CN109659617A - Lithium ion secondary battery and its electrolyte - Google Patents
Lithium ion secondary battery and its electrolyte Download PDFInfo
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- CN109659617A CN109659617A CN201811620637.5A CN201811620637A CN109659617A CN 109659617 A CN109659617 A CN 109659617A CN 201811620637 A CN201811620637 A CN 201811620637A CN 109659617 A CN109659617 A CN 109659617A
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses lithium ion secondary battery and its electrolyte.Wherein, electrolyte includes: lithium salts, organic solvent and additive, and the additive is compound shown in formula (I),In formula (I), R1For hydrogen, C1‑8Alkyl or C1‑8Alkenyl, R2And R3The C separately replaced for cyano or cyano1‑8Alkyl.By the way that the electrolyte to be applied in lithium ion secondary battery, be remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, solve battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
Description
Technical field
The present invention relates to electrochemical field, in particular to a kind of lithium ion secondary battery and its electrolyte.
Background technique
Lithium ion battery is the green high-capacity environment-protecting battery occurred the 1990s, since it is with voltage height, volume
Small, light weight, specific energy height, memory-less effect, the advantages that pollution-free, self discharge is small, the service life is long, mobile phone, laptop,
Video camera, digital camera, tablet computer etc. emphasize light and short, multi-functional portable electronic product using upper rapid proliferation.
In recent years, with the failure of the Global Oil energy and the development of new energy technology, applied on automobile power
Lithium ion battery technology rapidly develops, while also to the performance of lithium ion secondary battery, more stringent requirements are proposed.Due to country
Subsidy policy and energy density are linked up with, work long hours to meet electric car, high course continuation mileage, can high and low temperature environment just
It is often used, quickly-chargeable and the requirement with the long life, needing to develop has higher energy density, superior
The lithium ion secondary battery of high temperature circulation, storage performance and low temperature high rate performance.
Summary of the invention
In view of this, the present invention is directed to propose a kind of lithium ion secondary battery and its electrolyte.By the way that the electrolyte is answered
For in lithium ion secondary battery, being remarkably improved the room temperature and high-temperature storage performance of lithium ion secondary battery, solves battery and exist
Under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
According to an aspect of the present invention, the invention proposes a kind of electrolyte.According to an embodiment of the invention, the electrolysis
Liquid includes: lithium salts, organic solvent and additive, and the additive is compound shown in formula (I),
In formula (I), R1For hydrogen, C1-8Alkyl or C1-8Alkenyl, R2And R3The C separately replaced for cyano or cyano1-8
Alkyl.
Compared with the existing technology, the electrolyte of the above embodiment of the present invention has the advantage that
The phosphorus of electrolyte of the invention by using compound shown in formula (I) as additive, in compound shown in formula (I)
Oxygen double bond has lone pair electrons, is a kind of lewis base, can react to form protective film on positive electrode surface, to improve lithium
The high-temperature behavior of ion battery.In addition, complexing can occur with metal ion for the cyano (- CN) in compound shown in formula (I) instead
It answers, reduces metal ion activity, so that the side reaction in battery is reduced, when improving battery performance, and battery high-temperature being inhibited to store
Produce gas.As a result, by the way that the electrolyte to be applied in lithium ion secondary battery, it is remarkably improved the room temperature of lithium ion secondary battery
With high-temperature storage performance, solve battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
Further, the additive has the structure of one of:
Further, the quality of the additive is the 0.01~5% of the electrolyte gross mass.
Further, the organic solvent includes cyclic carbonate and/or linear carbonate.
Further, the cyclic carbonate be in ethylene carbonate, propene carbonate and gamma-butyrolacton at least
One of；The linear carbonate is selected from dimethyl carbonate, butylene, diethyl carbonate, dipropyl carbonate, carbonic acid
Methyl ethyl ester, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, second
At least one of propyl propionate, methyl propionate, ethyl propionate and propyl propionate.
Further, the lithium salts is selected from LiPF6、LiBF4, LiBOB (dioxalic acid lithium borate), LiDFOB (difluoro oxalate
Lithium borate), LiAsF6、Li(CF3SO2)2N、Li(FSO2)2N、LiCF3SO3And LiClO4At least one of.
Further, the electrolyte further comprises: Second addition, the Second addition have it is following wherein
One of structure:
Wherein, each R is separately H, F, Cl, Br, C1-8Alkyl or C1-8Fluoro-alkyl.
Further, the Second addition has the structure of one of:
Further, the quality of the Second addition is the 0.01~5% of the electrolyte gross mass.
According to another aspect of the present invention, the invention proposes a kind of lithium ion secondary batteries.Implementation according to the present invention
Example, which includes: positive plate, and the positive plate includes plus plate current-collecting body and is set to the anode collection
Positive diaphragm on body, the cathode film on piece contain positive electrode active materials；Negative electrode tab, the negative electrode tab include negative current collector
And it is set to the cathode membrane on the negative current collector, contain negative electrode active material in the cathode membrane；Isolation film, institute
Isolation film is stated to be arranged between the positive plate and the negative electrode tab；And the electrolyte of above-described embodiment.
Lithium ion secondary battery according to an embodiment of the present invention can be mentioned significantly by using the electrolyte of above-described embodiment
The room temperature and high-temperature storage performance of high-lithium ion secondary cell solve battery and cause in long term storage under room temperature or hot conditions
Capacity attenuation, flatulence the problems such as.
Further, the positive electrode active materials are the transition metal oxide of lithium.
Further, the positive electrode active materials are LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、
LiNixCoyMnzO2、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4And Li2Mn1-xO4In at least it
One, wherein M is 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
≤ 1,0≤y≤1,0≤z≤1.
Further, the negative electrode active material be selected from natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon,
At least one of silicon-carbon alloy and silicon oxygen alloy.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.
Inventor has found that existing lithium ion secondary battery is in room temperature or high temperature in the research to lithium ion secondary battery
Under the conditions of, phenomena such as capacity attenuation, flatulence are easy to appear in long-term storing process.By further investigation, this is mainly inventor
Since anode used in the lithium-ion-power cell that is commercialized at present mostly uses the tertiary cathode material of high nickel content
(LiNi0.6Co0.2Mn0.2O2, LiNi0.8Co0.1Mn0.1O2), structural instability, metal ion hold this positive electrode at high temperature
Easily dissolution, the Ni of high price4+It is easy that oxidation reaction occurs with electrolyte, leads to degradation of cell performance.
In consideration of it, in one aspect of the invention.The invention proposes a kind of electrolyte.The electrolyte includes: lithium salts, has
Solvent and additive, the additive are compound shown in formula (I),
In formula (I), R1For hydrogen, C1-8Alkyl or C1-8Alkenyl, R2And R3The C separately replaced for cyano or cyano1-8
Alkyl.
It should be noted that above-mentioned C1-8Alkyl and C1-8Alkenyl is also possible to either linear alkyl (straight chained alkyl)
Branch or cyclic alkyl；Above-mentioned C1-8Alkenyl is also possible to branch or cyclic alkyl either linear alkenyl (straight-chain alkenyl).
