CN114005971B - Positive electrode material with p-type doped conductive polymer coating and preparation method thereof - Google Patents
Positive electrode material with p-type doped conductive polymer coating and preparation method thereof Download PDFInfo
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 41
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 229920000128 polypyrrole Polymers 0.000 claims description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- 229920001197 polyacetylene Polymers 0.000 claims description 12
- 239000002019 doping agent Substances 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 229910019800 NbF 5 Inorganic materials 0.000 claims description 4
- 229910015253 MoF5 Inorganic materials 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- NBJFDNVXVFBQDX-UHFFFAOYSA-I molybdenum pentafluoride Chemical compound F[Mo](F)(F)(F)F NBJFDNVXVFBQDX-UHFFFAOYSA-I 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910013716 LiNi Inorganic materials 0.000 description 16
- 239000010406 cathode material Substances 0.000 description 14
- 238000007792 addition Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 5
- 229910011331 LiNi0.6Mn0.4O2 Inorganic materials 0.000 description 5
- 229910015746 LiNi0.88Co0.09Al0.03O2 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 2
- -1 nickel cobalt aluminum manganate Chemical compound 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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Abstract
The invention discloses a positive electrode material with a p-type doped conductive polymer coating and a preparation method thereof, wherein the preparation method comprises the following steps: a) Adding transition metal halide and conductive polymer into N-methyl pyrrolidone according to a certain proportion, and performing ultrasonic treatment to uniformly disperse the mixture to form a mixture A; b) Adding the positive electrode material into deionized water, and mechanically stirring to form a uniform mixture B; c) Adding the mixture A into the mixture B under the condition of continuous stirring, and continuously stirring; and (5) repeatedly washing and filtering, and performing heat treatment to obtain the anode material with the p-type doped conductive polymer coating. The coating has high conductivity of conductive polymer and excellent electrical property of transition metal element, and can be used as a physical barrier to prevent the positive electrode material from contacting with electrolyte to inhibit side reaction. The method has simple process and technology, and the modified positive electrode material has excellent cycle stability and rate capability.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a positive electrode material with a p-type doped conductive polymer coating and a preparation method thereof.
Background
Under the strong support of a series of national policies, the new energy automobile industry is greatly developed. Long endurance and fast charging of electric vehicles require high performance lithium ion batteries to achieve, and positive electrode materials are one of the most important components. However, the cathode material is easy to break in the circulation process, and has continuous side reaction with the electrolyte, so that the circulation life and the rate capability of the battery are seriously damaged. The surface coating is a common modification method, can reduce stress, increase wettability of liquid electrolyte, reduce interface charge transfer resistance and reduce side reaction, thereby effectively optimizing the anode material. However, most common coating agents belong to semiconductors or insulators, and after coating, the electronic conductivity of the material can be reduced, and the multiplying power performance of the material is affected. In addition, the electrical properties of the materials are affected differently by different coating thicknesses and coating uniformity, and the coating should be controlled to be uniform and thin to obtain more excellent electrical properties. Therefore, a more effective modification method of the positive electrode material is sought to improve the service life and the multiplying power performance of the positive electrode material, and the method has positive effects on promoting the development of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode material with a p-type doped conductive polymer coating, wherein the surface of the positive electrode material prepared by the method is a uniform and thin coating, and the positive electrode material consists of a conductive polymer and a transition metal halide. The coating has high conductivity of conductive polymer and excellent electrical property of transition metal element, and can be used as a physical barrier to prevent the positive electrode material from contacting with electrolyte to inhibit side reaction. The method has simple process and technology, and the modified positive electrode material has excellent cycle stability and rate capability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A preparation method of a positive electrode material with a p-type doped conductive polymer coating comprises the following steps:
a) Adding transition metal halide and conductive polymer into N-methyl pyrrolidone according to a certain proportion, and performing ultrasonic treatment to uniformly disperse the mixture to form a mixture A;
b) Adding the positive electrode material into deionized water, and mechanically stirring to form a uniform mixture B;
c) Adding the mixture A into the mixture B under the condition of continuous stirring, and continuously stirring;
d) And (5) repeatedly washing and filtering, and performing heat treatment to obtain the anode material with the p-type doped conductive polymer coating.
Preferably, the positive electrode material is selected from any one of nickel cobalt lithium manganate (NCM), nickel cobalt aluminum manganate (NCA), layered nickel lithium manganate (LNMO), and Lithium Nickelate (LNO).
Preferably, the transition metal halide is a p-type dopant and is selected from one or more of NbF 5、TaF5、MoF5、WF5、RuF5、PtCl4、TiCl4.
More preferably, in the step, the transition metal halide selects one or both of WF 5、TiCl4.
When the p-type dopant is used for doping a macromolecule, a single unpaired p ion (an electron similar to a free radical, also called dipole or soliton) exists in a conductive macromolecule long-chain structure, and the existence and transition of the p ion enable the p ion to have conductivity. The formation of p-ions corresponds to the injection of an electron in the conduction band or the extraction of an electron from the valence band. The transition metal halide has an unfilled valence layer d orbit, has a plurality of single electrons in an electronic configuration, is easy to lose, has electrochemical activity, plays roles in surface modification and protection of a lithium storage active electrode in a positive electrode material, and improves the circulation effect.
Preferably, the conductive polymer is selected from one or more of polyacetylene, polypyrrole, polythiophene, polyphenylene, polyphenylacetylene and polyaniline.
More preferably, in the step, the conductive polymer is one or two selected from polyacetylene and polypyrrole.
The main chain of the conductive polymer selected by the invention has a conjugated main electron system or a large delocalized pi-bond molecular structure, pi-bond electrons in a long chain are relatively active, and particularly after forming a charge transfer complex with a doping agent, the pi-bond electrons can easily escape from an orbit to form free electrons. The conductive energy band formed by overlapping and covering pi electron orbitals in the macromolecule chain and between chains provides a channel for the transfer and transition of carriers, and the longer the macromolecule conjugated chain is, the higher the conductivity is, the higher the structural regularity is, and the higher the conductivity is.
Preferably, the mass ratio of the conductive polymer to the N-methylpyrrolidone is (2.0-8.0): 1, a step of; the mass ratio of the conductive polymer to the positive electrode material is (0.001-0.1): 1, when the mass ratio is lower than (0.001-0.1): 1, the coating of the positive electrode material is uneven, cannot play a good role of a physical barrier, has poor inhibition effect on side reactions, and has a mass ratio higher than (0.001-0.1): 1, the coating of the positive electrode material is too thick, which affects Li + migration; the mass ratio of the transition metal element to the positive electrode material is (0.0005-0.01): 1, when the mass ratio is lower than (0.0005-0.01): 1, the excessive metal halide can not fully carry out p-type doping on the conductive polymer, and the partial conductive polymer has no conductivity due to insufficient p ions; when the mass ratio is higher than (0.0005-0.01): 1, the conductivity of the coating is not greatly improved, the material cost is increased, and the product performance is affected to different degrees by excessive transition metal halides.
Preferably, the positive electrode material: the mass ratio of the (N-methyl pyrrolidone and deionized water) is (0.6-2.0).
Preferably, the ultrasonic time in the step a) is 30-60min.
More preferably, the ultrasonic time in the step a) is 30-40min.
Preferably, in the step b), the stirring linear speed is 1.50-1.80m/s, and the stirring time is 10-30 min; the stirring linear speed in the step c) is 1.50-1.80m/s, and the stirring time is 30-60 min.
More preferably, the stirring line speed in the step b) is 1.50-1.60m/s, and the stirring time is 10-20 min; the stirring linear speed in the step c) is 1.50-1.60m/s, and the stirring time is 30-40 min.
Preferably, the heat treatment temperature is 200-320 ℃, and the heat treatment time is 2-5h.
More preferably, the heat treatment temperature is 220-250 ℃ and the heat treatment time is 2-3h.
The excellent effects of the invention are as follows: the coating material adopted by the method is p-type doped conductive polymer, and the conductive polymer can be converted into a conductor from an insulator by doping, so that the doping effect can be divided into n-doping and p-doping, wherein the conductivity of the p-type doped conductive polymer is generally lower than that of the n-type conductive polymer, so that the p-type doping, namely electron acceptor doping, is selected, electrons are taken from full orbitals of the conductive polymer by using a doping agent, the full orbitals become half-full energy bands, and a hole conductive layer appears. The doping agent selected by the invention is transition metal halide, and the prepared coating has the advantages of conductive polymer and transition metal element, wherein the conductive polymer has excellent conductivity, corrosion resistance and large-area film forming property, the transition metal halide has electrochemical activity, and the surface of the lithium storage active electrode is modified and protected, so that the multiplying power performance and the cycle performance of the material are improved together. The modification method has simple process and technology, and the modified cathode material has excellent cycle stability and rate capability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing a comparison of 100-cycle charge-discharge curves at 0.2C rate of a modified cathode material and an original material prepared in example 1 of the present invention.
Fig. 2 is a graph showing the charge-discharge curves of the modified cathode material prepared in example 1 of the present invention and the original material at 2C magnification.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
(1) Adding TiCl 4 and polypyrrole into N-methyl pyrrolidone, and performing ultrasonic treatment for 30min to uniformly disperse the mixture to form a mixture; adding LiNi 0.83Co0.11Mn0.06O2 into deionized water, mechanically stirring for 10min, keeping stirring, adding the mixture containing polyacetylene, and continuously stirring for 30min; and (3) repeatedly washing with water and filtering for 2 times, and performing heat treatment at 270 ℃ for 2.5 hours to obtain the positive electrode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the addition of polypyrrole to N-methyl pyrrolidone is 3.5, the mass ratio of the addition of polypyrrole to LiNi 0.83Co0.11Mn0.06O2 is 0.02, and the mass ratio of TiCl 4 to LiNi 0.83Co0.11Mn0.06O2 is 0.25%; the mass ratio of LiNi 0.83Co0.11Mn0.06O2 to (N-methylpyrrolidone+deionized water) was 1.2, and the stirring line speeds were 1.55m/s.
The electrochemical properties of the modified cathode material prepared according to the present invention are described in example 1 with reference to the accompanying drawings:
The buckling test results of the modified cathode material prepared in example 1 are shown in fig. 1-2, and it can be seen from fig. 1 that the capacity retention rate is still maintained at 94.3% after 100 weeks of cycling at 0.2C, and is superior to the original sample (the original sample refers to the cathode material which is not modified by coating, i.e. the experimental substrate selected in the example, and the original sample in the example is LiNi 0.83Co0.11Mn0.06O2, and the effect is blank comparison) by 85.6%; as can be seen from FIG. 2, the discharge capacity is 193.6mAh/g at 2C multiplying power, which is better than 188.9mAh/g of the original sample, and the modified positive electrode material prepared by the invention has good cycle stability and multiplying power performance.
Comparative example 1:
Adding polypyrrole into N-methyl pyrrolidone, and performing ultrasonic treatment for 30min to uniformly disperse the polypyrrole to form a mixture; adding LiNi 0.83Co0.11Mn0.06O2 into deionized water, mechanically stirring for 10min, keeping stirring, adding the mixture containing polyacetylene, and continuously stirring for 30min; and (3) repeatedly washing with water and filtering for 2 times, and performing heat treatment at 270 ℃ for 2.5 hours to obtain the positive electrode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the addition of polypyrrole to N-methyl pyrrolidone is 3.5, and the mass ratio of the addition of polypyrrole to LiNi 0.83Co0.11Mn0.06O2 is 0.02; the mass ratio of LiNi 0.83Co0.11Mn0.06O2 to (N-methylpyrrolidone+deionized water) was 1.2, and the stirring line speeds were 1.55m/s.
Comparative example 2:
Adding TiCl 4 and polypyrrole into N-methyl pyrrolidone, and performing ultrasonic treatment for 30min to uniformly disperse the mixture to form a mixture; adding LiNi 0.83Co0.11Mn0.06O2 into deionized water, mechanically stirring for 10min, keeping stirring, adding the mixture containing polyacetylene, and continuously stirring for 30min; and (3) repeatedly washing with water and filtering for 2 times, and performing heat treatment at 270 ℃ for 2.5 hours to obtain the positive electrode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the addition of polypyrrole to N-methyl pyrrolidone is 3.5, the mass ratio of the addition of polypyrrole to LiNi 0.83Co0.11Mn0.06O2 is 0.5, and the mass ratio of TiCl 4 to LiNi 0.83Co0.11Mn0.06O2 is 0.25%; the mass ratio of LiNi 0.83Co0.11Mn0.06O2 to (N-methylpyrrolidone+deionized water) was 1.2, and the stirring line speeds were 1.55m/s.
Comparative example 3:
Adding TiCl 4 and polypyrrole into N-methyl pyrrolidone, and performing ultrasonic treatment for 30min to uniformly disperse the mixture to form a mixture; adding LiNi 0.83Co0.11Mn0.06O2 into deionized water, mechanically stirring for 10min, keeping stirring, adding the mixture containing polyacetylene, and continuously stirring for 30min; and (3) repeatedly washing with water and filtering for 2 times, and performing heat treatment at 270 ℃ for 2.5 hours to obtain the positive electrode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the addition of polypyrrole to N-methyl pyrrolidone is 3.5, the mass ratio of the addition of polypyrrole to LiNi 0.83Co0.11Mn0.06O2 is 0.02, and the mass ratio of TiCl 4 to LiNi 0.83Co0.11Mn0.06O2 is 0.01%; the mass ratio of LiNi 0.83Co0.11Mn0.06O2 to (N-methylpyrrolidone+deionized water) was 1.2, and the stirring line speeds were 1.55m/s.
The performance of the cathode materials prepared in the original sample, example 1 and comparative examples 1 to 3 was examined, and the results are shown in table 1.
TABLE 1 Performance test results for the original sample, example 1 and comparative examples 1-3
Example 2:
(1) Adding WF 5 and polyacetylene into N-methyl pyrrolidone, and performing ultrasonic treatment for 40min to uniformly disperse the components to form a mixture; adding LiNi 0.88Co0.09Al0.03O2 into deionized water, mechanically stirring for 10min, keeping stirring, adding the mixture containing polyacetylene, and continuously stirring for 30min; and (3) repeatedly washing with water and filtering for 2 times, and performing heat treatment at 230 ℃ for 3 hours to obtain the anode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the polyacetylene addition amount to the N-methylpyrrolidone is 4.5, the mass ratio of the polyacetylene addition amount to the LiNi 0.88Co0.09Al0.03O2 is 0.005, and the mass ratio of the WF 5 to the LiNi 0.88Co0.09Al0.03O2 is 0.5%; the mass ratio of LiNi 0.88Co0.09Al0.03O2 to (N-methylpyrrolidone+deionized water) was 1.0, and the stirring line speeds were 1.60m/s.
The electrochemical performance of the modified anode material prepared by the invention is illustrated by combining the buckling test result: the capacity retention rate of the modified cathode material prepared in example 2 is still maintained at 93.7% after 100 weeks of circulation at 0.2C rate, and is better than 84.9% of that of the original sample (LiNi 0.88Co0.09Al0.03O2 is the original sample in the example), and the discharge capacity is 192.1mAh/g at 2C rate, which is better than 187.6mAh/g of that of the original sample, which indicates that the modified cathode material prepared in the invention has good circulation stability and rate performance.
Example 3:
(1) Adding NbF 5 and polyphenylacetylene into N-methyl pyrrolidone, and performing ultrasonic treatment for 50min to uniformly disperse the mixture to form a mixture; adding LiNi 0.6Mn0.4O2 into deionized water, mechanically stirring for 20min, keeping stirring, adding the mixture containing polyacetylene, and continuously stirring for 40min; and (3) repeatedly washing with water and filtering for 2 times, and performing heat treatment at 270 ℃ for 3.5 hours to obtain the positive electrode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the addition of the polyphenylacetylene to the N-methylpyrrolidone is 5.5, the mass ratio of the addition of the polyphenylacetylene to the LiNi 0.6Mn0.4O2 is 0.04, and the mass ratio of the NbF 5 to the LiNi 0.6Mn0.4O2 is 0.5%; the mass ratio of LiNi 0.6Mn0.4O2 to (N-methylpyrrolidone+deionized water) was 1.5, and the stirring line speeds were 1.65m/s.
The electrochemical performance of the modified anode material prepared by the invention is illustrated by combining the buckling test result: the capacity retention rate of the modified cathode material prepared in example 3 is still maintained at 91.8% after 100 weeks of circulation at 0.2C rate, and is better than 86.7% of that of the original sample (LiNi 0.6Mn0.4O2 is the original sample in the example), and the discharge capacity is 165.1mAh/g at 2C rate, which is better than 161.7mAh/g of the original sample, which indicates that the modified cathode material prepared in the invention has good circulation stability and rate performance.
Example 4:
(1) Adding MoF 5、TiCl4 and polyaniline into N-methyl pyrrolidone, and performing ultrasonic treatment for 50min to uniformly disperse the mixture to form a mixture; adding LiNi 0.5Co0.2Mn0.3O2 into deionized water, mechanically stirring for 30min, keeping stirring, adding mixture containing polyaniline, and continuously stirring for 50min; and (3) repeatedly washing and filtering for 2 times, and performing heat treatment at 300 ℃ for 4 hours to obtain the anode material with the p-type doped conductive polymer coating.
Wherein the mass ratio of the polyaniline added amount to the N-methylpyrrolidone is 6, the mass ratio of the polyaniline added amount to the LiNi 0.5Co0.2Mn0.3O2 is 0.05, and the mass ratio of the MoF 5、TiCl4 to the LiNi 0.5Co0.2Mn0.3O2 is 0.3 percent respectively: 0.4%; liNi 0.5Co0.2Mn0.3O2: the mass ratio of (N-methylpyrrolidone and deionized water) was 0.8, and the stirring line speeds were 1.70m/s.
The electrochemical performance of the modified anode material prepared by the invention is illustrated by combining the buckling test result: the capacity retention rate of the modified cathode material prepared in example 4 is still kept at 92.1% after 100 weeks of circulation at 0.2C rate, and is better than 86.5% of that of the original sample (LiNi 0.5Co0.2Mn0.3O2 is the original sample in the example), and the discharge capacity is 167.8mAh/g at 2C rate, and is better than 164.2mAh/g of that of the original sample, which indicates that the modified cathode material prepared in the invention has good circulation stability and rate performance.
The foregoing is merely illustrative of the structures of this invention and various modifications, additions and substitutions for those skilled in the art can be made to the described embodiments without departing from the scope of the invention or from the scope of the invention as defined in the accompanying claims.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The preparation method of the positive electrode material with the p-type doped conductive polymer coating is characterized by comprising the following steps of:
a) Adding transition metal halide and conductive polymer into N-methyl pyrrolidone according to a certain proportion, and performing ultrasonic treatment to uniformly disperse the mixture to form a mixture A;
b) Adding the positive electrode material into deionized water, and mechanically stirring to form a uniform mixture B;
c) Adding the mixture A into the mixture B under the condition of continuous stirring, and continuously stirring;
d) Repeatedly washing with water, filtering, and performing heat treatment to obtain the anode material with the p-type doped conductive polymer coating;
the transition metal halide is a p-type dopant and is selected from one or more of NbF 5、MoF5、WF5、TiCl4;
the conductive polymer is one or more selected from polyacetylene, polypyrrole, polyphenylacetylene and polyaniline;
The positive electrode material is selected from any one of nickel cobalt lithium manganate, nickel cobalt lithium aluminate and layered nickel lithium manganate;
the mass ratio of the conductive polymer to the N-methyl pyrrolidone is (2.0-8.0): 1, a step of; the mass ratio of the conductive polymer to the positive electrode material is (0.001-0.1): 1, a step of; the mass ratio of the transition metal element to the positive electrode material is (0.0005-0.01): 1, a step of;
The heat treatment temperature is 200-320 ℃, and the heat treatment time is 2-5h.
2. The method of manufacturing according to claim 1, wherein the positive electrode material: the mass ratio of (N-methyl pyrrolidone and deionized water) is (0.6-2.0): 1.
3. The method according to claim 1, wherein the ultrasonic time in step a) is 30 to 60 minutes.
4. The method according to claim 1, wherein the stirring line speed in the step b) is 1.50-1.80m/s and the stirring time is 10-30 min; the stirring linear speed in the step c) is 1.50-1.80m/s, and the stirring time is 30-60 min.
5. The positive electrode material with the p-type doped conductive polymer coating prepared by the preparation method according to any one of claims 1 to 4.
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