CN106785041A - A kind of additive for lithium ion battery, electrolyte and anode sizing agent - Google Patents
A kind of additive for lithium ion battery, electrolyte and anode sizing agent Download PDFInfo
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- CN106785041A CN106785041A CN201611237902.2A CN201611237902A CN106785041A CN 106785041 A CN106785041 A CN 106785041A CN 201611237902 A CN201611237902 A CN 201611237902A CN 106785041 A CN106785041 A CN 106785041A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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 belongs to technical field of lithium ion, a kind of additive for lithium ion battery, electrolyte and anode sizing agent are specifically disclosed.Additive of the present invention includes one or more bismaleimide amine compound containing formula I or the structure of formula II；Electrolyte includes electrolytic salt, nonaqueous solvents and the additive；Anode sizing agent includes positive active material, conductive agent, binding agent and the additive.Ion pair and polar functional group are not shared containing a large amount of in additive structure of the present invention, it is respectively provided with compared with strong interaction with metal oxide-type electrode material and collector, in electrode slurry, the dispersiveness of metal oxide-type positive electrode particle can be improved, cohesive force between electrode material coating and collector is significantly improved, cycle performance is improved.Contain a large amount of double bonds in additive structure, under high voltage can electrochemically oxidative polymerization, help to form more stable SEI films on positive electrode surface, effectively weaken the exothermic auxiliary reaction of positive electrode and electrolyte under high temperature high voltage.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of addition for high specific energy lithium ion battery
Agent, electrolyte and anode sizing agent.
Background technology
With expanding economy and the progress of science and technology, the mankind constantly rise to the demand of the energy.For oil, natural gas etc.
Fossil energy of tradition increasingly environmental problem such as air pollution, the greenhouse effects of deficient and its scale caused by is increasingly tight
The present situation of weight, development cleaning and regenerative resource have turned into the Major Strategic of international social development.Secondary cell can as one kind
With efficient, the cleaning energy storage device that recycle, be a comprehensive important technology for alleviating the energy, resource and environmental problem on the way
Footpath.Compared with other secondary cell systems such as lead-acid battery, nickel-cadmium cell, energy density is high, power because having concurrently for lithium ion battery
Density is high, operating voltage is high, have extended cycle life, operating temperature is wide and pollution-free, memory-less effect the advantages of and enjoy favor, no
Only it has been widely used in all kinds of portable type electronic products such as MP4, mobile phone, panel computer, notebook computer, digital camera,
And it is also considered to be the preferable supporting power supply of the high-technology fields such as following electric automobile, scale energy storage.
However, with the development of New Generation of Portable electronic product and electric automobile, the energy in the urgent need to improving battery
Density.Currently, the energy density of lithium ion battery is limited by the specific capacity of positive electrode；Therefore, high power capacity positive electrode is developed
The key problem in technology of lithium ion battery development is turned into.Compared with common anode material for lithium-ion batteries, rich lithium manganese base solid solution is just
Pole material is because with the advantage such as specific capacity (250-300mAh/g) high, environment-friendly, with low cost, being considered as most with prospects
Positive pole system.However, now, lithium-rich manganese-based anode still suffers from the problems of application aspect, such as first week efficiency is relatively low, appearance
Amount decay is very fast, high rate performance is not good, and voltage declines in cyclic process, security difference etc..
At present, lithium-rich manganese-based class electrode material performance improvement method is mainly by Surface coating, bulk phase-doped, regulation group
Dividing content etc. improves electrode material chemical property in itself.However, the electrode material with specific discharge capacity higher often because
With less primary particle, processing characteristics is poor, such as between collector cohesive force it is poor and easily take off paper tinsel；Lithium-rich manganese-based class electricity
Pole material operating voltage higher (4.6-4.8V) causes the side reaction between positive electrode and electrolyte more violent, security performance
It is worse.As can be seen here, only by changing material in itself, it is impossible to electrode material has been given play to optimal application performance, therefore, also need
Other modes are further developed to improve the application performance of high specific energy lithium ion battery.
Because of security and cost advantage, using more and more extensively, but it is in energy density and gram volume for tertiary cathode material
Aspect need to be improved.The content of nickel is improved in tertiary cathode material nickle cobalt lithium manganate, the energy of gram volume and battery can be improved
Metric density, but nickel content material water imbibition high is strong, stability is also decreased, particularly under high potential, nickel element
Catalytic action can accelerate the decomposition of conventional electrolysis liquid, cause cycle performance of battery reduction, hot conditions inflatable serious.Therefore, it is anxious
The new method that can improve electrode/electrolyte interface stability need to be developed.
Chinese patent CN101685875A discloses a kind of maleimide, BMI, poly maleimide, poly-
The copolymer or said mixture of BMI, BMI and maleimide are made as electrolysis additive
Standby lithium ion battery, improves efficiency for charge-discharge and the life-span of silicium cathode.
A kind of lithium-ion battery electrolytes electrochemical window of can improving is disclosed in Chinese patent CN103579675A
Electrolysis additive containing maleimide derivatives, bismaleimide amine derivative or both combination.
Prior art improves the performance of electrolyte by adding additive in the electrolytic solution, to meet under high voltage condition
Application requirement；Bismaleimide amine compound is added in non-aqueous electrolyte as additive by proper proportion, and it adds
Dosage is larger to electrode material Electrochemical Performances, it is necessary to accurate control；For high specific energy batteries, electrode coating is often
Thicker, wellability is poor, and ratio is improper to cause distribution of additives uneven, and easily in electrode diaphragm side, excessively enrichment forms thicker
Layer and influence the charge-discharge performance of battery, while can not be played a role to collector lateral electrode material.
Chinese patent CN102044675A discloses a kind of structure for the imide li ion described in formula I, formula II just
Pole slurry additive, additive is used to improve the stability of overall positive pole system, the high temperature of battery and the peace for overcharging in the patent
Full performance.
To be there is Chinese patent CN101212052A the modified maleimide for being similar to dendritic highly branched structure to make
It is electrode slurry additive, modified maleimide dispersant is to carry out modified maleimide by barbituric acid or derivatives thereof,
By the branched structure and the complexing reduction slurry viscosity of metal oxide of modified maleimide, improve stability and follow
The ring life-span.
By cyanamide be modified maleimide additive with melamine by Chinese patent CN103050706B, is made
Stability and cycle life are improved for the additive of electrode slurry.
Electrode slurry additive mentioned above is generally to be gathered by the branch shape structure of the modified formation of polyfunctional compound
Compound, the preparation of additive is relatively loaded down with trivial details, and the addition of polyfunctional compound can introduce new impurity in anode sizing agent, this
A little impurity equally can to some extent influence the chemical property of lithium ion battery；Such as modifying agent cyanamide and melamine, no
Cyano group impurity is only introduced, and because cyanide sheet is as extremely toxic substance, there is potential safety hazard in process of production, be unfavorable for work
Industry large-scale production.
Therefore, still need to develop that a kind of dispersiveness is high, viscosity is low, electrolyte and anode sizing agent performance can be improved, and can improve
Cycle performance of battery and the good high specific energy lithium ion battery additive of security performance, prior art are not efficiently solved also
Method.
The content of the invention
It is an object of the invention to overcome weak point of the prior art, there is provided one kind can effectively improve lithium-ion electric
The cycle performance in pond (especially rich lithium solid solution class high specific energy lithium ion battery) and the additive of security performance；Present invention addition
Ion pair and polar functional group are not shared containing a large amount of in the structure of agent, and it is equal with metal oxide-type electrode material and collector
With compared with strong interaction, in electrode slurry, the dispersiveness of metal oxide-type positive electrode particle can be improved, significantly improve electricity
Cohesive force between pole material coating and collector, improves cycle performance.Also containing a large amount of more active double bonds in additive structure,
Under high voltage can electrochemically oxidative polymerization, help to form more stable SEI films on positive electrode surface, improve that battery is overall to exist
Exothermic auxiliary reaction under stability under high temperature and high voltage, effectively decrease high temperature high voltage between positive electrode and electrolyte.
To achieve these goals, the technical solution adopted in the present invention is as follows：
The invention provides a kind of additive for lithium ion battery,
The additive includes one or more bismaleimide amine compound containing formula I or the structure of formula II；
The structure of the formula I is as follows：
The structure of the formula II is as follows：
R1Selected from-R- ,-RNH2R-、-C(O)CH2-、-CH2OCH2-、-C(O)-、-O-、-O-O-、-S-、-S-S-、-S
(O)-、-CH2S(O)CH2-、-(O)S(O)-、-C6H4-、-CH2(C6H4)CH2-、-CH2(C6H4) (O)-, stretch phenyl and stretch xenyl
In one or more；
R2Selected from-R- ,-C (O)-,-C (CH3)2-、-O-C6H4-C(CH3)2-C6H4-O-、-O-、-O-O-、-S-、-S-S-、-
S (O)-and-(O) S (O)-in one or more；
Wherein, the R is to contain the 1-6 alkyl of carbon.
Further, the R1And R2It is divalent organic substituent.
Further, the R1Also include-R-Si (CH3)2-O-Si(CH3)2-R-、-C6H4-、-C6H4C6H4-, substitution stretch
Phenyl and substitution stretch in xenyl one or more.
Further, the R1It is preferred that stretch phenyl, stretch xenyl, substitution stretch phenyl and it is substituted stretch in xenyl one
Plant or several.
Further, the R2It is preferred that-O-C6H4-C(CH3)2-C6H4-O-。
Present invention also offers a kind of electrolyte for lithium ion battery, including：
Electrolytic salt, nonaqueous solvents and the additive.
Further, additive adding proportion in the electrolytic solution is 0.1-10wt.%；It is preferred that 5.0-
6.5wt.%.
Further, the electrolytic salt includes LiCl, LiPF6、LiBF4、LiCH3SO3、LiCF3SO3、LiAsF6、
LiSbF6、LiClO4、Li[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3] and LiBOB in
One or more；It is preferred that LiBOB or LiPF6；
Further, the nonaqueous solvents include ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate,
Methyl ethyl carbonate, butylene, gamma-butyrolacton, gamma-valerolactone, dipropyl carbonate, 1-METHYLPYRROLIDONE (NMP), N- first
Base formamide, N- methylacetamides, dimethylformamide, DEF, diethyl ether, acetonitrile, propionitrile, methyl phenyl ethers anisole, fourth two
Nitrile, adiponitrile, glutaronitrile, dimethyl sulfoxide, dimethyl sulfite, vinylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon
Diethyl phthalate, fluorinated ethylene carbonate, chlorocarbonic acid propylene, acid anhydrides, sulfolane, methoxy sulfone, tetrahydrofuran, 2- first
Base tetrahydrofuran, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl propionate, methyl propionate, two
In NMF, 1,3- dioxolanes, 1,2- diethoxyethane, 1,2- dimethoxy-ethanes and 1,2- dibutoxy ethane
One or more；It is preferred that ethylene carbonate or propene carbonate in cyclic carbonate.
Present invention also offers it is a kind of for lithium ion battery and anode sizing agent, including：
Positive electrode active materials, binding agent, conductive agent and the additive；
Further, the adding proportion scope of the additive is 0.01-10wt.%, preferably 0.01-2wt.%.
Further, the adding proportion of the additive preferred 1wt.% or 2wt.%
Further, the additive is added with solid or solution form.
Further, the additive is added in solid form, preferably solid powder.
Further, the positive electrode active materials are lithium-rich manganese-based class positive electrode, and its chemical general formula is xLi2MnO3·
(1-x)LiMO2,
Wherein, M is the mixture of one or more in Co, Ni, Mn；0 ＜ x ＜ 1.
Further, the positive electrode active materials also include tertiary cathode material, lithium cobaltate cathode material, lithium manganate cathode
Material, lithium nickelate positive electrode and the mixture of one or more in lithium iron phosphate positive material, chemical general formula are respectively
LiNi1-x-yCoxMyO2、LiCoO2、LiMn2O4、LiNiO2And LiFePO4；
Wherein, M is at least one in Mn or Al.
Further, the conductive agent is selected from little particle carbon black, bulky grain graphite, acetylene black, CNT is gentle coordinates
One or more in long carbon fiber.
Further, the binding agent is selected from least one in Kynoar or polymethacrylate resin, and its
The group for being constituted.
A kind of application such as additive, electrolyte and anode sizing agent in sum in lithium ion battery.
Design principle of the invention is as follows：
Ion pair and polar functional groups are not shared containing a large amount of in the structure of additive of the present invention, itself and metal oxide-type
Electrode material and collector are respectively provided with compared with strong interaction, can improve the dispersiveness of metal oxide-type positive electrode particle, are improved
Cohesive force between electrode material coating and collector, improves cycle performance.
Containing a large amount of more active double bonds in additive structure of the present invention, under high voltages can electrochemically oxidative polymerization, have
Help form more stable SEI films on positive electrode surface, improve the overall stability under high temperature and high voltage of battery, effectively
The exothermic auxiliary reaction of positive electrode and electrolyte under decrease high temperature high voltage.
The present invention can compare bismaleimide amine compound additive as slurry additive during batch mixing
It is uniformly dispersed in around electrode material, and is evenly distributed in whole electrode structure network；It is simultaneously big in additive structure
Amount is not shared and is respectively provided with compared with strong interaction between ion pair and polar functional group and metal oxide-type electrode material and collector
Power, can not only improve the dispersing uniformity of metal oxide-type positive electrode particle, also be remarkably improved electrode material coating and afflux
Cohesive force between body.Additionally, a large amount of more active double bonds make to be attached to electrode material surface in additive structure of the invention
Additive molecule can form more stable SEI films by electrochemically oxidative polymerization under high voltages, therefore such additive is added
To in electrolyte or electrode slurry, the stability at electrode/electrolyte interface is remarkably improved, reduces positive electrode and electrolyte circle
The side reaction in face, and then improve the overall stability under high temperature and high voltage of battery.
Wherein, be small particle diameter the characteristics of conductive black, specific surface area is especially big, electric conductivity is especially good, in the battery it
Imbibition can be played a part of and protect liquid.Carbon black conductive agent has：Acetylene black, Super P, Super S, 350G, carbon fiber (VGCF),
CNT (CNTs), Ketjen black (KetjenblackEC300J, KetjenblackEC600JD, Carbon ECP, Carbon
ECP600JD).Acetylene black (Acetylene Black, abbreviation AB):By-product when being pyrolyzed by calcium carbide route or naphtha (raw gasoline)
The acetylene of the purity more than 99% that qi leel solution is refining to obtain, the carbon black obtained after continuous pyrolysis.Super-P：Carbon black conductive agent
Trade (brand) names of the Super-P from enterprise of Switzerland of the manufacturer TIMCAL of conductive carbon black.Little particle conductive carbon black, in both positive and negative polarity
In can use, completely without lithium storage function, only play electric action.Ketjen black：It is exclusively used in the high-efficiency superconducting carbon black of lithium battery, side chain
Shape, purity is high, and electric conductivity is especially good.It is Japanese LION public to compare popular its manufacturer of Japanese Ketjen black in the market
Department, is promoted and service by Shanghai Cui Ke Chemical Industry Science Co., Ltd.Graphite agent (KS, SO) graphite agent
Have：KS-6, KS-15, SFG-6, SFG-15 etc..KS-6：Bulky grain graphite powder, featheriness is actual with certain lithium storage function
It is used for positive pole in production.SFG-6：Conductive agent is done than conveniently, the graphite of flakey can improve negative terminal surface for negative pole
Energy.Graphene：Face contacts conductive agent, and electric conductivity is optimal, but is required for dispersion too high.
Wherein, it is Piezoelectricity under Kynoar (PVDF) normality, crystallinity is about 50%.Hitherto reported have α,
5 kinds of crystal formations such as β, γ, δ and ε, they are formed under different conditions, in the certain condition (work of heat, electric field, machinery and radiation energy
With) under again can mutually convert.In this 5 kinds of crystal formations, beta crystal is mostly important, used as piezoelectricity and the PVDF master of pyroelectricity application
If containing beta crystal.PVDF has excellent chemical resistance, excellent high temperature resistant color distortion and oxidative resistance；Excellent
Wearability, pliability, anti-intensity and the impact resistance intensity of rising very high；Excellent UV resistant and high-energy radiation；Hydrophily
It is poor；Can project and extrusion fluoride resin (being commonly called as thermoplasticity Teflon)；Heat resistance is good and has high dielectric strength.PVDF should
With being concentrated mainly on petrochemical industry, electric and fluorocarbon coating field.
The present invention has advantages below compared with prior art：
Ion pair and polar functional groups are not shared containing a large amount of in the structure of additive of the present invention, itself and metal oxide-type
Electrode material and collector are respectively provided with compared with strong interaction, can improve the dispersiveness of metal oxide-type positive electrode particle, are improved
Cohesive force between electrode material coating and collector, improves cycle performance.Containing a large amount of more active in additive structure of the present invention
Double bond, under high voltage can electrochemically oxidative polymerization, help to form more stable SEI films on positive electrode surface, improve electricity
The overall stability under high temperature and high voltage in pond, positive electrode is secondary with the heat release of electrolyte anti-under effectively weakening high temperature high voltage
Should.
The present invention can compare bismaleimide amine compound additive as slurry additive during batch mixing
It is uniformly dispersed in around electrode material, and is evenly distributed in whole electrode structure network；It is simultaneously big in additive structure
Amount is not shared and is respectively provided with compared with strong interaction between ion pair and polar functional group and metal oxide-type electrode material and collector
Power, can not only improve the dispersing uniformity of metal oxide-type positive electrode particle, also be remarkably improved electrode material coating and afflux
Cohesive force between body.Additionally, a large amount of more active double bonds can make to be attached to electrode material surface in additive structure of the invention
Additive molecule can form more stable SEI films by electrochemically oxidative polymerization under high voltages, therefore such additive is added
Being added in electrolyte or electrode slurry can significantly improve the stability at electrode/electrolyte interface, reduce putting between positive pole/electrolyte
Hot side reaction, so as to improve the overall stability under high temperature and high voltage of battery system.
With the lithium-rich manganese-based electrode material of high voltage as positive pole, after adding additive of the invention, the electrode obtained is applied the present invention
Layer has capability retention higher, more preferable processing characteristics, cycle performance and security performance；The present invention also improves lithium ion
The specific capacity and charging/discharging voltage of cell positive material；Can be widely applied to lithium ion battery, lithium macromolecule battery anode electrode
Various lithium battery materials such as film, applicability extensively, is suitable for industrial-scale production.
Brief description of the drawings
Fig. 1 schematically illustrates the loop test curve of embodiment 1 and comparative example under 2.0-4.8V voltages；
Fig. 2 schematically illustrates the loop test curve of embodiment 1 and comparative example under 2.0-4.6V voltages；
Fig. 3 schematically illustrates embodiment 1, embodiment 2 and comparative example electrode coating after cycling and current collector layers
Bonding situation schematic diagram；
Fig. 4 schematically illustrates the electrode AC impedance spectrogram of embodiment 1, embodiment 2 and comparative example before and after circulation
(EIS spectrograms).
Specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but technical scheme include but
It is not limited to the content of following embodiments.
The invention provides a kind of additive for lithium ion battery,
The additive includes one or more bismaleimide amine compound containing formula I or the structure of formula II；
The structure of the formula I is as follows：
The structure of the formula II is as follows：
Wherein, R1And R2It is divalent organic substituent；
Wherein, R1Selected from-R- ,-RNH2R-、-C(O)CH2-、-CH2OCH2-、-C(O)-、-O-、-O-O-、-S-、-S-S-、-
S(O)-、-CH2S(O)CH2-、-(O)S(O)-、-C6H4-、-CH2(C6H4)CH2-、-CH2(C6H4)(O)-、-R-Si(CH3)2-O-
Si(CH3)2-R-、-C6H4-、-C6H4C6H4-, stretch phenyl, stretch xenyl, substitution stretch phenyl and it is substituted stretch in xenyl one
Plant or several；
Wherein, R2Selected from-R- ,-C (O)-,-C (CH3)2-、-O-C6H4-C(CH3)2-C6H4-O-、-O-、-O-O-、-S-、-
S-S- ,-S (O)-and-(O) S (O)-in one or more；
Wherein, the R is to contain the 1-6 alkyl of carbon.
Preferably, the R1It is preferred that stretch phenyl, stretch xenyl, substitution stretch phenyl and substituted one kind stretched in xenyl
Or it is several.
It is further preferred that the R2It is preferred that-O-C6H4-C(CH3)2-C6H4-O-。
It is further preferred that the bismaleimide amine compound is selected from N, N '-BMI -4,4 '-diphenyl
For methane, 1,1 '-(di-2-ethylhexylphosphine oxide -4,1- phenylenes) BMIs, N, the N '-(methylene of 1,1 '-diphenyl -4,4 '-two
Base) BMI, N, N '-(4- methyl isophthalic acids, 3- phenylenes) BMI, 1,1 '-(3,3 '-dimethyl -1,1 ' -
Diphenyl -4,4 '-dimethylene) BMI, N, N '-vinyl BMI, N, N '-cyclobutenyl span carrys out acyl
Imines, N, N '-(1,2- phenylenes) BMI, N, N '-(1,3- phenylenes) BMI, N, N '-span come
Acid imide sulphur, N, the sulphur of N '-BMI two, N, N '-BMI imines ketone, N, N '-di-2-ethylhexylphosphine oxide maleimide
Amine, BMI methyl ether, 1,2- dimaleoyl imino -1,2- ethylene glycol, N, N ' -4,4 '-diphenyl ether-bismaleimide
One or more in amine and 4,4 '-BMI-diphenyl sulphone (DPS).
Present invention also offers a kind of electrolyte for lithium ion battery, including：
Electrolytic salt, nonaqueous solvents and the additive.
Preferably, additive adding proportion in the electrolytic solution is 0.1-10wt.%；It is preferred that 5.0-6.5wt.%.
It is further preferred that the electrolytic salt includes LiCl, LiPF6、LiBF4、LiCH3SO3、LiCF3SO3、LiAsF6、
LiSbF6、LiClO4、Li[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3] and LiBOB in
One or more.
It is further preferred that the electrolytic salt is di-oxalate lithium borate LiBOB or lithium hexafluoro phosphate LiPF6；It is preferred that double grass
Sour lithium borate LiBOB.
It is further preferred that the nonaqueous solvents includes ethylene carbonate, propene carbonate, diethyl carbonate, carbonic acid diformazan
Ester, methyl ethyl carbonate, butylene, gamma-butyrolacton, gamma-valerolactone, dipropyl carbonate, 1-METHYLPYRROLIDONE (NMP),
N-METHYLFORMAMIDE, N- methylacetamides, dimethylformamide, DEF, diethyl ether, acetonitrile, propionitrile, methyl phenyl ethers anisole,
Succinonitrile, adiponitrile, glutaronitrile, dimethyl sulfoxide, dimethyl sulfite, vinylene carbonate, methyl ethyl carbonate, carbonic acid diformazan
Ester, diethyl carbonate, fluorinated ethylene carbonate, chlorocarbonic acid propylene, acid anhydrides, sulfolane, methoxy sulfone, tetrahydrochysene furan
Mutter, 2- methyltetrahydrofurans, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl propionate, propionic acid
Methyl esters, dimethylformamide, 1,3- dioxolanes, 1,2- diethoxyethane, 1,2- dimethoxy-ethanes and the fourth oxygen of 1,2- bis-
One or more in base ethane.
It is further preferred that the nonaqueous solvents is the ethylene carbonate or propene carbonate in cyclic carbonate；It is preferred that carbon
Acid propylene ester.
Present invention also offers it is a kind of for lithium ion battery and anode sizing agent, including：
Positive electrode active materials, binding agent, conductive agent and the additive；
Wherein, the adding proportion scope of the additive is 0.01-10wt.%, preferably 0.01-2wt.%.
Preferably, the adding proportion of the additive preferred 1wt.% or 2wt.%
It is further preferred that the additive is with solid powder or solution form addition, preferably solid powder.
It is further preferred that the positive electrode active materials are lithium-rich manganese-based class positive electrode, its chemical general formula is xLi2MnO3·
(1-x)LiMO2, wherein, M is the mixture of one or more in Co, Ni, Mn；0 ＜ x ＜ 1.
It is further preferred that the positive electrode active materials are also including tertiary cathode material, lithium cobaltate cathode material, LiMn2O4 just
Pole material, lithium nickelate positive electrode and the mixture of one or more in lithium iron phosphate positive material, chemical general formula are respectively
LiNi1-x-yCoxMyO2、LiCoO2、LiMn2O4、LiNiO2And LiFePO4；Wherein, M is at least one in Mn or Al.
It is further preferred that the conductive agent is selected from little particle carbon black, bulky grain graphite, acetylene black, CNT and gas phase
Into one or more in long carbon fiber.
It is further preferred that the binding agent is selected from least one in Kynoar or polymethacrylate resin, and
Its group for being constituted.
The present invention can compare bismaleimide amine compound additive as slurry additive during batch mixing
It is uniformly dispersed in around electrode material, is evenly distributed in whole electrode structure network；It is simultaneously a large amount of in additive structure
Do not share and be respectively provided between ion pair and polar functional group and metal oxide-type electrode material and collector compared with strong interaction,
The dispersing uniformity of metal oxide-type positive electrode particle can not only be improved, be also remarkably improved between electrode material coating and collector
Cohesive force.Additionally, being attached to adding for electrode material surface containing a large amount of more active double bonds in additive structure of the invention
Plus agent molecule can also form more stable SEI films by electrochemically oxidative polymerization under high voltages, improve battery overall in high temperature and height
Stability under voltage, reduces the side reaction of positive electrode and electrolyte interface.
Above-mentioned additive, electrolyte and anode sizing agent in lithium ion battery using when, with specific capacity higher and
Charging/discharging voltage, good energy density；Excellent processing characteristics, cycle performance and security performance；Applicability extensively, can be used for
Industrial scale is produced.
Embodiment 1
It is the N, N '-(methylenediphenyl) BMI additive powder of positive electrode active materials quality 1% by quality
End is dissolved in appropriate NMP, and stirring forms homogeneous solution, is then added to containing 90% positive electrode active materials
Li1.18Ni0.15Co0.15Mn0.52O2, 4% conductive agent (mass ratio of conductive black and electrically conductive graphite be 1:1), 6% PVDF is bonded
In the mixed slurry of agent, dispersed with stirring uniformly prepares anode sizing agent；Anode sizing agent is coated on plus plate current-collecting body, through dry
Dry, roll-in, cut and obtain anode pole piece.
Embodiment 2
It is the N, N '-(methylenediphenyl) BMI additive powder of positive electrode active materials quality 2% by quality
End is dissolved in appropriate NMP, and stirring forms homogeneous solution, is then added to containing 90% positive electrode active materials
Li1.18Ni0.15Co0.15Mn0.52O2, 4% conductive agent (mass ratio of conductive black and electrically conductive graphite be 1:1), 6% PVDF is bonded
In the mixed slurry of agent, dispersed with stirring uniformly prepares anode sizing agent；Anode sizing agent is coated on plus plate current-collecting body, through dry
Dry, roll-in, cut and obtain anode pole piece.
Embodiment 3
It is the N of positive electrode active materials quality 1% by quality, N '-vinyl BMI additive powder is dissolved in suitable
In amount NMP, stirring forms uniform solution, is then added to containing 90% positive electrode active materials Li1.18Ni0.15Co0.15Mn0.52O2、
(conductive black is 1 with the mass ratio of electrically conductive graphite to 4% conductive agent:1), in the mixed slurry of 6% PVDF binding agents, stirring point
Dissipate and uniformly prepare anode sizing agent；Anode sizing agent is coated on plus plate current-collecting body, through drying, roll-in, is cut and is obtained positive pole
Pole piece.
Embodiment 4
It is the N of positive electrode active materials quality 2% by quality, N '-vinyl BMI additive powder is dissolved in suitable
In amount NMP, stirring forms uniform solution, is then added to containing 90% positive electrode active materials Li1.18Ni0.15Co0.15Mn0.52O2、
(conductive black is 1 with the mass ratio of electrically conductive graphite to 4% conductive agent:1), in the mixed slurry of 6% PVDF binding agents, stirring point
Dissipate and uniformly prepare anode sizing agent；Anode sizing agent is coated on plus plate current-collecting body, through drying, roll-in, is cut and is obtained positive pole
Pole piece.
Comparative example
By 90% positive electrode active materials Li1.18Ni0.15Co0.15Mn0.52O2, 4% conductive agent (conductive black and electrically conductive graphite
Mass ratio be 1:1), 6% PVDF binding agent dispersed with stirring uniformly prepares anode sizing agent；Anode sizing agent is coated on just
On the collector of pole, through drying, roll-in, cut and obtain anode pole piece.
