CN110247042A - A kind of interface modification method of lithium battery composite single crystal positive electrode - Google Patents
A kind of interface modification method of lithium battery composite single crystal positive electrode Download PDFInfo
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Abstract
The invention discloses a kind of interface modification methods of lithium battery composite single crystal positive electrode, the following steps are included: 1) prepare acrylonitrile monemer solution, photoinitiator is added thereto, monomer solution is atomized again, it sprays on monocrystalline positive electrode surface, then processed positive electrode is placed in mechanical fusion machine and is merged；2) in mechanical fusion machine, by the material of fusion under ultraviolet light irradiation, polymerization reaction is carried out, ionic liquid monomer is uniformly coated on positive electrode surface；3) after polymerization reaction, the positive electrode of polymer overmold is placed in tube furnace, is heat-treated at 150-300 DEG C, the composite single crystal positive electrode of interface modification is obtained.After interface modification, polymer is evenly coated at monocrystalline positive electrode surface, it can reduce the contact area of cell positive material and electrolyte, avoid side reaction and corrosion, to improve the cycle life and high rate performance of monocrystalline positive electrode, the lithium battery monocrystalline tertiary cathode material of excellent combination property is obtained.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of single crystal granular anode material of interface modification
And preparation method thereof.
Background technique:
Lithium ion battery has that operating voltage is high, energy density is high, specific capacity is big, self discharge is small, long service life etc. is prominent
Out advantage and gradually from mobile phone, computer, other consumer electronics products or even the ideal power supply of automobile.Since 1991
To today, lithium ion battery has been come into every household, lithium ion battery burning occurs with continuous, or even explode these
The generation of accident, the security performance of lithium ion battery is put forward higher requirements gradually；It is simultaneously to pursue in a limited space
Volume energy density, the sight of researcher are investing the higher monocrystalline of tap density (partial size D50 >=2 micron of primary particle) just
Pole material.The specific surface area of monocrystalline positive electrode can be reduced therewith, with the sum of the contact area of electrolyte can also be dropped
It is low, to reduce lithium ion battery in charge and discharge process due to gas caused by the side reaction of various electrolyte and electrode
Generation, thus to a certain extent promoted material safety energy.But the biggish partial size of monocrystalline positive electrode will lead to lithium from
Son increases ion diffusion length, while the electronic conductance that particle itself is poor with during insertion again in abjection, will lead to
The dynamic performance of monocrystalline positive electrode can decline, and it is not very excellent for leading to the high rate performance of material；Simultaneously because charge and discharge follow
The anisotropic dilation of crystal can occur for the monocrystalline positive electrode during ring, lead to the CEI (cathode of Surface Creation
Solid electrolyte interface) film is not enough to adapt to the variation, old CEI film rupture and new CEI film can be caused
It generates, cycle life is caused to will receive certain influence.Therefore it needs to be modified with meet demand positive electrode.
Modification to positive electrode includes doping vario-property, surface modification and blending and modifying.Studying at present more is doping
It is modified, i.e., some other elements are adulterated in positive electrode.It is less to the modified research in surface.With the depth to investigation of materials
Enter, to it, physically and electrically chemical property has a significant impact the surface nature of discovery positive electrode particle.Therefore recent much to grind
Study carefully and focus on modified to the surface of positive electrode, most of research concentrates on modified using surface of the inorganic matter to positive electrode
On.For example CN105489878A, CN105226256A are surface modified using some inorganic oxides, are avoided that or are reduced just
Contact of the pole material with electrolyte, can improve stability.But these methods will cause lithium ion deintercalation, lead to positive electrode
Structure change, and then battery performance declines.And this method needs to carry out material high-temperature process, metal oxide crystal grain point
The problems such as cloth is uneven, and partial size is unable to control, will lead to capacity reduces and the problems such as consistency is poor.
In the prior art there are also the method for some other positive electrodes modifications, patent CN105529458A discloses a kind of incite somebody to action
Nickel-cobalt-manganese ternary material is placed in the solution containing carboxyl or hydroxyl, and esterification occurs under esterification catalyst effect, passes through
The mode of chemical bond realizes that surface is modified, has obtained the ternary material of high-energy density.But this method is firstly the need of to ternary
Positive electrode carries out the modified introducing active group in surface, and the structure of second particle can occur to generate certain adverse effect even
It destroys, is unfavorable for the promotion of battery performance.
