CN117293273A - Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof - Google Patents

Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof Download PDF

Info

Publication number
CN117293273A
CN117293273A CN202311313241.7A CN202311313241A CN117293273A CN 117293273 A CN117293273 A CN 117293273A CN 202311313241 A CN202311313241 A CN 202311313241A CN 117293273 A CN117293273 A CN 117293273A
Authority
CN
China
Prior art keywords
positive electrode
benzoquinone
lithium ion
lithium
ion battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311313241.7A
Other languages
Chinese (zh)
Inventor
潘洪革
武志俊
金勤伟
邱飞龙
张宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Technological University
Original Assignee
Xian Technological University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Technological University filed Critical Xian Technological University
Priority to CN202311313241.7A priority Critical patent/CN117293273A/en
Publication of CN117293273A publication Critical patent/CN117293273A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a benzoquinone organic matter modified positive electrode for a lithium ion battery, which comprises a current collector and a positive electrode material deposited on the surface of the current collector, wherein the positive electrode material comprises a positive electrode active component, and the positive electrode active component comprises a layered lithium-rich manganese oxide positive electrode material and a coating layer containing benzoquinone organic matter coated on the surface of the layered lithium-rich manganese oxide positive electrode material; the benzoquinone organic matter is one or more selected from 1, 4-benzoquinone, 2, 5-di-tert-butyl-1, 4-benzoquinone and 2, 6-di-tert-butyl benzoquinone. The positive electrode disclosed by the invention has excellent high-capacity and high-rate performance and also has better cycle stability. The preparation method of the positive electrode is simple and efficient, and the positive electrode can be prepared by a traditional slurry coating process.

Description

Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a benzoquinone organic matter modified positive electrode for a lithium ion battery, and a preparation method and application thereof.
Background
The lithium ion battery is widely applied to various fields such as various mobile electronic devices, electric automobiles, large-scale energy storage and the like since commercialization is made by virtue of the advantages of high energy density, high working voltage, no memory effect, environmental friendliness and the like. With the rapid development of society, the energy density of lithium ions is not capable of meeting the demands of various industrial fields, especially in the field of electric automobiles, the urgent demands for the endurance mileage are raised, and the energy density, the cycle life, the power density, the safety, the cost, the environmental friendliness and the like of the power battery are raised.
Currently, lithium ion battery positive electrode materials are commercially used as ternary positive electrode LiNi x Co y Mn 1-x-y O 2 Lithium iron phosphate LiFePO 4 Lithium manganate LiMn 2 O 4 Lithium cobaltate LiCoO 2 And the like are mainly. The lithium cobaltate is only applied to high-end electronic equipment due to the high price of cobalt resources; the specific capacity of the lithium iron phosphate and the lithium manganate is lower and is lower than 160 milliamp hours/gram. While the high nickel positive electrodes NCM622, NCM811 and the like have the capacity of 200 milliamp hours/gram, the cycle stability of the high nickel positive electrodes is still to be improved, and the low thermal stability of the high nickel positive electrodes also brings potential safety hazards. Therefore, research into a new generation of positive electrode materials having high energy density, high safety and low cost is a common goal of the scientific and industrial industries.
The layered lithium-rich manganese anode has high discharge specific capacity (280 milliamp hours/gram), high average voltage (3.6 volts), high mass specific energy density (more than 1000 watt hours/kilogram), low cost, simple material synthesis and electrode preparation process, is widely concerned and researched, and is expected to become a next-generation high-energy-density anode material. However, the continuous attenuation of capacity and voltage, poor rate capability, low first coulombic efficiency and the like in the layered lithium-rich manganese positive electrode cycle make the commercialization application thereof hindered. Especially, the capacity of the layered lithium-rich manganese anode is obviously reduced under high current, and the requirement of the lithium ion battery on the quick charge performance cannot be met. The intrinsic mechanism of poor rate capability of the layered lithium-rich manganese anode is that the intrinsic electronic conductivity is low and the kinetics of the involved anion redox reactions are retarded.
At present, the ways for improving the multiplying power performance of the layered lithium-rich manganese anode material mainly comprise the following steps: 1. by adopting a surface coating method, the coating layer is usually made of lithium niobate, nickel niobate and the like, the electrochemical performance of the material can be improved, the discharge capacity can reach 265 milliamp hours/gram at the current density of 0.1C, and the discharge capacity can reach 231 milliamp hours/gram at the current density of 1C, and the capacity improvement is limited, because the surface coating only improves the conductivity of the surface, and the electrochemical activity of internal substances can not be activated. 2. The ionic doping is adopted to adjust the electronic structure to improve the conductivity, for example, aluminum ions, niobium ions, magnesium ions and the like are added, so that the transmission of lithium ions can be improved, the electrochemical performance is improved, the discharge capacity can reach 271 milliamp hours/gram at the current density of 0.1C, and the discharge capacity can reach 238 milliamp hours/gram at the current density of 1C, but the method can cause the problems of unstable lithium-rich manganese structure, long cycle life, low service life and the like of the battery.
Based on the above, the existing modification method has the disadvantages of complex preparation, high cost, low efficiency and relatively large structural damage to lithium-rich manganese. Therefore, the development of a simple, efficient, low-cost and environment-friendly method is particularly important.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a benzoquinone organic matter modified positive electrode for a lithium ion battery, which has excellent high capacity and high rate performance and better cycle stability. The preparation method of the positive electrode is simple and efficient, and the positive electrode can be prepared by a traditional slurry coating process.
