CN108666619A - A kind of electrolyte and the lithium ion battery containing the electrolyte and/or cathode - Google Patents
A kind of electrolyte and the lithium ion battery containing the electrolyte and/or cathode Download PDFInfo
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- CN108666619A CN108666619A CN201710197231.XA CN201710197231A CN108666619A CN 108666619 A CN108666619 A CN 108666619A CN 201710197231 A CN201710197231 A CN 201710197231A CN 108666619 A CN108666619 A CN 108666619A
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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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- 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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Abstract
The present invention provides a kind of electrolyte, including lithium salts, electrolyte solvent and additive, the additive is the alkenes compounds and its derivative of structure shown in the application.The present invention also provides the lithium ion batteries of a kind of cathode and the use electrolyte.In electrolyte provided by the invention, by using the alkenes compounds and its derivative of structure of the present invention as the specific additive of the present invention, cathode can be protected not to be damaged, while electrolyte solvent also being protected not to be reduced decomposition（It consumes excessively）, extend service life of the battery under high voltage and high/low temperature.
Description
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of electrolyte and containing the electrolyte and/or cathode
A kind of lithium ion battery.
Background technology
So far from the 1990s, lithium rechargeable battery has reached rapid development from birth.In general, it is electrolysed
The lithium ion battery of liquid includes shell and the battery core being contained in housing, electrolyte, and battery core is including anode, cathode and between anode
Diaphragm between cathode.The cyclicity of silicium cathode lithium battery is still unsatisfactory at present, can be effectively improved from electrolyte angle
The circulative method of silicium cathode lithium battery is that suitable film for additive is added in the electrolytic solution preferentially to be formed on silicium cathode surface
Stable SEI films.Document and the electrolysis additive that research or report are used for silicium cathode lithium battery in the industry include carbonic acid Asia at present
Vinyl acetate（VC）, fluorinated ethylene carbonate（FEC）, succinic anhydride（SA）, three pentafluorophenyl boranes（TPFPB）, some siloxanes
Compound.In addition to this, patent CN201110078105 reports a kind of pyrocarbonate and can effectively be carried as electrolysis additive
The charge-discharge performance of high silicon cathode lithium ion battery reduces the generation of side reaction, to reduce battery flatulence；Patent
CN201310628294 reports a kind of organosilicon isocyanide acid compound containing polyether chain and can effectively subtract as electrolysis additive
Few battery flatulence, improves the cycle life of battery；Patent CN201410487258 reports sulfite compounds as electrolysis
Solution additive can more effectively improve the charge-discharge performance of silicon cathode lithium ion battery, reduce the generation of side reaction, improve battery
Room temperature and high-temperature behavior are all；Patent CN201510174879 reports triethoxy methyl trimethoxy oxygroup silicon isocyanic acid, ethyoxyl
Change sodium alkyl sulfate, biphenyl, cyclohexyl benzene, fatty alcohol polyoxyethylene ether, tert-amyl benzene and adiponitrile as electrolysis additive
Silicium cathode cycle performance of battery can be improved.
The above additive in the prior art is although SEI films can be formed on silicium cathode surface, due to silica-base material
It will produce violent volume change during removal lithium embedded so that the SEI films formed before in material surface can rupture and newly
Increase interface to accelerate electrolyte to consume, above-mentioned electrolysis additive can delay silicium cathode battery capacity to decay, but cannot
Fundamentally solve the problems, such as that silicium cathode lithium battery long circulating performance is bad.
Invention content
The purpose of the present invention is to solve technical problems at least one in the prior art, provide a kind of electrolyte,
Including lithium salts, electrolyte solvent and additive, the additive is the alkenes compounds and its derivative of structure shown in formula (1)
Object, structure are as follows：
Formula (1)；
Wherein, R1, R2, R3, R4, R5, R6 are identical or different, separately one kind in-F ,-Cl ,-Br ,-I.
A kind of cathode, the cathode include negative current collector, the negative electrode material layer positioned at negative current collector surface, described negative
The surface of pole material layer has polymer film, and the ingredient of the polymer film includes the polymer of herein described additive.
The present invention also provides a kind of lithium ion battery, including shell and be contained in housing battery core, electrolyte, battery core
It is electrolyte provided by the invention and/or institute including anode, cathode and the diaphragm between positive electrode and negative electrode, the electrolyte
State cathode cathode extremely provided by the invention.
The present invention by adding the alkenes compounds and its derivative of structure of the present invention, Ke Yibao in the electrolytic solution
Shield cathode is not damaged, and can effectively be hindered electrolyte that redox reaction occurs in negative terminal surface, be hindered disappearing for electrolyte
Consumption.The charge-discharge performance that negative pole lithium battery can thus be effectively improved reduces the generation of side reaction, reduces battery flatulence, improves
The room temperature and high-temperature behavior of battery.
Inventor is by many experiments discovery, the alkenes compounds using structure of the present invention and its derivative conduct
The specific additive of the present invention, reduction decomposition current potential are 1.2V-1.4V, higher than the reduction electricity of carbonates electrolyte solvent
Position preferentially can form layer protecting film in negative terminal surface, prevent the further reduction decomposition of electrolyte.And this tunic is polymerization
Object film has certain elasticity, insulating properties, oxidative resistance and stability, it is ensured that volume of cathode during removal lithium embedded becomes
Change without rupturing；And effectively hinder electrolyte that redox reaction occurs in cathode, protect electrolyte not consumed excessively, with this
The charge-discharge performance for improving negative pole lithium battery reduces the generation of side reaction, reduces battery flatulence, improves the room temperature and high temperature of battery
Performance.
Electrolyte provided by the invention is used in battery, in the charge and discharge process of battery, the additive in electrolyte
Under 1.2V-1.4V current potentials, polymerisation occurs on the surface of cathode, for the first time completely, therefore reaction additives can be consumed all
The function of battery system is not influenced.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below to this
Invention is further elaborated.
The present invention provides a kind of electrolyte, including lithium salts, electrolyte solvent and additive, the additive includes this hair
The alkenes compounds and its derivative of the bright structure.
In electrolyte provided by the invention, make by using the alkenes compounds and its derivative of herein described structure
Reduction potential for the additive of electrolyte of the present invention, the additive is 1.2V-1.4V, molten higher than carbonates electrolyte
Agent preferentially can occur polymerisation in negative terminal surface by carbonates electrolyte solvent, generate one layer of polymeric film, avoid conduct
The carbonates substance of lithium salts solvent continues largely to be reduced decomposition and seriously reduce battery performance.Specifically, the polymer film
The frame structure of formation substantially increases the elastic property of polymer film so that the polymer film of negative terminal surface is in removal lithium embedded
It will not be ruptured in the process because of volume change, cathode is protected not to be damaged；Meanwhile the lithium halide generated in film formation reaction can be with
Filling in the frame, effectively improves insulating properties of the polymer film to electronics, prevents electrolyte from obtaining electronics from cathode, makes electrolyte
It can not be reduced, the side reaction of negative terminal surface may finally be efficiently controlled, hinder the consumption of electrolyte.Thus can effectively it carry
The charge-discharge performance of high negative pole lithium battery, reduces the generation of side reaction, reduces battery flatulence, improves the room temperature of battery and high temperatures
Energy.
In the present invention, used additive is the alkenes compounds and its derivative of structure shown in formula (1), under having
Structure shown in formula (1)：
Formula (1)
Wherein, R1, R2, R3, R4, R5, R6 are identical or different, separately one kind in-F ,-Cl ,-Br ,-I.This hair
The additive of bright specific structure has LUMO tracks more lower than carbonates electrolyte solvent（LUMO is the energy for not occupying electronics
The minimum track of grade）Energy, thus have higher reduction potential, can preferentially carbonates electrolyte solvent it pass through in negative terminal surface
Electrochemical reduction polymerization generates one layer of polymeric film, and first, herein described additive does not generate any gas in film forming procedure
Body reduces aerogenesis in battery forming process；Secondly, this layer contains a large amount of polyolefin compounds and/or halogenated polyolefin compound
Polymer film have elastic property outstanding, can avoid cathode during removal lithium embedded, the polymer film is due to volume change
Rupture；Finally, the lithium halide generated during film formation reaction can be filled in the gap of the frame of polymer film formation, be had
Effect improves polymer film to the insulating properties of electronics, may finally efficiently control the side reaction of negative terminal surface, slow down electricity significantly
Solve the depletion rate of liquid.The charge-discharge performance that negative pole lithium battery can thus be effectively improved reduces the generation of side reaction, reduces electricity
Pond flatulence improves the room temperature and high-temperature behavior of battery.