It is to use interface there are also interface modification, such as CN105702919A is carried out to positive electrode using high molecular material
Stabilisation of polymeric materials polymerized thylene carbonate vinyl acetate (PVCA) carries out surface package to lithium ion cell electrode, but this method is first
It is modified to positive electrode progress surface as binder that it is dissolved in organic solvent after so that monomer polymerization is obtained polymer material, is not
In-situ polymerization growth method, polymer modification material are unevenly distributed on positive electrode, still not can avoid general interface modified one
The poor defect of cause property.CN109273674A discloses a kind of side using acroleic acid polymerization to tertiary cathode material interface modification
Method is to be dissolved in polyacrylic acid after solvent is uniformly dispersed, and tertiary cathode material is added dropwise, heating removes solvent, neutralized with LiOH
The tertiary cathode material for obtaining Lithium polyacrylate cladding afterwards, is also to wrap again with positive electrode after first polymerizeing modified monomer
It covers, equally exists the bad problem of consistency.CN105633369A discloses a kind of method of carbon-coated LiFePO 4 for lithium ion batteries material, right
LiFePO4 progress surface is modified, coats one layer of ion liquid polymer on its surface, then Pintsch process ionic liquid is poly-
Object is closed, carbon-coated LiFePO 4 material is obtained.Ion liquid polymer is as carbon source, in order to which the high temperature sintering carbon of next step is mixed
Miscellaneous and carbon coating is prepared, and the polymer chain structure of ion liquid polymer is destroyed after sintering, not actually a kind of benefit
With the macromolecule method modified to positive electrode surface.And using the method for in-situ polymerization in solution, even with silane
After coupling agent changes positive electrode, polymer overmold it is also uneven, the good polymer wrapped of consistency can not obtained just
The surface modifying material of pole, and can have an adverse effect to the chemical property of positive electrode after having used silane coupling agent.
Summary of the invention
In order to overcome in the prior art to composite positive pole surface cladding, in terms of interface modification existing for deficiency and scarce
Fall into, the present invention by selecting specific organic monomer and polymerization technique to carry out interface modification to positive electrode, and it is an object of the present invention to provide
A kind of interface modification method of lithium battery composite single crystal positive electrode, it is intended to further decrease anode material for lithium-ion batteries and electricity
The contact area of liquid is solved, the electronic and ionic conductivity at positive electrode interface is improved, to improve the circulation longevity of monocrystalline positive electrode
Life and high rate performance.
The present invention solves the technical problem to be solved in the present invention by the following technical programs:
A kind of interface modification method of lithium battery composite single crystal positive electrode, comprising the following steps:
1) prepare acrylonitrile monemer solution, photoinitiator is added thereto, then monomer solution is atomized, spray monocrystalline just
Processed positive electrode is then placed in mechanical fusion machine and merges by pole material surface；
2) in mechanical fusion machine, by the material of fusion in the light source that the photoinitiator can be made to generate living radical
Under, polymerization reaction is carried out, polymer is uniformly coated on positive electrode surface；
3) after polymerization reaction, the positive electrode of polymer overmold is placed in tube furnace, at 150-300 DEG C at heat
Reason, obtains the composite single crystal positive electrode of interface modification.
There is no particular limitation for the monocrystalline positive electrode, and the ternary or polynary positive pole material of this field routine are all in this hair
Within the scope of bright restriction, representative example has LiNiO2、LiCoO2、LiNiMn2-bO4(N=Fe, Mn, V, Ni, 1 > b > 0),
LiNixCoyB1-x-yO2(B is Mn or Al, 1 > x > 0,1 > y > 0, rLi2MnO3·(1-r)LiRO2(R=Co, Mn, Ni, 1 > c > 0)
One or more of；It is preferred that LiNixCoyMn1-x-yO2, common wherein in ternary precursor based on nickel element (x >=0.5)
Nickel cobalt manganese ratio include 811,622,424,433,532,415 etc..The particle size range of the monocrystalline positive electrode primary particle
At 2-10 μm, preferably 3-8 μm.The interface modification method of the invention being characterized by monocrystalline positive electrode, it is preferred that emphasis is single
The selection of body and proportion and light-initiated polymerizing condition, rather than specific monocrystalline positive electrode, interface provided by the invention
Method of modifying is applicable in monocrystalline positive electrode with pervasive, and is not limited to the specific anode used in the embodiment of the present invention
Material.
The quality proportioning of monocrystalline composite positive pole and organic monomer is 5-30:1, preferably 10-15:1.Organic monomer is used
It measures very few, effectively positive electrode cannot be coated, not can avoid corrosion of the electrolyte to positive electrode；Organic monomer dosage
Excessively, monocrystalline positive electrode is wrapped up it is blocked up, be unfavorable for monocrystalline positive electrode conduction lead it is ionic, and then can be to battery capacity
It adversely affects.