The specific technical scheme is as follows:
the positive electrode for the benzoquinone organic matter modified lithium ion battery comprises a current collector and a positive electrode material deposited on the surface of the current collector, wherein the positive electrode material comprises a positive electrode active component, and the positive electrode active component comprises a layered lithium-rich manganese oxide positive electrode material and a coating layer containing benzoquinone organic matters, wherein the coating layer is coated on the surface of the layered lithium-rich manganese oxide positive electrode material;
the benzoquinone organic matter is one or more selected from 1, 4-benzoquinone, 2, 5-di-tert-butyl-1, 4-benzoquinone and 2, 6-di-tert-butyl benzoquinone.
The invention provides a layered lithium-rich manganese anode material coated by a specific kind of benzoquinone organic matters as an anode active material for preparing an anode for a lithium ion battery for the first time, and the capacity and the multiplying power performance of the layered lithium-rich manganese anode can be obviously improved and stable circulation can be realized through coating the layered lithium-rich manganese anode material by the benzoquinone organic matters. The performance of the benzoquinone organic matter coating for improving the layered lithium-rich manganese anode mainly comes from the following aspects:
(1) The benzoquinone organic matter forms a coordination compound with oxygen released in the layered lithium-rich manganese charging stage, and reduces the oxygen into lithium peroxide in the discharging stage, so that the attack of the oxygen on the electrolyte is effectively reduced, the oxidative decomposition of the electrolyte is inhibited, the oxygen release of the layered lithium-rich manganese anode is obviously inhibited, and the damage of the oxygen release to the layered lithium-rich manganese anode structure is reduced;
(2) The reduction reaction of the benzoquinone organic matters on oxygen changes the reaction path of oxygen in the layered lithium-rich manganese anode, reduces the reaction energy barrier in the oxygen reduction process, and simultaneously, the benzoquinone organic matters of specific types can accelerate the reaction kinetics, reduce the electrochemical reaction impedance and the reaction activation energy of the lithium-rich manganese anode, thereby obviously improving the lithium ion diffusion speed of the layered lithium-rich manganese anode and obviously improving the kinetic performance of the layered lithium-rich manganese anode.
(3) The benzoquinone organic matter remarkably enhances the reactivity and reversibility of the anion redox reaction inside the lamellar lithium-rich manganese positive electrode phase through the interaction with the lamellar lithium-rich manganese positive electrode oxygen, and more oxygen participates in the electrochemical reaction, so that the lamellar lithium-rich manganese positive electrode has higher capacity;
(4) The benzoquinone organic matter coating layer which exists stably also effectively protects the structure of the layered lithium-rich manganese anode, and reduces interface side reactions.
Through the synergistic effect of the multiple factors, the capacity and the multiplying power performance of the layered lithium-rich manganese anode are obviously improved, meanwhile, the decomposition of electrolyte and the side reaction of an electrode-electrolyte interface are inhibited, the structural stability is improved, and the stable circulation of the anode is realized.
In the invention, the structural general formula of the layered lithium-rich manganese oxide positive electrode material is xLi 2 MnO 3 -(1-x)LiMO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is selected from one or more of Ni, co, mn, cr, fe, al, nb, mo, ru, and x is more than or equal to 0 and less than or equal to 1.
Preferably, x is more than or equal to 0.3 and less than or equal to 0.7; further preferably, x=0.5.
In the invention, the thickness of the coating layer containing benzoquinone organic matters is 1-50 nm; preferably 2 to 20nm.
Preferably, the benzoquinone organic matter is selected from 2, 5-di-tert-butyl-1, 4-benzoquinone and/or 2, 6-di-tert-butylbenzoquinone; further preferred is 2, 5-di-tert-butyl-1, 4-benzoquinone. Experiments show that the capacity and the multiplying power performance of the prepared coated positive plate are gradually improved along with the optimization of the benzoquinone organic compound.
The invention also discloses a preparation method of the benzoquinone organic matter modified positive electrode for the lithium ion battery, which comprises the following steps:
and uniformly mixing the layered lithium-rich manganese oxide positive electrode material, benzoquinone organic matters, a conductive agent, a binder and a solvent to form slurry, and coating the slurry on a current collector to obtain the positive electrode for the lithium ion battery.
The mass ratio of benzoquinone organic matters is 1-30%, the mass ratio of the conductive agent is 1-20%, the mass ratio of the binder is 1-15% and the balance is the layered lithium-rich manganese oxide positive electrode material based on the total mass of all raw materials except the solvent.
Preferably, the mass ratio of the benzoquinone organic compound is 10 to 20%, more preferably 15%.
Experiments show that the electrochemical performance of the prepared coated positive plate is gradually improved along with the continuous optimization of the adding content of the benzoquinone organic matters.
In the present invention, there is no particular requirement for the kind of current collector, and it is sufficient to select from the kinds commonly used in the art, such as aluminum foil, carbon-coated aluminum foil, nickel foil, and the like.
In the invention, the type of the conductive agent is not particularly required, and the conductive agent is selected from one or more of Super P, graphite, ketjen black, acetylene black, carbon nano tubes and graphene which are commonly used in the field.
In the invention, the binder is selected from one or more of common types in the field, such as polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyvinyl alcohol, polyacrylonitrile, styrene-butadiene rubber, sodium alginate and sodium carboxymethyl cellulose.
