CN115632120A - Preparation method of quick conductive modified lithium iron manganese phosphate, battery positive plate and battery - Google Patents

Preparation method of quick conductive modified lithium iron manganese phosphate, battery positive plate and battery Download PDF

Info

Publication number
CN115632120A
CN115632120A CN202211353728.3A CN202211353728A CN115632120A CN 115632120 A CN115632120 A CN 115632120A CN 202211353728 A CN202211353728 A CN 202211353728A CN 115632120 A CN115632120 A CN 115632120A
Authority
CN
China
Prior art keywords
phosphate
modified lithium
manganese
coating
iron
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.)
Granted
Application number
CN202211353728.3A
Other languages
Chinese (zh)
Other versions
CN115632120B (en
Inventor
刘新利
刘沈澍
胡舜钦
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.)
Hunan Dongzhou Energy Co ltd
Original Assignee
Hunan Dongzhou Energy 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 Hunan Dongzhou Energy Co ltd filed Critical Hunan Dongzhou Energy Co ltd
Priority to CN202211353728.3A priority Critical patent/CN115632120B/en
Publication of CN115632120A publication Critical patent/CN115632120A/en
Application granted granted Critical
Publication of CN115632120B publication Critical patent/CN115632120B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • 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
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/136—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
    • H01M4/13—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
    • H01M4/58—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
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 preparation method of fast conductive modified lithium iron manganese phosphate, a battery positive plate and a battery, wherein the method comprises the following steps: grinding the lithium iron manganese phosphate anode material; carrying out heating chemical reaction coating on the lithium iron manganese phosphate particles by introducing mixed gas, wherein the mixed gas comprises 40-60% of methane, 20-30% of ethylene and 10-30% of acetylene, the pressure of the heating coating chemical reaction is 0.04-0.08MPa, and the reaction temperature is kept constant at 300-600 ℃ for 2-3 hours to obtain primary modified lithium iron manganese phosphate; carrying out secondary chemical coating on the primary modified lithium manganese iron phosphate to obtain the fast conductive modified lithium manganese iron phosphate; baking the rapid conductive modified lithium manganese iron phosphate, adding a conductive agent, a solvent and a mixed glue, mixing to obtain a mixed solution, and coating the mixed solution on a base material to obtain a battery positive plate; assembling the positive plate of the battery to obtain the battery; the invention has firm coating structure, is beneficial to the later processing treatment, obviously improves the performance advantage and has low cost.

