CN107240716A - A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery - Google Patents
A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery Download PDFInfo
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- CN107240716A CN107240716A CN201610182094.8A CN201610182094A CN107240716A CN 107240716 A CN107240716 A CN 107240716A CN 201610182094 A CN201610182094 A CN 201610182094A CN 107240716 A CN107240716 A CN 107240716A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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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- 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
- 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
Abstract
The invention provides a kind of electrolyte, including lithium salts, electrolyte solvent and additive, the additive is the boron nitrogen alkyl compound of structure shown in formula (1), wherein, R1, R3, R5 are H, and R2, R4, R6 are each independently selected from F, Cl, Br, CH3(CH2)n‑、CX3(CH2)n1‑、CX2H(CH2)n2‑、CHX2(CH2)n3, phenyl, the one or more in difluorophenyl；Or R2, R4, R6 are H, R1, R3, R5 are each independently selected from F, Cl, Br, CH3(CH2)n‑、CX3(CH2)n1‑、CX2H(CH2)n2‑、CHX2(CH2)n3, phenyl, the one or more in difluorophenyl；Wherein, one or more of the X in F, Cl, Br, I, 0≤n≤3,0≤n1≤3,0≤n2≤3,0≤n3≤3.Present invention also offers a kind of positive pole and preparation method thereof and a kind of lithium ion battery.In the electrolyte that the present invention is provided, by using the boron nitrogen alkyl compound of structure of the present invention as specific additive of the invention, positive pole can be protected to be not damaged by, be decomposed while also protection electrolyte solvent is not oxidized under high potential（Consume excessively）, the life-span of extension battery under high voltages.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly to a kind of electrolyte, positive pole and preparation method thereof and a kind of lithium
Ion battery.
Background technology
From 1990s so far, lithium rechargeable battery has reached rapid development from birth.In general, it is electrolysed
The lithium ion battery of liquid includes housing and the battery core being contained in housing, electrolyte, and battery core includes positive pole, negative pole and between positive pole
Barrier film between negative pole.In charging process, lithium ion is migrated to negative pole, and in discharge process from positive pole by electrolyte
It flows to opposite.In recent years, the secondary lithium battery of high-energy-density turns into object of concern, and therefore, people also note
Anticipate the new active materials that can be used to some as serondary lithium battery complete machine, such as describe new 5V high pressures in the prior art
Positive electrode, the raising of its operating voltage is directly integrally improved the use power of battery, has very big show in application aspect
Sincere justice.And at this stage, most of lithium battery electrolytes system stable under 4.2v and following voltage can only be used, when
When operating voltage reaches more than 4.2v, electrolyte system can occur oxidation Decomposition so that make battery can not normal work, to high pressure
The application of positive electrode forms great obstacle, cycle performance of battery reduction.
Also there is electrolyte solvent and easily occur side reaction with positive pole under high potential in above-mentioned electrolyte so that solvent is further
Oxidized decomposition causes the technical problem that electrolyte solvent is consumed excessively.
The content of the invention
The invention aims to solve electrolyte solvent in the prior art to be easily oxidized the skill decomposed under high potential
Art problem is there is provided a kind of electrolyte, including lithium salts, electrolyte solvent and additive, and the additive is structure shown in formula (1)
Boron nitrogen alkyl compound, its structure is as follows：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、
CX2H(CH2)n2-、CHX2(CH2)n3-, the one or more in phenyl, difluorophenyl；Or R2, R4, R6 are-H, R1, R3, R5 are each
From independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, phenyl, fluoro
One or more in phenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0
≤ n2≤3,0≤n3≤3.
The present invention provides a kind of positive pole, including plus plate current-collecting body, the positive electrode material layer positioned at plus plate current-collecting body surface, also wraps
Include the polymer film formed by additive generation polymerisation positioned at positive electrode layer surface；The additive is (1)
The boron nitrogen alkyl compound of shown structure：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、
CX2H(CH2)n2-、CHX2(CH2)n3-, the one or more in phenyl, difluorophenyl；Or R2, R4, R6 are-H, R1, R3, R5 are each
From independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, phenyl, fluoro
One or more in phenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0
≤ n2≤3,0≤n3≤3.
