CN115535992B - Ferromanganese phosphate precursor, lithium iron manganese phosphate anode material and preparation method - Google Patents

Ferromanganese phosphate precursor, lithium iron manganese phosphate anode material and preparation method Download PDF

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CN115535992B
CN115535992B CN202211528299.9A CN202211528299A CN115535992B CN 115535992 B CN115535992 B CN 115535992B CN 202211528299 A CN202211528299 A CN 202211528299A CN 115535992 B CN115535992 B CN 115535992B
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phosphate
iron
ferromanganese
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CN115535992A (en
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李健
司徒白雪
金晶
李良
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Shenzhen Zhongxinneng Technology Co ltd
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Abstract

The preparation method of the ferromanganese phosphate precursor provided by the embodiment of the application comprises the following steps: adding iron powder into a phosphoric acid solution, and reacting to obtain a first reaction mixed solution; adding manganese carbonate into the first reaction mixed solution, and reacting to obtain a second reaction mixed solution; grinding the second reaction mixed solution; carrying out spray granulation treatment to obtain manganese iron phosphate particles; calcining the ferromanganese phosphate particles to obtain a ferromanganese phosphate precursor; through the mode, the iron source is iron powder, the manganese source is manganese carbonate, the phosphorus source is phosphoric acid, the molar ratio of the elements is improved, the grain size of the single crystal particles of the prepared ferromanganese phosphate precursor is nano-scale, the conductivity and the cycle performance of the lithium iron manganese phosphate anode material prepared by utilizing the ferromanganese phosphate precursor and the lithium source are improved, and the lithium iron manganese phosphate anode material has a good low-temperature capacity retention rate; and the preparation method of the manganese iron phosphate precursor has simple process and easy control, and is beneficial to keeping the consistency of products.

Description

Ferromanganese phosphate precursor, lithium iron manganese phosphate anode material and preparation method
Technical Field
The application relates to the technical field of preparation of lithium ion battery anode materials, in particular to a ferromanganese phosphate precursor, a lithium iron manganese phosphate anode material and a preparation method thereof.
Background
The positive electrode material is an important component of the lithium ion power battery; the lithium iron manganese phosphate anode material inherits the advantages of low cost, high thermal stability, high safety and the like of the lithium iron phosphate anode material, overcomes the defects of low energy density, poor low-temperature stability and the like of the lithium iron phosphate anode material, and becomes one of potential candidate anode materials capable of being applied to the field of electric vehicles. However, the lithium iron manganese phosphate positive electrode material in the prior art has the problems of poor conductivity, poor cycle performance and the like, and the wide application of the lithium iron manganese phosphate positive electrode material is restricted.
Disclosure of Invention
In view of the above problems, embodiments of the present application provide a ferromanganese phosphate precursor, a lithium iron manganese phosphate positive electrode material, and a preparation method thereof, so as to solve the above technical problems.
In a first aspect, an embodiment of the present application provides a method for preparing a ferromanganese phosphate precursor, including:
adding iron powder into a phosphoric acid solution, and stirring and reacting for 3-5 hours at a first temperature to obtain a first reaction mixed solution;
adding manganese carbonate into the first reaction mixed solution, and stirring and reacting for 2-5 hours at a first temperature to obtain a second reaction mixed solution;
grinding the second reaction mixed solution to obtain a grinding mixed solution;
carrying out spray granulation treatment on the grinding treatment mixed liquid to obtain manganese iron phosphate particles;
calcining the ferromanganese phosphate particles to obtain a ferromanganese phosphate precursor;
wherein the molar ratio of manganese element in the manganese carbonate, iron element in the iron powder and phosphorus element in the phosphoric acid solution is 0.55-0.65.
In some embodiments, the molar ratio of the manganese element in the manganese carbonate, the iron element in the iron powder, and the phosphorus element in the phosphoric acid solution is 0.6.
In some embodiments, the milling time of the milling treatment is 5 hours to 8 hours.
In some embodiments, the sintering temperature of the calcination process is 500 ℃ to 700 ℃ and the holding time of the calcination process is 5 hours to 8 hours.
In some embodiments, the method of making further comprises:
and carrying out airflow crushing treatment on the manganese phosphate iron precursor to obtain a powdery manganese phosphate iron precursor.
In some embodiments, the first temperature is 50 ℃.
In a second aspect, the embodiment of the present application provides an ferromanganese phosphate precursor obtained by the above preparation method, where the particle size of the ferromanganese phosphate precursor is 5 μm to 20 μm.
In a third aspect, an embodiment of the present application provides a lithium iron manganese phosphate positive electrode material, where the lithium iron manganese phosphate positive electrode material is obtained by calcining a mixture of a ferric manganese phosphate precursor and a lithium source, and the ferric manganese phosphate precursor is obtained by using the preparation method.
In a fourth aspect, an embodiment of the present application provides a method for preparing a lithium iron manganese phosphate positive electrode material, including:
mixing a lithium source with the manganese iron phosphate precursor, and performing primary calcination treatment on the obtained mixture at a second temperature to obtain a manganese iron phosphate precursor;
performing airflow crushing treatment on the lithium iron manganese phosphate precursor, and performing secondary calcination treatment on the crushed lithium iron manganese phosphate precursor at a third temperature to obtain a lithium iron manganese phosphate anode material;
wherein the ferromanganese phosphate precursor is obtained by the preparation method.
In a fifth aspect, an embodiment of the present application provides a method for preparing a lithium iron manganese phosphate positive electrode material, including:
mixing a lithium source with the ferromanganese phosphate precursor, and calcining the obtained mixture at a fourth temperature to obtain a lithium iron manganese phosphate anode material;
wherein the ferromanganese phosphate precursor is obtained by the preparation method.
The preparation method of the ferromanganese phosphate precursor provided by the application embodiment comprises the following steps: adding iron powder into a phosphoric acid solution, and stirring and reacting at a first temperature to obtain a first reaction mixed solution; adding manganese carbonate into the first reaction mixed solution, and stirring and reacting at a first temperature to obtain a second reaction mixed solution; grinding the second reaction mixed solution to obtain a grinding mixed solution; carrying out spray granulation treatment on the grinding treatment mixed liquid to obtain manganese iron phosphate particles; calcining the ferromanganese phosphate particles to obtain a ferromanganese phosphate precursor; through the mode, the iron source is the iron powder, the manganese source is the manganese carbonate, the phosphorus source is the phosphoric acid, the molar ratio of the iron element in the iron powder, the phosphorus element in the phosphoric acid and the manganese element in the manganese carbonate is improved, the grain size of the single crystal particles of the prepared ferric manganese phosphate precursor is nano-scale, the conductivity and the cycle performance of the lithium iron manganese phosphate anode material prepared by utilizing the ferric manganese phosphate precursor and the lithium source are improved, and the lithium iron manganese phosphate anode material also has a good low-temperature capacity retention rate; and the preparation method of the manganese iron phosphate precursor combines chemical reaction and solid phase reaction, has simple process and easy control, and is beneficial to keeping the consistency of products.
These and other aspects of the present application will be more readily apparent from the following description of the embodiments.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 shows a flow chart of a preparation method of a ferromanganese phosphate precursor provided in an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In order to make the description of the disclosure more complete and complete, the following description is given for illustrative purposes with respect to the embodiments and specific examples of the present application; it is not intended to be the only form in which the embodiments of the present application may be practiced or utilized. The embodiments are intended to cover the features of the various embodiments as well as the method steps and sequences for constructing and operating the embodiments. However, other embodiments may be utilized to achieve the same or equivalent functions and step sequences.
In the embodiments of the present application, at least one means one or more; plural means two or more. In the description of the present application, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance, nor order.
Reference throughout this specification to "one embodiment" or "some embodiments," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in one or more embodiments of the present application. Thus, the terms "including," "comprising," "having," and variations thereof in this specification mean "including, but not limited to," unless expressly specified otherwise.
An embodiment of the present application provides a method for preparing a ferromanganese phosphate precursor, which is shown in fig. 1 and includes the following steps:
s10, adding iron powder into a phosphoric acid solution, and stirring and reacting for 3-5 hours at a first temperature to obtain a first reaction mixed solution;
s20, adding manganese carbonate into the first reaction mixed solution, and stirring and reacting for 2-5 hours at a first temperature to obtain a second reaction mixed solution;
s30, grinding the second reaction mixed solution to obtain a ground mixed solution;
s40, carrying out spray granulation treatment on the grinding treatment mixed liquid to obtain manganese iron phosphate particles;
and S50, calcining the ferromanganese phosphate particles to obtain a ferromanganese phosphate precursor.
In the embodiment, the iron source is iron powder, the manganese source is manganese carbonate, and the phosphorus source is phosphoric acid, wherein the molar ratio of manganese element in the manganese carbonate, iron element in the iron powder, and phosphorus element in the phosphoric acid solution is (0.55-0.65): (0.35-0.45): 1-1.05).
In step S10, iron powder reacts with phosphoric acid to produce iron hydrogen phosphate (FeHPO) 4 ）。
In one embodiment, the iron powder has a particle size of 100ml or less, which facilitates the reaction of the iron powder with phosphoric acid.
In one embodiment, the concentration of the phosphoric acid solution is 75mol/L to 85mol/L.
In step S20, manganese carbonate reacts with phosphoric acid to produce ferromanganese phosphate material.
In this embodiment, the reaction temperature in step S10 and step S20 is a first temperature, and the first temperature is 40 to 80 ℃. In some embodiments, the first temperature is 50 ℃.
In step S30, the second reaction mixture may be ground with a grinding material having a particle size of 1 μm to 2 μm, and the particle size of the ferromanganese phosphate material in the second reaction mixture may be adjusted. For example, the second reaction mixture may be added to a high energy ball mill, and the ferromanganese phosphate material may be crushed into micron level particles by using the rotation or vibration of the ball mill to cause the grinding material to strongly impact, grind and stir the ferromanganese phosphate material. And then carrying out spray granulation treatment on the grinding treatment mixed liquid obtained by grinding to obtain the manganese iron phosphate particles.
In one embodiment, the polishing time of the polishing treatment is 5 to 8 hours.
In step S50, the ferromanganese phosphate particles are calcined to obtain a ferromanganese phosphate precursor. For example, the ferromanganese phosphate particles may be calcined in an air furnace, first raised to a sintering temperature, and held at the sintering temperature to sinter the ferromanganese phosphate particles.
In one embodiment, the sintering temperature of the calcination treatment is 500 to 700 ℃, and the holding time of the calcination treatment is 5 to 8 hours.
In one embodiment, the molar ratio of the iron element in the iron powder, the phosphorus element in the phosphoric acid solution, and the manganese element in the manganese carbonate is 0.6 (1.02 to 1.04). The molar ratio of the iron element, the manganese element and the phosphorus element is further limited, the grain size of single crystal particles of the manganese iron phosphate precursor is more favorably reduced, meanwhile, the molar quantity of the phosphorus element is slightly larger than the sum of the molar quantities of the manganese element and the iron element, the subsequent processing of the manganese iron phosphate precursor and a lithium source is favorably realized, and the grain size of primary particles of the precursor can be properly increased by excessive phosphoric acid at high temperature, so that the subsequent processing of the precursor is facilitated.
The grain size of the single crystal grains of the ferromanganese phosphate precursor prepared by the preparation method of the embodiment is nano-scale, the average grain size of the single crystal grains is less than 100nm, the average grain size of the agglomerated secondary grains of the prepared ferromanganese phosphate precursor is 2-20 μm, and the secondary grains are spherical. The conductivity and cycle performance of the lithium iron manganese phosphate cathode material prepared by using the ferric manganese phosphate precursor can be improved.
As an embodiment, after step S50, the method further includes the following steps:
and S60, performing airflow crushing treatment on the ferromanganese phosphate precursor to obtain a powdery ferromanganese phosphate precursor.
An embodiment of the application provides a lithium iron manganese phosphate anode material, which is obtained by calcining a mixture of a ferric manganese phosphate precursor and a lithium source, wherein the ferric manganese phosphate precursor is obtained by adopting the preparation method of the ferric manganese phosphate precursor.
In this embodiment, the ferromanganese phosphate precursor is doped with lithium and calcined sequentially, the single crystal particles of the ferromanganese phosphate precursor are in a nanoscale, and the single crystal particles of the obtained lithium iron manganese phosphate anode material are also in a nanoscale, which is beneficial to improving the conductivity and cycle performance of the lithium iron manganese phosphate anode material. The applicant finds that the gram capacity of the obtained lithium iron manganese phosphate cathode material is more than 150mAh/g, the cycle number is more than 3500, the capacity retention rate at minus 40 ℃ reaches 80%, and the lithium iron manganese phosphate cathode material of the embodiment has the advantages of improved conductivity, prolonged cycle life and better low-temperature performance.
An embodiment of the application provides a preparation method of a lithium iron manganese phosphate positive electrode material, which comprises the following steps:
s21, mixing a lithium source with the manganese iron phosphate precursor, and performing primary calcination treatment on the obtained mixture at a second temperature to obtain a manganese iron phosphate precursor;
and S22, performing air flow crushing treatment on the lithium iron manganese phosphate precursor, and performing secondary calcination treatment on the crushed lithium iron manganese phosphate precursor at a third temperature to obtain the lithium iron manganese phosphate anode material.
In step S21, the lithium source is, for example, lithium carbonate or lithium hydroxide, and the molar ratio of the phosphorus element in the ferromanganese phosphate precursor to the lithium element in the lithium source is 1 (1 to 1.2).
In one embodiment, in step S21, a carbon source may be further added to dope carbon, a lithium source and the ferromanganese phosphate precursor are mixed to obtain a first mixture, the carbon source is added to the first mixture to obtain a second mixture, and the second mixture is subjected to a first calcination treatment at a second temperature to obtain the ferromanganese phosphate precursor, wherein a mass ratio of the carbon source to the first mixture is (5-15): 100, and the carbon source may be glucose or sucrose.
In one embodiment, the second temperature is 200 to 550 ℃, the third temperature is 600 to 900 ℃, the calcination time of the first calcination is 2 to 8 hours, and the calcination time of the second calcination is 5 to 20 hours.
An embodiment of the application provides a preparation method of a lithium iron manganese phosphate positive electrode material, which comprises the following steps:
s31, mixing a lithium source with the ferromanganese phosphate precursor, and calcining the obtained mixture at a fourth temperature to obtain a lithium iron manganese phosphate anode material;
wherein the ferromanganese phosphate precursor is obtained by the preparation method.
As an embodiment, step S31 specifically includes: grinding a mixture of a lithium source and a manganese iron phosphate precursor to obtain grinding treatment liquid; carrying out spray granulation on the grinding treatment liquid to obtain lithium iron manganese phosphate particles; and calcining the lithium iron manganese phosphate particles at a fourth temperature to obtain the lithium iron manganese phosphate anode material.
In some embodiments, the fourth temperature is from 650 ℃ to 700 ℃ and the calcination time of the calcination treatment is from 9 hours to 13 hours.
Example 1
Example 1 provides a method for preparing a ferromanganese phosphate precursor, and in this example, the obtained ferromanganese phosphate precursor is Mn 0.6 Fe 0.4 PO 4 With Mn 0.6 ：Fe 0.4 P, the mol ratio of Mn element in manganese carbonate, fe element in iron powder and phosphorus element in phosphoric acid is 0.6:0.4: the preparation method of the embodiment comprises the following steps:
2.28kg of 85% strength H 3 PO 4 Adding the mixture into deionized water to prepare an acid solution, adding 0.43KG of metallic iron (Fe) powder with the particle size of less than 100 mu m into the mixed acid solution, stirring and soaking the mixture for reaction for 5 hours under the heating (50 ℃) condition, then adding 1.35KG of manganese carbonate into the mixture, continuously stirring and soaking the mixture for 2 hours, and then adding the material into a high-energy mill for grinding for 5 hours.
And (3) carrying out spray drying treatment on the ground material in a centrifugal sprayer to obtain spherical particles with the particle size of 5-15 microns.
Calcining the spray-dried spherical particle powder in an air furnace at 650 ℃, and preserving heat for 5 hours.
And (3) carrying out airflow crushing treatment on the calcined material to obtain the ferromanganese phosphate precursor with the size of single crystal particles of 80-100 nanometers and the D50: 2-5 micrometers of secondary particles.
Example 2
Example 1 provides a method for preparing a ferromanganese phosphate precursor, and in this example, the obtained ferromanganese phosphate precursor is Mn 0.6 Fe 0.4 （PO 4 ） 1.04 With Mn 0.6 ：Fe 0.4 :P 1.04 The mol ratio of Mn element in manganese carbonate, fe element in iron powder and phosphorus element in phosphoric acid is 0.6:0.4:1.04, the preparation method of this example includes the following steps:
adding 2.45kg of 85% H3PO4 into deionized water to prepare an acid solution, adding 0.43kg of metallic iron (Fe) powder with the particle size of less than 100 mu m into the mixed acid solution, stirring and soaking under the heating (50 ℃) condition for reaction for 5 hours, then adding 1.35 of manganese carbonate, continuously stirring and soaking for 2 hours, and then adding the materials into a high-energy mill for grinding for 5 hours.
And (3) carrying out spray drying treatment on the ground material in a centrifugal sprayer to obtain spherical particles with the particle size of 5-15 microns.
Calcining the spray-dried spherical particle powder in an air furnace at 700 ℃, and preserving heat for 5 hours.
And (3) performing jet milling treatment on the calcined material to obtain the ferromanganese phosphate precursor with the monocrystal particle size of 80-100 nanometers and the secondary particle D50: 2-5 micrometers.
Example 3
In this embodiment, an adopted ferromanganese phosphate precursor is Mn 0.6 Fe 0.4 （PO 4 ） 1.02 With Mn 0.6 ：Fe 0.4 :P 1.02 The mol ratio of Mn element in manganese carbonate, fe element in iron powder and phosphorus element in phosphoric acid is 0.6:0.4:1.02, the preparation method of the embodiment comprises the following steps:
1kg of ferromanganese phosphate precursor and 0.25kg of lithium carbonate are mixed and then ground, and the grinding particle size D50 is 0.2-0.4 mu m;
carrying out spray drying treatment on the ground material in a centrifugal sprayer to obtain spherical particles of 10-25 mu m;
calcining the spray-dried spherical particle powder in a nitrogen furnace at 650 ℃, and preserving heat for 13 hours;
and (3) carrying out jet milling treatment on the calcined material to obtain the lithium iron manganese phosphate anode material with the size of single crystal particles of 80-200 nanometers and the D50 of secondary crushed particles of 1.5-2.3 micrometers.
Example 4
In this embodiment, a ferromanganese phosphate precursor adopted is Mn 0.6 Fe 0.4 （PO 4 ） 1.04 With Mn 0.6 ：Fe 0.4 :P 1.04 The mol ratio of Mn element in manganese carbonate, fe element in iron powder and phosphorus element in phosphoric acid is 0.6:0.4:1.04, the preparation method of the embodiment comprises the following steps:
1.2kg of ferromanganese phosphate precursor and 0.306kg of lithium carbonate are mixed and then ground, and the grinding particle size D50 is 0.2-0.4 mu m;
carrying out spray drying treatment on the ground material in a centrifugal sprayer to obtain spherical particles of 10-25 mu m;
calcining the spray-dried spherical particle powder in a nitrogen furnace at 700 ℃, and preserving heat for 9 hours;
and (3) carrying out jet milling treatment on the calcined material to obtain the lithium iron manganese phosphate anode material with the single crystal particle size of 200-400 nanometers and the secondary crushed particle D50 of 1.3-1.8 micrometers.
Example 5
The embodiment provides a preparation method of a battery, which comprises the following steps:
step 1, stirring and mixing the lithium iron manganese phosphate positive electrode material obtained in the embodiment 3, a conductive agent, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain positive electrode slurry;
specifically, the positive electrode slurry includes 100 parts by weight of a lithium iron manganese phosphate positive electrode material, 1 part by weight of a conductive agent, 2.5 parts by weight of PVDF, and 100 parts by weight of NMP; the conductive agent comprises Carbon Nanotubes (CNTs) and graphene in a mass ratio of 1.
Step 2, coating the anode slurry on an aluminum foil to obtain an anode material;
wherein the aluminum foil is an aluminum foil with the diameter of 12mm, and the anode slurry is coated on one surface of the aluminum foil.
Step 3, drying the positive electrode material under vacuum, pressing the dried positive electrode material into a sheet shape, wherein the thickness of the sheet positive electrode material is less than 0.3mm, and the sheet positive electrode material is a positive electrode sheet;
and 4, assembling the sheet-shaped positive electrode material, the metal lithium sheet, the diaphragm and the electrolyte into the button cell for carrying out capacity test and charge-discharge test.
And (4) assembling the positive plate obtained in the step (3) and the graphite negative electrode into a 2025 button type full cell for low-temperature capacity test.
The gram capacity of the obtained battery is 152mAh/g, the cycle number is 3800 times, and the capacity retention rate at-40 ℃ is 80%.
Although the present application has been described with reference to the preferred embodiments, it is to be understood that the present application is not limited to the disclosed embodiments, but rather, the present application is intended to cover various modifications, equivalents and alternatives falling within the spirit and scope of the present application.

Claims (7)

1. A preparation method of a manganese iron phosphate precursor is characterized by comprising the following steps:
adding iron powder into a phosphoric acid solution, and stirring and reacting for 3-5 hours at a first temperature to obtain a first reaction mixed solution, wherein the concentration of the phosphoric acid solution is 75-85 mol/L;
adding manganese carbonate into the first reaction mixed solution, and stirring and reacting for 2-5 hours at a first temperature to obtain a second reaction mixed solution;
grinding the second reaction mixed solution to obtain a grinding mixed solution;
carrying out spray granulation treatment on the grinding treatment mixed liquid to obtain manganese iron phosphate particles;
calcining the ferromanganese phosphate particles to obtain a ferromanganese phosphate precursor;
wherein the molar ratio of manganese element in the manganese carbonate, iron element in the iron powder and phosphorus element in the phosphoric acid solution is 0.6.
2. The method for preparing a ferromanganese phosphate precursor according to claim 1, wherein the milling time of the milling treatment is 5 to 8 hours.
3. The method for preparing a ferromanganese phosphate precursor according to claim 1, wherein the sintering temperature of the calcination treatment is 500 to 700 ℃, and the holding time of the calcination treatment is 5 to 8 hours.
4. The method of preparing an ferromanganese phosphate precursor according to claim 1, further comprising:
and carrying out airflow crushing treatment on the manganese phosphate iron precursor to obtain a powdery manganese phosphate iron precursor.
5. The method of preparing an ferromanganese phosphate precursor as claimed in claim 1, wherein the first temperature is 50 ℃.
6. A preparation method of a lithium iron manganese phosphate positive electrode material is characterized by comprising the following steps:
obtaining a ferromanganese phosphate precursor by the preparation method according to any one of claims 1 to 5;
mixing a lithium source with the manganese iron phosphate precursor, and performing primary calcination treatment on the obtained mixture at a second temperature to obtain a manganese iron phosphate precursor;
and performing airflow crushing treatment on the lithium iron manganese phosphate precursor, and performing secondary calcination treatment on the crushed lithium iron manganese phosphate precursor at a third temperature to obtain the lithium iron manganese phosphate anode material.
7. A preparation method of a lithium iron manganese phosphate positive electrode material is characterized by comprising the following steps:
obtaining a ferromanganese phosphate precursor by the preparation method according to any one of claims 1 to 5;
and mixing a lithium source with the ferromanganese phosphate precursor, and calcining the obtained mixture at a fourth temperature to obtain the lithium iron manganese phosphate anode material.
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