Acrylonitrile monemer solution concentration is the solution of 0.5-1.5M.The solvent prepared in monomer solution is not particularly limited,
As long as the organic solvent that can have certain solubility to organic monomer and will not be adversely affected to polymerization reaction, preferably matter
Sub- polar organic solvent, including methanol, ethyl alcohol, acetone, acetonitrile, dimethyl sulfoxide, n,N-Dimethylformamide, N- methylpyrrole
Alkanone, tetrahydrofuran, at least one of ethyl acetate.
Preferably, in acrylonitrile monemer solution, the imidazolium ion liquid with carbon carbon unsaturated double-bond can also be added
Body monomer.The molar ratio of acrylonitrile and imidazolium ionic liquid monomer is 10-15:1.
The ionic liquid thermal stability of imidazoles is better than the ionic liquid of pyrroles's type and pyridine type, and its conductivity and
Lithium ion mobility speed is all than convenient.Preferably, the cation of ionic liquid is the glyoxaline cation replaced containing alkenyl group,
It is described to be selected from vinyl, acrylic, cyclobutenyl, acrylate-based or methacrylate containing alkenyl group；Anion is six
In fluorophosphoric acid root, tetrafluoroborate, bis- (fluoroform sulphonyl) imines roots, double fluorine sulfimide roots, chloride ion and bromide ion
It is a kind of.
It is further preferable that ionic liquid monomer is 1- acrylic acid alkyl ester group-imidazoles salt, structure leads to formula (I) institute as follows
Show:
Wherein, n is the integer of 1-20, the preferably integer of 4-10；R is the alkyl of carbon atom number 1-6, such as methyl, second
Base, propyl, butyl, amyl or hexyl or carbon atom are the aryl of 6-20, such as phenyl, even phenyl, Nai Ji, the alkyl or
Aryl can optionally be replaced by groups such as halogen, alkyl, halogenated alkyl, alkoxy, hydroxyl, nitros.The alkyl, halogenated alkyl,
The carbon atom numerical digit of alkoxy 1-6；X-Anion is selected from hexafluoro-phosphate radical, tetrafluoroborate, bis- (fluoroform sulphonyl) Asia
One of amine root, double fluorine sulfimide roots, chloride ion and bromide ion.
The example of adducible ionic liquid monomer includes but is not limited to 1- vinyl -3- methylimidazole tetrafluoro boric acid
Salt, 1- vinyl -3- ethyl imidazol(e) hexafluorophosphate, 1- vinyl -3- methylimidazole bis- (fluoroform sulphonyl) inferior amine salts, 1-
The double fluorine sulfimide salts of butyl acrylate -3- methylimidazole, the double fluorine sulfimide salts of 1- Hexyl 2-propenoate -3- methylimidazole, 1-
The double fluorine sulfimide salts of Hexyl 2-propenoate -3- phenylimidazole, the double fluorine sulfimide salts of 1- decyl acrylate -3- methylimidazole and 1-
The double fluorine sulfimide salts of dodecylacrylate -3- methylimidazole.
There is no particular limitation for the mode being atomized in step 1), as long as monomer solution to be passed through to atomization under a certain pressure
Nozzle, so that liquid is atomized into fine droplet, liquid-drop diameter range is at 50-200 microns.The equipment of its achievable atomization process has
Compression atomizing pump, power spraye, power driven sprayer etc., wherein the aperture of the pressure and atomizer of control water pump can be passed through
Aperture controls the diameter of atomized liquid.
The mode for causing monomer polymerization in the present invention causes the freedom of carbon-carbon double bond using photoinitiator under light source irradiation
Base polymerization.It is typically chosen the moderate photoinitiator of activity, such as diphenylethan, benzophenone, 2,4-DihydroxyBenzophenone,
Benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether.The dosage of initiator is monomer gross mass
0.1-1%, preferably 0.3-0.5%.Initiator amount is very few, and the monocrystalline positive electrode that can not be effectively evenly coated draws
Hair agent dosage is excessive, and polymer molecular weight is few, and polymer segment is short, is not enough to coat monocrystalline positive electrode.
The mechanical fusion machine fusion is that material is put into mechanical fusion machine, operates 0.5-1h at 1000-2000rpm,
Realize the fusion of monocrystalline positive electrode and ionic liquid monomer solution.