Test 1
Above-mentioned dried pole piece is punched into the disk of a diameter of 14mm, weighing, roll-in control the compacted density of pole piece
It is 2.0gcm-3.The pole piece that will be prepared is vacuum dried 12h, then with electrode plates as working electrode, lithium metal at 80 DEG C
Piece is that, to electrode and reference electrode, microporous polypropylene membrane is barrier film, using BASF high-voltage electrolytes, in the gloves full of argon Ar
Case (H2O<0.1ppm, O2<2032 button cells are assembled into 0.1ppm).With the electricity of 0.1C in the voltage range of 2.0-4.8V
Current density constant current charge and discharge is activated two weeks, then with the current density of 1C respectively in the voltage range of 2.0-4.8V or 2.0-4.6V
Constant current charge and discharge circulate, 1C=200mA/g, test result as shown in Figure 1, Figure 2 with shown in table 1, table 2.
Cycle performance under table 1,2.0-4.8V voltages
Cycle performance under table 2,2.0-4.6V voltages
Test 2
The bonding situation of the electrode after circulation, observation electrode material coating and collector is disassembled, as shown in Fig. 3 and Biao 3.
The bonding situation of electrode coating and current collector layers after table 3, pole piece processing characteristics and circulation
Test 3
Using the ac impedance spectroscopy that the front and rear electrode of circulation is measured on the PARSTAT2273 electrochemical workstations of U.S. Gamry,
Test result is as shown in Figure 4.
Test 4
The height of capacity 3Ah will be assembled into conventional SiC negative poles respectively by the anode pole piece of gained in embodiment and comparative example
Than can soft-package battery, overcharged, hot tank experiment test, test result such as table 4 is represented.
Table 4, overcharge, hot tank experimental results
In the anode sizing agent that the present invention is provided, due to not sharing ion pair and polarity containing a large amount of in the additive structure
Functional group, these interaction forces do not shared between ion pair and polar functional group and metal oxide-type electrode material can be improved
The dispersive property of electrode material, significantly improves the cohesive force between electrode material coating and collector, improves cycle performance.It is attached to
Double bond structure in the additive on material granule surface is additionally aided and forms more stable SEI films (see figure on material granule surface
4) side reaction between electrode material and electrolyte, is reduced.It is a large amount of in the structure of additive not share ion pair and polar functional group
With between collector also have stronger interaction force, be remarkably improved between electrode material coating and collector cohesive force (see
A is comparative example, b for embodiment 1, c is embodiment 2 in Fig. 3, Fig. 3), make institute's preparing lithium ion battery that there is capacity higher to keep
Rate (see Tables 1 and 2).
The above embodiment of the present invention and test proof, with the addition of lithium ion battery anode glue size of the invention in processability
Energy, cycle performance and security performance aspect, are presented good result, improve the specific capacity of anode material for lithium-ion batteries and fill
Discharge voltage；Various lithium battery materials such as lithium ion battery, lithium macromolecule battery anode electrode film are the composite can be widely applied to,
Applicability extensively, is suitable for industrial-scale production.
For the ordinary skill in the art, specific embodiment is that the present invention is exemplarily described,
Specific implementation of the present invention is not limited by aforesaid way.The present invention can have various modifications and variations, all of the invention
Within spirit and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (22)
1. a kind of additive for lithium ion battery, it is characterised in that
The additive includes one or more bismaleimide amine compound containing formula I or the structure of formula II；
The structure of the formula I is as follows：
The structure of the formula II is as follows：
Wherein, R1Selected from-R- ,-RNH2R-、-C(O)CH2-、-CH2OCH2-、-C(O)-、-O-、-O-O-、-S-、-S-S-、-S
(O)-、-CH2S(O)CH2-、-(O)S(O)-、-C6H4-、-CH2(C6H4)CH2-、-CH2(C6H4) (O)-, stretch phenyl and stretch xenyl
In one or more；
Wherein, R2Selected from-R- ,-C (O)-,-C (CH3)2-、-O-C6H4-C(CH3)2-C6H4-O-、-O-、-O-O-、-S-、-S-
S- ,-S (O)-and-(O) S (O)-in one or more；
Wherein, the R is to contain the 1-6 alkyl of carbon.
2. the additive for lithium ion battery according to claim 1, it is characterised in that
The R1And R2It is divalent organic substituent；
The R1Also include-R-Si (CH3)2-O-Si(CH3)2-R-、-C6H4-、-C6H4C6H4-, substitution stretch phenyl and substituted
Stretch one or more in xenyl.
3. the additive for lithium ion battery according to claim 2, it is characterised in that
The R1Phenyl and substituted one or more stretched in xenyl are stretched to stretch phenyl, stretching xenyl, substitution.
4. the additive for lithium ion battery according to claim 2, it is characterised in that
The R2For-O-C6H4-C(CH3)2-C6H4-O-。
5. a kind of electrolyte for lithium ion battery, it is characterised in that including：
Electrolytic salt, nonaqueous solvents and the additive according to any one of claim 1-3.
6. the electrolyte for lithium ion battery according to claim 5, it is characterised in that
Additive adding proportion in the electrolytic solution is 0.1-10wt.%.
7. the electrolyte for lithium ion battery according to claim 6, it is characterised in that
Additive adding proportion in the electrolytic solution is 5.0-6.5wt.%.
8. the electrolyte for lithium ion battery according to claim 5, it is characterised in that
The electrolytic salt includes LiCl, LiPF6、LiBF4、LiCH3SO3、LiCF3SO3、LiAsF6、LiSbF6、LiClO4、Li
[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3] and LiBOB in one or more.
9. the electrolyte for lithium ion battery according to claim 8, it is characterised in that
The electrolytic salt is LiBOB or LiPF6。
10. the electrolyte for lithium ion battery according to claim 5, it is characterised in that
The nonaqueous solvents includes ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, carbon
Sour butene esters, gamma-butyrolacton, gamma-valerolactone, dipropyl carbonate, 1-METHYLPYRROLIDONE (NMP), N-METHYLFORMAMIDE, N- first
Yl acetamide, dimethylformamide, DEF, diethyl ether, acetonitrile, propionitrile, methyl phenyl ethers anisole, succinonitrile, adiponitrile, penta 2
Nitrile, dimethyl sulfoxide, dimethyl sulfite, vinylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, fluoro carbon
Vinyl acetate, chlorocarbonic acid propylene, acid anhydrides, sulfolane, methoxy sulfone, tetrahydrofuran, 2- methyltetrahydrofurans, epoxy
Propane, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl propionate, methyl propionate, dimethylformamide, 1,3-
One or more in dioxolane, 1,2- diethoxyethane, 1,2- dimethoxy-ethanes and 1,2- dibutoxy ethane.
11. electrolyte for lithium ion battery according to claim 10, it is characterised in that
The nonaqueous solvents is the ethylene carbonate or propene carbonate in cyclic carbonate.
12. electrolyte for lithium ion battery according to claim 11, it is characterised in that
The nonaqueous solvents is propene carbonate.
A kind of 13. anode sizing agents for lithium ion battery, it is characterised in that including：
Positive electrode active materials, binding agent, conductive agent and the additive as described in claim any one of 1-3.
14. anode sizing agents for lithium ion battery according to claim 13, it is characterised in that
The adding proportion scope of the additive is 0.01-10wt.%.
15. anode sizing agents for lithium ion battery according to claim 14, it is characterised in that
The adding proportion of the additive is 0.01-2wt.%.
16. anode sizing agents for lithium ion battery according to claim 13, it is characterised in that
The additive is added with solid or solution form.
17. anode sizing agents for lithium ion battery according to claim 16, it is characterised in that
The additive is added in solid form.
18. anode sizing agents for lithium ion battery according to claim 13, it is characterised in that
The positive electrode active materials are lithium-rich manganese-based class positive electrode, and its chemical general formula is xLi2MnO3·(1-x)LiMO2,
Wherein, M is the mixture of one or more in Co, Ni, Mn；0 ＜ x ＜ 1.
19. anode sizing agents for lithium ion battery according to claim 13, it is characterised in that
The positive electrode active materials include tertiary cathode material, lithium cobaltate cathode material, manganate cathode material for lithium, lithium nickelate positive pole
The mixture of one or more in material and lithium iron phosphate positive material, chemical general formula is respectively LiNi1-x-yCoxMyO2、
LiCoO2、LiMn2O4、LiNiO2And LiFePO4；
Wherein, M is at least one in Mn or Al.
20. anode sizing agents for lithium ion battery according to claim 13, it is characterised in that
The conductive agent is selected from little particle carbon black, bulky grain graphite, acetylene black, the gentle long carbon fiber that coordinates of CNT
Plant or several.
21. anode sizing agents for lithium ion battery according to claim 13, it is characterised in that
The binding agent is selected from least one in Kynoar or polymethacrylate resin, and its group for being constituted.
A kind of 22. additives as described in claim any one of 1-21, electrolyte and anode sizing agent are in lithium ion battery
Using.
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| JP2019106369A (en) * | 2017-12-12 | 2019-06-27 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Positive electrode plate and method for forming slurry to be used for the same |
| CN111740147A (en) * | 2020-06-29 | 2020-10-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| CN112448035A (en) * | 2020-11-25 | 2021-03-05 | 东莞市天丰电源材料有限公司 | High-voltage lithium ion battery electrolyte and preparation method thereof |
| CN113614976A (en) * | 2019-01-17 | 2021-11-05 | 株式会社Lg新能源 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN114094102A (en) * | 2021-11-03 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Secondary battery |
| CN115043970A (en) * | 2022-06-20 | 2022-09-13 | 吉林大学 | Cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing maleimide structure, preparation method and application thereof |
| CN115117348A (en) * | 2022-06-30 | 2022-09-27 | 合肥国轩高科动力能源有限公司 | Lithium battery positive electrode slurry, positive electrode plate and lithium battery |
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