In the invention, the solvent is selected from water or a mixed solvent consisting of water and an organic solvent; the organic solvent is selected from the conventional classes in the art, such as ethanol, N-methylpyrrolidone, p-xylene, etc.
Preferably, the solvent is selected from water and the binder is selected from water-soluble binders such as sodium carboxymethyl cellulose.
In the slurry, the mass ratio of all raw materials except the solvent to the solvent is 1:2 to 10. Either too thin or too thick a slurry is detrimental to coating, further preferably 1:5.
the mixing may be by mixing means common in the art, such as mechanical ball milling, mechanical stirring, or magnetic stirring, among others.
Post-treatment, including drying, cold pressing or rolling treatment, is also required after coating, and the pressure adopted is 5-40 MPa.
The invention also discloses a lithium ion battery, which comprises a positive electrode and a negative electrode, wherein the positive electrode adopts the benzoquinone organic matter modified positive electrode for the lithium ion battery.
Experiments show that the lithium ion battery assembled by the positive electrode disclosed by the invention has high capacity, high rate performance and excellent cycle stability.
Compared with the prior art, the invention has the following advantages:
the invention discloses a positive electrode for a lithium ion battery, which takes a layered lithium-rich manganese positive electrode material coated by benzoquinone organic matters as a positive electrode active material, and experiments show that the capacity and the multiplying power performance of the positive electrode can be obviously improved and the cycling stability can be improved through the coating of the layered lithium-rich manganese positive electrode material by the benzoquinone organic matters; the capacity of the lithium ion battery assembled by the positive electrode can reach 328 milliamp hours/gram at the current density of 0.1C, and the capacity retention rate can reach 93.3 percent after 1000 times of circulation at the current density of 1C. The retention rate of 1000 cycles of the high-rate catalyst reaches 89.5% when the high-rate catalyst is circulated for 1000 times at 20C, and the retention rate of 95.6% when the high-rate catalyst is circulated for 1000 times at 30C.
The preparation method of the positive electrode for the lithium ion battery disclosed by the invention is a conventional coating process in the field, the preparation process is formed in one step, benzoquinone organic matters are uniformly distributed in slurry, the dispersibility is good, and the electrode is dried to form a uniform coating layer, and the uniform coating layer is coated on the surface of a lithium-rich manganese positive electrode material; the preparation process does not increase electrode preparation steps, does not increase extra preparation cost, is simple to operate, has strong material preparation controllability, and is completely suitable for industrial production requirements.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the positive electrode material of the positive electrode sheet surface prepared in example 1;
FIG. 2 is an in situ differential electrochemical mass spectrum of the positive electrode material prepared in example 1 during the first cycle of the positive electrode sheet surface;
FIG. 3 is an X-ray photoelectron Spectroscopy (XPS) of Li of the positive electrode sheet surface positive electrode material prepared in example 1 before and after the first charge and discharge;
FIG. 4 shows the first charge and discharge process of the positive electrode material prepared in example 1 after 20 minutes of argon ion etchingX-ray photoelectron spectrum (a) of O; peroxy ion O during first cycle 2 2- A change in the proportion (b);
fig. 5 is a first charge-discharge curve (a) at 0.1C rate for the assembled battery of example 1; a 1C rate cycle performance curve (b);
FIG. 6 is a plot of the median voltage decay for the assembled battery of example 1;
fig. 7 is a plot of the rate performance of the assembled battery of example 1;
fig. 8 is a cycle performance curve of the assembled battery of example 1 at a 20C rate;
fig. 9 is a cycle performance curve of the assembled battery of example 1 at a rate of 30C;
FIG. 10 is an electrochemical impedance spectrum for the assembled battery of example 1 at various voltages during initial charge and discharge;
FIG. 11 is electrochemical impedance spectra (a-e) of the assembled battery of example 1 when first charged to 4.6V at different temperatures; fitting the obtained electrochemical reaction activation energy (f);
FIG. 12 is a spherical aberration correcting transmission electron microscope morphology of positive electrode material on the surface of a positive electrode sheet after 500 cycles at a current density of 200 mA/g for the assembled battery of example 1;
fig. 13 is a first charge-discharge curve (a) of the assembled battery of example 2; a rate capability curve (b);
fig. 14 is a first charge-discharge curve (a) of the assembled battery of example 3; a rate capability curve (b);
FIG. 15 is a Transmission Electron Microscope (TEM) image of the positive electrode material of the positive electrode sheet surface prepared in comparative example 1;
FIG. 16 is an in situ differential electrochemical mass spectrum of the positive electrode material prepared in comparative example 1 during the first cycle;
FIG. 17 is an X-ray photoelectron Spectrometry (XPS) of Li of the positive electrode sheet surface positive electrode material prepared in comparative example 1 before and after the first charge and discharge;
FIG. 18 is an X-ray photoelectron spectrum (a) of O in the first charge and discharge process after etching with argon ions for 20 minutes of the positive electrode material on the surface of the positive electrode sheet prepared in comparative example 1; during the first cycleIs (are) peroxy ions O 2 2- A change in the proportion (b);
fig. 19 is a first charge-discharge curve (a) at 0.1C magnification of the assembled battery of comparative example 1; a 1C rate cycle performance curve (b);
FIG. 20 is a plot of the median voltage decay for the assembled battery of comparative example 1;
fig. 21 is a rate performance curve of the assembled battery of comparative example 1;
fig. 22 is a cycle performance curve of the assembled battery of comparative example 1 at a rate of 20C;
fig. 23 is a cycle performance curve of the assembled battery of comparative example 1 at a rate of 30C;
FIG. 24 is an electrochemical impedance spectrum for the assembled battery of comparative example 1 at various voltages during initial charge and discharge;
FIG. 25 is electrochemical impedance spectra (a-e) of the assembled battery of comparative example 1 when first charged to 4.6V at different temperatures; fitting the obtained electrochemical reaction activation energy (f);
fig. 26 is a spherical aberration correcting transmission electron microscope morphology of positive electrode material on the surface of a positive electrode sheet after 500 cycles at a current density of 200 milliamp/g for the assembled battery of comparative example 1.