It is preferred that the additive can be in perfluorobutadiene, hexachlorobutadiene, five fluoro- 1,3-butadiene of 2- chloros
One or more.Concrete structure is as follows：
Perfluorobutadiene:
It is preferred that butadiene structure determines the higher reduction potential of additive, it is halogenated be in order to promote the inoxidizability of additive,
More easily scission of link polymerize simultaneously.
It is preferred that on the basis of electrolyte gross mass, the content of the additive is 0.1 ~ 10wt%, further preferably 0.2
~5wt%.Content is preferably 0.6 ~ 1.2wt%, and additive can either form the film of adequate thickness and enough coverages in negative terminal surface
Layer, while there will not be extra additive and system is impacted.
Under preferable case, in electrolyte provided by the invention, a concentration of 0.1 ~ 1.2mol/L of lithium salts.The lithium salts is this
The common various lithium salts of field technology personnel, such as LiPF can be selected from6、LiClO4、LiBF4、LiAsF6、LiSiF6、
LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、Lil、LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、Li(SO2C2F5)2N、Li(SO3CF3)2N、LiB(C2O4)2In one or more be used in mixed way.Further preferred scheme,
The present invention uses LiPF6As main lithium salts.
The present invention uses those skilled in the art's commonly various electrolyte solvents, such as can be selected from ethylene carbonate
Ester（EC）, propene carbonate（PC）, dimethyl carbonate（DMC）, diethyl carbonate（DEC）, methyl ethyl carbonate（EMC）, formic acid first
Ester（MF）, methyl acetate（MA）, methyl propionate（MP）, ethyl acetate（EP）, 1,3- propane sultones（1,3-PS）, sulfuric acid second
Enester（DTD）, sulfuric acid acrylic ester, ethylene sulfite（ES）, propylene sulfite（PS）, adiponitrile（ADN）, succinonitrile
（SN）, sulfurous acid diethyl ester（DES）, gamma-butyrolacton（BL）, dimethyl sulfoxide (DMSO) (DMSO), fluorinated ethylene carbonate（FEC）In
It is one or more of.It is preferred that ethylene carbonate（EC）, propene carbonate（PC）, dimethyl carbonate（DMC）, diethyl carbonate
（DEC）, methyl ethyl carbonate（EMC）, fluorinated ethylene carbonate（FEC）One or more of, inventor has found carbon under study for action
In the prior art, there are electrolyte solvents to occur continued reduction reaction to esters of gallic acid electrolyte solvent in cathode, leads to electrolyte
It is consumed, cathode is damaged, service life for reducing battery at ambient and elevated temperatures.And add this Shen in carbonates electrolyte solvent
Please the additive, electrolyte solvent can effectively be prevented by so that additive is preferentially formed the firm electrolyte interface film of elasticity in cathode
Ground last decomposition reduces active lithium in battery and consumes, reduce irreversible capacity loss, there is significantly effect compared with prior art
Fruit, while electrolyte system is more stable, is widely used, lithium salts degree of dissociation is high, and additive solubility is more preferable, additive reductive polymerization
The advantages that process will not be influenced by electrolyte solvent.
It is preferred that on the basis of electrolyte gross mass, the content of the fluorinated ethylene carbonate is 1~5wt%；The carbonic acid
Vinyl acetate and the volume ratio of dimethyl carbonate are 1:1 ~ 5, further preferably, the volume of the ethylene carbonate and dimethyl carbonate
Than being 1:2~4.Dielectric constant and ionic conductivity are relatively high so that the effect higher of electrolyte.
Additive also can be directly used for cathode, and the present invention provides a kind of cathode, and the cathode includes negative current collector, is located at
The negative electrode material layer on negative current collector surface, the negative material layer surface have polymer film, the ingredient of the polymer film
Include the polymer of additive of the present invention.
It is preferred that polymer film forms frame structure, filler, the ingredient of the filler are contained in the frame structure
Lithium halide in the lithium halide and electrolyte that are generated in film formation reaction including additive of the present invention, is concretely fluorinated
Lithium.Lithium halide can fill the insulating properties for effectively improving polymer film in the frame to electronics, and electrolyte cannot be obtained from cathode
Electronics also can not be just reduced, and may finally efficiently control the side reaction of negative terminal surface, prevented electrolyte from consuming and subtracted significantly
The depletion rate of electrolyte is delayed.