The preferred ultraviolet lamp of light source that photoinitiator can be made to generate living radical, in particular to photoinitiator are in 250-
400nm wavelength, intensity of illumination 2.0-3.5mW/cm2Ultraviolet light under, generate have polymerization activity free radical, cause
The polymerization reaction of carbon carbon unsaturated double-bond, irradiation time 3-6h in monomer.After polymerization reaction, by obtained solid in inertia
3-6h is heat-treated in the tube furnace of atmosphere protection at 150-300 DEG C, it is more to remove preferably in 200-240 DEG C of heat treatment 2-4h
Remaining solvent and unreacted monomer.The interface consistency for further strengthening polymer and positive electrode is beneficial to promote ionic liquid
The conductivity and lithium ion transference number of polymer are conducive to the high rate performance and cyclical stability that promote monocrystalline positive electrode.
After the present invention is using first positive electrode and monomer solution is merged, cause monomer polymerization with light-initiated mode, gathers
The surface that object can be coated on to even compact positive electrode is closed, uniform interface is formed, has been obviously improved monocrystalline positive electrode
High rate performance and cyclical stability, circular flow 100 times under 1C multiplying power, capacity retention ratio is 90% or more.
Compared with the existing technology, the beneficial effects of the present invention are:
One, method of modifying of the invention is by acquired lithium ion battery monocrystalline positive electrode, using carbon containing carbon
The acrylonitrile and imidazole salt ionic liquid of double bond are as monomer, and free radical polymerization under ultraviolet light, obtains after mechanical fusion
The monocrystalline composite positive pole of ion liquid polymer even compact cladding is arrived.After carrying out interface modification to positive electrode, have
Effect reduces the side reaction that contact of the positive electrode with electrolyte generates, and high rate performance, the cyclical stability of positive electrode all obtain
It is obviously improved.
Two, polymer is to grow to obtain in positive electrode surface by situ aggregation method in the present invention, high poly- compared to being first made
Object, then the method that high polymer is coated on electrode material surface is compared, using the method for in-situ polymerization, polymer can be coated more
For uniform densification, be conducive to the further promotion of positive electrode performance.And the present invention is by spray pattern that monomer is molten
Liquid is sprayed at positive electrode surface, and in-situ polymerization obtains by way of light initiation polymerization, compared in the polymerization side of solution phase
Method, monomer concentration is bigger in light-initiated polymerization system, and the surface of positive electrode can more closely be coated on after polymerization, and
And the molecular weight of polymer is adjusted by light application time and intensity of illumination and the dosage of photoinitiator with can be convenient, so that
Ion liquid polymer macromolecular chain suitable length, being capable of preferably clad anode material.
Three, positive electrode interface modification method provided by the invention is that polymer is coated on to positive electrode surface, is gathered
Closing object clad not only can be reduced contact of the positive electrode with electrolyte, reduce the area of side reaction, reduce inside battery gas
Generation, to enhance the safety of battery；Simultaneously because contact area reduces, corrosion of the corresponding electrolyte to anode
It can reduce, to improve the cycle life of positive electrode.
Four, when carrying out cladding of the polymer to anode, a certain amount of ionic liquid monomer and acrylonitrile compolymer is added, removes
Reduction side reaction, improves the cyclical stability of positive electrode, moreover it is possible to improve the contact internal resistance at material interface, to a certain degree
On improve the electronics and ionic conductivity of material, to enhance the deintercalation dynamics of monocrystalline positive electrode, improve monocrystalline anode
The high rate performance of material enables lithium ion battery in high-power lower charge and discharge, more has to the performance boost of lithium ion battery
It helps.Particularly with tertiary cathode material containing Ni-Co-Mn (or wherein any two kinds, or containing only Co), it is difficult to accomplish height
Warm carbon coating, because under hot conditions, if carbon directly can generate carbon dioxide and run away with oxygen reaction under oxygen atmosphere.
Under an inert atmosphere, carbon has reproducibility, and the metallic element of high-valence state is reacted with carbon in tertiary cathode material, also becomes titanium dioxide
Carbon is run away, and metallic element becomes lower valency by high-valence state.Therefore the cladding and high temperature carbon coating of polymer are that there is no comparative
's.
Five, for the present invention to the interface modification method simple process of tertiary cathode material, raw material is cheap and easy to get, is suitable for industrialization
Extensive implementation, to lithium battery performance further increase have greatly promoted, compared to without modifying interface just
Pole material, positive electrode after modification have superior high rate performance and cyclical stability, have very high application value and
Research significance.
Detailed description of the invention
Fig. 1 is the shape appearance figure for the scanning electron microscope that embodiment 1 carries out the positive electrode after interface modification.