Detailed Description
The following examples are provided to further illustrate the present invention and should not be construed as limiting the scope of the invention.
Example 1
The component is 0.5Li 2 MnO 3 -0.5LiNi 0.33 Co 0.33 Mn 0.33 O 2 The particle size of the layered lithium-rich manganese anode material is 200-400 nm. Mixing the layered lithium-rich manganese anode, a conductive agent Super P, an aqueous binder sodium carboxymethyl cellulose (CMC) and 2, 5-di-tert-butyl-1, 4-benzoquinone (DBBQ) according to the mass ratio of 70:10:5:15, adding deionized water as a solvent (the mass ratio of the total mass of the raw materials to the deionized water is 1:5), magnetically stirring for 2 hours, ultrasonically dispersing for 2 hours, magnetically stirring for 2 hours to obtain slurry, and uniformly stirring the slurryCoating the positive plate on aluminum foil, drying in vacuum at 80 ℃, and pressing under 10MPa to obtain the positive plate which is 15wt% DBBQ coated.
The morphology of the positive electrode material in the positive electrode plate prepared in the embodiment is characterized, a photo of a transmission electron microscope is shown in fig. 1, and a coating layer with the thickness of about 7nm is arranged on the surface of the layered lithium-manganese-rich positive electrode particle. The coating was analyzed by fast fourier transform, as shown in the inset of fig. 1, and the electron diffraction pattern was a diffuse halo, indicating that the coating was amorphous. The electron microscope photo shows that DBBQ is coated on the surface of the layered lithium-rich manganese oxide particles, and the crystal structure of the lithium-rich manganese material is not damaged.
The electrochemical performance of the positive plate prepared in the embodiment is characterized by adopting 2025 button cells, and the positive plate is assembled in a glove box filled with Ar, wherein the water content and the oxygen content of the glove box are both less than 0.1 ppm. The anode is an electrode slice prepared by adopting a metal Li slice as a reference electrode and a counter electrode, the diaphragm adopts Celgard-2400, and the electrolyte is LiPF 6 (1 mol/L)/EC+DEC+EMC (volume ratio 1:1:1). The test voltage window is 2.0-4.8V, and the electrochemical performance of the battery is tested by adopting a constant current charging and discharging mode.
Fig. 2 is an in-situ differential electrochemical mass spectrum of the positive electrode material on the surface of the positive electrode sheet prepared in this example in the first charge and discharge process, and shows the gas generation condition in the charge and discharge process. Compared with the uncoated layered lithium-rich manganese positive electrode material (comparative example 1, fig. 16), the oxygen and carbon dioxide content released by the positive electrode in this example is greatly reduced, which indicates that the addition and coating of DBBQ can effectively reduce the oxygen release and electrolyte side reaction of the layered lithium-rich manganese positive electrode material.
Fig. 3 is an X-ray photoelectron spectrum of lithium before and after the first charge and discharge of the positive electrode material on the surface of the positive electrode sheet prepared in this example. Lithium exists in the form of lattice lithium before charging (upper graph); at the end of the first cycle, when discharged to 2.0V (lower panel), lithium carbonate/fluoride is also present, in addition to lattice lithium, due to the formation of the positive electrolyte interface layer, while lithium peroxide is also generated. The layered lithium-rich manganese anode without DBBQ coating was free from lithium peroxide formation after discharge (comparative example 1, fig. 17), indicating that oxygen released from the layered lithium-rich manganese anode coated with DBBQ was adsorbed by DBBQ, and then reduced during discharge to combine with lithium ions to form lithium peroxide.
Fig. 4 (a) is an X-ray photoelectron spectrum of oxygen during the first charge and discharge process of the positive electrode material on the surface of the positive electrode sheet prepared in this example, and etched by argon ions for 20min, which is used to characterize the internal portion of the bulk phase of the positive electrode material. In the charging process, oxygen in the lithium-rich manganese phase is gradually oxidized to generate peroxy ion O 2 2- Is gradually reduced to lattice oxygen in the discharging process, and has high reversibility. O under different charge and discharge voltages 2 2- The ratio of (a) to (b) shows that, at any charge-discharge voltage, O 2 2- The content is far higher than that of the lithium-rich manganese positive electrode which is not subjected to coating treatment, and no residue exists after the discharge is finished (comparative example 1, fig. 18), which shows that the oxidation-reduction reaction of the bulk oxygen in the lithium-rich manganese positive electrode after DBBQ coating treatment has stronger reactivity and reaction reversibility.
