, silicon
One or more of film, 3D porous structure silicon and hollow porous silicon.The negative electrode tab may also include conductive agent and bonding
Agent.The not specific limitation of the type of the conductive agent and binder, can be selected according to actual needs.The negative electrode tab may be used also
Use lithium metal or lithium metal alloy.
In lithium ion battery, the electrolytic salt is lithium salts, and the specific type of the lithium salts is unrestricted, can be according to reality
Border demand is selected.Preferably, the lithium salts can be selected from lithium hexafluoro phosphate, bis- (trifluoromethyl) sulfimide lithiums, tetrafluoro boron
One or more of sour lithium, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium, di-oxalate lithium borate, lithium perchlorate.Further preferably
Ground, the lithium salts are selected from lithium hexafluoro phosphate.
In lithium ion battery, the type of the isolation film is not specifically limited, and can be selected according to actual needs, tool
Body, the isolation film can be selected from polyethylene film, polypropylene screen, polyvinylidene fluoride film and their multilayer complex films.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The case where electrochemical energy storage device is lithium ion battery, but this Shen are only shown in embodiment
It please be without being limited thereto.
Lithium ion battery in embodiment 1-19 and comparative example 1-12 is prepared by the following method.
(1) preparation of electrolyte
In the glove box full of argon gas (water content < 10ppm, oxygen content < 1ppm), it will add shown in table 1, table 3
Add agent to be added in non-aqueous organic solvent (EC:DEC=30:70, mass ratio), after mixing, is slowly added to suitable lithium salts
(LiPF6), after lithium salts is completely dissolved, obtain the electrolyte that lithium salt is 1mol/L.In table 1, each additive level is
The mass percent that gross mass based on electrolyte is calculated.
(2) preparation of positive plate
By positive electrode active materials LiNi0.8Co0.1Mn0.1O2, conductive agent Super P, binder Kynoar (PVDF) exist
Anode sizing agent is made in N-Methyl pyrrolidone (NMP).Wherein, solid content is 50wt% in anode sizing agent,
LiNi0.8Co0.1Mn0.1O2, Super P, PVDF mass ratio be 8:1:1.Anode sizing agent is coated on plus plate current-collecting body aluminium foil
And be cold-pressed after being dried at 85 DEG C, after then carrying out trimming, cut-parts, slitting, 4h is dried under 85 DEG C of vacuum condition, is made
At positive plate.
(3) preparation of negative electrode tab
Negative electrode active material artificial graphite and conductive agent Super P, thickener CMC, bonding agent butadiene-styrene rubber (SBR) are existed
It is uniformly mixed in deionized water, negative electrode slurry is made.Wherein, in negative electrode slurry solid content be 40wt%, graphite, Super P,
The mass ratio of CMC, SBR are 89:6:3:2.Negative electrode slurry is coated on negative current collector copper foil and is dried at 85 DEG C, then
It is cold-pressed, trimming, cut-parts, after slitting, dries 12h under 120 DEG C of vacuum conditions, negative electrode tab is made.
(4) preparation of isolation film
Select polyethylene (PE) film of 16 μ m-thicks as isolation film.
(5) preparation of lithium ion battery
Positive plate, isolation film, negative electrode tab are folded in order, make isolation film be among positive/negative plate play isolation it is positive and negative
The effect of pole piece, winding obtain naked battery core, and naked battery core is placed in outer packing by soldering polar ear, and the electrolyte of above-mentioned preparation is infused
Enter in the battery core to after drying, the preparation of lithium ion battery is completed in encapsulation, standing, chemical conversion, shaping, volume test etc..
Table 1: the electrolyte parameter of embodiment 1-18 and comparative example 1-11
The test process of lithium ion battery will be illustrated next.
(1) the high temperature cyclic performance test of lithium ion battery
At 45 DEG C, by lithium ion battery with 1C constant-current charge to 4.2V, then with 4.2V constant-voltage charge to 0.05C, so
Afterwards with 1C constant-current discharge to 2.8V, this is a charge and discharge cycles, this discharge capacity is the discharge capacity recycled for the first time, with
The discharge capacity recycled for the first time is 100%, and lithium ion battery is carried out to 300 cycle charging/discharge tests according to the method described above,
Detection obtains the discharge capacity of the 300th circulation.
45 DEG C of lithium ion battery circulation 300 times after capacity retention ratio (%)=300th time circulation discharge capacity/for the first time
Discharge capacity × 100% of circulation.
(2) high temperature storage of lithium ion battery produces gas test
Under room temperature, by lithium ion battery with 1C constant-current charge to 4.2V, then extremely with the voltage constant-voltage charge of 4.2V
0.05C, Man Chonghou using the volume of drainage test lithium ion battery, and are denoted as V0.Then lithium ion battery is placed on 80 DEG C
Lower storage 24 hours, then takes out lithium ion battery, at room temperature, 60min is stood, in 1 hour after being cooled to room temperature
With the volume of drainage test lithium ion battery, storage test was carried out every 24 hours by above-mentioned steps later until storage full 30
It, the volume that lithium ion battery stores 30 days is denoted as V1.