Description

Preparation method of rapid conductive modified lithium iron manganese phosphate, battery positive plate and battery
Technical Field
The invention relates to the technical field of modified lithium manganese iron phosphate, and particularly relates to a preparation method of rapid conductive modified lithium manganese iron phosphate, a battery positive plate and a battery.
Background
The theoretical specific capacity of the positive active material for the lithium manganese iron phosphate lithium ion battery can reach 170 mAh.g -1 The method has the advantages of good cycle performance, excellent safety performance, wide raw material source, low cost, environmental friendliness and the like. In addition, compared with lithium iron phosphate, lithium manganese iron phosphate has higher discharge voltage and has certain advantages in specific energy and specific power. Therefore, it is one of the hot spots in the research of lithium ion batteries to develop lithium manganese iron phosphate with excellent electrochemical performance as a positive electrode active material. However, the conductivity of the lithium manganese iron phosphate is poor, the reversibility of the material in the charging and discharging process is also poor, and polarization is easy to occur, so that the actual specific capacity of the lithium manganese iron phosphate hardly reaches the theoretical value. Currently, the main improvement methods of lithium iron manganese phosphate include the following aspects: the size of primary particles is reduced, the crystallinity and the element composition uniformity of the material are improved, and the material resistivity is reduced by coating and doping a carbon material with better conductivity.
The existing method for modifying lithium iron manganese phosphate, for example, a graphene-coated modified lithium ion battery positive electrode material with the patent number of 201910265605.6 and a preparation method thereof, comprises the following steps: the method comprises the following steps of (1) mixing graphene-Mn/lithium manganese iron phosphate slurry, ternary material slurry and polyvinylidene fluoride according to a weight ratio, coating the mixture on the surface of an aluminum foil, and drying the aluminum foil, (2) adding graphite oxide into deionized water, ultrasonically scattering the mixture, then adding potassium permanganate and lithium manganese iron phosphate, drying the mixture, and preparing slurry with PVDF, wherein a solvent is NMP, the viscosity of the slurry is 4000-6000mpa · s, namely obtaining the graphene-Mn/lithium manganese iron phosphate slurry, preparing the ternary material, the graphite oxide and the PVDF into the slurry, and adjusting the viscosity of the slurry to 5000-10000mpa · s by using the NMP as a solvent, thus obtaining the ternary material slurry, and (3) preparing the ternary material from one of NCM523, NCM622 and NCM 811. The graphene forms a conductive network on the surface of the anode material, so that the transmission rate of lithium ions is greatly improved, and the formation of manganese ions of Mn/lithium manganese iron phosphate and a lithium ion conductor coating layer is beneficial to improving the transmission performance of the lithium ions. However, the coating in the patent document is physical coating, the firmness of the formed coating structure is not strong, the phenomenon of falling off is easy to occur in the later processing process, the performance of the final product is affected, and meanwhile, the raw material adopted by the patent document is graphene, so that the cost is high.
The traditional lithium battery for the unmanned aerial vehicle is made of a ternary material and lithium cobaltate as main anode materials, is short in service life, can fly for 300 times at most, is few in flying times and is high in cost; the low-temperature performance is poor, the adaptive temperature range is narrow, and the application environment is limited; the security is not good, and the lithium cell of ordinary positive plate production is inseparable with unmanned aerial vehicle's combination, easily catches fire, falls into the aircraft easily.
Disclosure of Invention
The invention aims to provide a preparation method of rapid conductive modified lithium iron manganese phosphate, a battery positive plate and a battery, which solve the problems that the existing modification is physical coating, the formed coating structure has low firmness, the phenomenon of falling off easily occurs in the later processing process, the performance of a final product is influenced, and the adopted raw material is graphene, so that the cost is high.
The invention is realized in such a way that a preparation method of rapid conductive modified lithium iron manganese phosphate comprises the following steps:
grinding a lithium iron manganese phosphate anode material to obtain uniform lithium iron manganese phosphate particles;
step two, primary modification of lithium manganese iron phosphate: heating and coating the lithium iron manganese phosphate particles by introducing mixed gas, wherein the mixed gas comprises 40-60% of methane, 20-30% of ethylene and 10-30% of acetylene, the pressure of the heating and coating chemical reaction is 0.04-0.08MPa, the reaction temperature is kept constant at 300-600 ℃ for 2-3 hours, and graphene, carbon black and graphite generated by the chemical reaction are subjected to chemical growth coating on the lithium iron manganese phosphate particles to obtain primary modified lithium iron manganese phosphate;
step three, secondary modification of lithium manganese iron phosphate: adding 1-5% of starch and sucrose by mass into the primary modified lithium manganese iron phosphate material, mixing, heating, carrying out chemical reaction, and generating graphene and carbon black again on the surface of the primary modified lithium manganese iron phosphate material by the starch and the sucrose for secondary chemical growth coating.
The further technical scheme of the invention is as follows: and in the second step, the lithium iron manganese phosphate particles are subjected to heating coating chemical reaction in a microwave oven, and when the pressure in the microwave oven reaches 0.04-0.08MPa, the introduction of the mixed gas is stopped.
The invention further adopts the technical scheme that: the heating coating chemical reaction is that the temperature of the lithium iron manganese phosphate particles which are introduced with mixed gas is raised in a microwave oven, and the temperature is controlled to be 300-600 ℃ and is kept constant for 2-3 hours.
The invention further adopts the technical scheme that: the step I of grinding the lithium iron manganese phosphate cathode material comprises the following steps: grinding the lithium iron manganese phosphate anode material for 3-5 hours, and uniformly grinding the material with the particle size of 10-50 micrometers.
The further technical scheme of the invention is as follows: in the third step, the heating after mixing is as follows: mixing for 1-2 hr, and reacting at 650-750 deg.C for 2-3 hr.
The further technical scheme of the invention is as follows: in the third step, the mass ratio of starch to sucrose is as follows: (4-7): (2-4).
The invention further adopts the technical scheme that: the step three is followed by a step four: and carrying out carbon coating on the fast conductive modified lithium manganese iron phosphate to obtain third modified lithium manganese iron phosphate, wherein the carbon coating is physical coating. The step four of carbon coating the secondary modified lithium manganese iron phosphate comprises the following specific steps: and mixing and coating graphene, graphite and carbon black with a binder and secondary modified lithium manganese iron phosphate, and sintering and crystallizing the dried product in an inert gas atmosphere to obtain the tertiary modified lithium manganese iron phosphate.
The inert gas is one or more of nitrogen and helium.
The binder includes any one or a combination of two or more of polyvinylidene fluoride (PVDF), polyamide, polyimide, polyacrylic acid, polyvinyl alcohol, and styrene butadiene rubber, but is not limited thereto.
The invention also provides a battery positive plate of the fast conductive modified lithium manganese iron phosphate, and the preparation method of the battery positive plate comprises the following steps: baking the rapid conductive modified lithium manganese iron phosphate or the tertiary modified lithium manganese iron phosphate, adding a conductive agent, a solvent and a mixed glue, mixing to obtain a mixed solution, and coating the mixed solution on a substrate to obtain the battery positive plate.
The invention further adopts the technical scheme that: the content of the conductive agent in the fast conductive modified lithium manganese iron phosphate is 0.1-10 wt%.
The further technical scheme of the invention is as follows: the content of the mixed glue in the fast conductive modified lithium manganese iron phosphate is 0.1-10 wt%.
The further technical scheme of the invention is as follows: the conductive agent is selected from at least one of conductive carbon black, conductive graphite, superconducting carbon black, acetylene black, ketjen black, carbon nanotubes, VGCF, and graphene.
The further technical scheme of the invention is as follows: the solvent may be one or more of N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, absolute ethanol, isopropanol, and the like.
The further technical scheme of the invention is as follows: the mixed glue comprises the following raw materials in percentage by mass: 5-12% of ethyl cyanoacrylate glue, 15-20% of ethylene copolymer glue, 25-35% of ethylene-vinyl acetate copolymer glue, 20-25% of polyimide glue and 15-30% of polybutadiene glue, wherein the mixed glue is prepared by the following steps: mixing the raw materials with ultrapure water according to a mass ratio of 1.
The further technical scheme of the invention is as follows: the preparation method of the battery positive plate comprises the following baking steps: putting the ground fast conductive modified lithium manganese iron phosphate into a microwave oven, covering the microwave oven, filling inert gas, stopping filling gas when the pressure reaches 0.5 atmospheric pressure, then starting to heat to 150-180 ℃, and baking for 2-2.5 hours.
The further technical scheme of the invention is as follows: the inert gas is one or more of nitrogen and helium.
The further technical scheme of the invention is as follows: and adding the mixed glue, the solvent and the conductive agent into the rapid conductive modified lithium manganese iron phosphate or the three-time modified lithium manganese iron phosphate to mix, stirring at the speed of 550-620 revolutions per minute for 50-70 minutes, and then stirring at the speed of 1400-1550 revolutions per minute for 80-100 minutes, wherein the stirring temperature is controlled at 30-50 ℃.
The further technical scheme of the invention is as follows: according to the preparation method of the battery positive plate, the mixed solution is uniformly coated on the base material, the thickness is controlled to be 90-150 micrometers, the thickness is adjusted at any time, and the material can be uniformly coated on the base material.
The invention also provides an unmanned aerial vehicle battery, and the battery comprises the battery positive plate of the rapid conductive modified lithium manganese iron phosphate.
The first modification method comprises the steps of putting a common lithium manganese iron phosphate material into a microwave tunnel furnace, introducing mixed gas under the condition of air isolation, and carrying out chemical reaction sintering when the temperature is raised to 300-600 ℃, so that a layer of graphene-containing mixed material coating with the thickness of 50-300 nanometers is grown on the surface of the common lithium manganese iron phosphate particles (the graphene mixture of the growth layer and the surfaces of the lithium manganese iron phosphate particles are tightly combined together through ionic bonds and covalent bonds, the damage is difficult to obtain in the physical production process, the stability of the chemical property and the physical property of the modified lithium manganese iron phosphate and the structural firmness are ensured), wherein the material components of the coating are mainly graphene, graphite and carbon black through chemical analysis; the content of graphene is about 8-15%, the content of graphite is 45-50%, and the content of carbon black is 30-43%; the ultralow temperature performance and the high rate performance of the lithium manganese iron phosphate coated by the graphene, the graphite and the carbon black are obviously improved.
The second modification method comprises the steps of regenerating graphene and carbon black on the surfaces of the lithium manganese iron phosphate particles by starch and cane sugar for secondary chemical growth and coating, controlling the reaction temperature to be 650-750 ℃, and controlling the reaction time to be 2-3 hours. The material coated by the chemical reaction on the lithium iron manganese phosphate particles is combined more firmly, the positive plate is not easy to be powdered in the production, manufacturing and processing processes, the lithium battery made of the positive plate is more high-temperature resistant and can resist the temperature of more than 85 ℃, the lithium battery on the general market can only resist the temperature of 55 ℃, so that the self-discharge rate of the battery is lower, and the cycle life is longer.
The invention provides an application of a fast conductive modified lithium manganese iron phosphate positive plate battery in an unmanned aerial vehicle, which takes a metal base layer as a carrier and comprises a fast conductive modified lithium manganese iron phosphate positive plate layer and the metal base layer, wherein the fast conductive modified lithium manganese iron phosphate positive plate material layer is symmetrically sprayed on two sides of the metal base layer; the metal base layer is preferably made of a copper strip or an aluminum strip; the thickness of the metal base layer is 0.01-0.03 mm; the thickness of an application layer of the rapid conductive modified lithium iron manganese phosphate positive plate battery in the unmanned aerial vehicle is 90-150 micrometers.
The invention has the beneficial effects that: the invention carries out secondary chemical coating on the lithium manganese iron phosphate, and thoroughly solves the problem of poor conductivity of the common lithium manganese iron phosphate; the method comprises the following steps of carrying out chemical coating reaction on lithium manganese iron phosphate in microwave to grow graphene, graphite and carbon black, wherein introduced mixed gas is used for carrying out chemical reaction between atoms on the surface of particles of the lithium manganese iron phosphate, compared with the traditional reaction coating between molecules, the chemical reaction coating between the atoms is firmer than the coating between the molecules, the coating combination of the chemical reaction on the lithium manganese iron phosphate particles is firmer, and a positive plate is not easy to remove powder in the production and manufacturing process, so that the self-discharge rate of the battery is lower, and the cycle life is longer; the ultralow temperature performance and the high rate performance of the manganese lithium iron phosphate coated by the graphene, the graphite and the carbon black are obviously improved; the starch and the sucrose are enabled to regenerate graphene and carbon black on the surfaces of the manganese lithium iron phosphate particles for secondary chemical growth coating, the coated materials are combined more firmly, the positive plate is not easy to powder fall off in the production, manufacturing and processing processes, the lithium battery made of the positive plate is more resistant to high temperature, the internal resistance of the lithium battery is low at 85 ℃, the self-discharge rate of the battery is low, the conductivity and the physical and chemical properties of the battery are good, and the cycle life is longer;
the rapid conductive modified lithium manganese iron phosphate is subjected to heating coating chemical reaction through a microwave oven, and compared with the common infrared heating coating reaction, the rapid conductive modified lithium manganese iron phosphate saves more than 50% of energy and can also reduce the damage to the material.
Drawings
FIG. 1 is a process flow diagram of a fast conductive modified lithium iron manganese phosphate, a battery positive plate and a battery provided by the invention;
fig. 2 is a scanning electron microscope image of the fast conductive modified lithium manganese iron phosphate obtained in the first embodiment of the present invention;
fig. 3 is a scanning electron microscope image of the fast conductive modified lithium manganese iron phosphate obtained in the first embodiment of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be noted that the structures, ratios, sizes, and the like shown in the drawings attached to the present specification are only used for matching the disclosure of the present specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions of the present invention, so that the present invention has no technical essence, and any structural modification, ratio relationship change, or size adjustment should still fall within the scope of the present invention without affecting the efficacy and the achievable purpose of the present invention. In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
The first embodiment is as follows:
fig. 1 shows a preparation method of a fast conductive modified lithium iron manganese phosphate, which comprises the following steps:
grinding a lithium iron manganese phosphate anode material to obtain uniform lithium iron manganese phosphate particles;
step two, primary modification of lithium manganese iron phosphate: heating and coating the lithium manganese iron phosphate particles by introducing mixed gas, wherein the mixed gas comprises 40% of methane, 30% of ethylene and 30% of acetylene, the pressure of the heating and coating chemical reaction is 0.04MPa, the reaction temperature is kept constant at 360 ℃ for 2 hours, and graphene, carbon black and graphite are subjected to growth and coating on the lithium manganese iron phosphate particles to obtain primary modified lithium manganese iron phosphate;
step three, secondary modification of lithium manganese iron phosphate: adding 2% by mass of starch and sucrose into the material of the primary modified lithium manganese iron phosphate, mixing, heating, performing a chemical reaction, and generating graphene and carbon black again on the surface of the material of the primary modified lithium manganese iron phosphate by using the starch and the sucrose to perform secondary chemical growth coating to obtain the fast conductive modified lithium manganese iron phosphate, wherein electron microscope scanning images are shown in fig. 2 and 3, and it can be known that the fast conductive modified lithium manganese iron phosphate obtained in the first embodiment has conductivity.
In this embodiment, in the second step, the heating and coating chemical reaction of the lithium iron manganese phosphate particles is performed in a microwave oven, and when the pressure in the microwave oven reaches 0.04MPa, the introduction of the mixed gas is stopped.
In this embodiment, the heating coating chemical reaction is to heat the lithium iron manganese phosphate particles into which the mixed gas is introduced in a microwave oven, and the temperature is controlled at 360 ℃ for 2 hours.
In this embodiment, the grinding of the lithium iron manganese phosphate positive electrode material in the first step is: grinding the lithium iron manganese phosphate anode material for 3 hours, and uniformly grinding the material with the particle size of 10 micrometers.
In this embodiment, in the third step, the heating after mixing is: fully mixing in a mixing kettle for 1 hour, then putting the mixed material into a microwave oven for chemical reaction, allowing starch and sucrose to generate graphene and carbon black again on the surfaces of the lithium iron manganese phosphate particles for secondary chemical growth coating, and reacting for 2 hours at the temperature of 650 ℃.
In this example, the mass ratio of starch to sucrose was: 6:4.
Example two:
fig. 1 shows a preparation method of a fast conductive modified lithium iron manganese phosphate, which comprises the following steps:
grinding a lithium manganese iron phosphate anode material to obtain uniform lithium manganese iron phosphate particles;
step two, primary modification of lithium manganese iron phosphate: heating and coating the lithium iron manganese phosphate particles by introducing mixed gas, wherein the mixed gas comprises 50% of methane, 25% of ethylene and 25% of acetylene, the pressure of the heating and coating chemical reaction is 0.06MPa, the reaction temperature is kept constant at 500 ℃ for 2.5 hours, and graphene, carbon black and graphite grow and coat on the lithium iron manganese phosphate particles to obtain primary modified lithium iron manganese phosphate;
step three, quickly conducting and modifying the lithium manganese iron phosphate: adding starch and sucrose with the mass ratio of 4% into the material of the primary modified lithium manganese iron phosphate, mixing, heating, carrying out chemical reaction, and generating graphene and carbon black again on the surface of the material of the primary modified lithium manganese iron phosphate by using the starch and the sucrose to carry out secondary chemical growth and coating to obtain the fast conductive modified lithium manganese iron phosphate.
In this embodiment, in the second step, the heating and coating chemical reaction of the lithium iron manganese phosphate particles is performed in a microwave oven, and when the pressure in the microwave oven reaches 0.06MPa, the introduction of the mixed gas is stopped.
In this embodiment, the heating coating chemical reaction is to heat the lithium iron manganese phosphate particles with the mixed gas in a microwave oven, and control the temperature to be 500 ℃ and keep the temperature for 2.5 hours.
In this embodiment, the grinding of the lithium iron manganese phosphate positive electrode material in the first step is as follows: and grinding the lithium iron manganese phosphate anode material for 4 hours, wherein the grinding is uniform, and the particle size is 30 micrometers.
In this embodiment, the post-mixing heating is: fully mixing in a mixing kettle, mixing for 2 hours, then putting the mixed material into a microwave oven for chemical reaction, generating graphene and carbon black again on the surfaces of the manganese lithium iron phosphate particles by starch and sucrose for secondary chemical growth coating, and reacting for 3 hours at the temperature of 750 ℃.
In this example, the mass ratio of starch to sucrose was: 4:4.
Example three:
fig. 1 shows a preparation method of a fast conductive modified lithium iron manganese phosphate, which comprises the following steps:
grinding a lithium manganese iron phosphate anode material to obtain uniform lithium manganese iron phosphate particles;
step two, primary modification of lithium manganese iron phosphate: carrying out heating coating chemical reaction on the lithium iron manganese phosphate particles by introducing mixed gas, wherein the mixed gas comprises 60% of methane, 20% of ethylene and 20% of acetylene, the pressure of the heating coating chemical reaction is 0.08MPa, the reaction temperature is kept constant at 600 ℃ for 3 hours, and graphene, carbon black and graphite grow and coat on the lithium iron manganese phosphate particles to obtain primary modified lithium iron manganese phosphate;
step three, quickly conducting and modifying the lithium manganese iron phosphate: and adding starch and sucrose in a mass ratio of 5% into the material of the primary modified lithium manganese iron phosphate, mixing, heating, carrying out chemical reaction, and generating graphene and carbon black again on the surface of the material of the primary modified lithium manganese iron phosphate by using the starch and the sucrose to carry out secondary chemical growth coating to obtain the fast conductive modified lithium manganese iron phosphate. The structure of the fast conductive modified lithium manganese iron phosphate is similar to that of the fast conductive modified lithium manganese iron phosphate obtained in the first embodiment, and the fast conductive modified lithium manganese iron phosphate also has electric conductivity.
In this embodiment, in the second step, the heating and coating chemical reaction on the lithium iron manganese phosphate particles is performed in a microwave oven, and when the pressure in the microwave oven reaches 0.08MPa, the introduction of the mixed gas is stopped.
In this embodiment, the heating coating chemical reaction is to heat the lithium iron manganese phosphate particles into which the mixed gas is introduced in a microwave oven, and the temperature is controlled at 600 ℃ and kept constant for 3 hours.
In this embodiment, the grinding of the lithium iron manganese phosphate positive electrode material in the first step is: and grinding the lithium iron manganese phosphate anode material for 5 hours, wherein the grinding is uniform, and the particle size is 50 micrometers.
In this embodiment, in the third step, the heating after mixing is: fully mixing in a mixing kettle for 1 hour, then putting the mixed material into a microwave oven for chemical reaction, allowing starch and sucrose to generate graphene and carbon black again on the surfaces of the lithium iron manganese phosphate particles for secondary chemical growth coating, and reacting for 2.5 hours at the temperature of 700 ℃.
In this example, the mass ratio of starch to sucrose was: 7:2.
Example four:
fig. 1 shows a preparation method of a fast conductive modified lithium iron manganese phosphate, which comprises the following steps:
grinding a lithium iron manganese phosphate anode material to obtain uniform lithium iron manganese phosphate particles;
step two, primary modification of lithium manganese iron phosphate: carrying out heating coating chemical reaction on the lithium iron manganese phosphate particles by introducing mixed gas, wherein the mixed gas comprises 55% of methane, 25% of ethylene and 20% of acetylene, the pressure of the heating coating chemical reaction is 0.08MPa, the reaction temperature is kept constant at 600 ℃ for 3 hours, and graphene, carbon black and graphite grow and coat on the lithium iron manganese phosphate particles to obtain primary modified lithium iron manganese phosphate;
step three, quickly conducting and modifying the lithium manganese iron phosphate: and adding starch and sucrose in a mass ratio of 2% into the material of the primary modified lithium manganese iron phosphate, mixing, heating, carrying out chemical reaction, and generating graphene and carbon black again on the surface of the material of the primary modified lithium manganese iron phosphate by using the starch and the sucrose to carry out secondary chemical growth coating to obtain the fast conductive modified lithium manganese iron phosphate. The structure of the fast conductive modified lithium manganese iron phosphate is similar to that of the fast conductive modified lithium manganese iron phosphate obtained in the first embodiment, and the fast conductive modified lithium manganese iron phosphate also has conductivity.
In this embodiment, the heating and coating chemical reaction of the lithium iron manganese phosphate particles in the second step is performed in a microwave oven, and when the pressure in the microwave oven reaches 0.08MPa, the introduction of the mixed gas is stopped.
In this embodiment, the heating coating chemical reaction is to heat the lithium iron manganese phosphate particles into which the mixed gas is introduced in a microwave oven, and the temperature is controlled at 600 ℃ and kept constant for 3 hours.
In this embodiment, the grinding of the lithium iron manganese phosphate positive electrode material in the first step is as follows: and grinding the lithium iron manganese phosphate anode material for 5 hours, wherein the grinding is uniform, and the particle size is 50 microns.
In this embodiment, in the third step, the heating after mixing is: fully mixing in a mixing kettle for 1 hour, then putting the mixed material into a microwave oven for chemical reaction, generating graphene and carbon black again on the surfaces of the lithium manganese iron phosphate particles by starch and sucrose for secondary chemical growth coating, and reacting for 2 hours at the temperature of 650 ℃.
In this example, the mass ratio of starch to sucrose was: 5:3.
Example five:
fig. 1 shows a preparation method of a fast conductive modified lithium iron manganese phosphate, which comprises the following steps:
grinding a lithium iron manganese phosphate anode material to obtain uniform lithium iron manganese phosphate particles;
step two, primary modification of lithium manganese iron phosphate: heating and coating the lithium manganese iron phosphate particles by introducing mixed gas, wherein the mixed gas comprises 50% of methane, 25% of ethylene and 25% of acetylene, the pressure of the heating and coating chemical reaction is 0.05MPa, the reaction temperature is kept constant at 600 ℃ for 3 hours, and graphene, carbon black and graphite are subjected to growth and coating on the lithium manganese iron phosphate particles to obtain primary modified lithium manganese iron phosphate;
step three, quickly conducting and modifying the lithium manganese iron phosphate: adding 1-3% of starch and sucrose by mass into the material of the primary modified lithium manganese iron phosphate, mixing, heating, carrying out chemical reaction, and generating graphene and carbon black again on the surface of the material of the primary modified lithium manganese iron phosphate by the starch and the sucrose to carry out secondary chemical growth coating to obtain the fast conductive modified lithium manganese iron phosphate. The structure of the fast conductive modified lithium manganese iron phosphate is similar to that of the fast conductive modified lithium manganese iron phosphate obtained in the first embodiment, and the fast conductive modified lithium manganese iron phosphate also has electric conductivity.
In this embodiment, in the second step, the heating and coating chemical reaction of the lithium iron manganese phosphate particles is performed in a microwave oven, and when the pressure in the microwave oven reaches 0.05MPa, the introduction of the mixed gas is stopped.
In this embodiment, the heating coating chemical reaction is to introduce mixed gas into lithium iron manganese phosphate particles, raise the temperature in a microwave oven, and control the temperature at 600 ℃ for 3 hours.
In this embodiment, the grinding of the lithium iron manganese phosphate positive electrode material in the first step is as follows: and grinding the lithium iron manganese phosphate anode material for 4 hours, wherein the grinding is uniform, and the particle size is 30 micrometers.
In this embodiment, in the third step, the heating after mixing is as follows: fully mixing in a mixing kettle for 1.5 hours, then putting the mixed material into a microwave oven for chemical reaction, generating graphene and carbon black again on the surfaces of the manganese lithium iron phosphate particles by starch and cane sugar for secondary chemical growth coating, and reacting for 2 hours at the temperature of 700 ℃.
In this example, the mass ratio of starch to sucrose was: 4:2.
Example six:
a preparation method of a battery positive plate of fast conductive modified lithium manganese iron phosphate comprises the following steps: baking the rapid conductive modified lithium manganese iron phosphate obtained in the first embodiment, adding a conductive agent, a solvent and a mixed glue, mixing to obtain a mixed solution, and coating the mixed solution on a base material to obtain a battery positive plate.
In this embodiment, the content of the conductive agent in the fast conductive modified lithium manganese iron phosphate is 5wt%. The content of the mixed glue in the rapid conductive modified lithium manganese iron phosphate is 5wt%.
In this embodiment, the conductive agent is selected from conductive carbon black. The solvents were N-methylpyrrolidone (NMP) and Dimethylformamide (DMF).
In this embodiment, the mixed glue includes the following raw materials in percentage by mass: 12% of ethyl cyanoacrylate glue, 20% of ethylene copolymer glue, 30% of ethylene-vinyl acetate copolymer glue, 20% of polyimide glue and 18% of polybutadiene glue.
The preparation of the mixed glue comprises the following steps: mixing the raw materials of the mixture for 30 minutes, mixing the raw materials with ultrapure water according to a mass ratio of 1.
In this embodiment, the baking step in the preparation method of the battery positive plate is as follows: and putting the ground fast conductive modified lithium manganese iron phosphate into a microwave oven, covering the microwave oven, filling inert gas, stopping filling gas when the pressure reaches 0.5 atmospheric pressure, then starting to heat to 150 ℃, and baking for 2.5 hours.
In this embodiment, the inert gas is nitrogen.
In this embodiment, the mixing glue, the solvent and the conductive agent are added into the fast conductive modified lithium manganese iron phosphate of the first embodiment to mix, the mixture is stirred at a speed of 600 rpm for 60 minutes, and then stirred at a speed of 1500 rpm for 90 minutes, and the stirring temperature is controlled at 40 ℃.
In this example, in the method for preparing the positive electrode plate of the battery, the mixed solution was uniformly coated on the base material, the thickness was controlled at 100 μm, and the thickness was adjusted as needed to ensure that the material could be uniformly coated on the base material.
According to the steps, the battery positive plates corresponding to the fast conductive modified lithium manganese iron phosphate in the first to fifth embodiments are respectively manufactured.
In this example, the mass ratio of starch to sucrose was: 5:3.
Example seven:
an unmanned aerial vehicle battery, the battery includes the battery positive plate of the quick electrically conductive modified lithium iron manganese phosphate in embodiment six. Thereby obtain including the unmanned aerial vehicle battery that embodiment first to fifth quick electrically conductive modification lithium iron manganese phosphate corresponds.
Comparative example one:
a preparation method of physically modified lithium iron manganese phosphate comprises the following steps:
grinding a lithium iron manganese phosphate anode material to obtain uniform lithium iron manganese phosphate particles;
step two, physically modifying the lithium manganese iron phosphate: and performing carbon coating on the lithium manganese iron phosphate particles to obtain physically modified lithium manganese iron phosphate, wherein the carbon coating is physical coating, specifically, mixing and coating graphene, graphite and carbon black with a binder and the lithium manganese iron phosphate particles, and sintering and crystallizing the dried product in an inert gas atmosphere to obtain the physically modified lithium manganese iron phosphate.
A preparation method of a physically modified lithium iron manganese phosphate battery positive plate comprises the following steps: and (3) baking the physically modified lithium manganese iron phosphate of the comparative example I, adding a conductive agent, a solvent and a binder, mixing to obtain a mixed solution, and coating the mixed solution on a base material to obtain the battery positive plate.
In this embodiment, the binder is polyvinylidene fluoride (PVDF). The inert gas is nitrogen.
In this embodiment, the content of the conductive agent in the physically modified lithium manganese iron phosphate is 5wt%.
In this embodiment, the content of the binder in the physically modified lithium manganese iron phosphate is 5wt%.
In this embodiment, the conductive agent is selected from conductive carbon black. The solvents were N-methylpyrrolidone (NMP) and Dimethylformamide (DMF). The binder is polyvinylidene fluoride (PVDF) and polyamide.
In this embodiment, the baking step in the preparation method of the battery positive plate is as follows: and putting the ground secondary modified lithium manganese iron phosphate into a microwave oven, covering the microwave oven, filling inert gas, stopping filling gas when the pressure reaches 0.5 atmospheric pressure, then starting to heat to 150 ℃, and baking for 2.5 hours.
In this example, the inert gas is nitrogen.
In this embodiment, in the preparation method of the battery positive plate, the solvent, the conductive agent and the binder are put into a container and stirred for 2 hours, and then the baked secondary modified lithium manganese iron phosphate is added in two times and stirred for 4 hours.
In this example, in the method for preparing the positive electrode plate of the battery, the mixed solution was uniformly coated on the base material, the thickness was controlled at 100 μm, and the thickness was adjusted as needed to ensure that the material could be uniformly coated on the base material.
According to the above steps, the battery positive electrode sheets corresponding to the secondary modified lithium manganese iron phosphate in the first to third embodiments were manufactured. The positive electrode sheet obtained in comparative example one was prepared in the same manner as in example one to obtain a battery.
Comparative example two:
the battery is as follows: the lithium battery available in the market at present is the model 103450, namely the battery has the thickness of 10mm, the width of 34mm, the height of 50mm and the capacity of 1000mAH; the positive electrode material is a lithium cobaltate material.
The positive electrode plates of the batteries corresponding to the fast conductive modified lithium manganese iron phosphate in the first to fifth examples were respectively manufactured and used in the unmanned aerial vehicle batteries, and the batteries obtained in the first and second comparative examples were subjected to performance tests at 85 ℃, and the results are shown in table 1.
Table 1 results of performance tests of examples one to five and comparative documents one and two
Figure BDA0003920084240000151
Figure BDA0003920084240000161
From the above, it can be seen from table 1 that the material combination of the fast conductive modified lithium manganese iron phosphate in the invention is firmer, the positive plate is not easy to be powdered in the production and processing process, the lithium battery made of the positive plate is more resistant to high temperature, and can resist the temperature of more than 85 ℃, while the lithium battery in the general market can only resist the temperature of 55 ℃, so that the self-discharge rate of the battery is lower, and the cycle life is longer.
The first modification method comprises the steps of putting a common lithium manganese iron phosphate material into a microwave tunnel furnace, introducing mixed gas under the condition of air isolation, and carrying out chemical reaction sintering when the temperature is raised to 300-600 ℃, so that a layer of graphene-containing mixed material coating with the thickness of 50-300 nanometers is grown on the surface of the common lithium manganese iron phosphate particles (the graphene mixture of the growth layer and the surfaces of the lithium manganese iron phosphate particles are tightly combined together through ionic bonds and covalent bonds, the damage is difficult to obtain in the physical production process, the stability of the chemical property and the physical property of the modified lithium manganese iron phosphate and the structural firmness are ensured), wherein the material components of the coating are mainly graphene, graphite and carbon black through chemical analysis; 8-15% of graphene, 45-50% of graphite and 30-43% of carbon black; the ultralow temperature performance and the high rate performance of the lithium manganese iron phosphate coated by the graphene, the graphite and the carbon black are obviously improved.
The second modification method comprises the steps of regenerating graphene and carbon black on the surfaces of the manganese iron phosphate particles by starch and cane sugar for secondary chemical growth and coating, controlling the reaction temperature to be 650-750 ℃, and controlling the reaction time to be 2 hours. The material coated by the chemical reaction on the lithium iron manganese phosphate particles is combined more firmly, the positive plate is not easy to be powdered in the production, manufacturing and processing processes, the lithium battery made of the positive plate is more high-temperature resistant and can resist the temperature of more than 85 ℃, the lithium battery on the general market can only resist the temperature of 55 ℃, so that the self-discharge rate of the battery is lower, and the cycle life is longer.
The invention provides an application of a fast conductive modified lithium manganese iron phosphate positive plate battery in an unmanned aerial vehicle, which takes a metal base layer as a carrier and comprises a fast conductive modified lithium manganese iron phosphate positive plate layer and the metal base layer, wherein the fast conductive modified lithium manganese iron phosphate positive plate material layer is symmetrically sprayed on two sides of the metal base layer; the metal base layer is preferably made of a copper strip or an aluminum strip; the thickness of the metal base layer is 0.01-0.03 mm; the thickness of an application layer of the rapid conductive modified lithium iron manganese phosphate positive plate battery in the unmanned aerial vehicle is 90-150 micrometers.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of rapid conductive modified lithium iron manganese phosphate is characterized by comprising the following steps: the preparation method comprises the following steps:
grinding a lithium iron manganese phosphate anode material to obtain uniform lithium iron manganese phosphate particles;
step two, primary modification of lithium manganese iron phosphate: heating and coating the lithium iron manganese phosphate particles by introducing mixed gas, wherein the mixed gas comprises 40-60% of methane, 20-30% of ethylene and 10-30% of acetylene, the pressure of the heating and coating chemical reaction is 0.04-0.08MPa, the reaction temperature is kept constant at 300-600 ℃ for 2-3 hours, and graphene, carbon black and graphite generated by the chemical reaction are subjected to growth coating on the lithium iron manganese phosphate particles to obtain primary modified lithium iron manganese phosphate;
step three, secondary modification of lithium manganese iron phosphate: adding 1-5% of starch and sucrose by mass into the material of the primary modified lithium manganese iron phosphate, mixing, heating, carrying out chemical reaction, and generating graphene and carbon black again on the surface of the material of the primary modified lithium manganese iron phosphate by using the starch and the sucrose to carry out secondary chemical growth coating to obtain the fast conductive modified lithium manganese iron phosphate.
2. The preparation method of the rapidly conductive modified lithium iron manganese phosphate as claimed in claim 1, wherein in the second step, the chemical reaction of heating and coating the lithium iron manganese phosphate particles is performed in a microwave oven, and when the pressure in the microwave oven reaches 0.04-0.08MPa, the introduction of the mixed gas is stopped, and the temperature is controlled at 300-600 ℃ for 2-3 hours.
3. The preparation method of the rapidly conductive modified lithium iron manganese phosphate according to claim 1 or 2, wherein in the third step, the mass ratio of starch to sucrose is: (4-7) and (2-4), wherein the heating after mixing is as follows: mixing for 1-2 hr, and reacting at 650-750 deg.C for 2-3 hr.
4. The preparation method of the rapid conductive modified lithium iron manganese phosphate according to claim 1 or 2, wherein the grinding of the lithium iron manganese phosphate positive electrode material in the first step is: grinding the lithium iron manganese phosphate anode material for 3-5 hours, and uniformly grinding the material to obtain the lithium iron manganese phosphate anode material with the particle size of 10-50 microns.
5. The preparation method of the rapidly conductive modified lithium iron manganese phosphate according to claim 1 or 2, characterized in that the step three is followed by a step four: and carrying out carbon coating on the rapid conductive modified lithium manganese iron phosphate to obtain the tertiary modified lithium manganese iron phosphate, wherein the carbon coating is physical coating.
6. A battery positive plate of fast conductive modified lithium manganese iron phosphate is characterized in that the preparation method of the battery positive plate comprises the following steps: baking the rapid conductive modified lithium manganese iron phosphate prepared by the preparation method of any one of claims 1 to 4 or the tertiary modified lithium manganese iron phosphate prepared by the preparation method of claim 5; adding a conductive agent, a solvent and mixed glue and mixing to obtain a mixed solution; and coating the mixed solution on a base material to obtain the battery positive plate.
7. The battery positive plate of the rapid conductive modified lithium iron manganese phosphate of claim 6, wherein the baking step in the preparation method of the battery positive plate is as follows: and putting the ground fast conductive modified lithium manganese iron phosphate or the three-time modified lithium manganese iron phosphate into a microwave oven, covering the microwave oven, filling inert gas, stopping filling when the pressure reaches 0.5 atmosphere, then starting to heat to 150-180 ℃, and baking for 2-2.5 hours.
8. The battery positive plate of the fast conductive modified lithium iron manganese phosphate of claim 6, wherein the mixed glue comprises the following raw materials in parts by mass: 5-12% of ethyl cyanoacrylate glue, 15-20% of ethylene copolymer glue, 25-35% of ethylene-vinyl acetate copolymer glue, 20-25% of polyimide glue and 15-30% of polybutadiene glue, wherein the mixed glue is prepared by the following steps: mixing the raw materials with ultrapure water according to a mass ratio of 1.
9. The battery positive plate of the fast conductive modified lithium manganese iron phosphate according to claim 6, wherein the mixing glue, the solvent and the conductive agent are added into the fast conductive modified lithium manganese iron phosphate according to any one of claims 1 to 4 or the triple modified lithium manganese iron phosphate according to claim 5 to mix, the mixture is stirred at 550-620 rpm for 50-70 minutes, then at 1400-1550 rpm for 80-100 minutes, and the stirring temperature is controlled at 30-50 ℃.
10. A battery comprising the battery positive electrode sheet of the rapid-conductive modified lithium iron manganese phosphate according to any one of claims 6 to 9.
CN202211353728.3A 2022-11-01 2022-11-01 Preparation method of quick conductive modified lithium manganese iron phosphate, battery positive plate and battery Active CN115632120B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211353728.3A CN115632120B (en) 2022-11-01 2022-11-01 Preparation method of quick conductive modified lithium manganese iron phosphate, battery positive plate and battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211353728.3A CN115632120B (en) 2022-11-01 2022-11-01 Preparation method of quick conductive modified lithium manganese iron phosphate, battery positive plate and battery

Publications (2)

Publication Number Publication Date
CN115632120A true CN115632120A (en) 2023-01-20
CN115632120B CN115632120B (en) 2023-07-04

Family

ID=84909394

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211353728.3A Active CN115632120B (en) 2022-11-01 2022-11-01 Preparation method of quick conductive modified lithium manganese iron phosphate, battery positive plate and battery

Country Status (1)

Country Link
CN (1) CN115632120B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012104290A (en) * 2010-11-08 2012-05-31 Sony Corp Positive electrode active material for nonaqueous electrolyte battery, positive electrode for nonaqueous electrolyte battery, and nonaqueous electrolyte battery
WO2019034105A1 (en) * 2017-08-18 2019-02-21 宁波致良新能源有限公司 Positive electrode material and preparation method thereof, positive electrode and lithium ion battery
CN113066969A (en) * 2021-03-26 2021-07-02 深圳市鹏冠新材料科技有限公司 Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material
CN114665058A (en) * 2022-05-05 2022-06-24 盐城工学院 Preparation method of lithium ion battery anode material lithium iron manganese phosphate
CN115224379A (en) * 2022-06-14 2022-10-21 佛山市德方纳米科技有限公司 Lithium iron manganese phosphate composite material, preparation method thereof and secondary battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012104290A (en) * 2010-11-08 2012-05-31 Sony Corp Positive electrode active material for nonaqueous electrolyte battery, positive electrode for nonaqueous electrolyte battery, and nonaqueous electrolyte battery
WO2019034105A1 (en) * 2017-08-18 2019-02-21 宁波致良新能源有限公司 Positive electrode material and preparation method thereof, positive electrode and lithium ion battery
CN113066969A (en) * 2021-03-26 2021-07-02 深圳市鹏冠新材料科技有限公司 Preparation method of conductive polymer coated lithium manganese iron phosphate cathode material
CN114665058A (en) * 2022-05-05 2022-06-24 盐城工学院 Preparation method of lithium ion battery anode material lithium iron manganese phosphate
CN115224379A (en) * 2022-06-14 2022-10-21 佛山市德方纳米科技有限公司 Lithium iron manganese phosphate composite material, preparation method thereof and secondary battery

Also Published As

Publication number Publication date
CN115632120B (en) 2023-07-04

Similar Documents

Publication Publication Date Title
WO2016074479A1 (en) Pyrolytic amorphous carbon material, preparation method and use thereof
KR101786714B1 (en) Negative active material for rechargeable lithium battery including core consisting of carbon, method of preparing the same, and rechargeable lithium battery including the same
US10727489B2 (en) Anode slurry for lithium ion battery
CN108598414B (en) Amorphous zinc oxide/carbon composite lithium ion battery cathode material and preparation method thereof
CN107026262B (en) High-capacity spherical hard carbon negative electrode material coated with graphene on surface
EP4116355A1 (en) Composite polymer, and preparation method therefor and application thereof
CN103928657A (en) High-power lithium ion battery pole piece and preparation process thereof
CN102569788B (en) Negative material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery
CN109192941A (en) Lithium ion battery, positive plate, lithium ion battery anode glue size and preparation method thereof
CN110783546A (en) Lithium ion battery positive electrode material and preparation method thereof, lithium ion battery positive electrode slurry and positive electrode, lithium ion battery and equipment
CN113651304A (en) Organic carbon-coated lithium iron phosphate cathode material and preparation method thereof
CN111689500A (en) Preparation method of low-expansibility SiO/graphite composite electrode material
CN106374086B (en) Nano lithium titanate-graphene composite material and preparation method thereof
EP4231383A1 (en) Silicon nanocomposite structure powder for negative electrode material, and method for manufacturing same
CN110600684A (en) Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN111755665B (en) Lithium ion battery negative electrode material, battery negative electrode and application thereof
CN115632120B (en) Preparation method of quick conductive modified lithium manganese iron phosphate, battery positive plate and battery
CN107256966B (en) Lithium ion battery positive pole piece and preparation method thereof
CN115588737B (en) Preparation method of secondary modified lithium iron manganese phosphate, battery positive plate and battery
CN108199042A (en) A kind of preparation method of spherical LiFePO 4 mixed type pole piece
CN113782824A (en) Sulfide electrolyte membrane and preparation method and application thereof
CN113036137A (en) Lithium ion battery cathode material and preparation method and application thereof
KR101468582B1 (en) Preparation method of electrode active material using porous silica support, and the electrode active material
KR20210030737A (en) Method for Preparing Cathode Mixture of Solid State Battery and Cathode Mixture of Solid State Battery Prepared Thereby
KR101888230B1 (en) Silicon-based anode active material and its fabrication method

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
GR01 Patent grant
GR01 Patent grant