The invention also provides a kind of preparation method of positive pole, including：
(1) show to form positive electrode material layer in plus plate current-collecting body；
(2) electrolyte described in claim 1-9 any one is contacted with positive electrode layer surface, voltage during contact is
3.5V-4.2V。
Present invention further proposes the positive pole that a kind of preparation method by above-mentioned positive pole is prepared.
Present invention also offers a kind of lithium ion battery, including housing and the battery core, electrolyte, battery core being contained in housing
Barrier film including positive pole, negative pole and between positive pole and negative pole, the positive pole that just extremely the present invention is provided.
Boron nitrogen alkyl compound of the invention by adding structure of the present invention in the electrolytic solution, the boron azane of the structure
Polymerisation formation polymer film can occur on the surface of positive electrode material layer for class compound, therefore, it is possible to effectively block electrolyte
Occur side reaction in positive electrode surface, positive pole can be protected to be not damaged by, while protecting electrolyte solvent under high potential not by oxygen
Change and decompose, the life-span of extension battery under high voltages.
Inventor has found by many experiments, using the boron nitrogen alkyl compound of structure of the present invention as of the invention special
Electric polymerization reaction preferentially occurs under 3.5V-4.2V current potentials for fixed additive, such additives, and deposits to be formed in positive electrode surface
One layer of fine and close polymer film, the polymer film has certain flexibility, oxidative resistance, and stability, while can be by just
The active site on pole surface is covered, can effectively hinder electrolyte in follow-up charge and discharge process positive electrode surface generation oxidation
Decomposition reaction, protects electrolyte not consumed excessively, can also protect positive pole to be not damaged by, while also protection electrolyte solvent is in height
It is not oxidized under current potential to decompose, the life-span of battery under high voltages is improved with this.Compared with the additive of prior art, this hair
Bright specific additive, which can be realized, applies common electrolyte solvent in 4.5V high voltage environments, with significant effect,
Prominent contribution is made to this area.
The electrolyte that the present invention is provided is used in battery, in the charge and discharge process of battery, the additive in electrolyte
Under 3.5V-4.2V current potentials, occur electric polymerization reaction in positive electrode surface, form polymer film, following for battery can be greatly improved
Ring performance, meanwhile, additive of the present invention does not constitute influence to other functions of battery system.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below to this
Invention is further elaborated.
The invention provides a kind of electrolyte, including lithium salts, electrolyte solvent and additive, the additive is the present invention
The boron nitrogen alkyl compound of the structure.
In the electrolyte that the present invention is provided, the present invention is used as by using the boron nitrogen alkyl compound of herein described structure
Under 3.5V-4.2V current potentials electric polymerization reaction occurs for the additive of the electrolyte, the additive, in one layer of positive electrode surface formation
Fine and close polymer film, the oxidative decomposition for effectively having blocked electrolyte to occur in positive electrode surface can protect positive pole not
It is damaged, is decomposed while also protection electrolyte solvent is not oxidized under high potential, compared with common additives, the present invention adds
Plus agent has significant superiority.In the electrolyte solvent that the application is provided, additive described herein is added, identical
Application environment in, equally can positive electrode surface formation one layer of fine and close polymer film.
In the present invention, the boron nitrogen alkyl compound of the additive used structure shown in formula (1), with knot as follows
Structure：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、
CX2H(CH2)n2-、CHX2(CH2)n3-, the one or more in phenyl, difluorophenyl；Or R2, R4, R6 are-H, R1, R3, R5 are each
From independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, phenyl, fluoro
One or more in phenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0
≤ n2≤3,0≤n3≤3.Specific additive of the invention, which can be realized, applies common electrolyte in 4.5V high voltage environments
In.
It is preferred that, R1, R3, R5 are-H, and R2, R4, R6 are identical, and R2, R4, R6 are selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3
(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, one kind in phenyl, difluorophenyl；Wherein, the X is selected from F, Cl ,-Br, I
In one or more, 0≤n≤3,0≤n1≤3,0≤n2≤3,0≤n3≤3.
It is preferred that, R2, R4, R6 are-H, and R1, R3, R5 are identical, and R1, R3, R5 are selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3
(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, one kind in phenyl, difluorophenyl；Wherein, the X is selected from F, Cl ,-Br, I
In one or more, 0≤n≤3,0≤n1≤3,0≤n2≤3,0≤n3≤3.
It is preferred that, the additive can be selected from the alkane of ring boron nitrogen six, 1,3,5- trimethylborazines, 2,4,6- tri--chlorine rings
Boron azane, tri--fluorine of 2,4,6- borazine, tri--bromines of 2,4,6- borazine, the alkane of 2,4,6- triphen basic ring boron nitrogen six, 1,2- bis-
Chlorine borazine, 1,4- dichloros borazine, 1,3- dichloros borazine, 2,4- dichloros borazine, 1,2- dibromo ring boron nitrogen
One or more in alkane.Concrete structure is as follows：
It is preferred that, on the basis of electrolyte gross mass, the content of the additive is 0.1 ~ 10wt%, and further preferred content is 0.1
~3wt%.Additive can either positive electrode surface formation adequate thickness and enough coverages film layer, while there will not be it is unnecessary
Additive is impacted to system.
Under preferable case, in the electrolyte that provides of the present invention, on the basis of electrolyte gross mass, the content of lithium salts for 10 ~
20wt%, the concentration of lithium salts is 0.3~2mol/L.The lithium salts is the various lithium salts commonly used of those skilled in the art, for example can be with
Selected from LiPF6, LiClO4, LiBF4, LiAsF6, LiSiF6, LiAlCl4, LiBOB, LiODFB, LiCl, LiBr, Lii,
LiCF3SO3、Li(CF3SO2)3、Li(CF3CO2)2N、Li(CF3SO2)2N、Li(SO2C2F5)2N、Li(SO3CF3)2N、LiB
(C2O4) one or more in 2 are used in mixed way.Further preferred scheme, the present invention is used as main lithium salts using LiPF6.
The various electrolyte solvents that the present invention is commonly used using those skilled in the art, for example, 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
Alkene ester（DTD）, sulfuric acid propylene, ethylene sulfite（ES）, propylene sulfite（PS）, adiponitrile（ADN）, succinonitrile
（SN）, sulfurous acid diethyl ester（DES）, gamma-butyrolacton（BL）, one or more in dimethyl sulfoxide (DMSO) (DMSO).It is preferred that, carbonic acid
Vinyl acetate（EC）, propene carbonate（PC）, dimethyl carbonate（DMC）, diethyl carbonate（DEC）, methyl ethyl carbonate（EMC）In
One or more, on the basis of electrolyte gross mass, the content of the electrolyte solvent is 77 ~ 89.9wt%.Inventor is in research
In the prior art, under high voltage environment, there is electrolyte solvent and occur oxygen in positive pole in middle discovery carbonic ester system electrolyte solvent
Change reduction reaction, cause electrolyte solvent be oxidized under the high potential decompose, positive pole is damaged, reduce battery under high voltages
Life-span.And when carbonic ester system electrolyte solvent adds herein described additive assistance and applied, electrolyte solvent application can be made
In 4.5V high voltage environments, there is remarkable result compared with prior art, while electrolyte system is more stable, using wide
General, lithium salts degree of dissociation is high, and more preferably, additive oxidation polymerization process will not be influenceed additive solubility by electrolyte solvent
Advantage.
The present invention provides a kind of positive pole, and the positive pole includes plus plate current-collecting body, the positive pole material positioned at plus plate current-collecting body surface
The bed of material, in addition to positioned at the polymer film formed by additive generation electric polymerization reaction of positive electrode layer surface；It is described
Additive is the boron nitrogen alkyl compound of structure shown in (1)：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、
CX2H(CH2)n2-、CHX2(CH2)n3-, the one or more in phenyl, difluorophenyl；Or R2, R4, R6 are-H, R1, R3, R5 are each
From independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, phenyl, fluoro
One or more in phenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0
≤ n2≤3,0≤n3≤3.
The positive electrode layer surface has polymer film, and the composition of the polymer film is given birth to for additive of the present invention
Into polymer.
It is preferred that, polymer is that additive generation polymerisation is formed, for the poly- alkane of boron nitrogen six, poly- 1,3,5- front three basic ring boron nitrogen
Alkane, poly- tri--chlorine of 2,4,6- borazine, poly- tri--fluorine of 2,4,6- borazine, poly- tri--bromines of 2,4,6- borazine, poly- 2,4,6-
It is the alkane of triphen basic ring boron nitrogen six, poly- 1,2- dichloros borazine, poly- 1,4- dichloros borazine, poly- 1,3- dichloros borazine, poly-
The electric polymer of 2,4- dichloros borazine, one or more of materials in poly- 1,2- dibromos borazine.
The polymer film be above-mentioned electrolyte in additive under 3.5V-4.2V current potentials, positive electrode surface formation
Layer protecting film.
The present invention provides a kind of preparation method of positive pole, including：
(1) positive electrode material layer is formed on plus plate current-collecting body surface；
(2) electrolyte described in claim 1-9 any one is contacted with positive electrode layer surface, voltage during contact is
3.5V-4.2V。
The present invention provides a kind of positive pole, is prepared by above-mentioned method.
The preparation method of lithium-ion battery electrolytes is the common method of those skilled in the art, i.e., by each component（Including
Lithium salts, electrolyte solvent and additive）Well mixed, mode and the order present invention to mixing are not particularly limited.
Present invention also offers a kind of lithium ion battery, including housing and the battery core, electrolyte, battery core being contained in housing
Barrier film including positive pole, negative pole and between positive pole and negative pole, wherein, the electrolyte that the electrolyte provides for the present invention,
The described positive pole that just extremely the present invention is provided.Wherein positive pole includes plus plate current-collecting body and positive electrode, and positive electrode is included just
Pole active material, conductive agent, positive electrode binder, the conductive agent, positive electrode binder can be conduction commonly used in the art
Agent, positive electrode binder；Negative pole includes negative current collector and negative material, and negative material includes negative electrode active material, negative pole and glued
Tie agent, the being also an option that property of negative material include conductive agent, the conductive agent be conventional conductive agent, can be with positive electrode
Conductive agent in layer is identical or different, and the negative electrode binder can be negative electrode binder commonly used in the art.
Due to the preparation technology of negative plate, positive plate, barrier film technology well known in the art, and the assembling of battery is also
Technology known in the field, is just repeated no more herein.
According to lithium ion battery proposed by the present invention, it is preferable that the positive active material is high voltage tertiary cathode material,
The positive active material is LiNixCoyMnzO2, wherein, the ＜ Z ＜ 1 of 0 ＜ X ＜, 1,0 ＜ Y ＜ 1,0, X+Y+Z=1.It is further excellent
Elect LiNi as1/3Co1/3Mn1/3O2, it has the advantages that specific capacity is high, had extended cycle life, good rate capability, but due to material sheet
The reason for body, general electrolytic liquid easily occurs oxidation reaction and manganese element and nickel element in material is easily analysed under high voltages
Go out, the additive of herein described structure assists application, one layer of barrier electrolyte oxidation can be pre-formed on positive electrode surface
The positive pole protection film layer of positive electrode is reacted and corroded, the broader electrochemical window of electrolyte can be embodied, and additive
Film forming protective value, can more protrude lifting of the electrolysis additive of the present invention to electrolyte high voltage capability.
It is preferred that, the negative electrode active material is lithium or graphite cathode, but is not limited to this, more preferably metal
Lithium.
It is preferred that, additive is contained in the electrolyte, the additive is the boron azane class chemical combination of structure shown in formula (1)
Thing：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、
CX2H(CH2)n2-、CHX2(CH2)n3-, the one or more in phenyl, difluorophenyl；Or R2, R4, R6 are-H, R1, R3, R5 are each
From independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, phenyl, fluoro
One or more in phenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0
≤ n2≤3,0≤n3≤3.
Additive can be finally totally consumed in positive electrode surface formation polymer film in a kind of lithium ion battery, electrolyte,
It is also possible to the presence of part residual in the electrolytic solution.
The preparation of battery in the present invention, can be the electrolysis for providing the conventional positive pole in this area, negative pole and the application
Liquid, which is packaged, prepares battery, and the additive described herein added in electrolyte initial stage can in battery charging and discharging
Generation electric polymerization reaction, and deposit to form polymer film in positive electrode surface.
Can also be to prepare after positive electrode layer surface has the positive pole of polymer film in the present invention simultaneously, by this
Positive pole is used to prepare battery；Now the preparation method of positive pole is not particularly limited, as long as enabling to described herein
Additive occurs polymerisation and deposits to form polymer film in positive electrode surface, and reaction condition is：Temperature is 20 DEG C ~ 55
DEG C, voltage is 3.5V-4.2V.
Other constructions and specific preparation method of battery are known to the skilled person, and therefore not to repeat here.
Make further below in conjunction with lithium ion battery of the specific embodiment to the electrolyte of the present invention and containing the electrolyte
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 ethylene carbonate in argon gas glove box（EC）, diethyl carbonate（DEC）, 12% parts by weight lithium hexafluoro phosphate
(LiPF6) be dissolved in the electrolyte solvent of 100% parts by weight, then add the 1 of 0.1% parts by weight, 3,5- front three basic ring boron nitrogen
Alkane (the boron azane of structure, wherein R shown in the application formula (1)1、R3、R5It is-H, R2、R4、R6For-CH3, obtain the present embodiment
Lithium-ion battery electrolytes, are designated as C1；
（2）The preparation of lithium ion battery：
By positive active material（LiNi1/3Co1/3Mn1/3O2）, acetylene black, Kynoar by proportioning 90：5：After 5 is well mixed
Suppress on aluminium foil, obtain positive plate；It regard metal lithium sheet as negative plate；Using PE/PP composite diaphragms as amberplex, use
The electrolyte C1 of the present embodiment, button cell S1 is made using this area conventional method.
Embodiment 2
Electrolyte and button cell are prepared using step same as Example 1, difference is：Step uses 0.5% in (1)
Three-chlorine borazine of parts by weight replaces 1,3,5- trimethylborazines, prepare lithium-ion battery electrolytes C2 and
Button cell S2.
Embodiment 3
Electrolyte and button cell are prepared using step same as Example 1, difference is：1% weight is used in step (1)
The 3- fluorine borazines of amount part replace 1,3,5- trimethylborazines, prepare lithium-ion battery electrolytes C3 and button
Battery S3.
Embodiment 4
Electrolyte and button cell are prepared using step same as Example 1, difference is：3% weight is used in step (1)
Amount part 2,4,6- tribromo borazines replace 1,3,5- trimethylborazines, prepare lithium-ion battery electrolytes C4 with
And button cell S4.
Embodiment 5
Electrolyte and button cell are prepared using step same as Example 1, difference is：Step is additionally added in (1)
2,4,6- triphen basic ring boron nitrogen six alkane of 7% parts by weight replaces 1,3,5- trimethylborazines, prepares lithium ion battery
Electrolyte C5 and button cell S5.
Embodiment 6
Electrolyte and button cell are prepared using step same as Example 1, difference is：10% is added in step (1)
1,2- dichloro borazines replace 1,3,5- trimethylborazines, prepare lithium-ion battery electrolytes C6 and button
Battery S6.
Embodiment 7
Electrolyte and button cell are prepared using step same as Example 1, difference is：Added in step (1)
Isosorbide-5-Nitrae-dichloro borazine is 12% parts by weight (not this Applicant's Abstract graph content range, on the high side), prepares lithium-ion battery electrolytes
C7 and button cell S7.
Comparative example 1
Electrolyte and button cell are prepared using step same as Example 1, difference is：Step is not used in (1)
Boron azane class additive, prepares lithium-ion battery electrolytes DC1 and button cell DS1.
Performance test
Electrolyte oxidation decomposition electric potential is tested
Using three electrode test methods, platinized platinum is as working electrode, and lithium piece does reference electrode and electrode is tested, and sign adds
Plus agent electropolymerization current potential and electrolyte oxidation decomposition electric potential.Test result is as shown in table 1.
Table 1
(2) battery charging/discharging performance testing
By each experiment button cell S1-S7, DS1 at normal temperatures with 0.1mA electric current constant-current charge to 4.5V, with 4.5V constant voltages
Electric current as low as 0.005mA is charged to, then with 0.1mA constant-current discharges to 3.0V, the discharge capacity and charging capacity of battery is recorded,
Calculate efficiency for charge-discharge (%)=charging capacity/discharge capacity × 100%.Test result is as shown in table 2.