Fig. 2 embodiment 1 carries out X-ray diffractometer (XRD) map of the positive electrode after interface modification.
Fig. 3 is the high-resolution-ration transmission electric-lens figure for the positive electrode that embodiment 1 carries out after interface modification.
Fig. 4 is the grain size distribution for the positive electrode that embodiment 1 carries out after interface modification.
Fig. 5 is that the high resolution scanning electricity of the positive electrode after the progress interface modification of embodiment 7 penetrates figure.
Fig. 6 is assembled into the multiplying power figure of lithium ion battery for the positive electrode after the progress interface modification of embodiment 1.
Fig. 7 specific discharge capacity conservation rate figure under 0.5C multiplying power for the positive electrode after the progress interface modification of embodiment 1.
Fig. 8 specific discharge capacity conservation rate figure under 1C multiplying power for the positive electrode after the progress interface modification of embodiment 1.
Fig. 9 charging and discharging curve figure under 0.1C multiplying power for the positive electrode after the progress interface modification of embodiment 7.
Figure 10 is the shape appearance figure for the scanning electron microscope that comparative example 1 carries out the positive electrode before interface modification.
Figure 11 is the transmission electron microscope picture of 3 gained positive electrode of comparative example.
Specific embodiment
Monocrystalline composite positive pole interface modification method of the invention is described further combined with specific embodiments below,
But the present invention is not limited to following embodiments.Unless otherwise defined, all technical terms used hereinafter and this field skill
The normally understood meaning of art personnel is identical.Technical term used herein is intended merely to the purpose of description specific embodiment,
It is not intended to and limits the scope of the invention.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Mechanical fusion is to be purchased using ZSJ-600 mechanical fusion machine from Zhong Yuan powder Science and Technology Ltd. in embodiment.
The lithium ion battery lithium ion battery monocrystalline stratiform is characterized with scanning electron microscope (JEOL-6701F)
Positive electrode high circulation stability member positive electrode.It is analyzed with powder x-ray diffraction (Rigaku DmaxrB, CuK alpha ray)
The crystal structure of high specific energy ternary anode material for lithium-ion batteries.
Embodiment 1
3.12g acrylonitrile is dissolved in n,N-Dimethylformamide, the monomer solution of 1mol/L is formulated as, is added thereto
Monomer solution is pumped by compression atomizing and is atomized after mixing evenly by 10mg diphenylethan, and the droplet diameter of atomization about exists
It 100 μm, sprays on 31.45g monocrystalline positive electrode surface, processed positive electrode is then placed in mechanical fusion machine,
0.5h is operated under 1500rpm, is sufficiently merged；The monocrystalline positive electrode is LiNi0.8Co0.1Mn0.1；
2) it in mechanical fusion machine, by fused material under the ultraviolet light high voltage mercury lamp radiation of power adjustable, carries out
Polymerization reaction, ionic liquid monomer are uniformly coated on positive electrode surface, and wherein ultraviolet lamp wavelength is 300-369nm, illumination
Time is 3h, intensity of illumination 2.55mW/cm2；
3) after polymerization reaction, the positive electrode of polymer overmold is placed in the tube furnace of inert atmosphere protection,
It is heat-treated 2h at 200 DEG C, obtains the composite single crystal positive electrode of interface modification.
Embodiment 2
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 1, difference is acrylonitrile
Dosage is changed to 2.10g
Embodiment 3
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 1, difference is acrylonitrile
Dosage is changed to 1.35g.
Embodiment 4
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 1, difference is acrylonitrile
Dosage is changed to 5.44g.
Embodiment 5
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 1, difference is that monomer is
The compounding of acrylonitrile and 1- vinyl -3- methyl imidazolium tetrafluoroborate, the use of 1- vinyl -3- methyl imidazolium tetrafluoroborate
Amount is the 10mol% of acrylonitrile.
Embodiment 6
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 1, difference is that monomer is
The compounding of acrylonitrile and 1- vinyl -3- ethyl imidazol(e) hexafluorophosphate, the use of 1- vinyl -3- methyl imidazolium tetrafluoroborate
Amount is the 7mol% of acrylonitrile.
Embodiment 7
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 5, difference is ionic liquid
Body monomer is the double fluorine sulfimide salts of 1- Hexyl 2-propenoate -3- methylimidazole.
Embodiment 8
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 5, difference is ionic liquid
Body monomer is the double fluorine sulfimide salts of 1- decyl acrylate -3- methylimidazole.
Embodiment 9
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 5, difference is ionic liquid
Body monomer is the double fluorine sulfimide salts of 1- dodecylacrylate -3- methylimidazole.
Embodiment 10
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 5, difference is monocrystalline just
Pole material replaces with LiNi0.6Co0.2Mn0.2。
Comparative example 1
First by lithium battery LiNi0.8Co0.1Mn0.1Monocrystalline positive electrode and ethanol solution are uniformly mixed, and stir 70min；
The solid in solution is collected, 0.5h is reacted at 200 DEG C, obtains the lithium battery monocrystalline positive electrode without polymer overmold.
Comparative example 2
According to the composite single crystal positive electrode for preparing interface modification with the identical method of embodiment 5, difference is to be heat-treated
It is the high temperature sintering 8h at 800 DEG C, destroys the macromolecular structure of ion liquid polymer, forms carbon-coated positive electrode.
Comparative example 3
3.12g acrylonitrile is dissolved in n,N-Dimethylformamide, the monomer solution of 1mol/L is formulated as, is added thereto
31.45g LiNi is added into monomer solution for 6mg dibenzoyl peroxide (BPO)0.8Co0.1Mn0.1Monocrystalline positive electrode, heating
It polymerize to 60-80 DEG C of initiation, reacts 2h；
2) after polymerization reaction, the positive electrode of polymer overmold is placed in tube furnace, is heat-treated at 200 DEG C
2h obtains the composite single crystal positive electrode of interface modification.
Application examplesThe characterization and performance test of the single crystal granular anode material of interface modification
The positive electrode for the interface modification that embodiment 1 obtains, stereoscan photograph are as shown in Figure 1, it can be seen that use
The method of the present invention, it is more coarse by the positive electrode particle surface of polymer overmold interface modification, this is because clad compared with
Good has been covered on particle surface.The XRD spectrum of the positive electrode for the interface modification that embodiment 1 obtains is as shown in Fig. 2, can see
Out, interface modification method of the invention, i.e. polymer overmold and low-temperature treatment do not have an impact the main body stratiform knot of positive electrode
Structure, the peak intensity ratio of the diffraction maximum of the diffraction maximum and 104 crystal faces for 003 crystal face that XRD is indicated are 1.394 greater than 1.2. explanation
The lithium ion mixing degree of material is small.Fig. 3 is the high-resolution-ration transmission electric-lens of the positive electrode for the interface modification that embodiment 1 obtains
Figure, can see that the certain covering material of polymer has been uniformly coated on monocrystalline positive electrode, and do not occur two-phase laminated flow this
Kind thing.The grain size distribution of positive electrode after the interface modification that embodiment 1 obtains is as shown in Figure 4.As can be seen that by poly-
The positive electrode particle diameter distribution for closing object cladding is uniform, and partial size is larger, illustrates interface modification method of the invention not to monocrystalline just
The partial size of pole material has an impact, and the monocrystal material of bulky grain is conducive to play the performance of tertiary cathode material.
Embodiment 7 is also added into the double fluorine sulfimide salts and third of ionic liquid monomer 1- Hexyl 2-propenoate -3- methylimidazole
Alkene nitrile is copolymerized together, the tertiary cathode material electromicroscopic photograph of obtained interface modification as shown in the high-resolution scanning electron microscope of Fig. 5,
Entire monocrystalline positive electrode particle color is uniform, illustrates the integrality coated to positive electrode particle.As can be seen that in ionic liquid monomer
In structure, the soft segment of certain length is added, the cladding to positive electrode can be better achieved.
For positive electrode without polymer overmold, stereoscan photograph is as shown in Figure 10 in comparative example 1, it can be seen that
Material without polymer overmold, surface is clean, smooth.Positive electrode uncoated in this way can not play clad to subtract
Few contact of the positive electrode with electrolyte, reduces the effect of side reaction.
Comparative example 3 is using water phase free radical polymerization, the positive electrode of obtained polymer overmold, transmission electron microscope photo
As shown in figure 11, it can be seen that water phase cladding is dotted cladding, does not have preferable protecting effect for monocrystalline anode.Therefore,
Cyclical stability is also had a greatly reduced quality.
The present invention also tests the chemical property of gained interface modification positive electrode, and specific method is by embodiment and comparison
Anode material for lithium-ion batteries that example is prepared, carbon black, Kynoar binder is with mass ratio are as follows: 8:1:1 mixing is made into
Slurry, the aluminum foil current collector for being homogeneously applied to utter misery obtains positive diaphragm, using metal lithium sheet as cathode, microporous polypropylene membrane
(Celgard2400) diaphragm, 1mol/L LiPF are used as6(solvent is ethylene carbonate (EC), the carbonic acid diformazan of volume ratio 1:1:1
The mixed liquor of ester (DMC) and diethyl carbonate (DEC)) it is used as electrolyte, 2032 knobs are assembled into the glove box of argon gas protection
Detain battery.The battery of assembly is subjected to constant current charge-discharge test, voltage range 3-4.3V, test on blue electric charge-discharge test instrument
Temperature is 25 DEG C, charge and discharge is carried out under different multiplying, the actual discharge specific capacity of test material is specifically tested at 0.1C
Specific discharge capacity is tested the cyclical stability of positive electrode at multiplying power 1C, and is obtained more by sweeping fast cyclic voltammetry calculating
Obtain the apparent lithium ion diffusion coefficient of positive electrode.As a result as shown in table 1 below:
Fig. 6 is assembled into the multiplying power figure of lithium ion battery, test curve for the positive electrode after the progress interface modification of embodiment 1
Be divided into it is stepped that 6 sections, respectively represent is 0.1C, 0.5C, 1C, 2C, 3C, the specific discharge capacity figure under 5C test condition can
To find out, 151mA h g can be reached the specific discharge capacity under the high magnification of 5C-1, illustrate material with one well
High rate performance.Fig. 7, Fig. 8 are respectively that embodiment 1 carries out the positive electrode after interface modification and discharges under 0.5C and 1C multiplying power specific volume
Measure conservation rate figure.Under low range and powerful test condition, cyclical stability obtains positive electrode after illustrating cladding
Raising is arrived.Fig. 9 charging and discharging curve figure under 0.1C multiplying power for the positive electrode after the progress interface modification of embodiment 7.Specific capacity
For 204.8mA h g-1, coulombic efficiency is 88.3% for the first time, illustrate to be added a certain amount of ionic liquid monomer with flexible chain with
Acrylonitrile compolymer can better play clad anode material, reduce and electrolyte contacts, while apparent lithium ion diffusion coefficient
It improves a lot, specific discharge capacity and cyclical stability are further improved.
Table 1
It can be seen that interface modification positive electrode provided by the invention by the data of Figure of description and table 1, it is comprehensive
Can be excellent, due to after positive electrode coated with uniform polymer material, effectively reducing positive electrode and electrolyte
Contact, reduces the generation of side reaction and corrosion.Especially when compounding using acrylonitrile and ionic liquid monomer, association has been played
Same-action, high rate performance, specific discharge capacity and the cyclical stability of positive electrode are all obviously improved, and have very high answer
With value and research significance.
Above content is merely a preferred embodiment of the present invention, and is not intended to limit embodiment of the present invention, and this field is general
Logical technical staff's central scope according to the present invention and spirit can very easily carry out corresponding flexible or modification, therefore
Protection scope of the present invention should be subject to protection scope required by claims.Such as monocrystalline used in the embodiment of the present invention
Positive electrode is LiNi0.8Co0.1Mn0.1And LiNi0.6Co0.2Mn0.2, but of the invention be characterized by monocrystalline positive electrode
Interface modification method, it is preferred that emphasis is the selection of monomer and proportion and light-initiated polymerizing condition, rather than monocrystalline positive electrode
Selection, interface modification method provided by the invention has universality for monocrystalline positive electrode, and is not limited to of the invention real
Apply the specific positive electrode used in example.
Claims (10)
1. a kind of interface modification method of lithium battery composite single crystal positive electrode, comprising the following steps:
1) acrylonitrile monemer solution is prepared, photoinitiator is added thereto, then monomer solution is atomized, is sprayed in monocrystalline anode material
Expect surface, then processed positive electrode is placed in mechanical fusion machine and is merged；
2) in mechanical fusion machine, by the material of fusion under the light source that the photoinitiator can be made to generate living radical,
Polymerization reaction is carried out, polymer overmold is on positive electrode surface；
3) after polymerization reaction, the positive electrode of polymer overmold is heat-treated at 150-300 DEG C, obtains interface modification
Composite single crystal positive electrode.
2. interface modification method as described in claim 1, which is characterized in that the monocrystalline positive electrode is selected from LiNiO2、
LiCoO2、LiNiMn2-bO4(N=Fe, Mn, V, Ni, 1 > b > 0), LiNixCoyB1-x-yO2(B be Mn or Al), 1 > x > 0,1 > y >
0、rLi2MnO3·(1-r)LiRO2One or more of (R=Co, Mn, Ni, 1 > c > 0)；It is preferred that LiNixCoyMn1-x-yO2,
Wherein in ternary precursor based on nickel element (x >=0.5), the particle size range of the monocrystalline positive electrode primary particle is in 2-10
μm, preferably 3-8 μm.