80 DEG C of lithium ion battery storage 30 days after cubical expansivity (%)=(V1/V0) × 100%-1.
(3) the high temperature storage volume test of lithium ion battery
Under room temperature, by lithium ion battery with 1C constant-current charge to 4.2V, then with 4.2V constant-voltage charge to 0.05C,
Then with 0.5C constant-current discharge to 2.8V, discharge capacity D0 is recorded；Lithium ion battery is completely filled according to above-mentioned charging modes
It is placed at 60 DEG C and stores 30 days, after storing, with 1C constant-current discharge to 2.8V, record discharge capacity D1.
60 DEG C of lithium ion battery storage 30 days after capacity retention ratio (%)=(D1/D0) × 100%.
(4) the low temperature performance test of lithium ion battery
Lithium ion battery is placed in high-low temperature chamber, adjusting furnace temperature is 25 DEG C, is 25 DEG C to surface temperature of lithium ion battery
Afterwards, with 1C constant-current charge to 4.2V, 4.2V constant-voltage charge to 0.05C records discharge capacity then with 1C constant-current discharge to 2.8V
For C0, lithium ion battery is completely filled according to above-mentioned charging modes, high-low temperature chamber is then adjusted to -30 DEG C, to lithium ion
After battery surface temperature is -30 DEG C, with 1C constant-current discharge to 2.8V, discharge capacity C1 is recorded.
Lithium ion battery low temperature discharge capacity conservation rate (%)=C1/C0 × 100%.
Table 2: the performance test results of embodiment 1-18 and comparative example 1-11
It can be seen that comparative example 11 from embodiment 1-18 and comparative example 1-11 test result and additive, lithium ion be not added
The properties of battery are poor, it is difficult to meet the actual needs.And the properties of embodiment 1-18 obtain significantly
Improve, after illustrating additive A, additive B, addition of C and additive D combination, can effectively inhibit transition metal ions molten
Out, metastable passivating film can be formed at positive and negative anodes interface, protects positive and negative anodes interface, not only significantly reduces electrode and electrolysis
Interface impedance between liquid improves low temperature performance, moreover it is possible to significantly improve cycle performance and storage performance.In comparative example 6 only
Additive A is added, although it can form a film at positive and negative anodes interface, its quality of forming film at positive interface is bad, in addition exists
In high temperature circulation, storing process, surface of positive electrode active material transition metal ions can also be dissolved out gradually, destroy positive electrode active materials
Structure, electrolyte occur more side reaction in positive electrode surface, cause the performance of lithium ion battery poor；Combining in comparative example 7 makes
Electrolyte decomposition is significantly inhibited, can not be inhibited although can be formed a film at positive and negative anodes interface with additive A and additive B
Digestion of metallic ion is crossed, in high temperature circulation, storing process, positive electrode active materials structure is gradually destroyed, and electrolyte is in anode
More side reaction occurs for surface, and the performance of lithium ion battery is still poor.Additive A, addition of C, addition is used in combination in comparative example 8
Agent D, although lithium ion battery in the available promotion of performance, can not be blunt at the positive and negative anodes interface good interface of forming properties
Change film, therefore limited to the performance boost of lithium ion battery.Additive A, additive B, additive D is used in combination in comparative example 9, though
It can so form a film at positive and negative anodes interface, and also relatively low at membrane impedance, but positive electrode active materials can not be effectively inhibited and filled
The dissolution of transition metal ions in electric process, the transition metal ions of dissolution can directly result in positive electrode active materials structure and be broken
It is bad, to deteriorate the chemical property of lithium ion battery.Additive B, addition of C, additive D is used in combination in comparative example 10, though
Right lithium ion battery is in the available promotion of performance, but cathode film formation impedance ratio is larger, in circulation and low temperature discharge process
In be easy to cause cathode to analyse lithium, not only deteriorate the chemical property of lithium ion battery, but also may cause security risk.
In comparative example 1, additive A, additive B, addition of C, the additional amount of additive D are on the high side, electrolyte thermostabilization
Property it is poor, be easy to happen under hot environment thermal decomposition generate gas, i.e., capacity retention ratio and height after deteriorating high temperature circulation
Capacity retention ratio after gentle storage, and increase the gas production after high temperature storage.
In comparative example 2, additive A/additive B mass ratio is relatively low, and additive A cannot be effective at positive and negative anodes interface
Film forming, can not effective deterioration of the suppressant additive B to cathode interface impedance, while also can not effectively inhibit electrolyte with just
The side reaction of cathode interface, therefore the properties of lithium ion battery are poor.In comparative example 3, additive A/additive B
Mass ratio is higher, since the thermal stability of additive A is poor, easily decomposes at high temperature, is deposited on the by-product at positive interface
The interface passivation film that additive B participates in being formed can be destroyed.In comparative example 4, additive A/addition of C mass ratio is relatively low, leads
Cause additive A to form a film at positive and negative anodes interface insufficient, can not suppressant additive C cathode reduction.In comparative example 5, additive
The mass ratio of A/ addition of C is higher, since the thermal stability of additive A is poor, easily decomposes at high temperature, is deposited on cathode circle
Decomposition product on face can destroy the SEI film of cathode interface to cannot effective suppressant additive C cathode reduction, in turn
The chemical property of lithium ion battery can be deteriorated.
Table 3: the electrolyte parameter of embodiment 19 and comparative example 12
Table 4: the performance test results of embodiment 19 and comparative example 12
As may be known from Table 3 and Table 4, the chemical property of lithium ion battery can significantly be deteriorated when in electrolyte containing FEC, this is
Since FEC decomposes generation corrosive gas hydrogen fluoride at high temperature, which can corrode positive interface, so that electrolyte composition meets with
It is destroyed to great, therefore deteriorates the comprehensive electrochemical of lithium ion battery.Therefore it in the electrolyte of the application, does not use
FEC。
Claims (10)
1. a kind of electrolyte, which is characterized in that including additive A, additive B, addition of C and additive D；
Additive A is selected from one or more of 1 compound represented of formula；
Additive B is selected from one or more of 2 compound represented of formula；
Addition of C is selected from one or more of 3 compound represented of formula；
Additive D is selected from one or more of 4 compound represented of formula, 5 compound represented of formula；
In formula 1, R11Alkenyl or halogenated alkenyl selected from H, halogen atom, the alkyl of C1~C6 or halogenated alkyl, C2~C6；
In formula 2, the integer that m is 2~10, R21Selected from H, halogen atom, C1~C6 alkyl or halogenated alkyl；
In formula 3, n be 1~10 integer；
In formula 4, R31、R32、R33、R34、R35、R36、R37、R38、R39It is each independently selected from the alkyl or alkyl halide of C1~C10
Base；
In formula 5, R41、R42、R43、R44、R45、R46、R47、R48、R49It is each independently selected from the alkyl or alkyl halide of C1~C10
Base.
2. electrolyte according to claim 1, which is characterized in that additive A, additive B, the quality between addition of C
Relationship are as follows: 1≤additive A/additive B≤4,1≤additive A/addition of C≤4.
3. electrolyte according to claim 1, which is characterized in that
Additive A is selected from one or more of following compounds:
Additive B is selected from one or more of following compounds:
Addition of C is selected from one or more of succinonitrile, glutaronitrile, adiponitrile, 1,4- sebacic dinitrile；
Additive D is selected from three (trimethyl silane) borates, three (triethylsilane) borates, three (tripropyl silane) boric acid
Ester, three (tributyl silane) borates, two (trimethyl silane) boron triethyl acid esters, three (trimethyl silane) phosphates, three (three
Ethylsilane) phosphate, three (tripropyl silane) phosphates, three (tributyl silane) phosphates, two (trimethyl silane) three second
One or more of base phosphate.
4. electrolyte according to claim 1, which is characterized in that
The content of the additive A is the 0.01%~3% of the electrolyte gross mass；
The content of the additive B is the 0.01%~3% of the electrolyte gross mass；
The content of the addition of C is the 0.01%~3% of the electrolyte gross mass；
The content of the additive D is the 0.01%~3% of the electrolyte gross mass.
5. electrolyte according to claim 1, which is characterized in that the electrolyte further includes organic solvent, described organic
Solvent is selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, carbon
Vinyl acetate, propene carbonate, butylene, gamma-butyrolacton, methyl formate, ethyl acetate, propyl acetate, methyl propionate,
One or more of ethyl propionate, tetrahydrofuran.
6. electrolyte according to claim 5, which is characterized in that the content of the organic solvent is the total matter of the electrolyte
The 65%~85% of amount.
7. electrolyte according to claim 1, which is characterized in that the electrolyte further includes electrolytic salt.
8. electrolyte according to claim 7, which is characterized in that the concentration of the electrolytic salt is 0.5M~1.5M, excellent
Selection of land, the concentration of the electrolytic salt are 0.8M~1.2M.
9. a kind of electrochemical energy storage device, which is characterized in that including electrolyte according to claim 1 to 8.
10. electrochemical energy storage device according to claim 9, which is characterized in that the electrochemical energy storage device be lithium from
Sub- battery, sodium-ion battery, Zinc ion battery, lithium metal battery, solid lithium battery or all solid state sode cell.
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| CN110265718A (en) * | 2019-06-18 | 2019-09-20 | 桑顿新能源科技(长沙)有限公司 | Electrolysis additive, electrolyte and battery |
| CN111446501A (en) * | 2020-04-08 | 2020-07-24 | 青岛滨海学院 | Electrolyte containing-F and-B two-group compound and electrochemical device thereof |
| CN111653829A (en) * | 2020-07-20 | 2020-09-11 | 中航锂电技术研究院有限公司 | Lithium ion battery electrolyte and lithium ion battery |
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