CN110247042B - Interface modification method for lithium battery composite single crystal positive electrode material - Google Patents
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Abstract
The invention discloses an interface modification method of a composite single crystal positive electrode material of a lithium battery, which comprises the following steps of: 1) preparing an acrylonitrile monomer solution, adding a photoinitiator into the acrylonitrile monomer solution, atomizing the monomer solution, spraying the atomized monomer solution on the surface of a single crystal anode material, and then placing the treated anode material into a mechanical fusion machine for fusion; 2) in a mechanical fusion machine, the fused material is subjected to polymerization reaction under the irradiation of an ultraviolet lamp, and the surface of the positive electrode material is uniformly coated with the ionic liquid monomer; 3) after the polymerization reaction is finished, the polymer-coated anode material is placed in a tubular furnace and is subjected to heat treatment at the temperature of 150-300 ℃ to obtain the interface modified composite single-crystal anode material. After interface modification, the polymer is uniformly coated on the surface of the single crystal anode, so that the contact area of the battery anode material and electrolyte can be reduced, and side reaction and corrosion are avoided, thereby improving the cycle life and rate performance of the single crystal anode material and obtaining the single crystal ternary anode material for the lithium battery with excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an interface modified single crystal particle positive electrode material and a preparation method thereof.
Background art:
lithium ion batteries have the outstanding advantages of high operating voltage, high energy density, large specific capacity, small self-discharge, long service life, etc., and are increasingly becoming ideal power sources for mobile phones, computers, other consumer electronics, and even automobiles. Since 1991 to today, lithium ion batteries have been moved into households, and with the continuous occurrence of accidents such as combustion and even explosion of the lithium ion batteries, higher requirements are gradually put forward on the safety performance of the lithium ion batteries; meanwhile, in order to pursue the volume energy density in a limited space, researchers are focusing on single crystal (the grain diameter D50 of primary particles is more than or equal to 2 microns) anode materials with higher tap density. The specific surface area of the single crystal anode material is reduced, and the contact area with the electrolyte is reduced, so that the generation of gas caused by side reactions of various electrolytes and electrodes in the charging and discharging processes of the lithium ion battery is reduced, and the safety performance of the material is improved to a certain extent. However, the larger particle size of the single crystal anode material can increase the ion diffusion distance in the processes of lithium ion extraction and re-insertion, and meanwhile, the poor electronic conductivity of the particles can reduce the dynamic performance of the single crystal anode material, so that the rate capability of the material is not very excellent; meanwhile, due to the anisotropic expansion and contraction of crystals of the single crystal cathode material in the charge-discharge cycle process, the CEI (cathode induced electrolyte interface) film generated on the surface is not enough to adapt to the change, the rupture of the old CEI film and the generation of a new CEI film are caused, and the cycle life is influenced to a certain extent. Therefore, modification of the positive electrode material is required to meet the demand.
The modification of the positive electrode material comprises doping modification, surface modification and blending modification. Currently, doping modification, i.e. doping some other elements in the cathode material, is being studied more. Surface modification is less studied. With the progress of the research on the materials, it was found that the surface properties of the positive electrode material particles have a great influence on the physical and electrochemical properties thereof. Much recent research has therefore been focused on surface modification of positive electrode materials, and most of the research has been focused on surface modification of positive electrode materials with inorganic substances. For example, CN105489878A and CN105226256A adopt some inorganic oxides for surface modification, which can avoid or reduce the contact between the cathode material and the electrolyte, and can improve the stability. However, these methods cause lithium ion deintercalation, resulting in structural changes of the positive electrode material, and thus, battery performance is degraded. Furthermore, this method requires high-temperature treatment of the material, and causes problems such as uneven distribution of metal oxide crystal grains and uncontrollable particle size, which leads to problems such as reduced capacity and poor uniformity.
In the prior art, other methods for modifying the anode material exist, and patent CN105529458A discloses that a nickel-cobalt-manganese ternary material is placed in a solution containing carboxyl or hydroxyl, an esterification reaction is performed under the action of an esterification catalyst, and surface modification is realized by a chemical bond manner, so as to obtain a ternary material with high energy density. However, the method firstly needs to modify the surface of the ternary cathode material to introduce active groups, which can cause certain adverse effects or even damage to the structure of secondary particles, and is not beneficial to improving the battery performance.