3. interface modification method as described in claim 1, which is characterized in that the matter of monocrystalline composite positive pole and organic monomer
Amount proportion is 5-30:1, preferably 10-15:1.
4. interface modification method as described in claim 1, which is characterized in that in acrylonitrile monemer solution, be additionally added and have
The molar ratio of the imidazolium ionic liquid monomer of carbon carbon unsaturated double-bond, acrylonitrile and imidazolium ionic liquid monomer is 10-15:
1。
5. interface modification method as claimed in claim 4, which is characterized in that the cation of the imidazolium ionic liquid monomer
It is described to be selected from vinyl, acrylic, cyclobutenyl, acrylate containing alkenyl group for the glyoxaline cation replaced containing alkenyl group
Base or methacrylate；Anion is hexafluoro-phosphate radical, tetrafluoroborate, bis- (fluoroform sulphonyl) imines roots, double fluorine
One of sulfimide root, chloride ion and bromide ion.
6. interface modification method as claimed in claim 5, which is characterized in that the ionic liquid monomer is 1- acrylic acid alkyl
Ester group-imidazoles salt, structure are led to as follows shown in formula (I):
Wherein, n is the integer of 1-20, the preferably integer of 4-10；R is the alkyl of carbon atom number 1-6, such as methyl, ethyl, third
The aryl that base, butyl, amyl or hexyl or carbon atom are 6-20, such as phenyl, company phenyl, Nai Ji, the alkyl or aryl can
Optionally replaced by groups such as halogen, alkyl, halogenated alkyl, alkoxy, hydroxyl, nitros；The alkyl, halogenated alkyl, alkoxy
Carbon atom numerical digit 1-6；X-Anion is selected from hexafluoro-phosphate radical, tetrafluoroborate, bis- (fluoroform sulphonyl) imines roots, double
One of fluorine sulfimide root, chloride ion and bromide ion.
7. interface modification method as claimed in claim 5, which is characterized in that the imidazolium ionic liquid monomer includes 1- second
Alkenyl -3- methyl imidazolium tetrafluoroborate, 1- vinyl -3- ethyl imidazol(e) hexafluorophosphate, 1- vinyl -3- methylimidazole are double
The double fluorine sulfimide salts of (fluoroform sulphonyl) inferior amine salt, 1- butyl acrylate -3- methylimidazole, 1- Hexyl 2-propenoate -3- first
The double fluorine sulfimide salts of base imidazoles, the double fluorine sulfimide salts of 1- Hexyl 2-propenoate -3- phenylimidazole, 1- decyl acrylate -3- first
In the double fluorine sulfimide salts of base imidazoles and the double fluorine sulfimide salts of 1- dodecylacrylate -3- methylimidazole.
8. interface modification method as described in claim 1, which is characterized in that cause the mode of monomer polymerization, use is light-initiated
Agent causes the free radical polymerization of carbon-carbon double bond under light source irradiation；Photoinitiator is selected from diphenylethan, benzophenone, 2,4- bis-
Dihydroxy benaophenonel, at least one of benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether；With/
Or the dosage of initiator is the 0.1-1%, preferably 0.3-0.5% of monomer gross mass.
9. interface modification method as described in claim 1, which is characterized in that the light source irradiation refers to that photoinitiator exists
250-400nm wavelength, intensity of illumination 2.0-3.5mW/cm2Ultraviolet light under, irradiation time 3-6h；And/or polymerization
After reaction, obtained solid is heat-treated 3-6h at 150-300 DEG C in the tube furnace of inert atmosphere protection, preferably existed
200-240 DEG C of heat treatment 2-4h.
10. a kind of interface modification lithium battery composite single crystal positive electrode, which is characterized in that pass through any one of claim 1-9 institute
The method of modifying stated is prepared.
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| CN112803007B (en) * | 2021-03-12 | 2022-02-22 | 合肥国轩高科动力能源有限公司 | Method for coating modified single crystal ternary cathode material with microporous conductive polymer film and modified single crystal ternary cathode material |
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| CN114744196A (en) * | 2022-03-28 | 2022-07-12 | 蜂巢能源科技股份有限公司 | C-doped and coated cobalt-free cathode material, preparation method and lithium ion battery |
| CN114744196B (en) * | 2022-03-28 | 2024-03-12 | 蜂巢能源科技股份有限公司 | C-doped and coated cobalt-free positive electrode material, preparation method and lithium ion battery |
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