CN107359342B - Lithium ferromanganese phosphate particles and lithium ferromanganese phosphate powder - Google Patents

Lithium ferromanganese phosphate particles and lithium ferromanganese phosphate powder Download PDF

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CN107359342B
CN107359342B CN201710624032.2A CN201710624032A CN107359342B CN 107359342 B CN107359342 B CN 107359342B CN 201710624032 A CN201710624032 A CN 201710624032A CN 107359342 B CN107359342 B CN 107359342B
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iron phosphate
manganese iron
lithium manganese
lithium
average particle
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CN107359342A (en
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黄信达
林泰宏
王易轩
许智宗
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Hongchen Materials Co., Ltd
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Hong Chen Battery Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/366—Composites as layered products
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
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    • 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
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

A lithium manganese iron phosphate powder comprises a plurality of lithium manganese iron phosphate particles. Each of the lithium manganese iron phosphate-based particles includes a core portion and a shell portion. The core portion includes a plurality of first lithium manganese iron phosphate-based nanoparticles bonded together and having a first average particle diameter. The shell portion includes a plurality of second lithium manganese iron phosphate-based nanoparticles bonded together and having a second average particle diameter that is greater than the first average particle diameter. The lithium manganese iron phosphate powder can be prepared by sequentially carrying out primary sintering treatment at 300-450 ℃, intermediate sintering treatment at more than 450-600 ℃ and final sintering treatment at more than 600-800 ℃. The lithium manganese iron phosphate powder is used as the cathode material of the lithium battery, so that the lithium battery has high energy density, good high-temperature charge-discharge cycle stability and good thermal stability.

Description

Lithium ferromanganese phosphate particles and lithium ferromanganese phosphate powder
Technical Field
The present invention relates to a lithium manganese iron phosphate powder suitable for use as a cathode material of a lithium battery and a method for preparing the same, and more particularly, to a lithium manganese iron phosphate powder including a plurality of core-shell-shaped lithium manganese iron phosphate particles, and a method for preparing the same.
Background
At present, lithium manganese iron phosphate powder used as a cathode material (or called a cathode material) of a lithium battery cannot reach a stage of mass commercialization, and mainly because the conductivity of the lithium manganese iron phosphate powder is low, how to consider the high energy density and the thermal stability of the lithium battery becomes the most critical problem. In the early technology, the primary particles (primary particles) of the lithium manganese iron phosphate powder with a relatively low specific surface area have an average particle size of about more than 300nm, so that the thermal stability and the charge-discharge cycle stability of the lithium battery meet the market requirements, but the lithium manganese iron phosphate powder has relatively low intrinsic conductivity, so that the performance of the discharge capacity of the lithium battery in the conditions of energy density and large current is still not ideal. Therefore, in order to improve the electrochemical characteristics of the lithium manganese iron phosphate powder, a few technologies prepare the lithium manganese iron phosphate powder with the average particle size of the primary particles being less than 100nm by improving a synthesis method, and the conductivity of the lithium manganese iron phosphate powder is improved by shortening the electron conduction distance of the lithium manganese iron phosphate powder.
Disclosure of Invention
It is a first object of the present invention to provide lithium manganese iron phosphate-based particles suitable for use as a cathode material for lithium batteries.
The lithium manganese iron phosphate-based particles of the present invention are suitable for use as a cathode material for a lithium battery, and comprise:
a core portion including a plurality of first lithium manganese iron phosphate-based nanoparticles, the first lithium manganese iron phosphate-based nanoparticles being bonded together and having a first average particle diameter; and
and the shell part coats the core part and comprises a plurality of second lithium manganese iron phosphate-based nanoparticles, wherein the second lithium manganese iron phosphate-based nanoparticles are combined together and have a second average particle size, and the second average particle size is larger than the first average particle size.
The first average particle diameter of the first lithium manganese iron phosphate-based nanoparticles is in the range of 30 to 150 nm.
The second average particle diameter of the second lithium manganese iron phosphate-based nanoparticles is in the range of 150 to 400 nm.
In the lithium manganese iron phosphate-based particle of the present invention, the stoichiometric composition of the first lithium manganese iron phosphate-based nanoparticles in the core portion is the same as the stoichiometric composition of the second lithium manganese iron phosphate-based nanoparticles in the shell portion.
The lithium manganese iron phosphate-based particles of the present invention comprise the first lithium manganese iron phosphate-based nanoparticles and the second lithium manganese iron phosphate-based nanoparticles having a stoichiometric composition of LixMn1-y-zFeyMzPO4And x is 0.9 ≦ 1.2, y is 0.1 ≦ 0.4, z is 0 ≦ 0.1, and y + z is 0.1 ≦ 0.4, wherein M is selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminum, or a combination thereof.
According to the lithium manganese iron phosphate-based particles, the first lithium manganese iron phosphate-based nanoparticles are combined together by sintering, and the second lithium manganese iron phosphate-based nanoparticles are combined together by sintering.
The second object of the present invention is to provide a lithium manganese iron phosphate powder suitable for use as a cathode material of a lithium battery.
The lithium manganese iron phosphate powder comprises a plurality of lithium manganese iron phosphate particles.
The lithium manganese iron phosphate powder has the average particle size of 0.6-20 mu m.
The lithium manganese iron phosphate powder has a specific surface area ranging from 5 to 30m2/g。
The tap density range of the lithium manganese iron phosphate powder is more than 0.5g/cm3。
The third objective of the present invention is to provide a method for preparing lithium manganese iron phosphate powder suitable for use as a cathode material of a lithium battery.
The preparation method of the lithium manganese iron phosphate powder comprises the following steps:
(A) providing a blend containing a lithium source, a manganese source, an iron source, and a phosphorus source;
(B) grinding and pelletizing the blend to form a pelletized mixture;
(C) subjecting the granulation mixture to a primary sintering process to form a preform, wherein the temperature of the primary sintering process is in the range of 300 to 450 ℃;
(D) subjecting the preform to an intermediate sintering process to form an intermediate sintered preform, wherein the temperature of the intermediate sintering process is in the range of greater than 450 to 600 ℃; and
(E) and carrying out final sintering treatment on the intermediate sintered preform to form lithium manganese iron phosphate powder, wherein the temperature range of the final sintering treatment is more than 600-800 ℃.
The lithium manganese iron phosphate powder of the invention further comprises a doped metal source selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminum or a combination thereof.
The invention has the beneficial effects that: the preparation method comprises the steps (A) to (E) to obtain the lithium manganese iron phosphate powder comprising a plurality of lithium manganese iron phosphate particles which are approximately in a core-shell shape, and the second average particle diameter of the second lithium manganese iron phosphate nanoparticles of the shell part of each lithium manganese iron phosphate particle is larger than the first average particle diameter of the first lithium manganese iron phosphate nanoparticles of the core part. When the lithium manganese iron phosphate powder is used as a cathode material of a lithium battery, the lithium battery has high energy density, high thermal stability and good charge-discharge cycle stability at high temperature.
Drawings
FIG. 1 is a photograph of a scanning electron microscope of lithium manganese iron phosphate-based particles of example 1 of the present invention;
FIG. 2 is a partially enlarged view of a photograph of the scanning electron microscope of example 1;
FIG. 3 is a scanning electron microscope photograph of lithium manganese iron phosphate-based particles of comparative example 1;
FIG. 4 is a partial enlarged view of a scanning electron microscope photograph of lithium manganese iron phosphate-based particles of comparative example 1;
FIG. 5 is a scanning electron microscope photograph of lithium manganese iron phosphate-based particles of comparative example 2;
FIG. 6 is a partially enlarged view of a SEM photograph of lithium ferromanganese phosphate-based particles of comparative example 2;
fig. 7 is a data graph of a 0.1C current charge and discharge test (Capacity) for CR2032 button-type lithium batteries of example 1 and comparative examples 1 and 2;
FIG. 8 is a graph of discharge current test (C-rate) data for 0.1C, 1.0C, 5.0C, 10.0C for the CR2032 button lithium cells of example 1 and comparative examples 1 and 2;
FIG. 9 is a graph of data from 55 ℃ high temperature cycling test (Cycle life) for the CR2032 button lithium cells of example 1 and comparative examples 1 and 2; and
fig. 10 is a data graph of thermal analysis test (Safety) of CR2032 button-type lithium batteries of example 1 and comparative examples 1 and 2.
Detailed Description
The present invention will be described in detail below:
in this context, the term "lithium battery" is intended to include within its scope: lithium batteries (lithium batteries) that are primary batteries (primary batteries), and lithium-ion batteries (lithium-ion batteries) that are secondary batteries (secondary batteries). The lithium manganese iron phosphate powder can be used as a cathode material of a lithium battery or a cathode material of a lithium ion battery, and is particularly applied to the cathode material of the lithium ion battery.
Lithium manganese iron phosphate series granule, lithium manganese iron phosphate series powder
Preferably, the first average particle size of the first lithium manganese iron phosphate-based nanoparticles of the lithium manganese iron phosphate-based particles is in a range of 30 to 150nm, so that the electric transmission rate and the mass transmission rate of the lithium manganese iron phosphate-based powder can be further improved.
Preferably, the second average particle size of the second lithium manganese iron phosphate nanoparticles of the lithium manganese iron phosphate-based particles is in a range of 150 to 400nm, which can further reduce the specific surface area of the lithium manganese iron phosphate-based powder.
Preferably, in the lithium manganese iron phosphate-based particles, the stoichiometric composition of the first lithium manganese iron phosphate-based nanoparticles of the core portion is the same as the stoichiometric composition of the second lithium manganese iron phosphate-based nanoparticles of the shell portion. More preferably, the first lithium manganese iron phosphate-based nanoparticle and the second lithium manganese iron phosphate-based nanoparticleThe stoichiometric composition of the particles is LixMn1-y-zFeyMzPO4And x is 0.9 ≦ 1.2, y is 0.1 ≦ 0.4, z is 0 ≦ 0.1, and y + z is 0.1 ≦ 0.4, wherein M is selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminum, or a combination thereof.
Preferably, in the lithium manganese iron phosphate-based particles, the first lithium manganese iron phosphate-based nanoparticles are bonded together by sintering, and the second lithium manganese iron phosphate-based nanoparticles are bonded together by sintering.
Preferably, in the lithium manganese iron phosphate-based powder, the average particle size of the lithium manganese iron phosphate-based particles is in a range of 0.6 to 20 μm.
Preferably, the specific surface area of the lithium manganese iron phosphate powder is in the range of 5 to 30m2/g。
Preferably, the tap density range of the lithium manganese iron phosphate powder is more than 0.5g/cm3。
Process for preparing lithium manganese iron phosphate powder
The preparation method of the lithium manganese iron phosphate powder comprises the following steps: grinding and pelletizing the blend containing the lithium source, manganese source, iron source, and phosphorus source to form the pelletized mixture; and sequentially carrying out primary sintering treatment, intermediate sintering treatment and final sintering treatment on the granulation mixture.
Preferably, the phosphorus source is water soluble. The kind of the phosphorus source is, for example, but not limited to, phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or the like, and the above phosphorus sources can be used singly or in combination of plural kinds. More preferably, the phosphorus source is phosphoric acid.
The kind of the manganese source is not limited to manganese oxide, manganese oxalate, manganese carbonate, manganese sulfate or manganese acetate, and the like, and the manganese source can be used singly or in combination of a plurality. Preferably, the manganese source is manganese oxide. The phosphorus source is used in an amount of 1 mol, and the manganese source is used in an amount ranging from 0.6 to 0.9 mol.
The kind of the iron source is, for example, but not limited to, iron oxalate, iron oxide, pure iron, iron nitrate, iron sulfate, etc., and the iron source can be used singly or in combination of plural kinds. Preferably, the iron source is iron oxalate. The using amount of the phosphorus source is 1 mol, and the using amount of the iron source ranges from 0.1 to 0.4 mol.
The kind of the lithium source is, for example, but not limited to, lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, or the like, and the above-mentioned lithium sources can be used singly or in combination of plural kinds. Preferably, the lithium source is lithium carbonate. The amount of the lithium source is in the range of 0.9 to 1.2 moles based on 1 mole of the phosphorus source.
Preferably, the blend further comprises a source of a dopant metal selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminum, or a combination thereof. The doped metal source can improve the structural stability of the lithium manganese iron phosphate powder. More preferably, the source of doping metal is selected from magnesium. The amount of the doping metal source is in the range of 0.01 to 0.1 mol based on 1 mol of the phosphorus source.
Preferably, the blend further comprises a carbon source. The carbon source functions as a reducing agent. The kind of the carbon source is, for example, but not limited to, glucose, citric acid, super-P (conductive carbon black), etc., and the above carbon sources can be used singly or in combination of one or more.
The blend optionally contains a solvent. Such as, but not limited to, water. The amount of the solvent to be used is not particularly limited, and is adjusted in accordance with the amounts of the metal source and the carbon source.
The blend is formed into the granulation mixture by, for example, but not limited to, grinding the blend prior to granulating the ground blend. The milling is carried out, for example, but not limited to, a ball milling method, conditions of which are not particularly limited, for example, but not limited to, milling the blend at a speed of 800 to 2400rpm./min for 1 to 5 hours. The granulation method is, for example, but not limited to, a spray granulation method, and conditions of the spray granulation method are not particularly limited, for example, but not limited to, forming the granulation mixture from the milled blend at an air inlet temperature of a spray granulator ranging from 160 to 210 ℃.
The temperature range of the primary sintering treatment is 300 to 450 ℃. The treatment time of the primary sintering treatment is, for example, but not limited to, 6 to 12 hours.
The temperature range of the intermediate sintering treatment is more than 450 to 600 ℃. The treatment time of the intermediate sintering treatment is, for example, but not limited to, 2 to 6 hours.
The temperature range of the final sintering treatment is more than 600 to 800 ℃. The treatment time of the final sintering treatment is, for example, but not limited to, 2 to 6 hours.
The invention will be further described in the following examples, but it should be understood that the examples are illustrative only and should not be construed as limiting the practice of the invention.
[ example 1]
Under the condition that the temperature is higher than 30 ℃, adding a proper amount of water, a manganese source (specifically manganese oxide), an iron source (specifically iron oxalate), a magnesium doped metal source (specifically magnesium oxide) and a phosphorus source (specifically phosphoric acid) according to a molar ratio of 0.8: 0.15: 0.05: 1.0, adding a lithium source (specifically lithium carbonate) after 1 hour, and mixing, wherein the molar ratio of the lithium source to the phosphorus source is 1.02: 1.00, followed by the addition of an appropriate amount of carbon source (specifically glucose) to obtain a blend. The blend was ground in a ball mill for 4 hours to give a ground blend. The milled blend was then spray dried in a spray granulator (the air inlet temperature of the spray granulator was controlled at 200 ℃ C.) to obtain a granulated mixture. Placing the granulation mixture into a bell jar furnace, and carrying out primary sintering treatment (sintering at the constant temperature of 450 ℃ for 10 hours) on the granulation mixture under nitrogen atmosphere to form a preform. Then, the preform is subjected to an intermediate sintering treatment (sintering at a constant temperature of 600 ℃ for 2 hours) to form an intermediate sintered preform. Finally, the intermediate sintered preform was subjected to a final sintering treatment (sintering at a constant temperature of 750 ℃ for 3 hours), and naturally cooled to room temperature (25 ℃) to obtain lithium manganese iron phosphate powder (specific surface area 18.1 m) of example 12(ii)/g, tap density 1.21g/cm3)。
The electron beam was measured by a scanning electron microscope (manufacturer model:hitachi su8000), and photographs of fig. 1 and 2 show that lithium manganese iron phosphate-based particles in the lithium manganese iron phosphate-based powder of example 1 include a core portion formed by bonding a plurality of first lithium manganese iron phosphate-based nanoparticles (having an average particle diameter of 50nm) together, and a shell portion formed by bonding a plurality of second lithium manganese iron phosphate-based nanoparticles (having an average particle diameter of 400nm) together. And the stoichiometric compositions of the first lithium manganese iron phosphate nano-particle and the second lithium manganese iron phosphate nano-particle are both Li by element analysis (the analysis instrument is Perkinelmer Optima 7000DV)1.02Mn0.8Fe0.15Mg0.05PO4。
Comparative example 1
Under the condition that the temperature is higher than 30 ℃, adding a proper amount of water, a manganese source (specifically manganese oxide), an iron source (specifically iron oxalate), a magnesium doped metal source (specifically magnesium oxide) and a phosphorus source (specifically phosphoric acid) according to a molar ratio of 0.8: 0.15: 0.05: 1.0, and after 1 hour, adding a lithium source (specifically lithium carbonate) in a molar ratio of the lithium source to the phosphorus source of 1.02: 1.00, followed by the addition of an appropriate amount of carbon source (specifically glucose) to obtain a blend. The blend was ground in a ball mill for 3 hours to give a ground blend. And then the ground mixture is spray-dried by a spray granulator (the temperature of an air inlet of the spray granulator is controlled to be 200 ℃) to obtain a granulation mixture. Placing the granulation mixture in a bell jar furnace, sintering the granulation mixture at 450 ℃ for 8 hours at constant temperature under nitrogen atmosphere, sintering at 650 ℃ for 6 hours at constant temperature, and naturally cooling to room temperature (25 ℃) to obtain the lithium manganese iron phosphate powder (the specific surface area is 26.3 m) of the comparative example 12(ii)/g, tap density 1.12g/cm3)。
The lithium ferromanganese phosphate powder of comparative example 1 was observed with a scanning electron microscope (product model: Hitachi su8000), and photographs of FIGS. 3 and 4 show that the lithium ferromanganese phosphate particles in the lithium ferromanganese phosphate powder of comparative example 1 were formed by bonding together a plurality of lithium ferromanganese phosphate nanoparticles (average particle size of 70 nm). And the lithium manganese phosphate is obtained through element analysis (the analytical instrument is Perkinelmer Optima 7000DV)The stoichiometric composition of the iron-based nanoparticles is Li1.02Mn0.8Fe0.15Mg0.05PO4。
Comparative example 2
Under the condition that the temperature is higher than 30 ℃, adding a proper amount of water, a manganese source (specifically manganese oxide), an iron source (specifically iron oxalate), a magnesium doped metal source (specifically magnesium oxide) and a phosphorus source (specifically phosphoric acid) according to a molar ratio of 0.8: 0.15: 0.05: 1.0, and after 1 hour, adding a lithium source (specifically lithium carbonate) in a molar ratio of the lithium source to the phosphorus source of 1.02: 1.00, followed by the addition of an appropriate amount of carbon source (specifically glucose) to obtain a blend. The blend was ground in a ball mill for 2 hours to give a ground blend. The milled blend was then spray dried in a spray granulator (the inlet temperature of the spray granulator was controlled at 200 ℃) to obtain a granulated mixture. Placing the granulation mixture in a bell jar furnace, sintering the granulation mixture at the constant temperature of 450 ℃ for 8 hours under nitrogen atmosphere, sintering the granulation mixture at the constant temperature of 750 ℃ for 6 hours, and naturally cooling the granulation mixture to room temperature (25 ℃) to obtain lithium manganese iron phosphate powder (the specific surface area is 14.2 m) of comparative example 22(ii)/g, tap density 1.15g/cm3)。
The lithium ferromanganese phosphate powder of comparative example 2 was observed with a scanning electron microscope (product model: Hitachi su8000), and as shown in the photographs of FIG. 5 and FIG. 6, the lithium ferromanganese phosphate particles in the lithium ferromanganese phosphate powder of comparative example 2 were formed by bonding together a plurality of lithium ferromanganese phosphate nanoparticles (average particle size of 250 nm). And the stoichiometric composition of the lithium manganese iron phosphate nano-particles is Li through element analysis (the analytical instrument is Perkinelmer Optima 7000DV)1.02Mn0.8Fe0.15Mg0.05PO4。
[ Property evaluation ]
CR2032 button lithium batteries were prepared using the lithium manganese iron phosphate powders of example 1 and comparative examples 1 and 2, and thermal analysis and various electrochemical characteristics were performed using the CR2032 button lithium batteries of example 1 and comparative examples 1 and 2. The manufacturing method of the CR2032 button type lithium battery is detailed as follows:
cathode: mixing lithium manganese iron phosphate powder, a mixture of graphite and carbon black, and polyvinylidene fluoride (polyvinylidene fluoride) according to a weight ratio of 93: 3: 4, and then adding 6g of N-Methyl pyrrolidone (N-Methyl-2-pyrrolidone) to be uniformly mixed to form slurry. After the slurry was coated on the surface of an aluminum foil (thickness 20 μm) using a doctor blade, the aluminum foil was dried on a heating table and then vacuum-dried to remove N-methylpyrrolidone, and a cathode was obtained. And rolling the cathode, and then cutting the cathode into coin types with the diameter of 12mm for later use.
Anode: the anode was made of lithium metal, and had a thickness of 0.3mm and a diameter of 1.5 cm.
Electrolyte solution: 1M lithium hexafluorophosphate (LiPF)6) Dissolved in Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), and dimethyl carbonate (DMC) (volume ratio of 1: 1: 1) in the solvent.
The CR2032 button lithium batteries of example 1 and comparative examples 1 and 2 were prepared according to the conventional CR2032 button lithium battery manufacturing method using the above-described cathode, anode and electrolyte.
1.0.1C Current Charge/discharge test (Capacity)
The discharge capacity of the CR2032 button-type lithium batteries of example 1, comparative examples 1 and 2 was measured at a charge and discharge current of 0.1C and a voltage range of 2.7 to 4.25V. The measurement results are shown in fig. 7.
2.0.1C, 1.0C, 5.0C, 10.0C discharge Current test (C-rate)
First discharge capacities of the CR2032 button-type lithium batteries of example 1, comparative examples 1 and 2 were measured at a charge current of 1.0C and an operating voltage in the range of 2.7 to 4.25V, at discharge currents of 0.1C, 1.0C, 5.0C and 10.0C, respectively. The measurement results are shown in fig. 8.
3. High temperature charge-discharge Cycle test (Cycle life)
The CR2032 button-type lithium batteries of example 1, comparative examples 1 and 2 were charged and discharged 200 times at a constant current of 2.0C and a voltage range of 2.7 to 4.25V in an environment of 55C. The measurement results are shown in fig. 9.
4. Thermal analysis test (Safety)
After the CR2032 button-type lithium batteries of example 1 and comparative examples 1 and 2 were charged to 4.25V, the button-type lithium batteries were disassembled, the cathodes were removed, and the lithium manganese iron phosphate-based powder on the cathodes was scraped off. Taking 3 mg of scraped lithium manganese iron phosphate powder, putting the scraped lithium manganese iron phosphate powder into an aluminum crucible, adding 3 mu l of electrolyte, riveting and sealing the aluminum crucible, then carrying out thermal analysis test by using a differential thermal scanning analyzer (DSC, manufacturer model: PerkinElmer DSC7), heating the aluminum crucible at a heating rate of 5 ℃/min, scanning the temperature range of 200-350 ℃, and recording the temperature of the aluminum crucible when 5% weight loss occurs, which is thermal decomposition temperature Td. The measurement results are shown in fig. 10.
As can be seen from the results of the discharge capacity test in FIG. 7, the discharge capacity of the CR2032 button-type lithium battery of example 1 was 146.7mAh/g, the discharge capacity of the CR2032 button-type lithium battery of comparative example 1 was 144.2mAh/g, and the discharge capacity of the CR2032 button-type lithium battery of comparative example 2 was 132.8 mAh/g.
As can be seen from the test results of fig. 8, the CR2032 button-type lithium battery of example 1 has a higher discharge capacity at discharge currents of 0.1C, 1.0C, 5.0C and 10.0C. At a discharge current of 10C, the CR2032 button-type lithium battery of example 1 still has a capacity of 75% compared to its discharge current of 0.1C, whereas the CR2032 button-type lithium batteries of comparative examples 1 and 2 have capacities of only about 68% and 47%, respectively, remaining.
As can be seen from the results of the 55 c high temperature cycle test of fig. 9, the CR2032 button lithium battery of example 1 maintained 97% (142.2 ÷ 146.1 × 100%) of the initial charge after 200 charges and discharges, the button lithium battery of comparative example 1 left only 82% (116.6 ÷ 142.5 × 100%) of the initial charge, and the button lithium battery of comparative example 2 left 98% (121.6 ÷ 124.1 × 100%) of the initial charge.
From the results of the thermal analysis test of fig. 10, it is understood that the thermal decomposition temperature of the lithium manganese iron phosphate-based powder scraped from the button lithium battery of example 1CR 2032 was 288.2 ℃ and the heat release was 84.5J/g after the button lithium battery was charged to 4.25V. The exothermic amounts of the lithium manganese iron phosphate powders scraped from the lithium button cells of comparative examples 1 and 2CR 2032 were 192.9J/g and 112.7J/g, respectively, after thermal decomposition.
Therefore, it can be seen from the test results shown in fig. 7 to 10 that the lithium manganese iron phosphate powder of example 1 can simultaneously achieve higher energy density, excellent high temperature cycle capability, and better thermal stability of the lithium battery compared to the lithium manganese iron phosphate powder of comparative examples 1 to 2.
In summary, in the method for preparing lithium manganese iron phosphate powder according to the present invention, the lithium manganese iron phosphate particles in the prepared lithium manganese iron phosphate powder are almost in the shape of core-shell through the steps (a) to (E), the second average particle diameter of the second lithium manganese iron phosphate nanoparticles in the shell of the lithium manganese iron phosphate particles is larger than the first average particle diameter of the first lithium manganese iron phosphate nanoparticles in the core, and the lithium manganese iron phosphate powder is used as a cathode material of a lithium battery, such that the lithium battery has high energy density, high thermal stability, and good charge-discharge cycle stability at high temperature, thereby achieving the object of the present invention.
The above description is only an example of the present invention, and the scope of the present invention should not be limited thereby, and all the simple equivalent changes and modifications made according to the claims and the contents of the specification should be included in the scope of the present invention.

Claims (10)

1. A lithium manganese iron phosphate-based particle suitable for use as a cathode material for a lithium battery, said lithium manganese iron phosphate-based particle comprising:
a core portion including a plurality of first lithium manganese iron phosphate-based nanoparticles, the first lithium manganese iron phosphate-based nanoparticles being bonded together and having a first average particle diameter; and
and the shell part coats the core part and comprises a plurality of second lithium manganese iron phosphate-based nanoparticles, wherein the second lithium manganese iron phosphate-based nanoparticles are combined together and have a second average particle size, and the second average particle size is larger than the first average particle size.
2. The lithium manganese iron phosphate-based particles according to claim 1, wherein the first average particle diameter of the first lithium manganese iron phosphate-based nanoparticles is in the range of 30 to 150 nm.
3. The lithium manganese iron phosphate-based particles according to claim 1, wherein the second average particle diameter of the second lithium manganese iron phosphate-based nanoparticles is in a range of 150 to 400 nm.
4. The lithium manganese iron phosphate-based particle according to claim 1, wherein a stoichiometric composition of the first lithium manganese iron phosphate-based nanoparticles of the core portion is the same as a stoichiometric composition of the second lithium manganese iron phosphate-based nanoparticles of the shell portion.
5. The lithium manganese iron phosphate-based particles according to claim 4, wherein the stoichiometric composition of said first lithium manganese iron phosphate-based nanoparticles and said second lithium manganese iron phosphate-based nanoparticles is LixMn1-y-zFeyMzPO4And x is 0.9 ≦ 1.2, y is 0.1 ≦ 0.4, z is 0 ≦ 0.1, and y + z is 0.1 ≦ 0.4, wherein M is selected from magnesium, calcium, strontium, cobalt, titanium, zirconium, nickel, chromium, zinc, aluminum, or a combination thereof.
6. The lithium manganese iron phosphate-based particles according to claim 1, wherein the first lithium manganese iron phosphate-based nanoparticles are bonded together by sintering and the second lithium manganese iron phosphate-based nanoparticles are bonded together by sintering.
7. A lithium ferromanganese phosphate powder suitable for use as a cathode material for a lithium battery, characterized in that the lithium ferromanganese phosphate powder comprises a plurality of lithium ferromanganese phosphate particles according to any one of claims 1 to 6.
8. The lithium manganese iron phosphate-based powder according to claim 7, wherein the average particle diameter of the lithium manganese iron phosphate-based particles is in the range of 0.6 to 20 μm.
9. The lithium manganese iron phosphate-based powder according to claim 7, wherein the specific surface area of the lithium manganese iron phosphate-based powder is in a range of 5 to 30m2/g。
10. The lithium ferromanganese phosphate powder according to claim 7, wherein the tap density range of the lithium ferromanganese phosphate powder is more than 0.5g/cm3。
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