The phosphorus of electrolyte of the invention by using compound shown in formula (I) as additive, in compound shown in formula (I)
Oxygen double bond has lone pair electrons, is a kind of lewis base, can react to form protective film on positive electrode surface, to improve lithium
The high-temperature behavior of ion battery.In addition, complexing can occur with metal ion for the cyano (- CN) in compound shown in formula (I) instead
It answers, reduces metal ion activity, so that the side reaction in battery is reduced, when improving battery performance, and battery high-temperature being inhibited to store
Produce gas.As a result, by the way that the electrolyte to be applied in lithium ion secondary battery, it is remarkably improved the room temperature of lithium ion secondary battery
With high-temperature storage performance, solve battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
According to an embodiment of the invention, compound shown in formula (I) can be synthesized by the cyanalation reaction of halogenated compound.Tool
Body method is as follows:
With reference to formula (A), using alkyl (R1) dichloro oxygen phosphorus that replaces and ethylene bromohyrin be in alkali (such as triethylamine, potassium carbonate
Deng) catalysis under the phosphate compound that replaces of synthetic bromide, then using cyanylation agent (such as potassium cyanide, third level natural division
Deng) cyanalation reaction is carried out, finally obtain formula (X) compound represented.It is as follows to react schematic diagram:
It will be appreciated by those skilled in the art that different carbon atom numbers can be replaced with ethylene bromohyrin according to actual needs
Bromhydrin, to obtain compound shown in formula (I).
Preferred embodiment in accordance with the present invention, additive have the structure of one of:
Inventor is by the way that the further preferred of compound structure shown in formula (I), discovery is using as shown in formula (1)~(4)
Additive of the compound as electrolyte, can be further improved the room temperature and high-temperature storage performance of lithium ion secondary battery,
Further advantageously account for battery under room temperature or hot conditions in long term storage caused by capacity attenuation, flatulence the problems such as.
According to an embodiment of the invention, the quality that above-mentioned additive adds in the electrolytic solution can be electrolyte gross mass
0.01~5%.The additive amount of additive is too low, effectively can not form protective film on anode material of lithium battery surface, it is difficult to rise
To the effect of protection anode, battery storage performance can not be effectively improved.And if the adding too much of additive, excessively high addition
The additive of amount is not obvious the effect for further increasing battery storage performance, and dissolubility is also insufficient.And then inventor is logical
Cross it is a large amount of experimental studies have found that, control the additive amount of additive the 0.01~5% of electrolyte gross mass, can effectively improve
While battery storage performance, the waste that agent is excessively added and solubility problem are avoided.
Further, by advanced optimizing to additive amount, preferred embodiment in accordance with the present invention, additive exists
The quality added in electrolyte can be the 0.5~2% of electrolyte gross mass, thus, it is possible to further increase the storage of battery
Performance.
According to an embodiment of the invention, above-mentioned solvent includes cyclic carbonate and/or linear carbonate.According to the present invention
Embodiment, cyclic carbonate can be for selected from least one of ethylene carbonate, propene carbonate and gamma-butyrolacton；Chain
Shape carbonic ester can for 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,
At least one of methyl propionate, ethyl propionate and propyl propionate.The above carbonats compound it is from a wealth of sources, it is at low cost
It is honest and clean, and there is good compatibility with additive above-mentioned.By using above-mentioned carbonats compound having as electrolyte
Solvent can further be conducive to the performance of additive effect, thus further increase lithium using electrolyte of the present invention from
The storage performance of sub- battery.
According to an embodiment of the invention, lithium salts can be for selected from LiPF6、LiBF4, LiBOB (dioxalic acid lithium borate),
LiDFOB (difluorine oxalic acid boracic acid lithium), LiAsF6、Li(CF3SO2)2N、Li(FSO2)2N、LiCF3SO3And LiClO4In at least it
One.The above lithium salts it is from a wealth of sources, it is low in cost, and with additive above-mentioned have good compatibility.
According to an embodiment of the invention, can further include in electrolyte of the invention: Second addition, described
Two additives have the structure of one of:
Wherein, each R is separately H, F, Cl, Br, C1-8Alkyl or C1-8Fluoro-alkyl.
Inventor has found that the additive of the compound shown in formula (I) is stored with good raising lithium battery in an experiment
On the basis of performance effect, by the way that Second addition is further added in the electrolytic solution, the room of lithium battery can be further improved
Mild high-temperature storage performance.
According to an embodiment of the invention, Second addition can be using commonly film forming addition in lithium battery preparation process
Agent.Specific example according to the present invention, Second addition can have the structure of one of:
Compound shown in above formula (5)~(8) it is from a wealth of sources, it is low in cost, and can be with compound shown in formula (I)
Additive generates synergistic effect, to further increase the storage performance of the lithium ion battery using electrolyte of the present invention.
According to an embodiment of the invention, the quality that above-mentioned Second addition adds in the electrolytic solution can be the total matter of electrolyte
The 0.01~5% of amount.If Second addition content is too low, SEI filming function is unobvious.Too high levels are easy to cause film forming
Internal resistance is excessively high, is unfavorable for the charge and discharge of battery low temperature and the performance of power-performance.
Further, by being advanced optimized to Second addition dosage, preferred embodiment in accordance with the present invention, second
The quality that additive adds in the electrolytic solution can be the 0.5~2% of electrolyte gross mass, thus, it is possible to further be conducive to
The additive of Second addition and compound shown in formula (I) generates synergistic effect, is electrolysed to further increase using the present invention
The storage performance of the lithium ion battery of liquid.
According to another aspect of the present invention, the invention proposes a kind of lithium ion secondary batteries.Implementation according to the present invention
Example, which includes: positive plate, negative electrode tab, isolation film and electrolyte.Wherein, positive plate includes anode collection
Fluid and the positive diaphragm being set on plus plate current-collecting body, cathode film on piece contain positive electrode active materials；Negative electrode tab includes negative
Pole collector and the cathode membrane being set on negative current collector contain negative electrode active material in cathode membrane；Isolation film is set
It sets between positive plate and negative electrode tab.
Lithium ion secondary battery according to an embodiment of the present invention can be mentioned significantly by using the electrolyte of above-described embodiment
The room temperature and high-temperature storage performance of high-lithium ion secondary cell solve battery and cause in long term storage under room temperature or hot conditions
Capacity attenuation, flatulence the problems such as.
According to an embodiment of the invention, above-mentioned positive electrode active materials are the transition metal oxide of lithium.
According to an embodiment of the invention, above-mentioned positive electrode active materials are LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、
LiFePO4、LiNixCoyMnzO2、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4And Li2Mn1-xO4In
At least one of, 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≤1,0≤y≤1,0≤z≤1.
According to an embodiment of the invention, above-mentioned negative electrode active material can for selected from natural graphite, artificial graphite, soft carbon,
At least one of hard carbon, lithium titanate, silicon, silicon-carbon alloy and silicon oxygen alloy.
It should be noted that the lithium ion secondary battery has all feature and advantage of hereinbefore described electrolyte,
This is no longer going to repeat them.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Conventional method
(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
(polyvinylidene fluoride) 96:2.0:2.0 in mass ratio, which is dissolved in being uniformly mixed in solvent N-methyl pyrilidone, is made anode sizing agent,
Anode sizing agent is uniformly coated in current collector aluminum foil later, coating weight 18mg/cm2, carried out after then being dried at 85 DEG C
Cold pressing, trimming, cut-parts, slitting, the lithium ion met the requirements is made in dry 4h, soldering polar ear under 85 DEG C of vacuum conditions later
The positive plate of secondary cell.
(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 (sodium carboxymethylcellulose), bonding agent
SBR (butadiene-styrene rubber) 96.5:1.0:1.0:1.5 in mass ratio, which is dissolved in being uniformly mixed in solvent deionized water, is made negative electrode slurry,
Negative electrode slurry is uniformly coated on copper foil of affluxion body later, coating weight 8.9mg/cm2, carried out after then being dried at 85 DEG C
Cold pressing, trimming, cut-parts, slitting, the lithium ion met the requirements is made in dry 4h, soldering polar ear under 110 DEG C of vacuum conditions later
The negative electrode tab of secondary cell.