In addition, a high molecular material is adopted to perform interface modification on the positive electrode material, for example, CN105702919A, which is a surface-coating method of an electrode of a lithium ion battery with an interface-stable polymer material, namely, polyvinyl carbonate (PVCA), but the method firstly polymerizes monomers to obtain a polymer material, and then dissolves the polymer material in an organic solvent to serve as a binder to perform surface modification on the positive electrode material, is not an in-situ polymerization growth method, and is not uniform in distribution of the polymer modified material on the positive electrode material, or cannot avoid the defect of poor consistency of general interface modification. CN109273674A discloses a method for modifying the interface of a ternary cathode material by utilizing acrylic acid polymerization, which is to dissolve polyacrylic acid in a solvent for uniform dispersion, then to drop the ternary cathode material, to heat to remove the solvent, to neutralize with LiOH to obtain the lithium polyacrylate coated ternary cathode material. CN105633369A discloses a method for coating a carbon-coated lithium iron phosphate material, which comprises performing surface modification on lithium iron phosphate, coating a layer of ionic liquid polymer on the surface of the lithium iron phosphate, and then cracking the ionic liquid polymer at high temperature to obtain the carbon-coated lithium iron phosphate material. The ionic liquid polymer is used as a carbon source, and preparation is made for high-temperature sintering carbon doping and carbon coating of the next step, and the macromolecular chain structure of the ionic liquid polymer is destroyed after sintering, so that the method is not a method for modifying the surface of the cathode material by utilizing macromolecules. And by adopting the in-situ polymerization method in the solution, even if the silane coupling agent is used for modifying the anode material, the coating of the polymer is not uniform, the surface modified material with the polymer coating the anode with good consistency can not be obtained, and the silane coupling agent is used for generating adverse effect on the electrochemical performance of the anode material.
Disclosure of Invention
In order to overcome the defects and defects of the surface coating and interface modification of the composite anode material in the prior art, the invention carries out interface modification on the anode material by selecting a specific organic monomer and a polymerization process, and aims to provide an interface modification method of the composite single crystal anode material of the lithium battery, which aims to further reduce the contact area between the anode material of the lithium ion battery and electrolyte and improve the electronic ionic conductivity of the interface of the anode material, thereby improving the cycle life and the rate capability of the single crystal anode material.
The technical problems to be solved by the invention are solved by the following technical scheme:
an interface modification method of a lithium battery composite single crystal positive electrode material comprises the following steps:
1) preparing an acrylonitrile monomer solution, adding a photoinitiator into the acrylonitrile monomer solution, atomizing the monomer solution, spraying the atomized monomer solution on the surface of a single crystal anode material, and then placing the treated anode material into a mechanical fusion machine for fusion;
2) in a mechanical fusion machine, the fused material is subjected to polymerization reaction under a light source which can enable the photoinitiator to generate active free radicals, and the surface of the positive electrode material is uniformly coated with a polymer;
3) after the polymerization reaction is finished, the polymer-coated anode material is placed in a tubular furnace and is subjected to heat treatment at the temperature of 150-300 ℃ to obtain the interface modified composite single-crystal anode material.
The single crystal positive electrode material is not particularly limited, and ternary or multicomponent positive electrode materials that are conventional in the art are within the scope of the present invention, and LiNiO is a representative example2、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; LiNi is preferredxCoyMn1-x-yO2Wherein the ternary precursor is mainly nickel (x is more than or equal to 0.5), and the common proportions of nickel, cobalt and manganese comprise 811, 622, 424, 433, 532, 415 and the like. The particle size of the primary particles of the single crystal cathode material is in the range of 2-10 μm, preferably 3-8 μm. The main point of the invention lies in the interface modification method of the single crystal anode material, and the main points are the selection and the proportion of the monomer and the polymerization condition of photoinitiation, but not the specific single crystal anode material.
The mass ratio of the single crystal composite anode material to the organic monomer is 5-30: 1, preferably 10-15: 1. The use amount of the organic monomer is too small, so that the anode material cannot be effectively coated, and the corrosion of the electrolyte to the anode material cannot be avoided; the use amount of the organic monomer is too much, the single crystal anode material is wrapped too thick, the conductive and ion-conducting performance of the single crystal anode material is not facilitated, and the battery capacity is further adversely affected.
The concentration of the acrylonitrile monomer solution is 0.5-1.5M. The solvent in the monomer solution is not particularly limited as long as it has a solubility for the organic monomer and does not adversely affect the polymerization reaction, and a protic polar organic solvent including at least one of methanol, ethanol, acetone, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, and ethyl acetate is preferable.
Preferably, in the acrylonitrile monomer solution, imidazolium salt ionic liquid monomer with carbon-carbon unsaturated double bonds can also be added. The molar ratio of the acrylonitrile to the imidazolium salt ionic liquid monomer is 10-15: 1.
The ionic liquid of imidazole has better thermal stability than that of pyrrole type and pyridine type ionic liquids, and the conductivity and lithium ion migration speed are both more suitable. Preferably, the cation of the ionic liquid is an imidazole cation substituted with an alkenyl-containing group selected from an ethylene group, a propylene group, a butylene group, an acrylate group or a methacrylate group; the anion is one of hexafluorophosphate radical, tetrafluoroborate radical, bis (trifluoromethanesulfonyl) imide radical, bis fluorosulfonyl imide radical, chloride ion and bromide ion.
More preferably, the ionic liquid monomer is a salt of 1-alkyl acrylate-imidazole, and the structure is shown in the following general formula (I):
wherein n is an integer of 1 to 20, preferably an integer of 4 to 10; r is alkyl with 1-6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl or hexyl, or aryl with 6-20 carbon atoms, such as phenyl, biphenylyl or naphthyl, wherein the alkyl or aryl can be optionally substituted by halogen, alkyl, halogenated alkyl, alkoxy, hydroxyl, nitro and the like. The carbon atoms of the alkyl, the halogenated alkyl and the alkoxy are 1 to 6 in number; x-The anion is selected from one of hexafluorophosphate, tetrafluoroborate, bis (trifluoromethanesulfonyl) imide, bis fluorosulfonyl imide, chloride and bromide.
Examples of ionic liquid monomers that may be mentioned include, but are not limited to, 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-ethylimidazolium hexafluorophosphate, 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl acrylate-3-methylimidazolium bis fluorosulfonyl imide, 1-hexyl acrylate-3-phenylimidazolium bis fluorosulfonyl imide, 1-decyl acrylate-3-methylimidazolium bis fluorosulfonyl imide and 1-dodecyl acrylate-3-methylimidazolium bis fluorosulfonyl imide.
The atomization mode in step 1) is not particularly limited, as long as the monomer solution passes through the atomization nozzle under a certain pressure, so that the liquid is atomized into tiny droplets, and the diameter of the droplets ranges from 50 to 200 microns. The equipment capable of accomplishing the atomization process is a compression atomizing pump, an electric atomizer, a motor atomizer and the like, wherein the diameter of the atomized liquid can be controlled by controlling the pressure of a water pump and the aperture of a small hole of an atomizing nozzle.
In the method for initiating monomer polymerization, a photoinitiator is adopted to initiate the free radical polymerization of carbon-carbon double bonds under the irradiation of a light source. Photoinitiators of moderate activity are generally chosen, such as diphenylethanone, benzophenone, 2, 4-dihydroxybenzophenone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether. The amount of initiator used is 0.1 to 1%, preferably 0.3 to 0.5% of the total mass of the monomers. The initiator dosage is too small, so that the single crystal anode material with uniform coating cannot be effectively obtained, the initiator dosage is too large, the polymer molecular weight is small, and the high molecular chain segment is short, so that the single crystal anode material cannot be coated sufficiently.
The mechanical fusion machine fusion is to put the materials into the mechanical fusion machine and operate for 0.5-1h at 1000-.
The light source capable of enabling the photoinitiator to generate active free radicals is preferably an ultraviolet lamp, and specifically means that the illumination intensity of the photoinitiator is 2.0-3.5mW/cm at the wavelength of 250-400nm2The ultraviolet light generates free radicals with polymerization activity to initiate the polymerization reaction of carbon-carbon unsaturated double bonds in the monomers, and the irradiation time is 3-6 h. After the polymerization reaction is finished, the obtained solid is subjected to heat treatment for 3-6h at the temperature of 150 ℃ and 300 ℃ in a tubular furnace protected by an inert atmosphere, and preferably is subjected to heat treatment for 2-4h at the temperature of 200 ℃ and 240 ℃ to remove redundant solvent and unreacted monomers. The interface consistency of the polymer and the anode material is further enhanced, the conductivity and the lithium ion mobility of the ionic liquid polymer are favorably improved, and the rate capability and the cycling stability of the single crystal anode material are favorably improved.
According to the invention, after the anode material and the monomer solution are fused, the monomer polymerization is initiated in a photoinitiation mode, the polymer can be uniformly and compactly coated on the surface of the anode material to form a uniform interface, the rate capability and the cycle stability of the single crystal anode material are obviously improved, the single crystal anode material can be circularly operated for 100 times under the rate of 1C, and the capacity retention rate is more than 90%.
Compared with the prior art, the invention has the beneficial effects that:
the modification method comprises the steps of taking acrylonitrile and imidazolium ionic liquid containing carbon-carbon double bonds as monomers through the obtained single crystal anode material for the lithium ion battery, and carrying out free radical polymerization under ultraviolet light after mechanical fusion to obtain the single crystal composite anode material uniformly and densely coated by the ionic liquid polymer. After the interface modification is carried out on the anode material, the side reaction generated by the contact of the anode material and the electrolyte is effectively reduced, and the rate capability and the cycling stability of the anode material are obviously improved.
Secondly, the polymer is obtained by growing on the surface of the anode through an in-situ polymerization method, and compared with a method of preparing the polymer and coating the polymer on the surface of the electrode material, the method of in-situ polymerization is adopted, so that the polymer can be coated more uniformly and compactly, and the performance of the anode material is further improved. The ionic liquid polymer is prepared by spraying a monomer solution on the surface of a positive electrode material in a spraying mode and carrying out in-situ polymerization in a photo-initiated polymerization mode, compared with a solution-phase polymerization method, the concentration of the monomer in a photo-initiated polymerization system is higher, the polymer can be more tightly coated on the surface of the positive electrode material after polymerization, and the molecular weight of the polymer can be conveniently adjusted through the illumination time, the illumination intensity and the dosage of a photoinitiator, so that the ionic liquid polymer is proper in high molecular chain length and can be better coated on the positive electrode material.
The polymer is coated on the surface of the anode material, so that the contact of the anode material and electrolyte can be reduced, the area of side reaction is reduced, and the generation of gas in the battery is reduced, thereby enhancing the safety of the battery; meanwhile, as the contact area is reduced, the corrosion of the corresponding electrolyte to the anode is also reduced, thereby prolonging the cycle life of the anode material.
And fourthly, when the polymer coats the anode, a certain amount of ionic liquid monomer and acrylonitrile are added for copolymerization, so that side reaction is reduced, the cycle stability of the anode material is improved, the contact internal resistance of a material interface can be improved, and the electronic and ionic conductivity of the material is improved to a certain extent, so that the de-intercalation kinetics of the single crystal anode material is enhanced, the rate capability of the single crystal anode material is improved, the lithium ion battery can be charged and discharged under high power, and the performance improvement of the lithium ion battery is more helpful. Particularly, for the ternary cathode material containing Ni-Co-Mn (or any two of the materials or only Co), high-temperature carbon coating is difficult to realize, because under the high-temperature condition, carbon can directly react with oxygen to generate carbon dioxide to run away under the oxygen atmosphere. Under the inert atmosphere, carbon has reducibility, high-valence metal elements in the ternary positive electrode material react with the carbon and are also changed into carbon dioxide to run away, and the metal elements are changed into low-valence metal elements from high-valence metal elements. Thus there is no contrast between polymer coating and high temperature carbon coating.
The interface modification method for the ternary cathode material has the advantages of simple process, cheap and easily-obtained raw materials, suitability for large-scale industrial implementation, great improvement on the performance of the lithium battery, and higher rate capability and cycle stability of the modified cathode material compared with the cathode material without interface modification, and has high application value and research significance.
Drawings
FIG. 1 is a scanning electron microscope topography of the cathode material after the interface modification of example 1.
Fig. 2X-ray diffractometer (XRD) pattern of the cathode material after interface modification in example 1.
FIG. 3 is a high-resolution TEM image of the cathode material after interface modification in example 1.
Fig. 4 is a particle size distribution diagram of the positive electrode material subjected to the interface modification in example 1.
Fig. 5 is a high-resolution scanning electron micrograph of the cathode material after the interface modification in example 7.
Fig. 6 is a rate diagram of a lithium ion battery assembled from the cathode material subjected to interface modification in example 1.
Fig. 7 is a graph of the specific capacity retention rate of the cathode material subjected to the interface modification in example 1 at a rate of 0.5C.
Fig. 8 is a graph showing the specific capacity retention rate at a 1C rate of the cathode material subjected to the interface modification in example 1.
Fig. 9 is a charge-discharge curve diagram of the cathode material subjected to the interface modification in example 7 at a magnification of 0.1C.
Fig. 10 is a morphology image of the positive electrode material before the interface modification of comparative example 1.
Fig. 11 is a transmission electron micrograph of the positive electrode material obtained in comparative example 3.
Detailed Description
The following will further describe the method for modifying the interface of the single crystal composite positive electrode material according to the present invention with reference to specific examples, but the present invention is not limited to the following examples. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the examples, the mechanical fusion was carried out by using a ZSJ-600 mechanical fusion machine, which was purchased from Zhongyuan powder technology Co.
A scanning electron microscope (JEOL-6701F) is used for characterizing the single crystal layered positive electrode material high cycle stability element positive electrode material for the lithium ion battery. The crystal structure of the high specific energy ternary lithium ion battery positive electrode material was analyzed by a powder X-ray diffractometer (Rigaku DmaxrB, CuK α ray).
Example 1
Dissolving 3.12g of acrylonitrile in N, N-dimethylformamide to prepare 1mol/L monomer solution, adding 10mg of diphenylethanone into the monomer solution, uniformly stirring, atomizing the monomer solution by a compression atomizing pump, spraying the atomized small liquid drops with the diameter of about 100 mu m on the surface of 31.45g of single crystal anode material, then placing the treated anode material in a mechanical fusion machine, and placing the treated anode material at 1500rpmRunning for 0.5h to perform full fusion; the single crystal anode material is LiNi0.8Co0.1Mn0.1；
2) In a mechanical fusion machine, the fused material is subjected to polymerization reaction under the irradiation of an ultraviolet high-pressure mercury lamp with adjustable power, and the ionic liquid monomer is uniformly coated on the surface of the anode material, wherein the wavelength of an ultraviolet lamp is 300-369nm, the illumination time is 3h, and the illumination intensity is 2.55mW/cm2；
3) And after the polymerization reaction is finished, placing the polymer-coated positive electrode material in a tubular furnace protected by inert atmosphere, and carrying out heat treatment for 2h at 200 ℃ to obtain the interface modified composite single crystal positive electrode material.
Example 2
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 1, except that the amount of acrylonitrile used was changed to 2.10g
Example 3
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 1, except that the amount of acrylonitrile was changed to 1.35 g.
Example 4
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 1, except that the amount of acrylonitrile used was changed to 5.44 g.
Example 5
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 1, except that the monomer was a combination of acrylonitrile and 1-vinyl-3-methylimidazolium tetrafluoroborate, and the amount of 1-vinyl-3-methylimidazolium tetrafluoroborate was 10 mol% based on acrylonitrile.
Example 6
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 1, except that the monomer was a combination of acrylonitrile and 1-vinyl-3-ethylimidazole hexafluorophosphate, and the amount of 1-vinyl-3-methylimidazole tetrafluoroborate was 7 mol% based on the acrylonitrile.
Example 7
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 5, except that the ionic liquid monomer was 1-hexyl acrylate-3-methylimidazolium bis fluorosulfonyl imide salt.
Example 8
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 5, except that the ionic liquid monomer was 1-decyl acrylate-3-methylimidazolium bis (fluorosulfonyl) imide salt.
Example 9
An interface-modified composite single-crystal positive electrode material was prepared in the same manner as in example 5, except that the ionic liquid monomer was 1-dodecyl acrylate-3-methylimidazolium bis (fluorosulfonyl) imide salt.
Example 10
An interface-modified composite single crystal positive electrode material was prepared in the same manner as in example 5, except that the single crystal positive electrode material was replaced with LiNi0.6Co0.2Mn0.2。
Comparative example 1
Firstly, LiNi for lithium battery0.8Co0.1Mn0.1Uniformly mixing the single crystal anode material and the ethanol solution, and stirring for 70 min; and collecting the solid in the solution, and reacting at 200 ℃ for 0.5h to obtain the lithium battery single crystal positive electrode material without polymer coating.
