CN115411250A - Preparation method and application of modified lithium-rich manganese-based positive electrode of lithium ion battery - Google Patents
Preparation method and application of modified lithium-rich manganese-based positive electrode of lithium ion battery Download PDFInfo
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- CN115411250A CN115411250A CN202211121649.XA CN202211121649A CN115411250A CN 115411250 A CN115411250 A CN 115411250A CN 202211121649 A CN202211121649 A CN 202211121649A CN 115411250 A CN115411250 A CN 115411250A
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- rich manganese
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- 239000011572 manganese Substances 0.000 title claims abstract description 126
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 124
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 150000002641 lithium Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 134
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- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 23
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 52
- 239000007864 aqueous solution Substances 0.000 claims description 25
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- 238000002156 mixing Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
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- 239000010406 cathode material Substances 0.000 claims description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910008626 Li1.2Ni0.13Co0.13Mn0.54O2 Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
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- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/50—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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery with improved cycle performance by using an MXene modified lithium-rich manganese-based positive electrode with high electronic and ionic conductivities and a stable structure, and a preparation method and application thereof. The method comprises the following steps: MXene stably coats the surface of the lithium-rich manganese-based particle by utilizing the electrostatic adsorption effect of CTAB. MXene has high electronic and ionic conductivity, so that the ion conductivity of the lithium-rich manganese base is improved; and the rich end group on the surface of MXene has compatibility and stable structure based on the electrolyte, so that the isolated lithium-rich manganese group has side reaction with the electrolyte. The prepared battery formed by the anode material has the advantages of good cyclicity, high energy density, simple preparation, contribution to large-scale production and the like.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a preparation method and application of a lithium-rich manganese-based anode modified by MXene of a lithium ion battery.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Over the past several decades, lithium ion batteries have received widespread attention as the most potential commercial energy storage system. With the rapid development of various electronic devices, electric automobiles, and electric tools, there is a need to obtain a high-capacity positive electrode material, and a long cycle life and a high energy density are required. However, the specific capacity of the positive electrode material is a major obstacle affecting the energy density of the lithium ion battery. Until now, compared with various anode materials such as lithium manganate, ternary lithium iron phosphate and the like, the lithium-rich manganese-based anode material has higher specific capacity (>250mAh g -1 ) Lower cost and higher voltage range and is therefore a prominent candidate.
However, commercial application of lithium-rich manganese-based positive electrode materials still faces several obstacles, such as low coulombic efficiency, poor rate performance and poor cycle stability. These problems are caused by the irreversible release of lithium and O ions during the first charging, resulting in low coulombic efficiency; (2) The transition metal occupies Li sites to cause phase transition of the layered spinel; (3) The release of lattice oxygen (oxygen evolution reaction) and the further reaction of the lattice oxygen and the electrolyte induce the decomposition of the electrolyte and the lithium-rich manganese-based positive electrode; (4) The electron/ion conductivity of the lithium-rich manganese base is relatively low.
At present, aiming at the problem of the lithium-rich manganese-based anode material, various solutions such as an optimized material synthesis method, morphology control, ion doping surface modification, modified electrolyte, multifunctional separator design and the like are provided. In particular, the surface modification is an effective method, the synthesis process is simple, and the electrochemical performance can be obviously improved. Various coating materials are currently used to modify lithium rich manganese based surfaces, including fluorides, oxides, and phosphides.
MXene, as a novel two-dimensional flexible material, has attracted extensive attention and application in various fields due to the characteristics of high conductivity, good flexibility, good hydrophilicity and the like. But at present, MXene is not adopted to carry out surface modification research on the lithium-rich manganese-based positive electrode material.
Article "lithium-rich manganese-based cathode material Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Preparation and electrochemical Performance Regulation and control research of (1) Li is prepared by grinding and mixing method 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 A composite material. But the inventor researches and discovers that: the existing grinding and mixing method for improving the lithium-rich manganese base is only used for mixing two common substances, and MXene serves as a conductive agent and cannot structurally improve the performance of the lithium-rich manganese base.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method and application of a lithium-rich manganese-based anode modified by MXene of a lithium ion battery. MXene with flexibility and high electronic and ionic conductivity is uniformly coated on the surface of the lithium-rich manganese-based particles by utilizing the electrostatic adsorption effect, so that the electronic and ionic conductivity of the anode material is effectively improved, and the side reaction between the anode material and electrolyte is effectively isolated, so that the anode material has excellent electrochemical stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a modified lithium-rich manganese-based positive electrode material of a lithium ion battery, which comprises the following steps:
uniformly mixing lithium-rich manganese-based powder and Cetyl Trimethyl Ammonium Bromide (CTAB) powder in a solvent to obtain a lithium-rich manganese-based aqueous solution;
and adding the MXene dispersion liquid into the lithium-rich manganese-based aqueous solution, collecting the precipitate, performing suction filtration, washing and drying to obtain the lithium-rich manganese-based aqueous solution.
MXene can effectively coat the surface of the lithium-rich manganese base, improve the low electron/ion conductivity of the lithium-rich manganese base and isolate the reaction between the lithium-rich manganese base and an electrolyte. Based on the advantages, MXene can effectively improve the multiplying power and the cycling stability of the lithium-rich manganese-based anode.
In a second aspect of the invention, the modified lithium-rich manganese-based positive electrode material for the lithium ion battery prepared by the method is provided.
The third aspect of the invention provides an MXene modified lithium-rich manganese-based positive electrode, which is prepared by uniformly mixing the lithium ion battery modified lithium-rich manganese-based positive electrode material, a conductive agent and a binder, coating the mixture on a current collector and drying the current collector.
In a fourth aspect of the present invention, there is provided a lithium ion battery comprising: the above-described positive electrode, electrolyte, lithium negative electrode and separator;
or the electrolyte is lipid electrolyte or ether electrolyte;
or, the separator is selected from a PE separator, a PP separator, a glass fiber separator;
or the metal lithium negative electrode is any one of lithium foil, lithium sheet, lithium block, lithium powder, lithium belt and lithium alloy.
In a fifth aspect of the invention, the application of the modified lithium-rich manganese-based positive electrode material for the lithium ion battery in the preparation of a positive electrode, a lithium battery and an electric vehicle is provided.
The invention has the advantages of
(1) The MXene prepared by the method disclosed by the invention is flexible, few in layers, stable in structure and high in electronic and ionic conductivity, and can be coated on the surface of the lithium-rich manganese base, so that the electronic and ionic conductivity of the anode can be improved.
(2) The specific method can uniformly coat MXene on the surface of the lithium-rich manganese base through simple electrostatic adsorption, is simple to operate and can be used for large-scale production.
(3) The rich end of the MXene surface has hydrophilicity and compatibility with the electrolyte, so that the interface problem can be effectively improved, and the side reaction of the lithium-rich manganese base and the electrolyte can be isolated.
(4) The MXene modified lithium-rich manganese-based material prepared by the method has the advantages of good cycle stability and high energy density, and can effectively prolong the service life of a battery.
(5) Compared with a grinding and mixing method, the MXene disclosed by the invention is self-assembled on the surface of the lithium-rich manganese base through electrostatic adsorption, so that the surface of the lithium-rich manganese base is coated with a layer of high-conductivity MXene with uniform acting force for charge attraction, and the structure of the MXene is more stable in the charging and discharging processes. Therefore, the MXene modified lithium-rich manganese-based anode prepared by the electrostatic adsorption method has better performance than the existing grinding and mixing method.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to explain the exemplary embodiments of the invention and the description and are not intended to limit the invention.
FIG. 1 is a scanning electron microscope photograph of a blank lithium-rich manganese base of a comparative example of the present invention;
FIG. 2 shows Ti prepared in example 1 of the present invention 2 C 3 Coating a scanning electron microscope picture of the lithium-rich manganese-based particles;
FIG. 3 shows Ti prepared in example 1 of the present invention 2 C 3 A multiplying power performance test chart of the lithium ion battery coated with the lithium-rich manganese-based anode;
FIG. 4 shows Ti prepared in example 1 of the present invention 2 C 3 And (3) a cycle test chart of the lithium ion battery coated with the lithium-rich manganese-based positive electrode.
Fig. 5 is a cycle test chart of a battery formed by mixing the lithium-rich manganese base prepared in comparative example 2 of the present invention with MXene.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The existing lithium-rich manganese-based positive electrode still has the problems of poor ionic and electronic conductivity and poor rate capability and cycle performance caused by side reaction with electrolyte, which is extremely unfavorable for improving the electrochemical performance of a lithium ion battery. Therefore, the invention provides an MXene modified lithium-rich manganese-based positive electrode and a preparation method and application thereof,
in one or more embodiments of the invention, MXene modified lithium-rich manganese-based positive electrode is coated on the surface of a lithium-rich manganese base through electrostatic adsorption. The lithium-rich manganese-based material has the synergistic advantages of MXene with high ionic and electronic conductivity and a lithium-rich manganese-based material with high voltage and high specific capacity, improves the ionic and electronic conductivity, improves the side reaction between the lithium-rich manganese base and the electrolyte, and further improves the electrochemical performance of the lithium ion battery anode material.
Wherein MXene is Ti 2 C 3 、Nb 2 C、V 2 C、V 4 C 3 、Mo 2 C is a mixture of one or more of C; preferably, it is Ti 2 C 3 . MXene has high ionic and electronic conductivity, stable structure and good compatibility with electrolyte, and can effectively improve the conductivity of the cathode material and isolate side reactions between the cathode material and the electrolyte.
A preparation method of an MXene-coated lithium-rich manganese-based positive electrode of a lithium ion battery comprises the following steps:
etching the MAX phase to obtain a single-layer MXene dispersion liquid; dissolving the lithium-rich manganese-based powder and CTAB powder in water, and stirring for 24h; CTAB is used as a cationic surfactant to positively charge the surface of the material. Slowly and gradually dripping MXene dispersion liquid into the lithium-rich manganese-based aqueous solution; the modified lithium-rich manganese-based particles are immediately attracted to the surface of the MXene nanosheet through an electrostatic self-assembly process. And carrying out suction filtration, cleaning and drying on the obtained precipitate to obtain the MXene-coated lithium-rich manganese-based anode.
In one or more embodiments of the invention, a lithium ion battery comprises the MXene modified lithium-rich manganese-based positive electrode. The lithium ion battery based on the MXene modified lithium-rich manganese-based anode has more stable electrochemical performance and electrochemical activity.
The lithium ion battery also comprises a current collector, a lithium cathode, electrolyte and a diaphragm, wherein the electrolyte is filled in the battery; further, the electrolyte is an ester electrolyte or an ether electrolyte; further, the separator is selected from a PE separator, a PP separator, a glass fiber separator; preferably, a PE separator; further, the lithium metal negative electrode is any one of lithium foil, lithium sheet, lithium block, lithium powder, lithium ribbon, and lithium alloy, and preferably is a lithium sheet.
In one or more embodiments of the present invention, a method for preparing an MXene modified lithium-rich manganese-based positive electrode includes: etching the MAX phase to MXene dispersion liquid; coating the MXene dispersion liquid and the lithium-rich manganese base on the surface of the lithium-rich manganese base through electrostatic adsorption, filtering, cleaning and drying to obtain MXene coated powder; and mixing the powder with a conductive agent and a binder uniformly according to the proportion of 8.
Wherein the conductive agent is selected from one of Super-p, acetylene black and Ketjen black; the binder is PVDF.
In the preparation process, the current collector is any one of aluminum foil, aluminum mesh, foamed aluminum and carbon cloth, preferably aluminum foil.
In order to improve the electrochemical activity of the lithium ion battery, the loading capacity of the lithium-rich manganese base on a current collector is 0.1-2mg/cm 2 .
In order to improve the conductivity of the lithium-rich manganese base and obtain more stable electrochemical performance of the lithium ion battery, the coating amount of the MXene modified lithium-rich manganese base is 1-30%.
MXene can be a purchased finished product or prepared by a specific method, and specifically, mxene is Ti 2 C 3 、Nb 2 C、V 2 C、V 4 C 3 、Mo 2 C, one or more of the mixtures.
The present invention is described in further detail below with reference to specific examples, which should be construed as illustrative rather than restrictive.
In the following examples, a single layer or a few layers of Ti 2 C 3 The preparation method of the dispersion solution comprises the following steps: etching Ti with HCl and LiF 2 AlC 3 Then repeatedly centrifugally cleaning, and obtaining Ti through ultrasonic stripping 2 C 3 The dispersion of (4).
Single or few layer Nb 2 The preparation method of C comprises the following steps: etching Nb with HCl and LiF 2 Repeatedly centrifugally cleaning after AlC, and obtaining Nb by ultrasonic stripping 2 And (C) a dispersion liquid.
The composition of the lithium-rich manganese-based powder is as follows: li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 。
Example 1
After 1.2mg of CTAB powder was dissolved in 5mL of water to prepare an aqueous solution (1.2 mg/mL), 1g of a lithium-rich manganese base (Li) 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 ) The powder is put into the stirrer and fully stirred for 24 hours to charge the powder, and 10 mass percent of Ti is added 2 C 3 Slowly dripping the dispersion liquid into the solution, filtering the precipitate, repeatedly cleaning and drying to obtain Ti 2 C 3 The scanning electron microscope picture of the coated lithium-rich manganese-based powder is shown in fig. 2.
Ti of which thin layer can be sufficiently seen in the scanning electron microscope shown in FIG. 2 2 C 3 Coating on the surface of the lithium-rich manganese-based particles with spinel structures.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of (8).
The synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery are stacked and assembled, then the seal is carried out, and the 2032 type button battery is assembled, wherein a cycle test chart is shown in fig. 4.
Fig. 3 shows a rate performance test chart of the modified lithium-rich manganese-based battery and a rate performance test chart of a blank battery, and it can be seen from fig. 3 that the modified battery in example 1 has better reversibility when the current is gradually increased from 0.1C and then is recovered to 0.1C.
Fig. 4 shows a cycle test chart comparing the cycle of the modified lithium manganese rich based composition battery with that of a blank battery, and it can be seen from fig. 4 that the battery of example 1 still has a specific discharge capacity of 122mAh/g after 100 cycles, whereas the battery of comparative example 1 only has a specific discharge capacity of 104 mAh/g.
Example 2
Dissolving 1.2mg CTAB powder in 5mL of water to form an aqueous solution, placing 1g of lithium-rich manganese-based powder in the aqueous solution, fully stirring for 24h to enable the lithium-rich manganese-based powder to be charged, and adding 2% of Ti by mass fraction 2 C 3 Slowly dripping the dispersion liquid into the titanium dioxide dispersion liquid, filtering the precipitate, repeatedly cleaning and drying to obtain Ti 2 C 3 Coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 3
Dissolving 1.2mg CTAB powder in 5mL water to obtain an aqueous solution, adding 1g lithium-rich manganese-based powder into the aqueous solution, stirring for 24h to make the lithium-rich manganese-based powder charged, and adding 5% of Ti 2 C 3 Slowly dripping the dispersion liquid into the titanium dioxide dispersion liquid, filtering the precipitate, repeatedly cleaning and drying to obtain Ti 2 C 3 Coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 4
Dissolving 1.2mg CTAB powder in 5mL of water to obtain an aqueous solution, adding 1g of lithium-rich manganese-based powder into the aqueous solution, stirring for 24h to make the lithium-rich manganese-based powder charged, and adding 15% of Ti by mass fraction 2 C 3 Slowly dripping the dispersion liquid into the titanium dioxide dispersion liquid, filtering the precipitate, repeatedly cleaning and drying to obtain Ti 2 C 3 Coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of (8).
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 5
Dissolving 1.2mg CTAB powder in 5mL water to obtain an aqueous solution, adding 1g lithium-rich manganese-based powder into the aqueous solution, stirring for 24h to make the lithium-rich manganese-based powder charged, and adding 20% of Ti 2 C 3 Slowly dripping the dispersion liquid into the solution, filtering the precipitate, repeatedly cleaning and drying to obtain Ti 2 C 3 Coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, then sealing the opening of the opening, and assembling the 2032 type button battery.
Example 6
Dissolving 1.2mg CTAB powder in 5mL of water to form an aqueous solution, adding 1g of lithium-rich manganese-based powder into the aqueous solution, fully stirring for 24h to enable the lithium-rich manganese-based powder to be charged, and adding 2% of Nb in mass fraction 2 Slowly dripping the C dispersion liquid into the Nb-containing solution, filtering the precipitate, repeatedly cleaning and drying to obtain Nb 2 C-coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 7
Mixing 1.2mg CTAB powderDissolving in 5mL of water to obtain an aqueous solution, adding 1g of lithium-rich manganese-based powder into the aqueous solution, stirring for 24h to charge the lithium-rich manganese-based powder, and adding 5% mass fraction of Nb 2 Slowly dripping the C dispersion liquid into the Nb-containing solution, filtering the precipitate, repeatedly cleaning and drying to obtain Nb 2 C-coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 8
Dissolving 1.2mg CTAB powder in 5mL water to obtain water solution, adding 1g lithium-rich manganese-based powder into the water solution, stirring for 24h to charge, and adding 10% mass fraction of Nb 2 Slowly dripping the C dispersion liquid into the Nb-containing solution, filtering the precipitate, repeatedly cleaning and drying to obtain Nb 2 C-coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of (8).
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 9
Dissolving 1.2mg CTAB powder in 5mL of water to obtain an aqueous solution, adding 1g of lithium-rich manganese-based powder into the aqueous solution, stirring for 24h to make the lithium-rich manganese-based powder charged, and adding 15% of Nb in mass fraction 2 Slowly dripping the C dispersion liquid into the Nb-containing solution, filtering the precipitate, repeatedly cleaning and drying to obtain Nb 2 C-coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Example 10
Dissolving 1.2mg CTAB powder in 5mL water to obtain an aqueous solution, adding 1g lithium-rich manganese-based powder into the aqueous solution, stirring for 24h to charge, and adding 20% mass fraction of Nb 2 Slowly dripping the C dispersion liquid into the Nb-containing solution, filtering the precipitate, repeatedly cleaning and drying to obtain Nb 2 C-coated lithium-rich manganese-based powder.
And (3) mixing the synthesized coated lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Comparative example 1
Mixing the uncoated blank lithium-rich manganese-based positive electrode, super-P and PVDF (3%) according to the proportion of 8.
And stacking and assembling the synthesized positive pole piece, the metal lithium piece, the electrolyte and the positive and negative electrode shell layers of the battery, and then sealing the opening to assemble the 2032 type button battery.
Comparative example 2
The difference from the example 1 is that a grinding and mixing method is adopted to prepare the lithium-rich manganese-based positive pole piece. After mixing and grinding the uncoated lithium-rich manganese-based positive electrode and MXene powder (9.
Fig. 5 shows cycle test charts of the battery constituted by the conventional mixture of the lithium-rich manganese base and MXene, and it can be seen from fig. 5 that the specific discharge capacity of the battery in comparative example 2 after 100 cycles was 107mAh/g.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified lithium-rich manganese-based positive electrode material of a lithium ion battery is characterized by comprising the following steps:
uniformly mixing lithium-rich manganese-based powder and Cetyl Trimethyl Ammonium Bromide (CTAB) powder in a solvent to obtain a lithium-rich manganese-based aqueous solution;
and adding the MXene dispersion liquid into the lithium-rich manganese-based aqueous solution, collecting the precipitate, performing suction filtration, washing and drying to obtain the lithium manganese-rich aqueous solution.
2. The method for preparing the modified lithium-rich manganese-based positive electrode material of the lithium ion battery of claim 1, wherein MXene is Ti 2 C 3 、Nb 2 C、V 2 C、V 4 C 3 、Mo 2 C, a mixture of one or more of them.
3. The method for preparing the modified lithium-rich manganese-based cathode material of the lithium ion battery according to claim 1, wherein the amount of MXene coating is 1% -30% of that of the lithium-rich manganese base.
4. The method for preparing the modified lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein the mass fraction of MXene in the MXene dispersion is 2% -20%.
5. The method for preparing the modified lithium-rich manganese-based cathode material of the lithium ion battery as claimed in claim 1, wherein MXene dispersion liquid is added dropwise to the lithium-rich manganese-based aqueous solution.
6. The method for preparing the modified lithium-rich manganese-based positive electrode material of the lithium ion battery as claimed in claim 1, wherein the lithium-rich manganese-based powder and CTAB powder are mixed in water for 24-32 h.
7. The modified lithium-rich manganese-based positive electrode material of the lithium ion battery prepared by the method of any one of claims 1 to 6.
8. An MXene modified lithium-rich manganese-based positive electrode is characterized in that the modified lithium-rich manganese-based positive electrode material of the lithium ion battery in claim 7 is uniformly mixed with a conductive agent and a binder, coated on a current collector and dried to obtain the lithium-rich manganese-based positive electrode.
9. A lithium ion battery, comprising: the positive electrode, the electrolyte, the lithium negative electrode and the separator according to claim 8;
or the electrolyte is lipid electrolyte or ether electrolyte;
or, the separator is selected from a PE separator, a PP separator, a glass fiber separator;
or the metal lithium negative electrode is any one of lithium foil, lithium sheet, lithium block, lithium powder, lithium belt and lithium alloy.
10. The use of the modified lithium-rich manganese-based positive electrode material of lithium ion battery of claim 7 in the preparation of positive electrodes, lithium batteries, and electric vehicles.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107834061A (en) * | 2017-11-17 | 2018-03-23 | 中国科学院青岛生物能源与过程研究所 | A kind of method of modifying for improving lithium-rich manganese base material chemical property |
| WO2021184764A1 (en) * | 2020-03-18 | 2021-09-23 | 蜂巢能源科技有限公司 | Lithium-rich manganese-based positive electrode material for use in lithium-ion battery, preparation method for the material, positive electrode tab, lithium-ion battery, and electric vehicle |
| CN114447290A (en) * | 2021-12-21 | 2022-05-06 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107834061A (en) * | 2017-11-17 | 2018-03-23 | 中国科学院青岛生物能源与过程研究所 | A kind of method of modifying for improving lithium-rich manganese base material chemical property |
| WO2021184764A1 (en) * | 2020-03-18 | 2021-09-23 | 蜂巢能源科技有限公司 | Lithium-rich manganese-based positive electrode material for use in lithium-ion battery, preparation method for the material, positive electrode tab, lithium-ion battery, and electric vehicle |
| CN114447290A (en) * | 2021-12-21 | 2022-05-06 | 西安理工大学 | Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery |
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| CHUANLIANG WEI等: "Crumpled Ti3C2Tx (MXene) nanosheet encapsulated LiMn2O4 for high performance lithium-ion batteries", 《ELECTROCHIMICA ACTA》, vol. 309, 19 April 2019 (2019-04-19), pages 362 - 370, XP085676422, DOI: 10.1016/j.electacta.2019.04.094 * |
| ZHITANG FANG等: ""Enhanced electrochemical performance of Li1.2Ni0.13Co0.13Mn0.54O2 composited with Ti3C2Tx MXene nanosheets"", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》, vol. 23, 16 March 2019 (2019-03-16), pages 1419 - 1428 * |
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