Fig. 5 (a) is a graph showing the first charge and discharge curves of the assembled battery of this example at a current density of 20 milliamp/gram (0.1C), with a first discharge capacity up to 328 milliamp hours/gram and a first coulombic efficiency of 82.5%. (b) The assembled battery of this example has a cycling performance profile at a current density of 200 milliamp/gram (1C). The first discharge capacity reaches 253.6 milliampere hour/gram, the capacity slightly decreases in the first 100 weeks, the capacity slowly increases and remains stable after activation, and after 1000 cycles, the capacity still has 236.6 milliampere hour/gram, the capacity retention rate is 93.3%, and the high discharge capacity and excellent cycle stability are shown.
Fig. 6 is a graph of the median discharge voltage of the assembled battery of this example, after 500 cycles, at a median voltage of 2.89V and a retention of 82.3%.
Fig. 7 shows the rate performance curves of the assembled battery of this example, which shows excellent electrochemical capacities at various rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C, and 30C, respectively, at 321, 271, 243, 215, 181, 143, 118, and 87 milliamp hours/gram, respectively.
Fig. 8 is a graph showing the cycling performance of the assembled battery of this example at a current density of 4000 milliamp/gram (20C), after 1000 cycles, the capacity was still 102 milliamp hours/gram, and the capacity retention was 89.5%.
Fig. 9 is a graph showing the cycling performance of the assembled battery of this example at a current density of 6000 ma/g (30C), after 1000 cycles, the capacity was still 88 ma hours/g, and the capacity retention was 95.6%.
Fig. 10 is an electrochemical impedance spectrum of the positive electrode material of this example under different voltages at the first charge-discharge cycle, and the charge transfer impedances of the positive electrode material on the surface of the positive electrode sheet prepared in this example and comparative example 1, respectively, are shown in table 1. The charge transfer impedance of the layered lithium-rich manganese anode after DBBQ coating treatment is smaller than that of the uncoated anode in the charge-discharge process (comparative example 1, FIG. 24), and the change range is smaller, which shows that the layered lithium-rich manganese anode has more stable reaction kinetics.
TABLE 1
Fig. 11 (a-e) are electrochemical impedance spectra of the positive electrode sheet surface positive electrode materials prepared in this example and comparative example 1, respectively, at different temperatures after the positive electrode sheet surface positive electrode materials prepared in this example were charged to 4.6V for the first time, and the charge transfer impedances of the positive electrode sheet surface positive electrode materials prepared in this example and comparative example 1 are shown in table 2. The charge transfer impedance of the layered lithium-rich manganese anode after DBBQ coating treatment is smaller than that of the uncoated anode at different temperatures. Fig. 10 (f) is a plot of the calculated reaction activation energy fitting, with a significant reduction in reaction activation energy to 52.5 kj/mole compared to the uncoated positive electrode (comparative example 1, fig. 25).
TABLE 2
Fig. 12 is a spherical aberration correction transmission electron microscope image of the positive electrode material on the surface of the positive electrode sheet prepared in this example after 500 cycles, wherein the surface of the positive electrode material still maintains a coating layer of about 6nm (fig. 12 a) after 500 cycles, and meanwhile, the spinel structure is only in the surface 4nm range (fig. 12 b), and most of lithium-manganese-rich particles still maintain a complete layered structure. In contrast to the morphology of comparative example 1 after 500 cycles (fig. 26), the positive electrode particles in comparative example 1 exhibited a large number of voids, which resulted from dissolution of the transition metal and release of oxygen, and most of the crystal structure was converted from the layered structure to the spinel structure. The comparison shows that the DBBQ coating can obviously inhibit spinel phase change of the lithium-rich manganese anode in circulation and inhibit metal ion dissolution, and the integrity of the crystal structure is maintained.
Example 2
The preparation process is basically the same as that of example 1, except that the mass ratio of the layered lithium-rich manganese positive electrode material, super P, CMC and DBBQ is replaced by 75:10:5:10, and the obtained positive electrode sheet is recorded as a 10wt% DBBQ coated positive electrode sheet. The battery assembly and test conditions were the same as in example 1.
Fig. 13 (a) is a first charge-discharge curve of the assembled battery of this example at a current density of 20 milliamp/gram, with a first discharge capacity of 314 milliamp hours/gram. (b) For the rate performance curves of the assembled battery of this example, the electrochemical capacities at different rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C, and 30C reached 311, 264, 235, 209, 170, 132, 110, and 80 milliamp hours/gram, respectively, indicating that the assembled battery of this example has excellent rate performance.
Example 3
The preparation process is basically the same as that of example 1, except that the mass ratio of the layered lithium-rich manganese positive electrode material, super P, CMC and DBBQ is replaced by 65:10:5:20, and the obtained positive electrode sheet is recorded as a 20wt% DBBQ coated positive electrode sheet. The battery assembly and test conditions were the same as in example 1.
Fig. 14 (a) is a first charge-discharge curve of the assembled battery of this example at a current density of 20 ma/g, with a first discharge capacity of 299 ma/g. (b) For the rate performance curves of the assembled batteries of this example, the electrochemical capacities at different rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C and 30C were 295, 252, 220, 194, 158, 117, 100 and 74 milliamp hours/gram, respectively, indicating that the assembled batteries of this example also have excellent rate performance.
Example 4
The preparation process was substantially the same as in example 1 except that 2, 5-di-t-butyl-1, 4-benzoquinone was replaced with equal mass of 2, 6-di-t-butylbenzoquinone (DTBQ), and the resulting positive electrode sheet was recorded as 15wt% DTBQ-coated positive electrode sheet. The assembly and test conditions of the battery were the same as in example 1.
The gas release in the first charge and discharge process, the electrochemical impedance spectrum in the first charge and discharge process and the X-ray photoelectron spectrum of the O element in the first charge and discharge process of the positive plate prepared in the embodiment are characterized, and the result shows a similar rule as in the embodiment 1, so that the DTBQ can realize the adsorption and reduction of oxygen, enhance the transmission diffusion of lithium ions and reduce the reaction impedance and the reaction activation energy.
The assembled battery of this example was tested to have a first discharge capacity of 319 milliamp hours/gram at a current density of 20 milliamp/gram and electrochemical capacities of 315, 267, 236, 211, 174, 138, 113 and 82 milliamp hours/gram at different rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C and 30C, respectively, and exhibited excellent high capacity and high rate performance.
Example 5
The preparation process was substantially the same as in example 1 except that 2, 5-di-t-butyl-1, 4-benzoquinone was replaced with equal mass of 1, 4-Benzoquinone (BQ), and the resulting positive electrode sheet was denoted as 15wt% BQ-coated positive electrode sheet. The assembly and test conditions of the battery were the same as in example 1.
The assembled battery of this example was tested to have a first discharge capacity of 306 milliamp hours/gram at a current density of 20 milliamp/gram and electrochemical capacities of 302, 256, 223, 198, 162, 121, 105 and 77 milliamp hours/gram at different rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C and 30C, respectively, and exhibited excellent high capacity and high rate performance.
Example 6
The preparation process was substantially the same as in example 1, except that the layered lithium-rich manganese oxide positive electrode material was replaced with a composition of 0.7Li by mass 2 MnO 3 -0.3LiNi 0.33 Co 0.33 Mn 0.33 O 2 Layered lithium-rich manganese oxide positive electrodeA polar material. The battery assembly and test conditions were the same as in example 1.
The positive electrode sheet assembled battery prepared in this example was tested to have a first discharge capacity of 303 milliamp hours/gram at a current density of 20 milliamp/gram. The assembled batteries of this example also exhibited excellent high capacity and high rate performance at different rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C, and 30C, with electrochemical capacities of 298, 248, 215, 189, 154, 111, 98, and 71 milliampere hours/gram, respectively.
Comparative example 1
The preparation process was substantially the same as in example 1, except that 2, 5-di-t-butyl-1, 4-benzoquinone was not added. The layered lithium-rich manganese oxide, super P and CMC are mixed according to the mass ratio of 85:10:5. The battery assembly and test conditions were the same as in example 1.
Fig. 15 is a Transmission Electron Microscope (TEM) image of the positive electrode material on the surface of the positive electrode sheet prepared in this comparative example, and it can be seen that the surface of the lithium-rich manganese particles is bare, and no coating layer exists. Fig. 16 is an in-situ differential electrochemical mass spectrum of the positive electrode material on the surface of the positive electrode sheet prepared in this comparative example in the first charge and discharge process, and shows the gas generation condition in the charge and discharge process, and the contents of oxygen and carbon dioxide released by the positive electrode in this comparative example are very high.
Fig. 17 is an X-ray photoelectron spectrum of lithium before and after the first charge and discharge of the positive electrode material on the surface of the positive electrode sheet prepared in this comparative example. The layered lithium-rich manganese positive electrode of the comparative example was found to have no formation of lithium peroxide after the end of discharge, indicating that no adsorption or reduction of oxygen had occurred.
Fig. 18 (a) is an X-ray photoelectron spectrum of oxygen during the first charge and discharge of the positive electrode sheet surface positive electrode material prepared in this comparative example, and etched with argon ions for 20min, for characterizing the inside of the positive electrode material bulk phase. Peroxide ion O in lithium-rich manganese phase during charge and discharge 2 2- The content is lower, the highest duty ratio is only 12.4% when the charge is to 4.8V, and the residual peroxy ions remain after the discharge is finished and the peroxy ions are not reduced completely.
Fig. 19 (a) is a first charge-discharge curve of the assembled battery of this comparative example at a current density of 20 ma/g, with a first discharge capacity of 273 ma/g and a first coulomb efficiency of 75.9%. (b) The cycling performance curve of the cell assembled for this comparative example at a current density of 200 milliamp/gram (1C). The first discharge capacity is 214 milliampere hours/gram, the capacity is rapidly attenuated in the circulation process, after 1000 times of circulation, the capacity is only 119 milliampere hours/gram, and the capacity retention rate is only 55.6%. The comparative example has poor cycle stability and low capacity, and is obviously inferior to the examples of the present invention.
Fig. 20 is a graph of the median discharge voltage of the assembled battery of this comparative example at a current density of 200 milliamp/gram, with a rapid voltage decay after 500 cycles, a median voltage of 2.61V and a retention of 73.9%.
Fig. 21 is a graph showing the rate performance curves of the assembled batteries of this comparative example, with lower specific discharge capacities at different rates of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C, and 30C, respectively 257, 213, 189, 168, 135, 108, 77, and 65 milliamp hours/gram, indicating that the rate performance of this comparative example is significantly worse than that of the examples of the present invention.
Fig. 22 is a graph showing the cycling performance of the assembled battery of this comparative example at a current density of 4000 milliamp/gram (20C), after 1000 cycles, the capacity decays rapidly, with only 16 milliamp hours/gram and only 15.8% capacity retention.
Fig. 23 is a graph showing the cycle performance of the assembled battery of this comparative example at a current density of 6000 ma/g (30C), with the positive electrode substantially deactivated after 400 cycles, the capacity zeroed, and after 1000 cycles, the capacity was only 3 ma/g, with a capacity retention of 7.6%.
Fig. 24 is an electrochemical impedance spectrum of the positive electrode material in this comparative example at different voltages for the first charge-discharge cycle. In combination with table 1, the layered lithium-rich manganese positive electrode without DBBQ coating treatment had a larger charge transfer resistance during charge and discharge and increased rapidly in the discharge phase.
Fig. 25 (a-e) are electrochemical impedance spectra at different temperatures after the positive electrode material of the present comparative example is first charged to 4.6V. In combination with table 2, the layered lithium-rich manganese positive electrode without DBBQ coating had a greater charge transfer resistance at different temperatures. The reaction activation energy curve of fig. 25 (f) shows that the activation energy of the layered lithium-rich manganese anode without DBBQ coating treatment is greater, reaching 61.6 kj/mol.
Fig. 26 is a spherical aberration correction transmission electron microscope image of the positive electrode material in this comparative example after 500 cycles. After 500 cycles, a large amount of spinel phases are generated, and a large amount of oxygen defects and voids exist on the surface and the bulk phase, which indicates that the layered lithium-rich manganese oxide material of the comparative example undergoes serious structural damage and phase transformation in electrochemical cycles, and is obviously inferior to the structural stability of the embodiment of the invention.
Comparative example 2
The preparation process was substantially the same as in example 6, except that 2, 5-di-t-butyl-1, 4-benzoquinone was not added. The layered lithium-rich manganese oxide, super P and CMC are mixed according to the mass ratio of 85:10:5. The battery assembly and test conditions were the same as in example 1.
The positive electrode sheet assembled battery prepared in this comparative example was tested to have a discharge capacity of 252 milliamp hours per gram at a current density of 20 milliamp/gram and a first coulomb efficiency of 75.0%. The positive electrode sheets prepared in this comparative example had electrochemical capacities of 247, 207, 175, 151, 124, 87, 65 and 49 milliamp hours/g at different magnifications of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C and 30C, respectively, which were significantly inferior to example 6 of the present invention.
Comparative example 3
The preparation process was substantially the same as in example 1 except that 2, 5-di-t-butyl-1, 4-benzoquinone was replaced with equal mass of 2-chloro-1, 4-benzoquinone, and the resulting positive electrode sheet was recorded as 15wt% 2-chloro-1, 4-benzoquinone coated positive electrode sheet. The assembly and test conditions of the battery were the same as in example 1.
The positive electrode sheet assembled battery prepared in this comparative example was tested to have a discharge capacity of 246 milliamp hours per gram at a current density of 20 milliamp/gram and a first coulomb efficiency of 72.3%. The positive electrode sheets prepared in this comparative example had electrochemical capacities of 231, 198, 162, 141, 115, 69, 51 and 36 milliampere hours/g at various magnifications of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C and 30C, respectively, which were significantly inferior to example 1 of the present invention.
Comparative example 4
The preparation process was substantially the same as in example 1 except that 2, 5-di-t-butyl-1, 4-benzoquinone was replaced with equal mass of tetrachlorobenzoquinone, and the resulting positive electrode sheet was recorded as 15wt% of tetrachlorobenzoquinone coated positive electrode sheet. The assembly and test conditions of the battery were the same as in example 1.
The positive electrode sheet assembled battery prepared in this comparative example was tested to have a discharge capacity of 235 milliamp hours/gram at a current density of 20 milliamp/gram and a first coulomb efficiency of 70.8%. The positive electrode sheets prepared in this comparative example had electrochemical capacities of 221, 186, 153, 137, 106, 62, 45 and 29 milliamp hours/gram at different magnifications of 0.1C, 0.5C, 1C, 2C, 5C, 10C, 20C and 30C, respectively, which were significantly inferior to example 1 of the present invention.
The foregoing is merely a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and the present invention is described by using the specific examples, which are only for aiding in understanding the present invention, and are not limited thereto. Several simple deductions, variations, substitutions or combinations may also be made by those skilled in the art to which the invention pertains based on the inventive concept. Such deductions, modifications, substitutions or combinations are also within the scope of the claims of the present invention.

Claims (10)

1. The positive electrode for the benzoquinone organic matter modified lithium ion battery comprises a current collector and a positive electrode material deposited on the surface of the current collector, wherein the positive electrode material comprises a positive electrode active component and is characterized in that:
the positive electrode active component comprises a layered lithium-rich manganese oxide positive electrode material and a coating layer which is coated on the surface of the layered lithium-rich manganese oxide positive electrode material and contains benzoquinone organic matters;
the benzoquinone organic matter is one or more selected from 1, 4-benzoquinone, 2, 5-di-tert-butyl-1, 4-benzoquinone and 2, 6-di-tert-butyl benzoquinone.