Comparative example 2
An interface-modified composite single crystal positive electrode material was prepared in the same manner as in example 5, except that the heat treatment was high-temperature sintering at 800 ℃ for 8 hours, which destroyed the high molecular structure of the ionic liquid polymer to form a carbon-coated positive electrode material.
Comparative example 3
3.12g of acrylonitrile was dissolved in N, N-dimethylformamide to prepare a 1mol/L monomer solution, 6mg of dibenzoyl peroxide (BPO) was added thereto, and 31.45g of LiNi was added to the monomer solution0.8Co0.1Mn0.1Heating the single crystal anode material to 60-80 ℃ to initiate polymerization, and reacting for 2 h;
2) and after the polymerization reaction is finished, placing the polymer-coated positive electrode material in a tubular furnace, and carrying out heat treatment for 2h at 200 ℃ to obtain the interface modified composite single crystal positive electrode material.
Application exampleCharacterization and performance testing of interface modified single crystal particle cathode material
The scanning electron microscope photograph of the interface modified cathode material obtained in example 1 is shown in fig. 1, and it can be seen that, by using the method of the present invention, the surface of the cathode material particle coated with the polymer interface modification is rough, because the coating layer covers the surface of the particle well. As shown in fig. 2, the XRD spectrum of the interface-modified cathode material obtained in example 1 shows that the bulk layer structure of the cathode material is not affected by the interface modification method of the present invention, i.e., by the polymer coating and the low-temperature treatment, and that the ratio of the peak intensity of the diffraction peak of the 003 plane to the peak intensity of the diffraction peak of the 104 plane, which is shown by XRD, is 1.394 more than 1.2, indicating that the degree of lithium ion mixing and discharging of the material is small. FIG. 3 is a high-resolution TEM image of the interface-modified cathode material obtained in example 1, which shows that the polymer-coated material is uniformly coated on the single-crystal cathode material and that the two phases are not separated. The particle size distribution diagram of the interface-modified positive electrode material obtained in example 1 is shown in fig. 4. The particle size distribution of the anode material coated by the polymer is uniform, and the particle size is larger, so that the interface modification method does not influence the particle size of the single crystal anode material, and the large-particle single crystal material is beneficial to exerting the performance of the ternary anode material.
Example 7 further includes an ionic liquid monomer 1-hexyl acrylate-3-methylimidazole bis (fluorosulfonyl) imide salt and acrylonitrile to copolymerize together, and an electron micrograph of the obtained interface-modified ternary positive electrode material is shown in fig. 5, which is a high-resolution scanning electron microscope, and the color of the whole single crystal positive electrode particle is uniform, which indicates the integrity of the coating of the positive electrode particle. It can be seen that, in the structure of the ionic liquid monomer, a flexible chain segment with a certain length is added, so that the coating of the anode material can be better realized.
The scanning electron micrograph of the positive electrode material in comparative example 1, which is not coated with the polymer, is shown in fig. 10, and it can be seen that the surface of the material which is not coated with the polymer is clean and smooth. Therefore, the uncoated positive electrode material cannot play a role in reducing the contact between the positive electrode material and electrolyte and reducing side reactions.
Comparative example 3 is a polymer-coated positive electrode material obtained by aqueous phase radical polymerization, and a transmission electron micrograph of the polymer-coated positive electrode material is shown in fig. 11, and it can be seen that aqueous phase coating is punctiform coating and does not have a good protection effect on a single crystal positive electrode. Thus, cycle stability is also compromised.
The invention also tests the electrochemical performance of the obtained interface modified cathode material, and the specific method is that the lithium ion battery cathode material prepared in the embodiment and the comparative example, carbon black and polyvinylidene fluoride binder are mixed by mass ratio: 8: 1: 1, mixing the raw materials into slurry, uniformly coating the slurry on a carbon-coated aluminum foil current collector to obtain a positive membrane, taking a metal lithium sheet as a negative electrode, taking a polypropylene microporous membrane (Celgard2400) as a diaphragm, and taking 1mol/L LiPF6(the solvent is a mixed solution of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) in a volume ratio of 1: 1: 1) as an electrolyte, and the electrolyte is assembled into a 2032 coin cell in an argon-protected glove box. The assembled battery is subjected to constant-current charge and discharge test on a blue-ray charge and discharge tester, the voltage range is 3-4.3V, the test temperature is 25 ℃, charge and discharge are carried out under different multiplying factors, the actual discharge specific capacity of the material is tested, specifically, the discharge specific capacity is tested under 0.1C, the cycling stability of the anode material is tested under the multiplying factor of 1C, and the apparent lithium ion diffusion coefficient of the anode material is obtained through calculation of a multi-sweep rate cyclic voltammetry. The results are shown in table 1 below:
fig. 6 is a rate chart of lithium ion battery assembled by the cathode material subjected to interface modification in example 1, a test curve is divided into 6 stepped sections, which represent discharge specific capacities under test conditions of 0.1C, 0.5C, 1C, 2C, 3C and 5C, respectively, and it can be seen that the discharge specific capacity can reach 151mA h g even at a high rate of 5C-1The material has good rate capability. Fig. 7 and fig. 8 are graphs of specific discharge capacity retention rates of the cathode material subjected to the interface modification in example 1 at 0.5C and 1C rates, respectively. The result shows that the cycle stability of the coated cathode material is improved under the test conditions of low rate and high rate. FIG. 9 shows the positive electrode material of example 7 after interface modification at 0.1C magnificationAnd (4) a charge-discharge curve diagram. The specific capacity is 204.8mA h g-1The first coulombic efficiency is 88.3 percent, which shows that a certain amount of ionic liquid monomer with a flexible chain is added for copolymerization with acrylonitrile, so that the positive electrode material can be better coated, the contact with the electrolyte is reduced, the apparent lithium ion diffusion coefficient is greatly improved, and the discharge specific capacity and the cycling stability of the positive electrode material are further improved.
TABLE 1
As can be seen from the attached drawings of the specification and the data in the table 1, the interface modified cathode material provided by the invention has excellent comprehensive performance, and the contact between the cathode material and the electrolyte is effectively reduced and the occurrence of side reaction and corrosion is reduced after the polymer material is uniformly coated on the surface of the cathode material. Especially when acrylonitrile and ionic liquid monomer are adopted for compounding, the synergistic effect is exerted, the rate capability, the discharge specific capacity and the cycling stability of the anode material are obviously improved, and the method has high application value and research significance.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes or modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims. For example, the single crystal positive electrode material adopted in the embodiment of the present invention is LiNi0.8Co0.1Mn0.1And LiNi0.6Co0.2Mn0.2However, the main point of the present invention is an interface modification method for single crystal cathode materials, which focuses on the selection and mixture ratio of monomers and photoinitiated polymerization conditions, rather than the selection of single crystal cathode materials.
Claims (13)
1. An interface modification method of a lithium battery composite single crystal positive electrode material comprises the following steps:
1) preparing an acrylonitrile monomer solution, adding a photoinitiator into the acrylonitrile monomer solution, atomizing the monomer solution, spraying the atomized monomer solution on the surface of a single crystal anode material, and then placing the treated anode material into a mechanical fusion machine for fusion;
2) in a mechanical fusion machine, the fused material is subjected to polymerization reaction under the irradiation of an ultraviolet lamp, and the surface of the positive electrode material is uniformly coated with a polymer;
3) after the polymerization reaction is finished, placing the polymer-coated anode material in a tubular furnace, and carrying out heat treatment at the temperature of 150-300 ℃ to obtain an interface modified composite single-crystal anode material;
the mass ratio of the single crystal anode material to the acrylonitrile monomer is 5-30: 1;
in the acrylonitrile monomer solution, an imidazolium salt ionic liquid monomer with carbon-carbon unsaturated double bonds is also added, and the molar ratio of the acrylonitrile to the imidazolium salt ionic liquid monomer is 10-15: 1;
the cation of the imidazolium salt ionic liquid monomer is imidazole cation substituted by an alkenyl-containing group, wherein the alkenyl-containing group is selected from vinyl, propenyl, butenyl, acrylate or methacrylate; the anion is one of hexafluorophosphate radical, tetrafluoroborate radical, bis (trifluoromethanesulfonyl) imide radical, bis fluorosulfonyl imide radical, chloride ion and bromide ion.
2. The method of interface modification of claim 1, wherein the single crystal positive electrode material is selected from the group consisting of LiNiO2、LiCoO2、LiNiMn2-bO4In which 1 is>b>0、LiNixCoyB1-x-yO2Wherein B is Mn or Al,1>x>0、1>y>0，rLi2MnO3·(1-r)LiRO2Wherein R is one or more of Co, Mn and Ni, 1>r>0; the particle size range of the primary particles of the single crystal cathode material is 2-10 mu m.
3. The method of interface modification according to claim 2, characterized in thatCharacterized in that the single crystal anode material is LiNixCoyMn1-x- yO2Mainly nickel element, x is not less than 0.5.
4. The interface modification method of claim 2, wherein the primary particles of single crystal positive electrode material have a particle size in the range of 3-8 μm.
5. The interface modification method of claim 1, wherein the mass ratio of the single crystal positive electrode material to the acrylonitrile monomer is 10-15: 1.
6. The method of claim 1, wherein the ionic liquid monomer is a salt of 1-alkyl acrylate-imidazole having the following general formula (I):
(I)
wherein n is an integer of 1 to 20; r is alkyl with 1-6 carbon atoms or aryl with 6-20 carbon atoms, and the alkyl with 1-6 carbon atoms or the aryl with 6-20 carbon atoms are optionally substituted by halogen, alkyl, haloalkyl, alkoxy, hydroxyl and nitro; the carbon atoms of the alkyl, the halogenated alkyl and the alkoxy are 1 to 6 in number; x-The anion is selected from one of hexafluorophosphate, tetrafluoroborate, bis (trifluoromethanesulfonyl) imide, bis fluorosulfonyl imide, chloride and bromide.
7. The method for modifying an interface according to claim 6, wherein in the general formula (I), n is an integer of 4 to 10, and R is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a zonyl group or a naphthyl group.
8. The method of interface modification of claim 1, the imidazolium salt ionic liquid monomer is selected from at least one of 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-ethylimidazolium hexafluorophosphate, 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl acrylate-3-methylimidazolium bis fluorosulfonyl imide, 1-hexyl acrylate-3-phenylimidazolium bis fluorosulfonyl imide, 1-decyl acrylate-3-methylimidazolium bis fluorosulfonyl imide and 1-dodecyl acrylate-3-methylimidazolium bis fluorosulfonyl imide.
9. The method of claim 1, wherein the polymerization of the monomers is initiated by initiating a free radical polymerization of a carbon-carbon double bond with a photoinitiator under uv irradiation; the photoinitiator is at least one selected from diphenylethanone, benzophenone, 2, 4-dihydroxy benzophenone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether; and/or the amount of the initiator is 0.1-1% of the total mass of the monomers.
10. The method of interfacial modification of claim 9, wherein the initiator is used in an amount of 0.3 to 0.5% by weight of the total monomer.
11. The method for modifying an interface as claimed in claim 1, wherein the UV irradiation is performed with a photoinitiator at a wavelength of 400nm and an irradiation intensity of 2.0-3.5mW/cm2Under the irradiation of ultraviolet light, the irradiation time is 3-6 h; and/or after the polymerization reaction is finished, carrying out heat treatment on the obtained solid for 3-6h in a tubular furnace protected by inert atmosphere at the temperature of 150-300 ℃.
12. The method for modifying an interface as claimed in claim 11, wherein after the polymerization reaction is completed, the obtained solid is heat-treated in a tubular furnace protected by an inert atmosphere at 200 ℃ and 240 ℃ for 2-4 h.
13. An interface modified lithium battery composite single crystal positive electrode material, which is characterized by being prepared by the modification method of any one of claims 1 to 12.
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| CN113540417A (en) * | 2021-07-09 | 2021-10-22 | 北京理工大学 | Polythiophene-coated single crystal NCM ternary material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000345371A (en) * | 1999-06-10 | 2000-12-12 | Mitsubishi Rayon Co Ltd | Carbon thin film/metallic composite material and its production |
| CN103682354A (en) * | 2012-09-18 | 2014-03-26 | 华为技术有限公司 | All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery |
| CN105226235A (en) * | 2015-10-19 | 2016-01-06 | 湖南杉杉新能源有限公司 | Lithium ion cell positive that a kind of gelatin polymer is coated and preparation method thereof |
Family Cites Families (2)
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105226235A (en) * | 2015-10-19 | 2016-01-06 | 湖南杉杉新能源有限公司 | Lithium ion cell positive that a kind of gelatin polymer is coated and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "能源革命中的电化学储能技术";李先锋等;《低碳多能融合发展》;20190430;第34卷(第4期);全文 * |
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