CN111883749A - Method for preparing transition metal oxide composite electrode for lithium battery - Google Patents

Method for preparing transition metal oxide composite electrode for lithium battery Download PDF

Info

Publication number
CN111883749A
CN111883749A CN202010610780.7A CN202010610780A CN111883749A CN 111883749 A CN111883749 A CN 111883749A CN 202010610780 A CN202010610780 A CN 202010610780A CN 111883749 A CN111883749 A CN 111883749A
Authority
CN
China
Prior art keywords
metal oxide
composite electrode
preparing
lithium battery
lithium
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
CN202010610780.7A
Other languages
Chinese (zh)
Inventor
卢山龙
朱建楠
叶明刚
孙朝军
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.)
Anhui Nandu Huabo New Material Technology Co ltd
Jieshou Nandu Huayu Power Source Co Ltd
Original Assignee
Anhui Nandu Huabo New Material Technology Co ltd
Jieshou Nandu Huayu Power Source Co Ltd
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 Anhui Nandu Huabo New Material Technology Co ltd, Jieshou Nandu Huayu Power Source Co Ltd filed Critical Anhui Nandu Huabo New Material Technology Co ltd
Priority to CN202010610780.7A priority Critical patent/CN111883749A/en
Publication of CN111883749A publication Critical patent/CN111883749A/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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 discloses a method for preparing a transition metal oxide composite electrode for a lithium battery, which comprises the following steps: s1, taking nickel nitrate hexahydrate, ferric nitrate nonahydrate and metal oxide as raw materials to obtain a mixed solution; s2, alkalizing and drying to obtain a precursor material; s3, placing the precursor material in a tube furnace for sintering to obtain a coated material; and S4, preparing the composite electrode by taking N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a binder. According to the invention, the self-made coating material is used as a main substance of the motor, and the nickel-iron compound is used as a coating layer, so that the lithium manganate matrix material is protected from being corroded by electrolyte, the cycle performance of the motor is improved, the transmission rate of ions or electrons can be improved to a certain extent, and the electrochemical performance of the material is improved; the preparation method is simple and convenient, is easy to operate, is suitable for large-scale production, and the battery assembled by adopting the electrode material has high specific capacity and excellent cycle performance.