A large amount of additives aggregate into polymer film by electrochemical reduction in the application, which is formed with porous frame knot
On the one hand structure substantially increases the elastic property of polymer film so that cathode will not be because of volume change during removal lithium embedded
It acutely ruptures, cathode is protected not to be damaged；On the other hand, the lithium halide that will be generated in film formation reaction, is filled in polymer film
In the gap of frame, lithium halide is non-conductive to effectively improve insulating properties of the polymer film to electronics, may finally efficiently control
The side reaction of negative terminal surface hinders the consumption of electrolyte.The charge-discharge performance that negative pole lithium battery can thus be effectively improved, subtracts
The generation of few side reaction, reduces battery flatulence, improves the room temperature and high-temperature behavior of battery.
It is preferred that polymer is one in poly- perfluorobutadiene, poly- hexachlorobutadiene, five fluoro- 1,3-butadiene of poly- 2- chloros
Kind is several.Polyalkenyl halides compound in film forming product substantially increases the elastic property of polymer film so that cathode exists
It will not be ruptured because volume change is violent during removal lithium embedded, cathode is protected not to be damaged.
The polymer film be above-mentioned electrolyte in additive under 1.2V-1.4V current potentials, negative terminal surface formed
Layer protecting film.
The preparation method of lithium-ion battery electrolytes provided by the invention is the common method of those skilled in the art, i.e.,
By each component（Including lithium salts, electrolyte solvent and additive）It is uniformly mixed, it is equal to mixed mode and the sequence present invention
It is not particularly limited.
The electrolysis additive of the present invention can also contain other substances, such as other kinds of functional additive, this hair
It is bright that there is no limit.
The present invention also provides a kind of lithium ion battery, including shell and be contained in housing battery core, electrolyte, battery core
Including anode, cathode and the diaphragm between positive electrode and negative electrode, wherein the electrolyte is electrolyte provided by the invention
And/or the cathode is cathode provided by the invention.Wherein cathode includes negative current collector and negative material, negative material packet
Negative electrode active material, conductive agent, negative electrode binder are included, the conductive agent, negative electrode binder can be commonly used in the art
Conductive agent, negative electrode binder；Anode includes plus plate current-collecting body and positive electrode, and positive electrode includes positive active material, just
Pole binder, the being also an option that property of positive electrode includes conductive agent, which is conventional conductive agent, can be with cathode
Conductive agent in material layer is identical or different, and the positive electrode binder can be positive electrode binder commonly used in the art.
Due to the preparation process of negative plate, positive plate, diaphragm technology well known in the art, and the assembling of battery is also
Technology known in the field, details are not described herein again.
According to lithium ion battery proposed by the present invention, it is preferable that the positive active material is Li (Ni0.5Mn0.3Co0.2)O2,
It assists to apply, can embody electrolysis with high gram volume and high charging platform with the additive of herein described structure
The broader electrochemical window of liquid, stronger oxidation resistent susceptibility can more protrude electrolysis additive of the present invention to high-energy density
The promotion of silicium cathode lithium battery cycle performance.
It is preferred that the negative electrode active material is Si-C composite material, there is clad structure（Full cladding or non-full cladding）, example
Such as：Carbon coating silicon materials, silicon cladding carbon material etc..It is preferred that the carbon coating silicon materials with nucleocapsid, but not limited to this.
Make below in conjunction with lithium ion battery of the specific embodiment to the electrolyte of the present invention and containing the electrolyte further
Explanation.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.It is real
Raw material employed in example and comparative example is applied to be commercially available.
Embodiment 1
（1）The preparation of electrolyte：
By 20mL ethylene carbonates in argon gas glove box（EC）With 80mL dimethyl carbonates（DMC）It is mixed into mixed solvent, to
15.2g lithium hexafluoro phosphates are added in the mixed solvent（LiPF6）So that lithium salt 1mol/L.Then 3.8g is added thereto
Perfluorobutadiene so that the content of additive be the electrolyte gross mass 3 wt %.Obtain the lithium of the present embodiment from
Sub- battery electrolyte, is denoted as C1；
（2）The preparation of lithium ion battery：
By 100 parts of carbon coating silicon materials, 1 part of conductive agent super-p, 1.5 parts of thickener sodium carboxymethylcellulose（CMC）
Polyacrylate binder with 2.5 parts is mixed into uniform paste, is coated uniformly on the copper foil as negative current collector,
Drying obtains pole piece for 24 hours under 80 DEG C of vacuum.Anode uses ternary material Li (Ni0.5Mn0.3Co0.2)O2I.e.（NMC532）, will
100 parts of NMC532 and 2 part of carbon nanotube（CNT）And 2 parts of Kynoar（PVDF）It is mixed into uniform paste
Object is coated uniformly on the aluminium foil as plus plate current-collecting body, dry under 80 DEG C of vacuum to obtain pole piece for 24 hours.It is prepared by soft-package battery
Battery core is made to wind, prepares the silicium cathode soft package lithium battery of model SL562736, is less than the argon gas hand of 5ppm in water content
In casing, loop test battery S1 will be prepared in soft-package battery of the 2.0g electrolyte C1 injections with air bag.Button cell S11's
It is prepared as coating obtained negative plate to lithium piece, the button cell of model CR2016, reservoir quantity is about 0.1g, for testing electricity
Solve the reduction potential of liquid.
Chemical synthesis technology：Simulated battery is first with 35mA（0.05C）Electric current is charged to 1.9V, and keeps 10h in 1.9V, so that electric
Pond electrode slice fully soaks.After the completion of constant pressure, battery is initially with a smaller current 7mA（C/100）Charge 10h, to be formed
Stablize fine and close SEI films, then with 35mA（0.05C）Electric current is charged to 4.35V, after discharge into 3.0V.
Embodiment 2
Electrolyte test is prepared using step same as Example 1, the difference is that：With the chlordene of 5wt% in step (1)
Butadiene replaces perfluorobutadiene；In the mixed solvent ethylene carbonate（EC）For 20mL and dimethyl carbonate（DMC）For 100mL；
Prepared by soft-package battery and chemical synthesis technology is with embodiment 1, and lithium-ion battery electrolytes C2 and the electricity of test loop is prepared
Pond S2.The preparation of button cell tests the battery S21 of the reduction potential of electrolyte with embodiment 1.
Embodiment 3
Electrolyte test is prepared using step same as Example 1, the difference is that：With the 2- chlorine of 7wt% in step (1)
In generation, five fluoro- 1,3- butadiene replaced perfluorobutadiene；In the mixed solvent ethylene carbonate（EC）For 20mL and dimethyl carbonate
（DMC）For 60mL；Prepared by soft-package battery and chemical synthesis technology is with embodiment 1, and lithium-ion battery electrolytes C3 and survey is prepared
Try circulative battery S3.The preparation of button cell tests the battery S31 of the reduction potential of electrolyte with embodiment 1.
Embodiment 4
Electrolyte is prepared using step same as Example 1, the difference is that：The content of perfluorobutadiene in step (1)
For 10 wt %；In the mixed solvent ethylene carbonate（EC）For 20mL and dimethyl carbonate（DMC）For 40mL；Battery prepares and changes
At technique with embodiment 1, prepared by soft-package battery and chemical synthesis technology is with embodiment 1, be prepared lithium-ion battery electrolytes C4 with
And the battery S4 of test loop.The preparation of button cell tests the battery S41 of the reduction potential of electrolyte with embodiment 1.
Embodiment 5
Electrolyte test is prepared using step same as Example 1, the difference is that：Additive is 2- chlorine in step (1)
Five fluoro- 1,3-butadienes of generation, content are 1 wt %；In the mixed solvent ethylene carbonate（EC）For 20mL and dimethyl carbonate
（DMC）For 20mL；Prepared by soft-package battery and chemical synthesis technology is with embodiment 1, and prepared by battery and chemical synthesis technology is with embodiment 1, prepares
Obtain the lithium-ion battery electrolytes C5 and battery S5 of test loop.The preparation of button cell is the same as embodiment 1, test electrolysis
The battery S51 of the reduction potential of liquid.
Embodiment 6
Electrolyte test is prepared using step same as Example 5, the difference is that：Additive is 2- chlorine in step (1)
Five fluoro- 1,3-butadienes of generation, content are 12 wt %；Prepared by soft-package battery and chemical synthesis technology is with embodiment 1, battery prepare and
The lithium-ion battery electrolytes C6 and battery S6 of test loop is prepared with embodiment 1 in chemical synthesis technology.Button cell
It prepares with embodiment 1, tests the battery S61 of the reduction potential of electrolyte.
Comparative example 1
Electrolyte test is prepared using step same as Example 1, the difference is that：Additive is not contained in step (1),
Prepared by soft-package battery and chemical synthesis technology is with embodiment 1, and lithium-ion battery electrolytes DC1 and the electricity of test loop is prepared
Pond DS1.The preparation of button cell tests the battery DS11 of the reduction potential of electrolyte with embodiment 1.
Comparative example 2
Electrolyte test is prepared using step same as Example 1, the difference is that：Additive is 3.8g in step (1)
（3wt%）Vinylene carbonate（VC）, prepared by soft-package battery and chemical synthesis technology is with embodiment 1, and lithium ion battery electrolysis is prepared
The battery DS2 of liquid DC2 and test loop.The preparation of button cell tests the electricity of the reduction potential of electrolyte with embodiment 1
Pond DS21.
Performance test
（1）Electrolyte reduction potential decomposition electric potential is tested
By the obtained silicon-carbon cathode of coating be made to the CR2016 button cells of lithium piece be used to test additive in electrolyte or
The reduction potential of solvent injects electrolyte and seals.By conventional cyclic voltammetry, within the scope of 0 ~ 3V, with the speed of 0.1mV/s
It spends and cyclic voltammetry scan is carried out to lithium piece button cell to the silicium cathode of preparation, test result is shown in Table 1.
Table 1
(2) cycle performance of battery is tested
Air bag after Battery formation is subtracted into simultaneously vacuum-pumping and sealing, by each experiment test battery S1-S6, DS1-DS3（Each condition
20, as a result take its average value）With 1C between 3.0V to 4.35V（700mA）It is recycled in 25 DEG C and 60 DEG C of insulating boxs respectively
300 times.The test capacity conservation rate（%）Computational methods are the discharge capacity that will be recycled at the 300th time divided by recycle for the first time
The obtained percentage of initial discharge capacity, experimental results are shown in Table 2.
（3）Circulating battery flatulence volume is tested
Flatulence volume test method is to hang over battery on balance, and balance can measure the variation of battery buoyancy in real time, record each electricity
The pond buoyancy variation front and back in cycle, then according to Archimedes's drainage principle, battery producing gas volume, battery producing gas body can be calculated
Accumulating calculation formula is：V=△ m/ ρ, wherein V are battery flatulence volume, and △ m are that buoyancy change suffered by battery is converted into changing for quality
Become, can directly be read by balance registration, ρ is silicone oil density, and circulating battery flatulence experimental result is shown in Table 2.
Table 2
Additive of the present invention polymerization reduction potential is higher than vinylene carbonate it can be seen from 2 result of table 1- tables, can preferential electricity
The carbonate-based solvent solved in liquid forms a film in negative terminal surface.Additive of the present invention（Embodiment 1 ~ 6）It can carry when in use
The room temperature and high temperature cyclic performance 15% ~ 35% of negative pole lithium battery are risen, there is significant effect；Battery is reduced in cyclic process simultaneously
In flatulence, effectively extend battery service life, film for additive more common than our industries is more suitable for silicium cathode lithium battery.
（4）SEI film flexibility tests
After the completion of cycle, battery is dismantled, it is 1 × 1cm to cut cathode size2Small pieces, the elasticity of SEI films can be aobvious with atomic force
Micro mirror（AFM, Bruker Dimension Icon）Sonde method measures its Young's modulus, and SEI film elasticity is levied by Young film scale
Size.Young's modulus computational methodsF=(2/π)(E/(1-v 2))δ 2tan(σ), whereinFFor probe stress,EFor Young's modulus,vFor
Poisson coefficients,δFor SEI film thicknesses,σFor cone apex angle half.Test result is shown in Table 3.
Table 3
Table 3 is the result shows that the polyhalo additive containing the present invention（Embodiment 1 ~ 6）In the SEI film Young moulds that silicium cathode surface is formed
AmountE<10GPa, the SEI films formed than general electrolyte（Comparative example 1 ~ 2）Young's modulus wants small, illustrates SEI films elasticity very well,
Volume change of cathode during removal lithium embedded is adapted to, which does not rupture, and on the one hand cathode can be protected not to be destroyed；Another party
Face can prevent the side reaction of electrolyte, reduce the consumption of electrolyte, effectively extend the service life of battery.
Claims (12)
1. a kind of electrolyte, including lithium salts, electrolyte solvent and additive, which is characterized in that the additive is shown in formula (1)
The structure of the alkenes compounds and its derivative of structure, formula (1) is as follows：
Formula (1)；
Wherein, R1, R2, R3, R4, R5, R6 are identical or different, separately one kind in-F ,-Cl ,-Br ,-I.
2. electrolyte according to claim 1, which is characterized in that the additive is selected from perfluorobutadiene, chlordene fourth two
One or more of alkene, five fluoro- 1,3- butadiene of 2- chloros.
3. electrolyte according to claim 1, which is characterized in that on the basis of electrolyte gross mass, the additive
Content is 0.1 ~ 10wt%.
4. electrolyte according to claim 1, which is characterized in that the lithium salts is selected from LiPF6、LiClO4、LiBF4、
LiAsF6、LiSiF6、LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、Lil、LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、Li(SO2C2F5)2N、Li(SO3CF3)2N、LiB(C2O4)2In it is one or more.
5. electrolyte according to claim 1, which is characterized in that the electrolyte solvent is carbonate-based solvent, described
Carbonate-based solvent includes ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, fluoro carbon
One or more of vinyl acetate.
6. electrolyte according to claim 5, which is characterized in that on the basis of electrolyte gross mass, the fluoro carbonic acid
The content of vinyl acetate is 1~5wt%；The volume ratio of the ethylene carbonate and dimethyl carbonate is 1:1~5.
7. a kind of cathode, which is characterized in that the cathode includes negative current collector, the negative material positioned at negative current collector surface
The surface of layer, the negative electrode material layer has polymer film, and the ingredient of the polymer film includes additive described in claim 1
Polymer.
8. according to the cathode described in claim 7, which is characterized in that the polymer be poly- perfluorobutadiene, poly- hexachlorobutadiene,
One or more of five fluoro- 1,3- butadiene of poly- 2- chloros.
9. according to the cathode described in claim 7, which is characterized in that containing ingredient include also lithium halide in the polymer film.
10. according to the cathode described in claim 7, which is characterized in that the polymer film is claim 1-6 any one of them
Additive in electrolyte is under 1.2V-1.4V current potentials, in the layer protecting film that negative terminal surface is formed.
11. a kind of lithium ion battery, including shell and be contained in housing battery core, electrolyte, battery core include anode, cathode and
Diaphragm between positive electrode and negative electrode, which is characterized in that the electrolyte is claim 1-6 any one of them electrolyte
And/or the cathode is the cathode described in claim 8-10.
12. lithium ion battery according to claim 11, which is characterized in that the cathode includes negative current collector and cathode
Material, the negative material include negative electrode active material, conductive agent, negative electrode binder, and the negative electrode active material is multiple for silicon-carbon
Condensation material.
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| CN201710197231.XA CN108666619A (en) | 2017-03-29 | 2017-03-29 | A kind of electrolyte and the lithium ion battery containing the electrolyte and/or cathode |
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| CN201710197231.XA CN108666619A (en) | 2017-03-29 | 2017-03-29 | A kind of electrolyte and the lithium ion battery containing the electrolyte and/or cathode |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116659A (en) * | 2018-10-31 | 2020-05-08 | 张家港市国泰华荣化工新材料有限公司 | Compound, electrolyte and lithium ion battery |
| CN112467221A (en) * | 2020-12-02 | 2021-03-09 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
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| JPH04179049A (en) * | 1990-11-09 | 1992-06-25 | Ricoh Co Ltd | Negative electrode for battery |
| JP2009123498A (en) * | 2007-11-14 | 2009-06-04 | Sony Corp | Nonaqueous electrolyte composition and nonaqueous electrolyte battery |
| CN105845984A (en) * | 2016-06-23 | 2016-08-10 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte and lithium ion battery using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04179049A (en) * | 1990-11-09 | 1992-06-25 | Ricoh Co Ltd | Negative electrode for battery |
| JP2009123498A (en) * | 2007-11-14 | 2009-06-04 | Sony Corp | Nonaqueous electrolyte composition and nonaqueous electrolyte battery |
| CN105845984A (en) * | 2016-06-23 | 2016-08-10 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte and lithium ion battery using same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116659A (en) * | 2018-10-31 | 2020-05-08 | 张家港市国泰华荣化工新材料有限公司 | Compound, electrolyte and lithium ion battery |
| CN112467221A (en) * | 2020-12-02 | 2021-03-09 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
| CN112467221B (en) * | 2020-12-02 | 2022-02-11 | 珠海市赛纬电子材料股份有限公司 | Additive for inhibiting silicon negative electrode expansion and electrolyte containing additive |
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Application publication date: 20181016 |