(3) preparation of the electrolyte of lithium ion secondary battery
The electrolyte of lithium ion secondary battery is with the LiPF of 1mol/L6For lithium salts, with ethylene carbonate (EC), methyl ethyl carbonate
Ester (EMC), diethyl carbonate (DEC) mixture be non-aqueous organic solvent, wherein the mass ratio of EC:EMC:DEC be 30:50:
20.In addition, also containing additive in the electrolyte of lithium ion secondary battery.
(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 1
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 1% of the electrolyte of battery,
Embodiment 2
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 0.5% of the electrolyte of battery.
Embodiment 3
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 3% of the electrolyte of battery.
Embodiment 4
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 5% of the electrolyte of battery.
Embodiment 5
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 2) shown in the formula (2) of the gross mass 1% of the electrolyte of battery,
Embodiment 6
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 3) shown in the formula (3) of the gross mass 1% of the electrolyte of battery,
Embodiment 7
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 1% of the electrolyte of battery and the electrolyte for accounting for lithium ion secondary battery
Gross mass 1% formula (5) shown in compound (compound 5, vinylene carbonate),
Embodiment 8
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 1% of the electrolyte of battery and the electrolyte for accounting for lithium ion secondary battery
Gross mass 1% formula (6) shown in compound (compound 6, vinyl ethylene carbonate),
Embodiment 9
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 1% of the electrolyte of battery and the electrolyte for accounting for lithium ion secondary battery
Gross mass 1% formula (7) shown in compound (compound 7, maleic anhydride),
Comparative example 1
Lithium ion secondary battery is prepared according to conventional method, wherein does not add any additive in step (3).
Comparative example 2
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 0.001% of the electrolyte of battery.
Comparative example 3
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 1) shown in the formula (1) of the gross mass 8% of the electrolyte of battery.
Comparative example 4
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 5, vinylene carbonate) shown in the formula (5) of the gross mass 1% of the electrolyte of battery.
Comparative example 5
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 6, vinyl ethylene carbonate) shown in the formula (6) of the gross mass 1% of the electrolyte of battery.
Comparative example 6
Lithium ion secondary battery is prepared according to conventional method, wherein in step (3), additive is to account for lithium ion secondary
Compound (compound 7, maleic anhydride) shown in the formula (7) of the gross mass 1% of the electrolyte of battery.
The lithium ion secondary battery that Examples 1 to 9 and comparative example 1~6 are prepared respectively is tested for the property.
(1) high temperature cyclic performance is tested
At 60 DEG C, 4.2V is first charged to lithium ion secondary battery with the constant current of 1C, then with 4.2V constant voltage
Charging to electric current is 0.05C, is then discharged to 2.8V to lithium ion secondary battery with the constant current of 1C, this is a charge and discharge
Cyclic process, this discharge capacity are the discharge capacity of circulation for the first time.Lithium ion secondary battery is carried out in a manner described
Cyclic charging and discharging test 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) high-temperature storage performance is tested
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 before discharge capacity/lithium ion secondary battery high temperature storage] × 100%.
(3) high temperature storage gas generation property is tested
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 70 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) %
Next the performance test results of Examples 1 to 9 and comparative example 1~6 are analyzed.
From the comparison of Examples 1 to 6 and comparative example 1 as can be seen that compared with the battery for not adding any additive, with
The addition of additive (compound shown in formula (1)~(4)), lithium ion secondary battery 60 DEG C store 30 days after capacity keep
Rate increases, and the capacity retention ratio after 60 DEG C of circulations is also improved, and illustrates that such phosphate compound may inhibit at high temperature
The side reaction of electrolyte and positive electrode, to improve capacity retention ratio of the battery after high temperature circulation storage.
From comparative example 2 and comparative example 3 as can be seen that when the content of additive too low (< 0.01%), guarantor can not be played
The effect of anode is protected, and when additive level is excessively high (8%), the effect for further increasing battery storage performance is not obvious,
And dissolubility is also insufficient.In addition, the dissolubility of additive in the electrolytic solution is limited, and additive molecule amount is big, additive level
The excessively high electrolysis fluid viscosity that will lead to increases, and causes cycle performance improvement result limited, is unfavorable for battery performance performance.
From embodiment 5~6 and comparative example 1 as can be seen that compound shown in adding type (2) and formula (3), also plays improvement
The high-temperature lithium ion battery service life reduces the effect for producing gas.
From the comparison of embodiment 7~9 and comparative example 4~6 as can be seen that when to containing the electrolysis of Second addition
It being added in liquid with after the additive of compound shown in formula (I), the capacity retention ratio after battery high-temperature circulation storage further increases,
Illustrate that the additive can act synergistically with common film for additive, further increases the performance of battery.
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 in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
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 within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of electrolyte characterized by comprising lithium salts, organic solvent and additive, the additive are shown in formula (I)
Compound,
In formula (I), R1For hydrogen, C1-8Alkyl or C1-8Alkenyl, R2And R3The C separately replaced for cyano or cyano1-8Alkyl.
2. electrolyte according to claim 1, which is characterized in that the additive has the structure of one of:
3. electrolyte according to claim 1, which is characterized in that the quality of the additive is the electrolyte gross mass
0.01~5%.
4. electrolyte according to claim 1, which is characterized in that the organic solvent includes cyclic carbonate and/or chain
Shape carbonic ester；
Optionally, the cyclic carbonate is selected from least one of ethylene carbonate, propene carbonate and gamma-butyrolacton；
Optionally, the linear carbonate is selected from dimethyl carbonate, butylene, diethyl carbonate, dipropyl carbonic acid
Ester, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl formate, Ethyl formate, propyl formate, methyl acetate, acetic acid
At least one of ethyl ester, propyl acetate, methyl propionate, ethyl propionate and propyl propionate.
5. electrolyte according to claim 1, which is characterized in that the lithium salts is selected from LiPF6、LiBF4、LiBOB、
LiDFOB、LiAsF6、Li(CF3SO2)2N、Li(FSO2)2N、LiCF3SO3And LiClO4At least one of.
6. described in any item electrolyte according to claim 1~5, which is characterized in that further comprise: Second addition, institute
State the structure that Second addition has one of:
Wherein, each R is separately H, F, Cl, Br, C1-8Alkyl or C1-8Fluoro-alkyl.
7. electrolyte according to claim 6, which is characterized in that the Second addition has the knot of one of
Structure:
8. electrolyte according to claim 6, which is characterized in that the quality of the Second addition is that the electrolyte is total
The 0.01~5% of quality.
9. a kind of lithium ion secondary battery characterized by comprising
Positive plate, the positive plate includes plus plate current-collecting body and the positive diaphragm that is set on the plus plate current-collecting body, described
Cathode film on piece contains positive electrode active materials；
Negative electrode tab, the negative electrode tab includes negative current collector and the cathode membrane that is set on the negative current collector, described
Contain negative electrode active material in cathode membrane；
Isolation film, the isolation film are arranged between the positive plate and the negative electrode tab；And
Electrolyte according to any one of claims 1 to 8.
10. lithium ion secondary battery according to claim 9, which is characterized in that the positive electrode active materials are the mistake of lithium
Cross metal oxide；
Optionally, the positive electrode active materials are LiCoO2、LiMn2O4、LiMnO2、Li2MnO4、LiFePO4、LiNixCoyMnzO2、
Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4And Li2Mn1-xO4At least one of, wherein M is choosing
From at least one of Ni, Co, Mn, Al, Cr, Mg, Zr, Mo, V, Ti, B, F and Y, 0≤a < 0.2,0≤x≤1,0≤y≤1,0
≤z≤1；
Optionally, the negative electrode active material is to close selected from natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon, silicon-carbon
At least one of gold and silicon oxygen alloy.
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| CN115490210A (en) * | 2022-07-01 | 2022-12-20 | 合肥国轩电池材料有限公司 | Lithium manganese selenite coating material, and preparation method and application thereof |
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