Table 2
（3）Circulating battery is tested
Above-mentioned battery is charged to 4.5V with 200mA constant current constant voltages at normal temperatures, charge cutoff electric current is 20mA, then with 200mA
Constant-current discharge calculates discharging efficiency to 3.0V, record initial charge capacity and discharge capacity（%）；Such repeated charge is followed
Ring 20, after 40,80,100 times, record the 20th, the discharge capacity of 40,80,100 circulations calculate capability retention (%) after circulation
Discharge capacity × 100% of discharge capacity/first that=circulation is 100 times；Blanking voltage is 4.5V).Test result is as shown in table 3.
Table 3
Additive polymerization current potential minimum 4.05V, up to 4.20V of the present invention it can be seen from table 1-3 results；Using this hair
Electrolyte oxidation decomposition electric potential up to 5.85V, minimum 5.10V that bright special additive is prepared；Using above-mentioned electrolysis
The test of lithium ion battery charge-discharge performance and loop test performance prepared by liquid is good, and battery can be under 4.5V high voltage just
Often application.
Claims (18)
1. a kind of electrolyte, including lithium salts, electrolyte solvent and additive, it is characterised in that the additive is shown in formula (1)
The boron nitrogen alkyl compound of structure, its structure is as follows：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、
CX2H(CH2)n2-、CHX2(CH2)n3-, the one or more in phenyl, difluorophenyl；Or R2, R4, R6 are-H, R1, R3, R5 are each
From independently selected from-F ,-Cl ,-Br, CH3(CH2)n-、CX3(CH2)n1-、CX2H(CH2)n2-、CHX2(CH2)n3-, phenyl, fluoro
One or more in phenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0
≤ n2≤3,0≤n3≤3.
2. electrolyte according to claim 1, it is characterised in that described R1, R3, R5 are-H, R2, R4, R6 are identical, and
R2, R4, R6 be selected from-F ,-Cl ,-Br, CH3 (CH2) n-, CX3 (CH2) n1-, CX2H (CH2) n2-, CHX2 (CH2) n3-, phenyl,
One kind in difluorophenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0≤
N2≤3,0≤n3≤3.
3. electrolyte according to claim 1, it is characterised in that described R2, R4, R6 are-H, R1, R3, R5 are identical, and
R1, R3, R5 be selected from-F ,-Cl ,-Br, CH3 (CH2) n-, CX3 (CH2) n1-, CX2H (CH2) n2-, CHX2 (CH2) n3-, phenyl,
One kind in difluorophenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤3,0≤n1≤3,0≤
N2≤3,0≤n3≤3.
4. electrolyte according to claim 1, it is characterised in that the additive is selected from the alkane of ring boron nitrogen six, 1,3,5- tri-
Methyl borazine, tri--chlorine of 2,4,6- borazine, tri--fluorine of 2,4,6- borazine, tri--bromines of 2,4,6- borazine, 2,4,
The alkane of 6- triphen basic ring boron nitrogen six, 1,2- dichloros borazine, 1,4- dichloros borazine, 1,3- dichloros borazine, 2,4- bis-
One or more in chlorine borazine, 1,2- dibromo borazines.
5. electrolyte according to claim 1, it is characterised in that on the basis of electrolyte gross mass, the additive
Content is 0.1 ~ 10wt%.
6. electrolyte according to claim 5, it is characterised in that on the basis of electrolyte gross mass, the additive
Content is 0.1 ~ 3wt%.
7. electrolyte according to claim 1, it is characterised in that the lithium salts be selected from LiPF6, LiClO4, LiBF4,
LiAsF6、LiSiF6、LiAlCl4、LiBOB、LiODFB、LiCl、LiBr、Lii、LiCF3SO3、Li(CF3SO2)3、Li
(CF3CO2) one or more in 2N, Li (CF3SO2) 2N, Li (SO2C2F5) 2N, Li (SO3CF3) 2N, LiB (C2O4) 2.
8. electrolyte according to claim 7, it is characterised in that on the basis of electrolyte gross mass, the lithium salts contains
Measure as 10 ~ 20wt%.
9. electrolyte according to claim 1, it is characterised in that the electrolyte solvent includes methyl ethyl carbonate（EMC）、
Dimethyl carbonate（DMC）, diethyl carbonate（DEC）, ethylene carbonate (EC), propene carbonate (PC), butylene (BC),
Ethylene sulfite（ES）, propylene sulfite（PS）, sulfurous acid diethyl ester（DES）, gamma-butyrolacton（BL）, dimethyl sulfoxide (DMSO)
(DMSO), the one or more in ethyl acetate, methyl acetate.
10. electrolyte according to claim 9, it is characterised in that on the basis of the gross mass of electrolyte, the electrolyte
The content of solvent is 77 ~ 89.9wt%.
11. a kind of positive pole, including plus plate current-collecting body, the positive electrode material layer positioned at plus plate current-collecting body surface, it is characterised in that also wrap
Include the polymer film formed by additive generation polymerisation positioned at positive electrode layer surface；The additive is (1)
The boron nitrogen alkyl compound of shown structure：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3 (CH2) n-, CX3 (CH2)
One or more in n1-, CX2H (CH2) n2-, CHX2 (CH2) n3-, phenyl, difluorophenyl；Or R2, R4, R6 be-H, R1,
R3, R5 are each independently selected from-F ,-Cl ,-Br, CH3 (CH2) n-, CX3 (CH2) n1-, CX2H (CH2) n2-, CHX2 (CH2)
One or more in n3-, phenyl, difluorophenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤
3,0≤n1≤3,0≤n2≤3,0≤n3≤3.
12. according to the positive pole described in claim 11, it is characterised in that the polymer of the polymer film is the poly- alkane of boron nitrogen six, gathered
1,3,5- trimethylborazines, poly- tri--chlorine of 2,4,6- borazine, poly- tri--fluorine of 2,4,6- borazine, poly- 2,4,6- tri--
It is bromine borazine, the poly- alkane of 2,4,6- triphens basic ring boron nitrogen six, poly- 1,2- dichloros borazine, poly- 1,4- dichloros borazine, poly-
One or more in 1,3- dichloros borazine, poly- 2,4- dichloros borazine, poly- 1,2- dibromos borazine.
13. a kind of preparation method of positive pole, including：
(1) positive electrode material layer is formed on plus plate current-collecting body surface；
(2) electrolyte described in claim 1-9 any one is contacted with positive electrode layer surface, voltage during contact is
3.5V-4.2V。
14. a kind of positive pole, it is characterised in that the positive pole is prepared as the method described in claim 13.
15. a kind of lithium ion battery, including housing and be contained in housing battery core, electrolyte, battery core include positive pole, negative pole and
Barrier film between positive pole and negative pole, it is characterised in that described just extremely claim 11-14 any one is provided just
Pole.
16. lithium ion battery according to claim 15, it is characterised in that the positive electrode material layer includes positive electrode active material
Matter, conductive agent, positive electrode binder, the positive active material are LiNixCoyMnzO2, wherein, the ＜ Y ＜ 1,0 of 0 ＜ X ＜ 1,0
＜ Z ＜ 1, X+Y+Z=1.
17. lithium ion battery according to claim 16, it is characterised in that the positive active material is LiNi1/
3Co1/3Mn1/3O2。
18. lithium ion battery according to claim 15, it is characterised in that contain additive in the electrolyte, described
Additive is the boron nitrogen alkyl compound of structure shown in formula (1)：
Wherein, R1, R3, R5 are-H, and R2, R4, R6 are each independently selected from-F ,-Cl ,-Br, CH3 (CH2) n-, CX3 (CH2)
One or more in n1-, CX2H (CH2) n2-, CHX2 (CH2) n3-, phenyl, difluorophenyl；Or R2, R4, R6 be-H, R1,
R3, R5 are each independently selected from-F ,-Cl ,-Br, CH3 (CH2) n-, CX3 (CH2) n1-, CX2H (CH2) n2-, CHX2 (CH2)
One or more in n3-, phenyl, difluorophenyl；Wherein, one or more of the X in F, Cl ,-Br, I, 0≤n≤
3,0≤n1≤3,0≤n2≤3,0≤n3≤3.
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| CN110676447A (en) * | 2019-09-29 | 2020-01-10 | 中国科学院化学研究所 | High-voltage workable composite anode and preparation method thereof |
| CN113956282A (en) * | 2021-10-18 | 2022-01-21 | 广州天赐高新材料股份有限公司 | Electrolyte additive, electrolyte and lithium secondary battery |
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