Description

Method for preparing transition metal oxide composite electrode for lithium battery
Technical Field
The invention belongs to the field of lithium battery processing, and particularly relates to a method for preparing a transition metal oxide composite electrode for a lithium battery.
Background
The lithium battery has the advantages of high energy density, large output power, high average output voltage, small self-discharge, no memory effect, quick charge and discharge, excellent cycle performance and no environmental pollution, becomes a preferred object of rechargeable power sources of present portable electronic products, and is considered as the most promising chemical power source. In the lithium battery, the electrode material occupies the most important position, and the performance of the electrode material directly determines various performance indexes of the final lithium battery product. The transition metal oxide is used as an electrode material of the lithium battery, and has an excellent voltage platform and specific capacity. However, the oxide material with the traditional structure is difficult to have new breakthrough in the aspects of specific capacity and electrochemical cycle performance, and the cycle performance of the transition metal oxide material is not ideal due to low electronic conductivity, low lithium ion diffusion coefficient and structural change of a main crystal lattice, so that the design and preparation of the composite material with the nano structure become an effective way for obtaining the high-performance lithium battery electrode material.
Chinese patent No. CN201711480922.7 discloses a carbon-metal oxide composite coated lithium battery ternary positive electrode material, a preparation method thereof, and a lithium battery, wherein the ternary positive electrode material includes: a ternary positive electrode material substrate; the composite coating comprises a carbon-metal oxide composite, wherein the metal in the metal oxide is a metal with a reduction potential of less than-0.27V, and preferably the metal is selected from any one or more of magnesium, aluminum, zirconium, titanium, zinc, barium, strontium, vanadium, neodymium, cadmium and yttrium. Although the positive electrode material adopts carbon and metal composite, the conductive efficiency can be improved, but the coating layer is difficult to play the roles of conductivity and protection, and further influences the lithium battery
Disclosure of Invention
The invention aims to provide a method for preparing a transition metal oxide composite electrode for a lithium battery, which is characterized in that a self-made coating material is used as a main substance of a motor, and a nickel-iron compound is used as a coating layer, so that the lithium manganate matrix material is protected from being corroded by electrolyte, the cycle performance of the motor is improved, the transmission rate of ions or electrons can be improved to a certain extent, and the electrochemical performance of the material is improved; the preparation method is simple and convenient, easy to operate and suitable for large-scale production, the prepared electrode material has higher lithium ion and electron conductivity, and the battery assembled by the electrode material has high specific capacity and excellent cycle performance.
The purpose of the invention can be realized by the following technical scheme:
a method of preparing a transition metal oxide composite electrode for a lithium battery, comprising the steps of:
s1, adding nickel nitrate hexahydrate and ferric nitrate nonahydrate serving as raw materials into deionized water according to the molar ratio of 1:2.02, mechanically stirring for 30-40min at the speed of 150r/min, adding metal oxide after full dissolution, and continuously stirring for 110-120min to obtain a mixed solution;
s2, dropwise adding ammonia water with the mass concentration of 15% into the mixed solution, adjusting the pH value of the mixed solution to 9.0-9.2, continuously stirring for 30-40min, carrying out suction filtration, washing, and drying the product in a forced air drying oven at 80 ℃ to obtain a precursor material;
s3, placing the precursor material in a tubular furnace, heating the tubular furnace to 600-650 ℃ at the heating rate of 30 ℃/min, sintering for 3-4h under the air condition, cooling to room temperature along with the furnace, and discharging to obtain the cladding material;
s4, adding polyvinylidene fluoride into N-methyl pyrrolidone according to a solid-liquid ratio of 1g:20-25mL by taking N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a binder, uniformly stirring and mixing, weighing a coating material and carbon black according to a ratio, adding the coating material and the carbon black into the solvent, sealing and stirring overnight, uniformly coating the coating material on an aluminum foil, drying in vacuum, and punching into pieces to obtain the composite electrode.
Further, the amount of the metal oxide added in step S1 is 1.5 to 2 times the total mass of the nickel nitrate hexahydrate and the iron nitrate nonahydrate.
Further, the metal oxide is one or a mixture of more of spinel lithium manganate, a lithium-rich manganese oxide material, lithium manganese phosphate and nickel-cobalt-manganese.
Further, in step S4, the coating material: carbon black: polyvinylidene fluoride (PVDF) 8-9:1-1.2:0.8-1 in mass ratio.
Further, the step S4 vacuum drying is to dry in a vacuum drying oven at 120 ℃ for 9-10h and punch into round pieces with diameter of 10-12 mm.
The invention has the beneficial effects that:
the invention adopts a self-made coating material as a main substance of the motor, the coating material is a Ni-Fe compound coating metal oxide, the Ni-Fe compound coating layer is uniformly coated on the surface of the metal oxide in a film structure, the film layer is uniform and compact, and the thickness is about 12-15 nm; the compact coating layer is beneficial to inhibiting the direct contact of lithium manganate particles and electrolyte in the charge-discharge process of the battery, slowing down the erosion effect of the electrolyte on a lithium manganate material and inhibiting the dissolution of manganese, thereby achieving the effect of improving the cycle performance; the nickel ferrite has high ionic and electronic conductivity, and is used as a coating layer to protect the lithium manganate matrix material from being corroded by electrolyte and improve the transmission rate of ions or electrons to a certain extent, so that the electrochemical performance of the material is improved;
the preparation method is simple and convenient, easy to operate and suitable for large-scale production, the prepared electrode material has higher lithium ion and electron conductivity, and the battery assembled by the electrode material has high specific capacity and excellent cycle performance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A method of preparing a transition metal oxide composite electrode for a lithium battery, comprising the steps of:
s1, adding nickel nitrate hexahydrate and ferric nitrate nonahydrate serving as raw materials into deionized water according to the molar ratio of 1:2.02, mechanically stirring for 30-40min at the speed of 150r/min, adding metal oxide after full dissolution, and continuously stirring for 110-120min to obtain a mixed solution;
the addition amount of the metal oxide is 1.5 to 2 times of the total mass of the nickel nitrate hexahydrate and the ferric nitrate nonahydrate; the metal oxide is one or a mixture of more of spinel lithium manganate, a lithium-rich manganese oxide material, lithium manganese phosphate and nickel-cobalt-manganese;
s2, dropwise adding ammonia water with the mass concentration of 15% into the mixed solution, adjusting the pH value of the mixed solution to 9.0-9.2, continuously stirring for 30-40min, carrying out suction filtration, washing, and drying the product in a forced air drying oven at 80 ℃ to obtain a precursor material;
s3, placing the precursor material in a tubular furnace, heating the tubular furnace to 600-650 ℃ at the heating rate of 30 ℃/min, sintering for 3-4h under the air condition, cooling to room temperature along with the furnace, and discharging to obtain the cladding material;
s4, adding polyvinylidene fluoride (PVDF) into N-methyl pyrrolidone according to a solid-to-liquid ratio of 1g:20-25mL by taking N-methyl pyrrolidone (NMP) as a solvent and polyvinylidene fluoride (PVDF) as a binder, uniformly stirring and mixing, and then preparing a coating material: carbon black: weighing the coating material and carbon black in a ratio of 8-9:1-1.2:0.8-1, adding the coating material and the carbon black into the solvent, sealing and stirring overnight, then uniformly coating the coating material on an aluminum foil, drying the aluminum foil for 9-10 hours in a vacuum drying oven at 120 ℃, and stamping into a wafer with the diameter of 10-12mm to obtain the composite electrode;
the coating type material is a Ni-Fe compound coated metal oxide, the Ni-Fe compound coating layer is uniformly coated on the surface of the metal oxide in a film structure, the film layer is uniform and compact, and the thickness is about 12-15 nm; the compact coating layer is beneficial to inhibiting the direct contact of lithium manganate particles and electrolyte in the charge-discharge process of the battery, slowing down the erosion effect of the electrolyte on a lithium manganate material and inhibiting the dissolution of manganese, thereby achieving the effect of improving the cycle performance; the nickel ferrite has high ionic and electronic conductivity, and is used as a coating layer to protect the lithium manganate matrix material from being corroded by electrolyte and improve the transmission rate of ions or electrons to a certain extent, so that the electrochemical performance of the material is improved.
Example 1
A method of preparing a transition metal oxide composite electrode for a lithium battery, comprising the steps of:
s1, adding nickel nitrate hexahydrate and ferric nitrate nonahydrate serving as raw materials into deionized water according to the molar ratio of 1:2.02, mechanically stirring for 30min at the speed of 150r/min, adding metal oxide after full dissolution, and continuously stirring for 110min to obtain a mixed solution;
s2, dropwise adding ammonia water with the mass concentration of 15% into the mixed solution, adjusting the pH value of the mixed solution to 9.0, continuously stirring for 30min, carrying out suction filtration, washing, and drying the product in a forced air drying oven at 80 ℃ to obtain a precursor material;
s3, placing the precursor material in a tube furnace, heating the tube furnace to 600 ℃ at the heating rate of 30 ℃/min, sintering for 3h under the air condition, cooling to room temperature along with the furnace, and discharging to obtain a coated material;
s4, adding polyvinylidene fluoride into N-methyl pyrrolidone according to a solid-liquid ratio of 1g:20mL by taking N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a binder, uniformly stirring and mixing, and then preparing a coating material: carbon black: weighing the coating material and carbon black in a ratio of 8:1:0.8, adding the coating material and the carbon black into the solvent, sealing and stirring overnight, then uniformly coating the coating material on an aluminum foil, drying the aluminum foil for 9 hours at 120 ℃ in a vacuum drying oven, and punching the aluminum foil into a wafer with the diameter of 10mm to obtain the composite electrode.
Example 2
A method of preparing a transition metal oxide composite electrode for a lithium battery, comprising the steps of:
s1, adding nickel nitrate hexahydrate and ferric nitrate nonahydrate serving as raw materials into deionized water according to the molar ratio of 1:2.02, mechanically stirring for 35min at the speed of 150r/min, adding metal oxide after full dissolution, and continuously stirring for 115min to obtain a mixed solution;
s2, dropwise adding ammonia water with the mass concentration of 15% into the mixed solution, adjusting the pH value of the mixed solution to 9.1, continuously stirring for 35min, carrying out suction filtration, washing, and drying the product in a forced air drying oven at 80 ℃ to obtain a precursor material;
s3, placing the precursor material in a tube furnace, heating the tube furnace to 630 ℃ at the heating rate of 30 ℃/min, sintering for 3.5h under the air condition, cooling to room temperature along with the furnace, discharging, and preparing to obtain a coated material;
s4, adding polyvinylidene fluoride into N-methyl pyrrolidone according to a solid-liquid ratio of 1g:23mL by taking N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a binder, uniformly stirring and mixing, and then preparing a coating material: carbon black: and weighing the coating material and carbon black in a ratio of polyvinylidene fluoride to 8.5:1.1:0.9, adding the coating material and the carbon black into the solvent, sealing and stirring overnight, then uniformly coating the coating material on an aluminum foil, drying the aluminum foil for 9.5 hours in a vacuum drying oven at 120 ℃, and punching the aluminum foil into a wafer with the diameter of 11mm to obtain the composite electrode.
Example 3
A method of preparing a transition metal oxide composite electrode for a lithium battery, comprising the steps of:
s1, adding nickel nitrate hexahydrate and ferric nitrate nonahydrate serving as raw materials into deionized water according to the molar ratio of 1:2.02, mechanically stirring for 40min at the speed of 150r/min, adding metal oxide after full dissolution, and continuously stirring for 120min to obtain a mixed solution;
s2, dropwise adding ammonia water with the mass concentration of 15% into the mixed solution, adjusting the pH value of the mixed solution to 9.2, continuously stirring for 40min, carrying out suction filtration, washing, and drying the product in a forced air drying oven at 80 ℃ to obtain a precursor material;
s3, placing the precursor material in a tube furnace, heating the tube furnace to 650 ℃ at the heating rate of 30 ℃/min, sintering for 4h under the air condition, cooling to room temperature along with the furnace, and discharging to obtain a coated material;
s4, adding polyvinylidene fluoride into N-methyl pyrrolidone according to a solid-liquid ratio of 1g:25mL by taking N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a binder, uniformly stirring and mixing, and then preparing a coating material: carbon black: weighing the coating material and carbon black according to the proportion of 9:1.2:1, adding the coating material and the carbon black into the solvent, sealing and stirring overnight, then uniformly coating the coating material on an aluminum foil, drying the aluminum foil for 10 hours at 120 ℃ in a vacuum drying oven, and punching the aluminum foil into a circular sheet with the diameter of 12mm to obtain the composite electrode.
Comparative example
And a common electrode.
The following performance tests were performed on the electrodes prepared in examples 1-3 and comparative: an electric tester is adopted to test the electrochemical performance, the cyclic voltammetry and the alternating current impedance of the material under the condition of constant current, and the test results are shown in the following table:
Figure BDA0002560846350000071
as can be seen from the above table, the first discharge specific capacity of the electrode obtained in examples 1 to 3 was 120.8 to 121.5mAh g-1The charge-discharge efficiency is 88.6-88.9%, and after circulating for 400 times under 1C multiplying power, the first discharge specific capacity is 119.8-120.3 mAh.g-1The capacity retention rate is 90.6-90.7%, which shows that the electrode prepared by the invention has extremely high specific capacity of the battery and excellent cycle performance, and simultaneously shows that the coating material is Ni-Fe compound coated metal oxide, the Ni-Fe compound coating layer is uniformly coated on the surface of the metal oxide by a film structure, the film layer is uniform and compact, and the thickness is about 12-15 nm; the compact coating layer is beneficial toIn the charging and discharging process of the battery, the direct contact of lithium manganate particles and electrolyte is inhibited, the corrosion effect of the electrolyte on a lithium manganate material is slowed down, and the dissolution of manganese is inhibited, so that the effect of improving the cycle performance is achieved; the nickel ferrite has high ionic and electronic conductivity, and is used as a coating layer to protect the lithium manganate matrix material from being corroded by electrolyte and improve the transmission rate of ions or electrons to a certain extent, so that the electrochemical performance of the material is improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims.

Claims (5)

1. A method for preparing a transition metal oxide composite electrode for a lithium battery, comprising the steps of:
s1, adding nickel nitrate hexahydrate and ferric nitrate nonahydrate serving as raw materials into deionized water according to the molar ratio of 1:2.02, mechanically stirring for 30-40min at the speed of 150r/min, adding metal oxide after full dissolution, and continuously stirring for 110-120min to obtain a mixed solution;
s2, dropwise adding ammonia water with the mass concentration of 15% into the mixed solution, adjusting the pH value of the mixed solution to 9.0-9.2, continuously stirring for 30-40min, carrying out suction filtration, washing, and drying the product in a forced air drying oven at 80 ℃ to obtain a precursor material;
s3, placing the precursor material in a tubular furnace, heating the tubular furnace to 600-650 ℃ at the heating rate of 30 ℃/min, sintering for 3-4h under the air condition, cooling to room temperature along with the furnace, and discharging to obtain the cladding material;
s4, adding polyvinylidene fluoride into N-methyl pyrrolidone according to a solid-liquid ratio of 1g:20-25mL by taking N-methyl pyrrolidone as a solvent and polyvinylidene fluoride as a binder, uniformly stirring and mixing, weighing a coating material and carbon black according to a ratio, adding the coating material and the carbon black into the solvent, sealing and stirring overnight, uniformly coating the coating material on an aluminum foil, drying in vacuum, and punching into pieces to obtain the composite electrode.
2. The method of preparing a transition metal oxide composite electrode for a lithium battery as claimed in claim 1, wherein the amount of the metal oxide added in step S1 is 1.5-2 times the total mass of the nickel nitrate hexahydrate and the iron nitrate nonahydrate.
3. The method of claim 1, wherein the metal oxide is one or more of spinel lithium manganate, lithium-rich manganese oxide material, lithium manganese phosphate, and nickel cobalt manganese.
4. The method for preparing a transition metal oxide composite electrode for a lithium battery as claimed in claim 1, wherein the coating material in step S4: carbon black: polyvinylidene fluoride (PVDF) 8-9:1-1.2:0.8-1 in mass ratio.
5. The method of claim 1, wherein the step S4 of vacuum drying is drying at 120 ℃ for 9-10h in a vacuum oven, and punching into a circular piece with a diameter of 10-12 mm.
CN202010610780.7A 2020-06-29 2020-06-29 Method for preparing transition metal oxide composite electrode for lithium battery Pending CN111883749A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010610780.7A CN111883749A (en) 2020-06-29 2020-06-29 Method for preparing transition metal oxide composite electrode for lithium battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010610780.7A CN111883749A (en) 2020-06-29 2020-06-29 Method for preparing transition metal oxide composite electrode for lithium battery

Publications (1)

Publication Number Publication Date
CN111883749A true CN111883749A (en) 2020-11-03

Family

ID=73158189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010610780.7A Pending CN111883749A (en) 2020-06-29 2020-06-29 Method for preparing transition metal oxide composite electrode for lithium battery

Country Status (1)

Country Link
CN (1) CN111883749A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113823794A (en) * 2021-08-04 2021-12-21 北京泰和九思科技有限公司 Method for modifying positive electrode material coated by organic metal framework based polymer electrolyte

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150102267A1 (en) * 2012-05-14 2015-04-16 Guoguang Electric Company Limited METHOD FOR PREPARING GRAPHENE-BASED LiFePO4/C COMPOSITE MATERIAL
CN105826550A (en) * 2016-05-26 2016-08-03 广西师范大学 Preparation method of lithium manganate cathode material with ferri-containing compound coating
CN105932247A (en) * 2016-05-26 2016-09-07 广西师范大学 Preparation method of nickel ferrite-coated lithium nickel manganese oxide positive electrode material
US20180097228A1 (en) * 2015-03-10 2018-04-05 Institute Of Process Engineering, Chinese Academy Og Sciences Composite-coated lithium iron phosphate and preparation method therefor, and lithium ion battery
CN110085837A (en) * 2019-05-05 2019-08-02 贺州学院 Metal oxide/carbon composite single layer cladding manganese cathode material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150102267A1 (en) * 2012-05-14 2015-04-16 Guoguang Electric Company Limited METHOD FOR PREPARING GRAPHENE-BASED LiFePO4/C COMPOSITE MATERIAL
US20180097228A1 (en) * 2015-03-10 2018-04-05 Institute Of Process Engineering, Chinese Academy Og Sciences Composite-coated lithium iron phosphate and preparation method therefor, and lithium ion battery
CN105826550A (en) * 2016-05-26 2016-08-03 广西师范大学 Preparation method of lithium manganate cathode material with ferri-containing compound coating
CN105932247A (en) * 2016-05-26 2016-09-07 广西师范大学 Preparation method of nickel ferrite-coated lithium nickel manganese oxide positive electrode material
CN110085837A (en) * 2019-05-05 2019-08-02 贺州学院 Metal oxide/carbon composite single layer cladding manganese cathode material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113823794A (en) * 2021-08-04 2021-12-21 北京泰和九思科技有限公司 Method for modifying positive electrode material coated by organic metal framework based polymer electrolyte
CN113823794B (en) * 2021-08-04 2023-04-14 北京泰和九思科技有限公司 Method for modifying positive electrode material coated by organic metal framework based polymer electrolyte

Similar Documents

Publication Publication Date Title
CN109119592B (en) Lithium titanate negative electrode piece, preparation method and lithium titanate battery
CN110112388B (en) Porous tungsten trioxide coated modified positive electrode material and preparation method thereof
CN103682304A (en) Lithium-rich solid solution anode composite and preparation method thereof, lithium ion battery anode plate and lithium ion battery
CN108767226B (en) Metal phthalocyanine compound coated ternary cathode material and preparation method thereof
CN109659511B (en) SiO (silicon dioxide)2Coated ternary positive electrode material and preparation method thereof
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN113060775B (en) Cobalt-free positive electrode material and preparation method and application thereof
CN110098387B (en) Lithium phosphate and conductive carbon material coated ternary cathode material and preparation method and application thereof
CN112701277A (en) Lithium ion battery prelithiation additive and application thereof
CN109860509B (en) Preparation method of anion co-doped lithium-rich manganese-based solid solution cathode material
CN103413924A (en) La1-xCaxCoO3 coated lithium ion battery cathode material LiNi1/3Co1/3Mn1/3O2 and preparation method thereof
CN114927663A (en) Five-membered layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN113611839A (en) Novel mixed system lithium-rich manganese-based positive plate and preparation method thereof, and lithium ion battery
CN111883749A (en) Method for preparing transition metal oxide composite electrode for lithium battery
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery
CN115571929A (en) Nickel-manganese binary composite positive electrode material and preparation method thereof
CN115275168A (en) High-rate lithium ion battery negative electrode material and preparation method thereof
CN114142033A (en) Modified graphite negative electrode material for lithium ion battery
CN109360936B (en) Lithium ion battery positive plate and preparation method thereof
CN114229909A (en) High-capacity lithiated manganese-based layered oxide positive electrode material and preparation method and application thereof
CN113161534A (en) Co-doped modified lithium ion battery ternary cathode material and preparation method thereof
CN114583137B (en) Method for modifying carbon surface by sulfur doped phosphorus and application thereof
CN117317200B (en) Positive electrode material, preparation method thereof and sodium ion battery
CN115954465B (en) High-power hard carbon composite material and preparation method thereof
CN112952067B (en) Preparation method of yttrium oxide graphene modified nickel cobalt lithium manganate composite material for lithium ion battery and prepared composite material

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20201103