2. The positive electrode for a benzoquinone organic matter-modified lithium ion battery according to claim 1, wherein:
the structural general formula of the layered lithium-rich manganese oxide positive electrode material is xLi 2 MnO 3 -(1-x)LiMO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is selected from one or more of Ni, co, mn, cr, fe, al, nb, mo, ru, and x is more than or equal to 0 and less than or equal to 1.
3. The positive electrode for a benzoquinone organic matter-modified lithium ion battery according to claim 1, wherein:
the thickness of the coating layer containing benzoquinone organic matters is 1-50 nm.
4. The positive electrode for a benzoquinone organic material-modified lithium ion battery according to claim 1, wherein the benzoquinone organic material is selected from 2, 5-di-t-butyl-1, 4-benzoquinone and/or 2, 6-di-t-butylbenzoquinone.
5. The positive electrode for a benzoquinone organic material-modified lithium ion battery according to claim 1, wherein the benzoquinone organic material is selected from 2, 5-di-t-butyl-1, 4-benzoquinone.
6. A method for producing a positive electrode for a benzoquinone organic compound-modified lithium ion battery according to any one of claims 1 to 5, comprising:
and uniformly mixing the layered lithium-rich manganese oxide positive electrode material, benzoquinone organic matters, a conductive agent, a binder and a solvent to form slurry, and coating the slurry on a current collector to obtain the positive electrode for the lithium ion battery.
7. The method for preparing the benzoquinone organic matter modified positive electrode for lithium ion batteries according to claim 6, wherein the method comprises the following steps:
the mass ratio of benzoquinone organic matters is 1-30% based on the total mass of all raw materials except the solvent.
8. The method for preparing the benzoquinone organic matter modified positive electrode for lithium ion batteries according to claim 6, wherein the method comprises the following steps:
the mass ratio of benzoquinone organic matters is 10-20% based on the total mass of all raw materials except the solvent.
9. The method for preparing the benzoquinone organic matter modified positive electrode for lithium ion batteries according to claim 6, wherein the method comprises the following steps:
the mass ratio of the conductive agent is 1-20%, the mass ratio of the binder is 1-15% by the total mass of all raw materials except the solvent, and the balance is the layered lithium-rich manganese oxide positive electrode material.
10. A lithium ion battery comprising a positive electrode and a negative electrode, wherein the positive electrode is the positive electrode for a lithium ion battery modified with the benzoquinone organic compound according to any one of claims 1 to 5.
CN202311313241.7A 2023-10-11 2023-10-11 Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof Pending CN117293273A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311313241.7A CN117293273A (en) 2023-10-11 2023-10-11 Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311313241.7A CN117293273A (en) 2023-10-11 2023-10-11 Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN117293273A true CN117293273A (en) 2023-12-26

Family

ID=89238819

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311313241.7A Pending CN117293273A (en) 2023-10-11 2023-10-11 Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117293273A (en)

Similar Documents

Publication Publication Date Title
KR101342601B1 (en) Negative active material, manufacturing method thereof, and lithium battery containing the material
KR20170075596A (en) Positive electrode active material for rechargeable lithium battery, method for menufacturing the same, and rechargeable lithium battery including the same
Huang et al. Preparation and characterization of core–shell structure Fe3O4/C nanoparticles with unique stability and high electrochemical performance for lithium-ion battery anode material
US20210328217A1 (en) Lithium battery and anode material thereof
CN113471415A (en) Composite coated lithium ion battery anode material and preparation method thereof
CN113113586B (en) Positive electrode for lithium ion battery and preparation method and application thereof
KR20090020882A (en) Surface-coated lithium titanate powder, electrode, and secondary battery comprising the same
KR20080029479A (en) Cathode active material, lithium secondary battery comprising same, and hybrid capacitor comprising same
CN112467116A (en) Graphite coating material, preparation method thereof and battery cathode
CN115881917A (en) Positive electrode active material, preparation method thereof, sodium ion battery and electric equipment
CN112151779A (en) Binary anode composite material and preparation method and application thereof
WO2024146611A1 (en) Lithium ion battery
CN113066988B (en) Negative pole piece and preparation method and application thereof
Garhi et al. Coprecipitation synthesis of Co-doped LiMn1. 5Ni0. 5O4 material as 5 V cathode of Li-ion batteries with huge rate capability for high power applications
Şahan et al. Effect of silver coating on electrochemical performance of 0.5 Li 2 MnO 3. 0.5 LiMn 1/3 Ni 1/3 Co 1/3 O 2 cathode material for lithium-ion batteries
CN109216692B (en) Modified ternary cathode material, preparation method thereof and lithium ion battery
CN115911324A (en) Positive electrode material, secondary battery, and electric device
CN117293273A (en) Positive electrode for benzoquinone organic matter modified lithium ion battery, and preparation method and application thereof
KR20130003591A (en) Positive-electrode active material with improved output and lithium secondary battery including them
CN113991081B (en) Modified layered lithium-rich manganese oxide positive electrode material and application thereof
CN117154007A (en) Positive electrode for phthalocyanine compound modified lithium ion battery, and preparation method and application thereof
CN116779832B (en) Intercalation sodium ion battery layered oxide positive electrode material, preparation and application thereof
CN117154006A (en) Organic nitrogen oxide modified positive electrode for lithium ion battery, and preparation method and application thereof
CN115395019B (en) Sodium-ion battery positive electrode material, preparation method thereof, positive electrode piece and sodium-ion battery
US20240105930A1 (en) Transition metal layered oxides, positive electrode material, and sodium-ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination