CN107331892A - 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
- Publication number
- CN107331892A CN107331892A CN201610278018.7A CN201610278018A CN107331892A CN 107331892 A CN107331892 A CN 107331892A CN 201610278018 A CN201610278018 A CN 201610278018A CN 107331892 A CN107331892 A CN 107331892A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- ester
- boric acid
- additive
- frequency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery, the electrolyte includes lithium salts, electrolyte solvent and additive, the additive be the boric acid that provides of the application frequently where ester type compound；In the electrolyte that the present invention is provided, by using boric acid frequency any ester type 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)
Boric acid frequency any ester type compound, its structure is as follows：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
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 boric acid frequency of shown structure is which ester type compound：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
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-4.5V。
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.
The present invention by adding the boric acid frequency of structure of the present invention which ester type compound, the boron of the structure in the electrolytic solution
Polymerisation formation polymer film can occur on the surface of positive electrode material layer for sour which ester type compound of frequency, therefore, it is possible to effectively resistance
In positive electrode surface side reaction occurs for disconnected electrolyte, positive pole can be protected to be not damaged by, while protecting electrolyte solvent in high potential
Under it is not oxidized decompose, extension battery life-span under high voltages.
Inventor has found which ester type compound is used as this hair using the boric acid frequency of structure of the present invention by many experiments
Electric polymerization reaction preferentially occurs under 3.5V-4.5V current potentials for bright specific additive, such additives, and in positive electrode surface deposition
One layer of fine and close polymer film is formed, the polymer film has certain flexibility, oxidative resistance, and stability, while can
The active site of positive electrode surface covered, generation of the electrolyte in positive electrode surface in follow-up charge and discharge process can be effectively hindered
Oxidative decomposition, protects electrolyte not consumed excessively, can also protect positive pole to be not damaged by, while also protecting electrolyte solvent
It is not oxidized under high potential to decompose, the life-span of battery under high voltages is improved with this.Compared with the additive of prior art,
Specific additive of the invention, which can be realized, applies common electrolyte solvent in 4.5V high voltage environments, with significant effect
Really, 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-4.5V 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 boric acid frequency of the structure is which ester type compound.
In the electrolyte that the present invention is provided, by using the boric acid frequency of herein described structure, which ester type compound is used as this
The additive of the electrolyte is invented, under 3.5V-4.5V current potentials electric polymerization reaction occurs for the additive, is formed in positive electrode surface
One layer of fine and close polymer film, the oxidative decomposition for effectively having blocked electrolyte to occur in positive electrode surface can be protected just
Pole is not damaged by, and is decomposed while also protection electrolyte solvent is not oxidized under high potential, compared with common additives, this hair
Bright additive has significant superiority.In the electrolyte solvent that the application is provided, additive described herein is added,
, equally can be in positive electrode surface one layer of fine and close polymer film of formation in identical application environment.
In the present invention, the boric acid frequency of the additive used structure shown in formula (1) is which ester type compound, with following institute
Show structure：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
It is preferred that, alkyl is selected from CH3(CH2)n-、(CH3)2CH(CH2)n1-、(CH3)3C (CH2)n2- in one kind, wherein 0≤
N≤3,0≤n1≤3,0≤n2≤3.
It is preferred that, haloalkyl is selected from CX3(CH2)n3-、CX2H(CH2)n4-、CH2X(CH2)n5-、CH3(CX2)n6-、CH3
(CXH)n7- in one kind, wherein, one or more of the X in F, Cl, Br, I, 0≤n3≤3,0≤n4≤3,0≤n5
≤ 3,0≤n6≤3,0≤n7≤3.
It is preferred that, alkylene is selected from (CH2)n8CH-、(CH2)n9(CH)2CH3-、(CH2)2CHCn10-、CH2(CH)2Cn11CH3-、
(CH)2Cn12CH3- in one kind, wherein 1≤n8≤2,1≤n9≤2,1≤n10≤2,1≤n11≤2,0≤n12≤2.
It is preferred that, haloalkene alkyl is selected from (CH2)n13CX-、(CHX)n14CH、(CX2)n15CH-、(CHX)n16(CH)2CH3-、
(CX2)n17(CH)2CH3-、(CH2)n18(CX)2CH3-、(CH2)n19(CH)2CH2X-、(CH2)n20(CH)2CHX2-、(CH2)n21(CH)2CX3-、(CHX)2CHCn22-、(CX2)2CHCn23-、(CH2)2CXCn24-、CHX(CH)2Cn25CH3-、CX2(CH)2Cn26CH3-、CH2
(CX)2Cn27CH3-、CH2(CH)2Cn28CHX2-、CH2(CH)2Cn29CH2X-、CH2(CH)2Cn30CX3-、(CX)2Cn31CH3-、(CH)2Cn32CHX2-、(CH)2Cn33CH2X-、(CH)2Cn34CX3- in one kind, wherein, one kind in F, Cl, Br, I of the X or
It is several, 1≤n13≤2,1≤n14≤2,1≤n15≤2,1≤n16≤2,1≤n17≤2,1≤n18≤2,1≤n19≤2,1
≤ n20≤2,1≤n21≤2,1≤n22≤2,1≤n23≤2,1≤n24≤2,1≤n25≤2,1≤n26≤2,1≤n27≤
One in 2,1≤n28≤2,1≤n29≤2,1≤n30≤2,0≤n31≤2,0≤n32≤2,0≤n33≤2,0≤n34≤2
Kind.
It is preferred that, the additive is selected from 4- bromomethyl benzene boric acids frequency which ester, vinyl boronic acids frequency which ester, 2- fluorine pyridines -4-
Boric acid frequency any ester, 2- chloropyridine -4- boric acid frequency any ester, 3- fluorine pyridine -4- boric acid frequency any ester, 2- chloropyridine -3- boric acid frequency any ester,
One or more in 6- chloropyridine -2- boric acid frequency any ester.Concrete structure is as follows：
4- bromomethyl benzene boric acids frequency is which ester
Vinyl boronic acids frequency is which ester
2- fluorine pyridine -4- boric acid frequency is which ester
2- chloropyridine -4- boric acid frequency is which ester
3- fluorine pyridine -4- boric acid frequency is which ester
2- chloropyridine -3- boric acid frequency is which ester
6- chloropyridine -2- boric acid frequency is which ester
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)2
In one or more be used in mixed way.Further preferred scheme, the present invention uses LiPF6It is used as main lithium salts.
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 which ester type compound of the boric acid frequency of structure shown in (1)：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
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, specifically, and the polymer of the polymer film is poly- 4-
Bromomethyl benzene boric acid frequency any ester, polyvinyl boric acid frequency any ester, poly- 2- fluorine pyridine -4- boric acid frequency which ester, poly- 2- chloropyridines -4- boron
Sour frequency any ester, poly- 3- fluorine pyridine -4- boric acid frequency any ester, poly- 2- chloropyridines -3- boric acid frequency any ester, poly- 6- chloropyridines -2- boric acid frequency
One or more in any ester.
The polymer film be above-mentioned electrolyte in additive under 3.5V-4.5V 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-4.5V。
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 spinel structure
LiNi0.5Mn1.5O4Or the LiNi of layer structure0.5Mn0.5O2Positive electrode, more preferably spinel structure
LiNi0.5Mn1.5O4, it has higher charge and discharge potential platform, assists to apply with the additive of herein described structure, can be with
The broader electrochemical window of electrolyte is embodied, electrolysis additive of the present invention can be more protruded and electrolyte high voltage capability is carried
Rise.
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 which esters of the boric acid frequency of structure shown in formula (1)
Compound：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
Additive can be finally totally consumed and in positive electrode surface formation polymer in a kind of lithium ion battery, electrolyte
Film, it is also possible to there is part in the electrolytic solution and remain.
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-4.5V.
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 0.1% parts by weight 4- bromomethyl benzene boric acids frequency which
(which ester of the boric acid frequency of structure shown in the application formula (1), wherein M is 4- bromomethyl benzene to ester, obtains the lithium ion battery of the present embodiment
Electrolyte, is designated as C1；
（2）The preparation of lithium ion battery：
By positive active material（LiNi0.5Mn1.5O4）, acetylene black, Kynoar by proportioning 90：5：5 it is well mixed after suppress
In on aluminium foil, positive plate is obtained；It regard metal lithium sheet as negative plate；Using PE/PP composite diaphragms as amberplex, using this reality
The electrolyte C1 of example is applied, 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)
Which ester of the vinyl boronic acids frequency of parts by weight replaces which ester of 4- bromomethyl benzene boric acids frequency, prepare lithium-ion battery electrolytes C2 with
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)
2- fluorine pyridine -4- boric acid frequency any ester of part is measured instead of 4- bromomethyl benzene boric acids frequency any ester, lithium-ion battery electrolytes are prepared
C3 and button cell S3.
Embodiment 4
Electrolyte and button cell are prepared using step same as Example 1, difference is：3% weight is used in step (1)
2- chloropyridine -4- boric acid frequency any ester of part is measured instead of 4- bromomethyl benzene boric acids frequency any ester, lithium-ion battery electrolytes are prepared
C4 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)
Which ester of the 2- chloropyridine -4- boric acid frequency of 7% parts by weight replaces which ester of 4- bromomethyl benzene boric acids frequency, 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)
3- fluorine pyridine -4- boric acid frequency any ester 4- bromomethyl benzene boric acids frequency any ester replaced, prepare lithium-ion battery electrolytes C6 with
And button cell S6.
Embodiment 7
Electrolyte and button cell are prepared using step same as Example 1, difference is：Added in step (1)
Which ester of 4- bromomethyl benzene boric acids frequency is 12% parts by weight (not this Applicant's Abstract graph content range, on the high side), prepares lithium ion battery battery
Solve liquid 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)
Boric acid frequency is which esters 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, then with 0.1mA
Constant-current discharge records the discharge capacity and charging capacity of battery to 3.0V, calculates efficiency for charge-discharge (%)=charging capacity/electric discharge and holds
Amount × 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 4.15V, up to 4.30V of the present invention it can be seen from table 1-3 results；Using this hair
Electrolyte oxidation decomposition electric potential up to 5.95V, minimum 5.60V 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 (17)
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 boric acid frequency of structure is which ester type compound, and its structure is as follows：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
2. electrolyte according to claim 1, it is characterised in that the alkyl is selected from CH3(CH2)n-、(CH3)2CH
(CH2)n1-、(CH3)3C (CH2)n2- in one kind, wherein 0≤n≤3,0≤n1≤3,0≤n2≤3；The haloalkyl choosing
From CX3(CH2)n3-、CX2H(CH2)n4-、CH2X(CH2)n5-、CH3(CX2)n6-、CH3(CXH)n7- in one kind, wherein, the X
One or more in F, Cl, Br, I, 0≤n3≤3,0≤n4≤3,0≤n5≤3,0≤n6≤3,0≤n7≤3；It is described
Alkylene is selected from (CH2)n8CH-、(CH2)n9(CH)2CH3-、(CH2)2CHCn10-、CH2(CH)2Cn11CH3-、(CH)2Cn12CH3- in
One kind, wherein 1≤n8≤2,1≤n9≤2,1≤n10≤2,1≤n11≤2,0≤n12≤2；The haloalkene alkyl is selected from
(CH2)n13CX-、(CHX)n14CH、(CX2)n15CH-、(CHX)n16(CH)2CH3-、(CX2)n17(CH)2CH3-、(CH2)n18(CX)2CH3-、(CH2)n19(CH)2CH2X-、(CH2)n20(CH)2CHX2-、(CH2)n21(CH)2CX3-、(CHX)2CHCn22-、(CX2)2CHCn23-、(CH2)2CXCn24-、CHX(CH)2Cn25CH3-、CX2(CH)2Cn26CH3-、CH2(CX)2Cn27CH3-、CH2(CH)2Cn28CHX2-、CH2(CH)2Cn29CH2X-、CH2(CH)2Cn30CX3-、(CX)2Cn31CH3-、(CH)2Cn32CHX2-、(CH)2Cn33CH2X-、(CH)2Cn34CX3- in one kind, wherein, one or more of the X in F, Cl, Br, I, 1≤n13≤
2,1≤n14≤2,1≤n15≤2,1≤n16≤2,1≤n17≤2,1≤n18≤2,1≤n19≤2,1≤n20≤2,1≤
N21≤2,1≤n22≤2,1≤n23≤2,1≤n24≤2,1≤n25≤2,1≤n26≤2,1≤n27≤2,1≤n28≤2,
One kind in 1≤n29≤2,1≤n30≤2,0≤n31≤2,0≤n32≤2,0≤n33≤2,0≤n34≤2.
3. electrolyte according to claim 1, it is characterised in that where the additive is selected from 4- bromomethyl benzene boric acids frequency
Ester, vinyl boronic acids frequency any ester, 2- fluorine pyridine -4- boric acid frequency any ester, 2- chloropyridine -4- boric acid frequency which ester, 3- fluorine pyridine -4- boron
One or more in sour frequency any ester, 2- chloropyridine -3- boric acid frequency any ester, 6- chloropyridine -2- boric acid frequency any ester.
4. electrolyte according to claim 1, it is characterised in that on the basis of electrolyte gross mass, the additive
Content is 0.1 ~ 10wt%.
5. electrolyte according to claim 4, it is characterised in that on the basis of electrolyte gross mass, the additive
Content is 0.1 ~ 3wt%.
6. electrolyte according to claim 1, it is characterised in that the lithium salts is 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)2In one or more.
7. electrolyte according to claim 6, it is characterised in that on the basis of electrolyte gross mass, the lithium salts contains
Measure as 10 ~ 20wt%.
8. 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.
9. electrolyte according to claim 8, it is characterised in that on the basis of the gross mass of electrolyte, the electrolyte
The content of solvent is 77 ~ 89.9wt%.
10. 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 boric acid frequency of shown structure is which ester type compound：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
11. according to the positive pole described in claim 10, it is characterised in that the polymer of the polymer film is poly- 4- bromomethyls benzene boron
Sour frequency any ester, polyvinyl boric acid frequency any ester, poly- 2- fluorine pyridine -4- boric acid frequency any ester, poly- 2- chloropyridines -4- boric acid frequency any ester,
One in poly- 3- fluorine pyridine -4- boric acid frequency any ester, poly- 2- chloropyridines -3- boric acid frequency any ester, poly- 6- chloropyridines -2- boric acid frequency any ester
Plant or several.
12. 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-4.5V。
13. a kind of positive pole, it is characterised in that the positive pole is prepared as the method described in claim 12.
14. 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 10-13 any one is provided just
Pole.
15. lithium ion battery according to claim 14, it is characterised in that the positive electrode includes positive electrode active material
Matter, conductive agent, positive electrode binder, the positive active material are the LiNi of spinel structure0.5Mn1.5O4Or layer structure
LiNi0.5Mn0.5O2。
16. lithium ion battery according to claim 15, it is characterised in that the positive active material is
LiNi0.5Mn1.5O4。
17. lithium ion battery according to claim 14, it is characterised in that contain additive in the electrolyte, described
Additive is which ester type compound of the boric acid frequency of structure shown in formula (1)：
Formula (1)；
Wherein, M is selected from phenyl ring, a halides of phenyl ring, a halides of toluene, pyridine, a halides of pyridine, alkyl, halogen
One kind in substituted alkyl, alkylene, haloalkene alkyl.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610278018.7A CN107331892B (en) | 2016-04-28 | 2016-04-28 | Electrolyte, positive electrode and preparation method thereof, and lithium ion battery |
| PCT/CN2017/080486 WO2017185997A1 (en) | 2016-04-28 | 2017-04-13 | Electrolyte, positive electrode, preparation method therefor and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610278018.7A CN107331892B (en) | 2016-04-28 | 2016-04-28 | Electrolyte, positive electrode and preparation method thereof, and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107331892A true CN107331892A (en) | 2017-11-07 |
| CN107331892B CN107331892B (en) | 2021-06-18 |
Family
ID=60160745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610278018.7A Active CN107331892B (en) | 2016-04-28 | 2016-04-28 | Electrolyte, positive electrode and preparation method thereof, and lithium ion battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN107331892B (en) |
| WO (1) | WO2017185997A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417894A (en) * | 2018-03-13 | 2018-08-17 | 广州天赐高新材料股份有限公司 | A kind of lithium secondary cell electrolyte and lithium secondary battery |
| CN109148952A (en) * | 2018-07-26 | 2019-01-04 | 华中科技大学 | A kind of electrolyte and its application and product |
| CN111162312A (en) * | 2019-12-23 | 2020-05-15 | 珠海冠宇电池有限公司 | Solid polymer electrolyte containing boron-fluorine structure and preparation method and application thereof |
| CN111261941A (en) * | 2020-03-30 | 2020-06-09 | 山东海容电源材料股份有限公司 | Electrolyte for high-power lithium battery and preparation method thereof |
| CN112820940A (en) * | 2019-11-15 | 2021-05-18 | 华南师范大学 | Non-aqueous electrolyte containing 2-fluoro-3-pyridineboronic acid, and lithium metal battery containing same |
| CN112952197A (en) * | 2021-01-26 | 2021-06-11 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN113224370A (en) * | 2020-01-21 | 2021-08-06 | 南开大学 | Gel electrolyte, preparation method and application thereof |
| CN113299989A (en) * | 2021-04-21 | 2021-08-24 | 湖南立方新能源科技有限责任公司 | Electrolyte additive, electrolyte and sodium ion battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220131148A1 (en) * | 2020-10-28 | 2022-04-28 | Enevate Corporation | Boron-containing chemicals as cathode additives, si anode additives, electrolyte additives or separator modifiers for li-ion batteries |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080020286A1 (en) * | 2006-07-24 | 2008-01-24 | Hiroshi Haruna | Lithium secondary battery |
| CN102683746A (en) * | 2012-05-04 | 2012-09-19 | 百顺松涛（天津）动力电池科技发展有限公司 | Lithium battery electrolyte additive and electrolyte using same as well as battery |
| CN103518284A (en) * | 2011-05-09 | 2014-01-15 | 新神户电机株式会社 | Nonaqueous electrolyte solution and lithium ion battery |
| CN105074995A (en) * | 2013-08-21 | 2015-11-18 | 积水化学工业株式会社 | Electrolyte and lithium ion secondary battery |
| CN105406121A (en) * | 2015-12-16 | 2016-03-16 | 东莞市杉杉电池材料有限公司 | Matched silicon-carbon anode lithium-ion battery electrolyte and silicon-carbon anode lithium-ion battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012105377B4 (en) * | 2012-06-20 | 2018-11-15 | Jacobs University Bremen Ggmbh | 1,2,4-THIADIAZINAN-3,5-DION-1,1-DIOXIDE DERIVATIVES, THEIR PREPARATION AND USE |
| CN104518239A (en) * | 2013-09-26 | 2015-04-15 | 中国科学院过程工程研究所 | Lithium ion battery amide-type additive having film-forming and stabilizing functions and electrolyte containing same |
-
2016
- 2016-04-28 CN CN201610278018.7A patent/CN107331892B/en active Active
-
2017
- 2017-04-13 WO PCT/CN2017/080486 patent/WO2017185997A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080020286A1 (en) * | 2006-07-24 | 2008-01-24 | Hiroshi Haruna | Lithium secondary battery |
| CN103518284A (en) * | 2011-05-09 | 2014-01-15 | 新神户电机株式会社 | Nonaqueous electrolyte solution and lithium ion battery |
| CN102683746A (en) * | 2012-05-04 | 2012-09-19 | 百顺松涛（天津）动力电池科技发展有限公司 | Lithium battery electrolyte additive and electrolyte using same as well as battery |
| CN105074995A (en) * | 2013-08-21 | 2015-11-18 | 积水化学工业株式会社 | Electrolyte and lithium ion secondary battery |
| CN105406121A (en) * | 2015-12-16 | 2016-03-16 | 东莞市杉杉电池材料有限公司 | Matched silicon-carbon anode lithium-ion battery electrolyte and silicon-carbon anode lithium-ion battery |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417894A (en) * | 2018-03-13 | 2018-08-17 | 广州天赐高新材料股份有限公司 | A kind of lithium secondary cell electrolyte and lithium secondary battery |
| CN108417894B (en) * | 2018-03-13 | 2020-11-06 | 广州天赐高新材料股份有限公司 | Lithium secondary battery electrolyte and lithium secondary battery |
| CN109148952A (en) * | 2018-07-26 | 2019-01-04 | 华中科技大学 | A kind of electrolyte and its application and product |
| CN112820940A (en) * | 2019-11-15 | 2021-05-18 | 华南师范大学 | Non-aqueous electrolyte containing 2-fluoro-3-pyridineboronic acid, and lithium metal battery containing same |
| CN112820940B (en) * | 2019-11-15 | 2022-05-10 | 华南师范大学 | Non-aqueous electrolyte containing 2-fluoro-3-pyridineboronic acid, and lithium metal battery containing same |
| CN111162312A (en) * | 2019-12-23 | 2020-05-15 | 珠海冠宇电池有限公司 | Solid polymer electrolyte containing boron-fluorine structure and preparation method and application thereof |
| CN111162312B (en) * | 2019-12-23 | 2022-04-01 | 珠海冠宇电池股份有限公司 | Solid polymer electrolyte containing boron-fluorine structure and preparation method and application thereof |
| CN113224370A (en) * | 2020-01-21 | 2021-08-06 | 南开大学 | Gel electrolyte, preparation method and application thereof |
| CN111261941A (en) * | 2020-03-30 | 2020-06-09 | 山东海容电源材料股份有限公司 | Electrolyte for high-power lithium battery and preparation method thereof |
| CN112952197A (en) * | 2021-01-26 | 2021-06-11 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN113299989A (en) * | 2021-04-21 | 2021-08-24 | 湖南立方新能源科技有限责任公司 | Electrolyte additive, electrolyte and sodium ion battery |
| CN113299989B (en) * | 2021-04-21 | 2024-03-19 | 湖南钠方新能源科技有限责任公司 | Electrolyte additive, electrolyte and sodium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017185997A1 (en) | 2017-11-02 |
| CN107331892B (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107331892A (en) | A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery | |
| Oesten et al. | Advanced electrolytes | |
| CN105655639B (en) | electrolyte and lithium ion battery including the electrolyte | |
| CN103825047B (en) | A kind of electrolyte for lithium ion battery | |
| EP3314689B1 (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN102496737A (en) | Lithium ion battery electrolyte and lithium ion battery prepared therefrom | |
| US10991972B2 (en) | Electrolyte solution, positive electrode, and lithium-ion battery comprising the electrolyte solution and/or the positive electrode | |
| CN101548425A (en) | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery | |
| CN109309226A (en) | Electrochemical energy storage device | |
| CN108736065B (en) | Electrolyte and lithium ion battery containing electrolyte and/or anode | |
| JP6765510B2 (en) | Electrolyte and electrochemical equipment | |
| CN109193028B (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same | |
| Shieh et al. | Effect of mixed LiBOB and LiPF6 salts on electrochemical and thermal properties in LiMn2O4 batteries | |
| CN106558732A (en) | A kind of lithium-ion battery electrolytes and lithium ion battery | |
| CN111048840B (en) | Lithium ion battery electrolyte and lithium ion battery | |
| US10283814B2 (en) | Electrolyte for lithium-based energy stores | |
| CN109004275A (en) | Electrolyte solution and secondary battery | |
| CN108232299A (en) | A kind of high-voltage electrolyte containing new additive agent | |
| CN107240716A (en) | A kind of electrolyte, positive pole and preparation method thereof and a kind of lithium ion battery | |
| CN104409771A (en) | Nitrile ethyl hydrofluoroether-containing electrolyte and lithium secondary battery | |
| CN112582673A (en) | Lithium ion battery electrolyte and lithium ion battery | |
| JP6765504B2 (en) | Electrolyte and electrochemical equipment | |
| CN105914403B (en) | Electrolyte and lithium ion battery using same | |
| CN108736067A (en) | The lithium-ion battery electrolytes of flatulence and cycle performance under a kind of improvement high voltage | |
| KR20070012094A (en) | Nonaqueous electrolyte for lithium battery and lithium secondary battery comprising the electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |