CN109786832A - Electrolysis additive, electrolyte and lithium ion secondary battery - Google Patents
Electrolysis additive, electrolyte and lithium ion secondary battery Download PDFInfo
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- CN109786832A CN109786832A CN201910020535.8A CN201910020535A CN109786832A CN 109786832 A CN109786832 A CN 109786832A CN 201910020535 A CN201910020535 A CN 201910020535A CN 109786832 A CN109786832 A CN 109786832A
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention provides a kind of electrolysis additive, electrolyte and lithium ion secondary batteries.The electrolysis additive has Formulas IShown structure, R in Formulas I1, R2, R3It is each independently hydrogen atom or cyano, R1, R2, R3In at least one be cyano, R4, R5It is each independently alkyl, the general formula of the alkyl is CnH2n+1, n=1~8.The present invention enables the SEI film of the formation high-temperature stable and stable circulation of electrolyte during the charging process by the way that the additive is added in the electrolytic solution.It can effectively inhibit electrolyte in the reaction of electrode material surface, inhibit the dissolution of positive electrode metal, improve the high temperature circulation and storage performance of lithium ion battery, inhibit production gas when high temperature storage, to improve the comprehensive performance of battery core under high voltages.
Description
Technical field
The present invention relates to battery technology field, in particular to a kind of electrolysis additive, electrolyte and lithium ion secondary electricity
Pond.
Background technique
Consumer electronics product is popularized, such as laptop, smart phone, wearable device, unmanned plane.Lithium ion
Battery be last century the nineties occur green high-capacity environment-protecting battery because its with voltage high, small in size, light weight, ratio
Energy height, memory-less effect, the advantages that pollution-free, self discharge is small, the service life is long, are widely used in mobile phone, laptop, take the photograph
Camera, digital camera, tablet computer etc. emphasize light and short, multi-functional portable electronic product.But lithium ion secondary simultaneously
Battery needs to possess higher capacity in the volume of restriction or the quality of restriction.So the energy for how improving lithium ion battery is close
It spends, and how to improve the security performance of battery in the case where lithium ion battery high-energy density, always be that needs are long-term
The problem captured.Under present circumstances, battery core operating voltage is improved, is one of the effective way of raising energy density, and high voltage
Under stability, the stability of especially high-temperature behavior is a huge challenge.
Summary of the invention
The problem of mentioning in view of the aforementioned technical background, the purpose of the present invention is to provide a kind of electrolysis additives, will
The additive is added in electrolyte, has better high temperature storage by the preparation-obtained lithium ion secondary battery of the electrolyte
Performance.
The present inventor has found in the course of the research: in high temperature storage environment, facing challenges are inside battery core:
First, stability at a high temperature of " solid electrolyte interface film " above cathode: SEI film causes electrolyte negative in the decomposition of high temperature
Extremely upper decomposition reaction, can make battery core generate bulk gas and influence the storage chemical property of battery core.Second, high oxidation activity
Anode and the stability of electrolyte at high temperature；Anode incites somebody to action the oxygenolysis of electrolyte under high voltage and the condition of high temperature
To reinforcement, this reaction is the main reason for leading to battery core big volume production gas.This two big main cause will lead to lithium ion secondary electricity
The dilatancy in pond, and cause lithium ion secondary battery short circuit occurred inside or battery packages to rise brokenly to lead to flammable electricity
Liquid leakage is solved, there is the risk for causing the safety accidents such as fire.
Work long hours to meet electric car, high course continuation mileage, can in high and low temperature environment normal use, can quickly fill
Electricity and the requirement with the long life, needing to develop has higher energy density, superior high temperature circulation, storage
The lithium ion secondary battery of energy and low temperature high rate performance.
To solve the above-mentioned problems, and it is based on the demand, needs a kind of additive or one group of additive combination, it can be with
So that being capable of forming the SEI film of high-temperature stable and stable circulation on the positive and negative anodes of lithium ion secondary battery.To improve battery core
In the comprehensive performance of high voltage.
In view of this, the present invention is directed to propose a kind of electrolysis additive, electrolyte and include this lithium ion secondary electricity
The lithium ion secondary battery of pond electrolyte.Battery is able to solve at ambient temperature or elevated temperature using additive provided by the invention, it is long
Capacity attenuation caused by phase storing process, flatulence.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
According to the first aspect of the invention, the present invention provides a kind of battery electrolyte additive, the additive has
Structure shown in Formulas I；
Wherein, R1, R2, R3It is each independently hydrogen atom or cyano, and R1, R2, R3In at least one be cyano, R4, R5
It is each independently alkyl, the general formula of the alkyl is CnH2n+1, n=1~8.Inventor is in the course of the research, it is realized that at present
Tertiary cathode material (the LiNi that anode used in lithium-ion-power cell is mostly high nickel content is commercialized0.6Co0.2Mn0.2O2,
LiNi0.8Co0.1Mn0.1O2), at high temperature, structural instability, metal ion is easy dissolution, the Ni of high price to this positive electrode4+
It is easy that oxidation reaction occurs with electrolyte, leads to degradation of cell performance.And the phosphate compound of aromatics provided by the invention
In phosphorus oxygen double bond have lone pair electrons, be a kind of lewis base, can react to form layer protecting film on positive electrode surface,
To improve the high-temperature behavior of lithium ion battery.In addition, in aromatics phosphate compound provided by the present invention cyano (-
CN) complex reaction can occur with metal ion, reduces metal ion activity, so that the side reaction in battery is reduced, raising property
Energy.Using the electrolyte that electrolysis additive provided by the invention obtains, and thus lithium ion secondary battery obtained, have
Performance, show themselves in that with improve lithium ion battery high temperature circulation and storage performance, the production gas of the high temperature storage of inhibition,
To be more applicable for the demand of high voltage.
Further, the R4, R5It is each independently selected from one of methane, ethane.These additives are added to electricity
It solves in liquid, the SEI film of high-temperature stable and stable circulation can be formed during the charging process, and these additive structures are simple, make
Standby simple process, yield are high.
Further, the additive is selected from least one of following compounds:
According to the second aspect of the invention, the present invention provides a kind of battery electrolytes, comprising: non-aqueous organic solvent, it is molten
Lithium salts of the solution in non-aqueous organic solvent, and the additive being dissolved in the non-aqueous organic solvent, the additive are this hair
Additive described in bright first aspect any embodiment.
Further, the quality of the additive accounts for the 0.01%~5% of the non-aqueous organic solvent gross mass.Work as addition
When agent content is too low, since content is too low, the protective effect for electrode cannot occur；When additive level is excessively high, can make
The viscosity for obtaining electrolyte increases, to be degrading the cycle performance of lithium ion secondary battery.When the quality of additive account for it is described non-
When the ratio of aqueous organic solvent gross mass is 0.01%~5%, the room temperature and high temperature circulation that lithium ion secondary battery can be improved are deposited
Store up performance.Such as can be 0.05~5%, 0.1%~5%, 1%~5%, 1%~4% etc. and these ranges in appoint
Meaning value range.
Further, the quality of the additive accounts for the 0.5~3% of the non-aqueous organic solvent gross mass.Additive
When quality accounts for the 0.5~3% of non-aqueous organic solvent gross mass, the room temperature and high temperature circulation that can significantly improve lithium ion battery are deposited
Performance is stored up, the protective effect for electrode is played.
Further, the non-aqueous organic solvent includes cyclic carbonate and linear carbonate, the cyclic carbonate choosing
From at least one of ethylene carbonate, propene carbonate, gamma-butyrolacton；The linear carbonate is selected from dimethyl carbonate, carbonic acid
Butene esters, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, first
Acetoacetic ester, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, in propyl propionate at least
It is a kind of.Using these cyclic carbonates and linear carbonate as solvent used in lithium ion battery, there is oxidation-reduction resistance
Good, dielectric constant is high, the low advantage of viscosity.
Further, the lithium salts is selected from LiPF6, LiBF4、LiBOB、LiDFOB、LiAsF6、Li(CF3SO2)2N、Li
(FSO2)2N、LiPO2F2、LiCF3SO3、LiClO4At least one of.The conductive high, thermal stability of these lithium salts and electricity
The good advantage of chemical stability.Applied in the preparation process of battery electrolyte, can enhance battery electrolyte electric conductivity and
Electrochemical stability.
According to the third aspect of the invention we, the present invention provides a kind of lithium ion secondary batteries, comprising: positive plate, it is described
Positive plate includes plus plate current-collecting body and the positive diaphragm containing positive electrode active materials that is set on the plus plate current-collecting body；It is negative
Pole piece, the negative electrode tab include negative current collector and are set to negative containing negative electrode active material on the negative current collector
Pole diaphragm；Spacer film, the spacer film are set between the positive plate and the negative electrode tab；Electrolyte, the electrolyte are
Electrolyte described in second aspect of the present invention any embodiment.
Further, the positive electrode active materials are selected from the transition metal oxide of lithium.
Further, the transition metal oxide of the lithium is selected from LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、
LiFePO4、LiNixCoyMnzO2、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4、Li2Mn1-xO4In
It is at least one, wherein M be selected from least one of Ni, Co, Mn, Al, Cr, Mg, Zr, Mo, V, Ti, B, F and Y, 0≤a <
0.2,0≤x, y, z≤1.Using these materials as positive electrode active materials, have many advantages, such as energy density height, good cycle.
Further, the negative electrode active material is selected from natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon, silicon
At least one of carbon alloy, silicon oxygen alloy.These substances are easy to happen lithium ion insertion abjection reaction, and it is living to can be used as cathode
The preferable selection of property material.
Specific embodiment
The embodiment of the present invention is described below in detail, these embodiments are intended to be used to explain the present invention, and should not be understood as
Limitation of the present invention.
According to an aspect of the present invention, the present invention provides a kind of electrolysis additive, the additive has Formulas I knot
Structure formula:
Wherein, R1, R2, R3It is each independently hydrogen atom or cyano, and R1, R2, R3In at least one be cyano, R4, R5
It is each independently alkyl, the general formula of the alkyl is CnH2n+1, n=1~8.
Phosphorus oxygen double bond in the phosphate compound for the aromatics that cyano shown in Formulas I replaces has lone pair electrons, application
In electrolyte, it can react to form protective film on positive electrode surface, improve the high-temperature behavior of battery.And in the compound
Cyano (- CN) can and complexing of metal ion, so that the activity of metal ion is reduced, to reduce the side reaction in battery.Using
The compound can significantly improve the performance of battery as battery electrolyte additive.
In some preferred embodiments, the additive may include at least one of following several compounds:
It in some embodiments, can be with the synthesis side of the similar common pesticides cyanogen sulphur phosphorus (Cyanophos) of reference configuration
Method prepares the additive.For example, the synthetic method of compound 1 is as follows by taking compound 1 as an example: the use of acetonitrile being solvent, by 4-
Cyanophenol and O, it is small that O- solutions of dimethyl phosphoryl chlorine is stirred at room temperature 8 under the catalysis of alkali (such as Anhydrous potassium carbonate or triethylamine)
When, it is dried under reduced pressure to obtain product after filtering.Reaction equation is as follows:
It similarly, is solvent using acetonitrile, by 3,4- dicyano phenol and O, O- dimethyl phosphorus in prepare compound 2
Acyl chlorides is stirred at room temperature 10 hours under the catalysis of alkali (such as Anhydrous potassium carbonate or triethylamine), is dried under reduced pressure to obtain after filtering
Compound 2.Similarly, other additives can be prepared referring to above method.For example, by means of acetonitrile as solvent, with methyl
Phosphoryl chloride phosphorus oxychloride and cyanophenol react under the catalysis of alkali, are dried under reduced pressure after filtering and obtain corresponding compound.Obtained chemical combination
Object is confirmed by magnetic resonance detection.
When using the additive prepare battery electrolyte when, the content of additive in the electrolytic solution be not easy it is excessively high, also not
It is easily too low.In some embodiments, the content of additive accounts for the gross mass of the electrolyte of the lithium ion secondary battery
0.01%~5%.
The present invention also provides a kind of electrolyte of lithium ion secondary battery, including non-aqueous organic solvent, lithium salts and described
Additive.
In certain embodiments of the present invention, the non-aqueous organic solvent includes cyclic carbonate and linear carbonate.
The cyclic carbonate is selected from one or more of ethylene carbonate, propene carbonate, gamma-butyrolacton；The chain carbonic acid
Ester be selected from dimethyl carbonate, butylene, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate,
Ethyl propyl carbonic acid ester, methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, third
One or more of acetoacetic ester, propyl propionate.
In other embodiment of the invention, the lithium salts is selected from LiPF6、LiBF4、LiBOB、LiDFOB、
LiAsF6、Li(CF3SO2)2N、Li(FSO2)2N、LiPO2F2、LiCF3SO3、LiClO4One or more of.
The present invention also provides a kind of lithium ion secondary batteries, comprising: positive plate, the positive plate include plus plate current-collecting body
And it is set to the positive diaphragm containing positive electrode active materials on plus plate current-collecting body；Negative electrode tab, the negative electrode tab include cathode
Collector and the cathode membrane containing negative electrode active material being set on negative current collector；Spacer film, the spacer film are set
It is placed between the positive plate and the negative electrode tab；And the electrolyte.Certainly, according to this field it is generally understood that lithium from
There are also packagings on the outside of sub- secondary cell, such as can be aluminum plastic film, stainless steel cylinder, rectangular aluminum hull etc..
In some embodiments, the positive electrode active materials are selected from the transition metal oxide of lithium, wherein the lithium
Transition metal oxide is LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、LiNixCoyMnzO2、Li1+aMn1-xMxO2、
LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4、Li2Mn1-xO4, wherein M be selected from Ni, Co, Mn, Al, Cr, Mg, Zr, Mo,
V, one of Ti, B, F and Y or a variety of, 0≤a < 0.2,0≤x, y, z≤1.
In some embodiments, the negative electrode active material include but is not limited to natural graphite, artificial graphite, soft carbon,
One in the negative electrode material of lithium ion insertion abjection reaction can occur for hard carbon, lithium titanate, silicon, silicon-carbon alloy, silicon oxygen alloy etc.
Kind is several.
In at least some embodiments, the blanking voltage of lithium ion secondary battery provided by the present invention be 4.1v~
4.8v.In at least some embodiments, the capacity of 500 charge and discharge cycles of lithium ion secondary battery provided by the present invention
Conservation rate is 85% or more.In at least some embodiments, lithium ion secondary battery provided by the present invention is at 60 degrees Celsius
The memory capacity conservation rate of lower storage 30 days is 85% or more.In at least other embodiments, lithium provided by the present invention
Ion secondary battery stores 30 atmospheric electricity core volume expansion rates below 30% at 60 c.Thus, it is possible to provide various aspects
Can preferable lithium ion secondary battery, especially have improve high temperature circulation and storage performance, keep under high voltages excellent
Different performance.
The solution of the present invention will be specifically described by specific embodiment below.It should be noted that following real
Applying example is only specific embodiments of the present invention, is not intended to limit the invention, and all within the spirits and principles of the present invention, is made
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.It is not specified in embodiment specific
Technology or conditions, it described technology or conditions or is carried out according to the literature in the art according to product description.It is used
Production firm person is not specified in reagent or instrument, and being can be with conventional products that are commercially available.
Embodiment 1
(1) preparation of the positive plate of lithium ion secondary battery
By positive electrode active materials nickle cobalt lithium manganate (LiNi0.6Co0.2Mn0.2O2), conductive agent Super-P, bonding agent PVDF press
Mass ratio 96:2.0:2.0, which is dissolved in being uniformly mixed in solvent N-methyl pyrilidone, is made anode sizing agent, later that anode sizing agent is equal
It is even to be coated in current collector aluminum foil, coating weight 18mg/cm2, it is cold-pressed, trimming, cut-parts, is divided after then being dried at 85 DEG C
Item, the positive plate of the lithium ion secondary battery met the requirements is made in dry 4h, soldering polar ear under 85 DEG C of vacuum conditions later.
(2) preparation of the negative electrode tab of lithium ion secondary battery
By negative electrode active material artificial graphite, conductive agent Super-P, thickener CMC, bonding agent SBR in mass ratio 96.5:
1.0:1.0:1.5, which is dissolved in being uniformly mixed in solvent deionized water, is made negative electrode slurry, and negative electrode slurry is uniformly coated on collection later
On fluid copper foil, coating weight 8.9mg/cm2, it is cold-pressed after then being dried at 85 DEG C, trimming, cut-parts, slitting, Zhi Hou
The negative electrode tab of the lithium ion secondary battery met the requirements is made in dry 4h, soldering polar ear under 110 DEG C of vacuum conditions.
(3) preparation of the electrolyte of lithium ion secondary battery
The electrolyte of lithium ion secondary battery is with LiPF6For lithium salts (concentration of the sylvite in the electrolytic solution is 1mol/L),
Using ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) mixture as non-aqueous organic solvent, wherein
The mass ratio of EC:EMC:DEC is 30:50:20.In addition, also containing additive, additive in the electrolyte of lithium ion secondary battery
For account for lithium ion secondary battery electrolyte gross mass 0.5% compound 1.
(4) preparation of lithium ion secondary battery
The positive plate of the lithium ion secondary battery prepared according to previous process, negative electrode tab and isolation film (PE film) are passed through
The battery core that it is 130mm with a thickness of 8mm, width 60mm, length that winding process, which is fabricated to, and vacuum bakeout 10h, note at 75 DEG C
Enter electrolyte, stand for 24 hours, later with the constant current charging of 0.1C (160mA) to 4.2V, then with 4.2V constant-voltage charge to electricity
It flows down and drops to 0.05C (80mA), 2.8V is then discharged to the constant current of 0.1C (160mA), is repeated 2 times charge and discharge, finally
With the constant current charging of 0.1C (160mA) to 3.8V, the preparation of lithium ion secondary battery is completed.
Embodiment 2
Lithium ion secondary battery is prepared according to the method for embodiment 1, only in the system of the electrolyte of lithium ion secondary battery
In standby (i.e. step (3)), the amount of additive compound 1 accounts for the 1% of electrolyte gross mass.
Embodiment 3
Lithium ion secondary battery is prepared according to the method for embodiment 1, only in the system of the electrolyte of lithium ion secondary battery
In standby (i.e. step (3)), the amount of additive compound 1 accounts for the 2% of electrolyte gross mass.
Embodiment 4
Lithium ion secondary battery is prepared according to the method for embodiment 1, only in the system of the electrolyte of lithium ion secondary battery
In standby (i.e. step (3)), the amount of additive compound 1 accounts for the 3% of electrolyte gross mass.
Embodiment 5
Lithium ion secondary battery is prepared according to the method for embodiment 1, only in the system of the electrolyte of lithium ion secondary battery
In standby (i.e. step (3)), additive is compound 2, and the amount of compound accounts for the 1% of electrolyte gross mass.
Comparative example 1
Lithium ion secondary battery is prepared according to the method for embodiment 1, difference from example 1 is that: only in lithium
In the preparation (i.e. step (3)) of the electrolyte of ion secondary battery, any additive is not added.
Comparative example 2
Lithium ion secondary battery is prepared according to the method for embodiment 1, difference from example 1 is that: only in lithium
In the preparation (i.e. step (3)) of the electrolyte of ion secondary battery, the amount of additive compound 1 accounts for electrolyte gross mass
0.001%.
Comparative example 3
Lithium ion secondary battery is prepared according to the method for embodiment 1, difference from example 1 is that: only in lithium
In the preparation (i.e. step (3)) of the electrolyte of ion secondary battery, the amount of additive compound 1 accounts for the 8% of electrolyte gross mass.
Then respectively as follows to the property of the embodiment 1-5 and comparative example 1-3 lithium ion secondary battery prepared
It can be carried out test.
1, the high temperature cyclic performance test of lithium ion secondary battery
Lithium ion secondary battery prepared by the lithium ion secondary battery to Examples 1 to 4 preparation and comparative example 1~3 respectively
High temperature cyclic performance tested, method particularly includes: at 60 DEG C, first lithium ion secondary battery is filled with the constant current of 1C
Electricity is 0.05C to 4.2V, then with 4.2V constant voltage charging to electric current, then with the constant current of 1C to lithium ion secondary battery
It is discharged to 2.8V, this is a charge and discharge cycles process, this discharge capacity is the discharge capacity of circulation for the first time.By lithium from
Sub- secondary cell carries out cyclic charging and discharging test in a manner described, takes the discharge capacity of the 500th circulation.
Capacity retention ratio (%)=[discharge capacity/the of the 500th circulation after lithium ion secondary battery 500 times circulations
The discharge capacity of one cycle] × 100%.
The test result of battery is as shown in table 1.
2, the high-temperature storage performance test of lithium ion secondary battery
At 25 DEG C, 4.2V is first charged to lithium ion secondary battery with the constant current of 1C, it is further constant with 4.2V
It is 0.05C that voltage, which charges to electric current, is then discharged to 2.8V to lithium ion secondary battery with the constant current of 1C, this electric discharge
Capacity is the discharge capacity before lithium ion secondary battery high temperature storage；Then lithium ion secondary battery is filled with the constant current of 1C
Lithium ion secondary battery is placed at 60 DEG C and stores 30 days, after storing, lithium ion secondary battery is placed in 4.2V by electricity
Under 25 DEG C of environment, 2.8V is then discharged to lithium ion secondary battery with the constant current of 0.5C, later with the constant current of 1C
4.2V is charged to lithium ion secondary battery, is further 1C with 4.2V constant voltage charging to electric current, then with the constant of 1C
Electric current is discharged to 2.8V to lithium ion secondary battery, and the discharge capacity of last time is after lithium ion secondary battery high temperature storage
Discharge capacity.Capacity retention ratio (%) after lithium ion secondary battery high temperature storage=[after lithium ion secondary battery high temperature storage
Discharge capacity/lithium ion secondary battery high temperature storage before discharge capacity] × 100%.
3, the high temperature storage gas generation property test of lithium ion secondary battery
At 25 DEG C, 4.2V is first charged to lithium ion secondary battery with the constant current of 1C, it is further constant with 4.2V
It is 0.05C that voltage, which charges to electric current, is then discharged to 2.8V to lithium ion secondary battery with the constant current of 1C, this electric discharge
Capacity is the discharge capacity before lithium ion secondary battery high temperature storage；Then lithium ion secondary battery is filled with the constant current of 1C
Electricity is 0.05C with 4.2V constant voltage charging to electric current to 4.2V, and lithium ion battery is fully charged.Electricity is tested using drainage
The volume of core, with the thickness of miking battery core.
Lithium ion battery is placed at 60 DEG C later and is stored 30 days, after storing, lithium ion secondary battery is placed in
Under 25 DEG C of environment, using the volume of drainage test battery core, with the thickness of miking battery core.Then with the constant electricity of 0.5C
Stream is discharged to 2.8V to lithium ion secondary battery, charges to 4.2V to lithium ion secondary battery with the constant current of 1C later, into
One step is 1C with 4.2V constant voltage charging to electric current, is then discharged to the constant current of 1C to lithium ion secondary battery
2.8V, the discharge capacity of last time are the discharge capacity after lithium ion secondary battery high temperature storage.
Battery core cubical expansivity=(volume -1 before volume/storage after storage) %
The parameter and the performance test results of 1 Examples 1 to 5 of table and comparative example 1~3
From the point of view of the result that table 1 provides, comparing embodiment 1~5 and comparative example 1 as a result, with any additive is not added
Battery compare, with the addition of phosphate compound 1, lithium ion secondary battery stored 30 days at 60 DEG C after capacity retention ratio
Increase, the capacity retention ratio after 60 DEG C of circulations is also improved, and high temperature storage reduces after producing gas, illustrates that such phosphate compound can
The side reaction of electrolyte and positive electrode can be inhibited at high temperature, to improve capacity of the battery after high temperature circulation storage
Conservation rate.
From comparative example 2 and comparative example 3 as can be seen that when content too low (0.001%) of additive phosphate,
The effect of protection anode can not be played, and when additive level is excessively high (8%), it may be possible to since too high levels lead to electricity
It solves fluid viscosity to increase, is degrading the cycle performance of battery.
Although it should be pointed out that only being carried out by taking additive compound 1, compound 2 as an example in the embodiment of this specification
Explanation, still, the other embodiment of lithium ion secondary battery according to the present invention, electrolyte of lithium-ion secondary battery additive
It is also possible to one or more of the additive compound mentioned in other claims.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art.It the announcement of book and retouches according to the above description
It states, those skilled in the art in the invention can also change and modify the above embodiment.Therefore, the present invention is not
It is confined to specific embodiment disclosed and described above, some modifications and changes of the invention should also be as falling into of the invention
In scope of protection of the claims.In addition, although using some specific terms in this specification, these terms are only
Facilitate explanation, does not limit the present invention in any way.
Claims (10)
1. a kind of electrolysis additive, which is characterized in that the additive has structure shown in Formulas I；
Wherein, R in Formulas I1, R2, R3It is each independently hydrogen atom or cyano, and R1, R2, R3In at least one be cyano；R4,
R5It is each independently alkyl, the general formula of the alkyl is CnH2n+1, n=1~8.
2. additive according to claim 1, which is characterized in that the R4, R5It is each independently selected from methane, in ethane
One kind.
3. additive according to claim 1, which is characterized in that the additive in following compounds at least one
Kind:
4. a kind of electrolyte characterized by comprising
Non-aqueous organic solvent,
The lithium salts being dissolved in the non-aqueous organic solvent,
With the additive being dissolved in the non-aqueous organic solvent, the additive is according to any one of claims 1 to 3
Additive.
5. electrolyte according to claim 4, which is characterized in that the quality of the additive accounts for the non-aqueous organic solvent
The 0.01%~5% of gross mass；
Optionally, the quality of the additive accounts for the 0.5%~3% of the non-aqueous organic solvent gross mass.
6. electrolyte according to claim 4, which is characterized in that the non-aqueous organic solvent includes cyclic carbonate and chain
Shape carbonic ester,
The cyclic carbonate is selected from least one of ethylene carbonate, propene carbonate, gamma-butyrolacton；
The linear carbonate is selected from dimethyl carbonate, butylene, diethyl carbonate, dipropyl carbonate, carbonic acid first
Ethyl ester, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, acetic acid
At least one of propyl ester, methyl propionate, ethyl propionate, propyl propionate.
7. electrolyte according to claim 4, which is characterized in that the lithium salts is selected from LiPF6, LiBF4、LiBOB、
LiDFOB、LiAsF6、Li(CF3SO2)2N、Li(FSO2)2N、LiPO2F2、LiCF3SO3、LiClO4At least one of.
8. a kind of lithium ion secondary battery characterized by comprising
Positive plate, the positive plate include plus plate current-collecting body and be set on the plus plate current-collecting body containing positive-active material
The positive diaphragm of material；
Negative electrode tab, the negative electrode tab include negative current collector and are set on the negative current collector and contain negative electrode active material
The cathode membrane of material；
Spacer film, the spacer film are set between the positive plate and the negative electrode tab；
Electrolyte, the electrolyte are electrolyte described in any one of claim 4~7.
9. lithium ion secondary battery according to claim 8, which is characterized in that the positive electrode active materials are selected from the mistake of lithium
Metal oxide is crossed,
Optionally, the transition metal oxide of the lithium is selected from LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、
LiNixCoyMnzO2、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4、Li2Mn1-xO4In at least one
Kind, wherein M is 0≤a < 0.2,0≤x selected from least one of Ni, Co, Mn, Al, Cr, Mg, Zr, Mo, V, Ti, B, F and Y,
y,z≤1。
10. lithium ion secondary battery according to claim 8, which is characterized in that the negative electrode active material is selected from natural
At least one of graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon, silicon-carbon alloy, silicon oxygen alloy.
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| CN109786832B (en) | 2021-08-20 |
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