CN110212244A - Lithium ion battery, lithium-ion battery electrolytes and preparation method thereof - Google Patents
Lithium ion battery, lithium-ion battery electrolytes and preparation method thereof Download PDFInfo
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- CN110212244A CN110212244A CN201910486808.8A CN201910486808A CN110212244A CN 110212244 A CN110212244 A CN 110212244A CN 201910486808 A CN201910486808 A CN 201910486808A CN 110212244 A CN110212244 A CN 110212244A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M10/058—Construction or manufacture
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Present invention discloses a kind of lithium ion batteries, lithium-ion battery electrolytes and preparation method thereof, comprising: additive；The additive includes bridged ring type carboxylate.Advantageous effects of the present invention: by the similar compound of a large amount of structures the study found that the branch for increasing alkane structure on the α carbon of active group side facilitates the activity of decrease active group.Therefore the present invention is by being added alkane in the side of carboxylate; improve the compatibility of carboxylate and lithium salts; furthermore; open loop is easy when cathode is reduced using alkane in bridged ring and forms free radical; form copolymer; enable the presence that protective film is more stable, and then improve the cycle performance of power battery, reduces and produce gas.
Description
Technical field
The present invention relates to new energy fields, especially relate to lithium ion battery, lithium-ion battery electrolytes and its system
Preparation Method.
Background technique
As electric car is in mondial universal, course continuation mileage and security performance of the market for electric car
It is proposed higher demand, nickelic ternary power battery has sizable energy density, and with the content of nickel in ternary material
Increase, the specific capacity of material also increases with it, but the decomposition reaction of the unstability of anode structure and electrolyte also adds therewith
Play causes high temperature storage to produce gas and increases, and then influences the service life of battery.
In order to improve high temperature gas production, one is be added as additive to electrolysis by anhydride for method used at present
In liquid, battery producing gas can be improved although the additive of anhydride is added, the polarity of acid anhydride structure is larger, the protection resulted in
Film ionic conductivity is poor, significantly increases to battery impedance；Another kind be by gamma-butyrolacton (GBL) as additive be added to
In electrolyte, make it in power battery anode Surface Creation anode protective film, but GBL and the lithium salts in electrolyte are incompatible,
And GBL is unstable in cathode film formation, is not suitable for lithium ion battery with high energy density, therefore needs a kind of new lithium ion battery
Electrolyte.
Summary of the invention
The main object of the present invention is to provide a kind of lithium-ion battery electrolytes, it is intended to solve existing nickelic ternary power electric
The technical problem that pond loop attenuation is fast, gas production is big.
The present invention proposes a kind of lithium-ion battery electrolytes, comprising: additive；The additive includes bridged ring type carboxylic acid
Ester, the general structure of the bridged ring type carboxylate are as follows:
Wherein, n is positive integer, and R1, R2 are respectively H, F, alkyl, alkenyl, aryl, halogenated alkyl, halogenated alkenyl, halogenated virtue
One of base.
Further, the additive further includes fluorinated ethylene carbonate.
Further, the quality of the fluorinated ethylene carbonate and the bridged ring type carboxylate includes 1:2~3 than range:
2。
Further, the quality percentage accounting range of the bridged ring type carboxylate includes 1%-20%.
Further, in the general structure of the bridged ring type carboxylate, n is the positive integer less than 4.
Further, the halogenated alkyl, halogenated alkenyl, halogenated aryl respectively correspond as fluoro-alkyl, fluoro alkenyl, fluorine
For aryl.
Further, carbon atom number is 1~10 in the alkyl, and carbon atom number is 2~10 in the alkenyl, the aryl
Middle carbon atom number is 6~20, in the halogenated alkyl carbon atom number be 1~10, in the halogenated alkenyl carbon atom number be 2~
10, carbon atom number is 6~20 in the halogenated aryl.
Further, the bridged ring type carboxylate includes compound 1 one or more of to compound 6.
The present invention also provides a kind of preparation methods of lithium-ion battery electrolytes, are used to prepare lithium ion described above
Battery electrolyte, comprising: by the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate according to certain volume ratio
It is mixed, is added after being sufficiently mixed and is based on a certain proportion of lithium salts of lithium-ion battery electrolytes total weight, added a certain amount of
Additive, the lithium-ion battery electrolytes are made after being sufficiently mixed.
The present invention also provides a kind of lithium ion batteries, which is characterized in that including negative electrode tab, positive plate and described above
Lithium-ion battery electrolytes, the positive plate includes positive electrode active materials, conductive carbon and binder, the positive electrode active materials
For ternary material.
Advantageous effects of the present invention: by the similar compound of a large amount of structures the study found that in active group side
α carbon on increase alkane structure branch facilitate weaken active group activity.Therefore the present invention is by the one of carboxylate
Alkane is added in side, the compatibility of carboxylate and lithium salts is improved, in addition, being easy out using alkane in bridged ring when cathode is reduced
Ring forms free radical, forms copolymer, enables the presence that protective film is more stable, and then improve the cycle performance of power battery,
It reduces and produces gas.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
The present invention provides a kind of lithium-ion battery electrolytes, comprising: organic solvent, lithium salts and additive；Additive includes
Bridged ring type carboxylate, the general structure of bridged ring type carboxylate are as follows:
Wherein, n is positive integer；
R1, R2 are respectively one of H, F, alkyl, alkenyl, aryl, halogenated alkyl, halogenated alkenyl, halogenated aryl.
In the present embodiment, by the way that the bridged ring type carboxylate of above structure is added in lithium-ion electrolyte, will be added with this
When the lithium-ion battery electrolytes of additive are reacted with positive ternary material composition battery, due to its asymmetric carboxylate
Structure is easy to be oxidized easily by catalysis scission of link in positive electrode surface, forms positive protective film, and due to the knot of asymmetric carboxylate
The film being configured to is for the film that acid anhydrides is formed, and the film that asymmetry carboxylate structure is formed is thinner, the resistance to battery
Resist function that is small, and being also equipped with certain reduction production gas, side reaction will not be generated with lithium salts, is a kind of and its ideal material.
In the present embodiment, additive further includes fluorinated ethylene carbonate.Fluorinated ethylene carbonate can be with bridged ring type carboxylate
Form more completely more stable protective film, the side reaction being further reduced in positive and negative pole surface, so that lithium ion battery is normal
The lower circulation volume conservation rate of temperature is further up, and further, the quality of fluorinated ethylene carbonate and bridged ring type carboxylate compares model
It encloses including 1:2~3:2, since with the density that bridged ring type carboxylate forms a film to be greater than bridged ring type carboxylate independent for fluorinated ethylene carbonate
The density of film forming, therefore the content of fluorinated ethylene carbonate can be properly added, and then control the density of film forming, on the one hand improve at
Film integrality and stability, cycle performance of battery are promoted, and on the other hand prevent from generating HF, battery because fluorinated ethylene carbonate decomposes
Gas production increase, and quality than range within 1:2~3:2 when, can be in power battery between gas production and cycle performance
Equalization point is found, battery is advanced optimized.It should be appreciated that lithium ion battery ingredient change when, quality than range meeting above and below
It floats, and floating range should also be included in interest field of the invention.
In the present embodiment, it is 1%-20% that bridged ring type carboxylate, which accounts for the mass percent in lithium-ion battery electrolytes,.If
Mass percent in battery electrolyte shared by bridged ring type carboxylate then can not form less than 1% with the protective film for reducing production gas
The transition metal ions that (or even can not form film), i.e. positive electrode active materials are precipitated in reaction can enter in electrolyte easily,
The decomposition of catalytic electrolysis liquid, and then lead to the increase of gas production；If the quality hundred in battery electrolyte shared by bridged ring type carboxylate
Divide than being greater than 20%, then the film formed is blocked up, and the lithium ion plasma for participating in reacting is difficult to the film by formation, causes to battery
Big impedance prevents battery from normal charge and discharge.If therefore taking the mass percent in battery electrolyte shared by bridged ring type carboxylate
For 1%-20%, lithium ion etc. can be made to pass through and effectively inhibit gas production.
In the present embodiment, in the general structure of bridged ring type carboxylate, n is preferably smaller than 4 positive integer.With the number of carbon atom
Mesh increases, and the active force of adjacent functionality's (ester bond) can reduce, that is, the density to form a film is small, n be greater than certain value when even at
Not film, on the cathode of lithium ion battery at film be by ring-opening reaction (not including the ring of ester bond) rather than be the anti-of ester bond
It answers, the film density that equally will lead in battery cathode if n is excessive becomes smaller, therefore n is preferably smaller than 4 positive integer.
In the present embodiment, carbon atom number is 1~10 in alkyl, and carbon atom number is 2~10 in alkenyl, carbon atom number in aryl
Be 1~10 for carbon atom number in 6~20, halogenated alkyl, in halogenated alkenyl carbon atom number be 2~10, carbon atom in halogenated aryl
Number is 6~20.If the carbon atom number on branch is excessive, the density of film forming equally will affect, therefore carbon atom number should not be too
More, preferably, carbon atom number is 1~10 in alkyl, and carbon atom number is 2~10 in alkenyl, in aryl carbon atom number be 6~20,
In halogenated alkyl carbon atom number be 1~10, in halogenated alkenyl carbon atom number be 2~10, in halogenated aryl carbon atom number be 6~
20。
In the present embodiment, due to halogen chlorine, bromine etc. is replaced, excessive containing harmful element in one side product, no
Meet international standard, on the other hand, chlorine and bromine are easily oxidized and generate chlorine, bromine vapor, have to human body, environment different degrees of
Influence that all there is certain harmfulness, and fluorine is not easy to be oxidized, therefore in actual production process, it is preferred to use in halogen
Fluorine replace alkyl, alkenyl, the hydrogen on phenyl.It should be appreciated that a small amount of other halogen families member can also be mixed into fluoro alkyl
The halohydrocarbyl that element replaces.
In the present embodiment, fluoro-alkyl, fluoro alkenyl, the fluorine on fluorinated aryl include one or more, and fluorine is former thereon
Subnumber mesh is more, and the SEI film formed is more stable, and impedance is smaller, and cycle performance is more preferable, therefore optimal for all substitutions.But it is practical
Fluorine-containing more in production, synthesis is more difficult, and cost is corresponding also to be increased substantially, therefore in process of production, it can be according to battery
Actual use situation and cost, as much as possible increase fluorine atom number.
In the present embodiment, lithium salts is lithium hexafluoro phosphate, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, difluorophosphate, double
One of fluorine sulfimide lithium or a variety of mixtures.
In the present embodiment, the mass percent of lithium salts in the electrolytic solution is 0.2%~15%.
In the present embodiment, non-aqueous organic solvent includes ethylene carbonate, propene carbonate, butylene, carbonic acid diformazan
Ester, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, formic acid second
One of ester, propyl formate, butyl formate, ethyl acetate, methyl propionate or a variety of mixtures.
In the present embodiment, bridged ring type carboxylate includes one or more of following compound.
In above-mentioned bridged ring type carboxylate, it should be understood that with the increase of C atom number, molecular weight can also increase accordingly
Add, and the boiling point that the increase of molecular weight also results in compound increases, and improves the high-temperature stability of positive protective film, therefore not
In the case where influencing other performances, the compound that can suitably select C atom number more.It, can in a preferred embodiment
To take the mixture of above compound 1-6, the anode protection membrane structure generated is made to be unlikely to too close, it can be according to actual need
It is adjusted.
It can also include anhydride additive, the anode generated due to anhydride additive in additive in the present embodiment
Protective film is comparatively closeer, therefore a part of anhydride additive is added in bridged ring type carboxylate, makes the film close one generated
Point, and the film generated is closeer, the gas production of battery can be reduced, and comparatively the impedance of battery will increase, therefore add acid anhydrides
Class additive is suitable for the relatively high application scenarios of security performance, specifically additive amount can also according to the actual situation depending on.
In the present embodiment, the positive protective film generated on positive plate be by being easy to lose electronics on positive plate surface, from
And ester bond is opened, then the C=O group between two neighboring bridged ring type carboxylate and C-O group regenerate new ester bond,
Make molecule aggregation, to form positive protective film.Film forming is the reduction due to battery cathode in negative electrode tab, is made close to C=O
The C-C key of key is easy to get electronics, obtains two free radicals to disconnect, two neighboring free radical forms new C-C key, in turn
Result in the protective film in negative electrode tab.
The present invention also provides a kind of preparation method of lithium-ion battery electrolytes, including organic solvent described above,
Lithium salts and additive.
In the present embodiment, organic solvent is the mixture of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate, and lithium salts is
Lithium hexafluoro phosphate；
Ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are mixed according to certain volume ratio, are sufficiently mixed
It is added afterwards and is based on a certain proportion of lithium hexafluoro phosphate of lithium-ion battery electrolytes total weight, a certain amount of additive is added.It is preferred that
The volume ratio on ground, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate is 1:1:1, and lithium hexafluoro phosphate accounts for lithium ion battery battery
The 13wt% for solving liquid total weight, is prepared lithium-ion battery electrolytes by above step.The content of HF is small in the electrolyte
In 50ppm, H2The content of O is less than 20ppm, can satisfy the needs of practical application.
The present invention also provides a kind of lithium ion batteries, including lithium-ion battery electrolytes described above.
It further include negative electrode tab and positive plate in the present embodiment, positive plate includes positive electrode active materials, conductive carbon and bonding
Agent, positive electrode active materials are ternary material, and lithium-ion battery electrolytes are used to generate passivating film with positive electrode active materials.
The preparation of positive plate: by positive electrode active materials LiNi0.8Co0.1Mn0.1O2, conductive carbon, (English is complete by binder PVDF
Claim, polyvinylidene fluoride) it is uniformly mixed with N-Methyl pyrrolidone (NMP) anode sizing agent is made.Anode sizing agent solid content is
72wt%, wherein LiNi0.8Co0.1Mn0.1O2: conductive carbon: the mass ratio of PVDF is 97:2:1.Anode sizing agent is coated with collector
It on aluminium foil, dries at 80 DEG C and is cold-pressed again, then slitting cut-parts, place 12h in 85 DEG C of vacuum drying ovens, lithium ion battery is made
Positive plate.
The preparation of negative electrode tab: by negative electrode active material graphite and SiOx, conductive carbon, thickener CMC, binder butadiene-styrene rubber
(SBR) it is uniformly mixed in deionized water and negative electrode slurry is made.Negative electrode slurry solid content is 51%, wherein graphite: SiOx: it leads
Electrical carbon: the mass ratio of CMC:SBR is 65:30:2:0.5:2.5.Negative electrode slurry is coated on copper foil of affluxion body, is dried at 80 DEG C
Dry, then slitting cut-parts place 12h in 85 DEG C of vacuum drying ovens, anode plate for lithium ionic cell are made.
Comparative example 1
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
Mixing is added the lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt%, any addition is not added after being sufficiently mixed
Agent.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Comparative example 2
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
Mixing is added the lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt%, adds 8wt% fluoro carbon after being sufficiently mixed
The additive of vinyl acetate.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Comparative example 3
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
Mixing is added the lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt%, adds 5wt% γ-fourth after being sufficiently mixed
The additive of lactone.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 1
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 1wt% chemical combination is added
The additive of object 1.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 2
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 5wt% chemical combination is added
The additive of object 1.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 3
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 1.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 4
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 20wt%ization is added
Close the additive of object 1.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 5
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 2.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 6
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 3.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 7
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 4.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 8
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 5.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 9
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 6.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 10
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 1 and 5wt% fluorinated ethylene carbonate.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 11
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 1 and 8wt% fluorinated ethylene carbonate.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
Embodiment 12
The preparation of electrolyte: by ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to volume ratio be 1:1:1 carry out
The lithium hexafluoro phosphate based on lithium-ion battery electrolytes total weight 13wt% is added in mixing after being sufficiently mixed, 10wt%ization is added
Close the additive of object 1 and 15wt% fluorinated ethylene carbonate.
The preparation of lithium ion battery with high energy density: by the positive plate of above-mentioned preparation, the polyethylene separators of 18um, cathode
Piece is folded in order in a manner of lamination and square electric cell is made, soldering polar ear, and uses laminated aluminum film, and above-mentioned preparation is perfused
Battery is made after the techniques such as aging, chemical conversion, shaping, volume test in electrolyte.
The parameter and battery performance test result of 1 embodiment 2~7 of table and comparative example 1~3
The parameter and battery performance test that upper table is embodiment 2~12 and comparative example 1~3 from top as a result, can be seen that
Compared to comparative example 1-3, it is 1% to 20% that mass fraction is added in the lithium ion battery of embodiment 1-4 preparation, in electrolyte
After compound 1, cycle performance of the lithium ion battery at 25 DEG C is had been significantly improved, meanwhile, lithium ion battery is at 60 DEG C
The production gas expansion rate of lower storage 4 days is also substantially reduced.On the one hand its reason may be due to carboxylate compound and lithium
Salt compatibility is promoted, and another aspect compound 1 forms stable protective film in positive and negative pole surface.With mentioning for 1 content of compound
It rises, circulation volume conservation rate is higher, and it is smaller to produce gas expansion rate.
In embodiment 5-9, the compound 2 that mass fraction is 10% is added, compound 3, compound 4, compound 5, changes
Object 6 is closed, circulation volume conservation rate of the lithium ion battery at 25 DEG C can be also obviously improved, the high temperature of lithium ion battery is inhibited to produce
Gas.
In embodiment 10-12, compound 1 and fluorinated ethylene carbonate are combined, in the positive and negative anodes table of lithium ion battery
Face forms more completely more stable protective film, the side reaction of electrode surface is further reduced, so that lithium ion secondary battery is 25
Circulation volume conservation rate is further promoted at DEG C, shows that fluorinated ethylene carbonate and compound 1 have certain synergistic effect, but
It is in the content increase of fluorinated ethylene carbonate, capacity retention ratio will increase, but due to fluorinated ethylene carbonate part
It decomposes and generates HF, the expansion rate of gas also will increase accordingly, therefore unsuitable increased too many, when compound is 10wt%,
The content of fluorinated ethylene carbonate is preferably 8%.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by present specification is applied directly or indirectly in other relevant technologies
Field is included within the scope of the present invention.
Claims (10)
1. a kind of lithium-ion battery electrolytes characterized by comprising additive；The additive includes bridged ring type carboxylate,
The general structure of the bridged ring type carboxylate are as follows:
Wherein, n is positive integer, R1, R2 be respectively H, F, alkyl, alkenyl, aryl, halogenated alkyl, halogenated alkenyl, in halogenated aryl
One kind.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that the additive further includes fluoro carbonic acid
Vinyl acetate.
3. according to lithium-ion battery electrolytes as claimed in claim 2, which is characterized in that the fluorinated ethylene carbonate and the bridge
The quality of ring-like carboxylate includes 1:2~3:2 than range.
4. lithium-ion battery electrolytes according to claim 1, which is characterized in that the quality hundred of the bridged ring type carboxylate
Point accounting range includes 1%-20%.
5. lithium-ion battery electrolytes according to claim 1, which is characterized in that the structure of the bridged ring type carboxylate is logical
In formula, n is the positive integer less than 4.
6. lithium-ion battery electrolytes according to claim 1, which is characterized in that the halogenated alkyl, halogenated alkenyl, halogen
It respectively corresponds for aryl as fluoro-alkyl, fluoro alkenyl, fluorinated aryl.
7. lithium-ion battery electrolytes according to claim 1, which is characterized in that in the alkyl carbon atom number be 1~
10, carbon atom number is 2~10 in the alkenyl, and carbon atom number is carbon atom number in 6~20, halogenated alkyl in the aryl
For carbon atom number in 1~10, halogenated alkenyl be 2~10, carbon atom number is 6~20 in the halogenated aryl.
8. according to the described in any item lithium-ion battery electrolytes of claim 5 to 7, which is characterized in that the bridged ring type carboxylic acid
Ester includes compound 1 one or more of to compound 6.
9. a kind of preparation method of lithium-ion battery electrolytes, which is characterized in that be used to prepare any one of claim 1-8 institute
The lithium-ion battery electrolytes stated, comprising:
The ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate are mixed according to certain volume ratio, filled
It is added after dividing mixing based on a certain proportion of lithium salts of lithium-ion battery electrolytes total weight, adds a certain amount of additive, fill
The lithium-ion battery electrolytes are made after dividing mixing.
10. a kind of lithium ion battery, which is characterized in that including negative electrode tab, described in any one of positive plate and claim 1-8
Lithium-ion battery electrolytes, the positive plate includes positive electrode active materials, conductive carbon and binder, the positive electrode active materials
For ternary material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006318761A (en) * | 2005-05-12 | 2006-11-24 | Sony Corp | Electrolyte and battery |
| JP2006318760A (en) * | 2005-05-12 | 2006-11-24 | Sony Corp | Electrolyte and battery |
| CN108598574A (en) * | 2018-04-16 | 2018-09-28 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
| CN108962627A (en) * | 2017-05-26 | 2018-12-07 | 北京师范大学 | A kind of supercapacitor or capacitor batteries of organic system |
-
2019
- 2019-06-05 CN CN201910486808.8A patent/CN110212244B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006318761A (en) * | 2005-05-12 | 2006-11-24 | Sony Corp | Electrolyte and battery |
| JP2006318760A (en) * | 2005-05-12 | 2006-11-24 | Sony Corp | Electrolyte and battery |
| CN108962627A (en) * | 2017-05-26 | 2018-12-07 | 北京师范大学 | A kind of supercapacitor or capacitor batteries of organic system |
| CN108598574A (en) * | 2018-04-16 | 2018-09-28 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
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