The present disclosure relates to the field of lithium ion batteries, and particularly to a lithium iron phosphate positive electrode active material, a positive electrode sheet, and a lithium ion battery.
Lithium iron phosphate material has wide use due to the high safety, low cost, environmental friendliness and other advantages. However, the lithium iron phosphate material also has obvious defects. That is, the compaction density of the lithium iron phosphate material is low, which leads to the low energy density of batteries prepared with the lithium iron phosphate material, so the demand for batteries with long battery life cannot be met. To improve the energy density of the battery, a lithium iron phosphate material having a high compaction density is needed. However, when the compaction density of the lithium iron phosphate material is increased, the electrochemical performance of the battery is often reduced.
In a first aspect, the present disclosure provides a lithium iron phosphate positive electrode active material, which includes: a first lithium iron phosphate material and a second lithium iron phosphate material. A particle size of the first lithium iron phosphate material is D1v50 μm at 50% cumulative volume distribution of the first lithium iron phosphate material, a particle size of the second lithium iron phosphate material is D2v50 μm at 50% cumulative volume distribution of the second lithium iron phosphate material, D1v50 is in a range of 0.3-0.95, and D2v50 is in a range of 1.0-3.5. Particle sizes of the lithium iron phosphate positive electrode active material are respectively Dv90 μm, Dv10 μm, and Dv50 μm at 90%, 10%, and 50% cumulative volume distribution of the lithium iron phosphate positive electrode active material, a particle size of the lithium iron phosphate positive electrode active material is Dn50 μm at 50% cumulative number distribution of the lithium iron phosphate positive electrode active material, and Dv90, Dv10, and Dv50, and Dn50 meet:
In some embodiments of the present disclosure, the maximum compaction density is 2.55-2.85 g/cm3.
In some embodiments of the present disclosure, D1v50 of the first lithium iron phosphate material is in the range of 0.4-0.85, and D2v50 of the second lithium iron phosphate material is in the range of 1.2-3.0.
In some embodiments of the present disclosure, Dv90, Dv10, Dv50, and Dn50 meet:
In some embodiments of the present disclosure, Dv50×Dn50 is in the range of 0.05-4.9.
In some embodiments of the present disclosure, Dv50 of the lithium iron phosphate positive electrode active material is in the range of 0.25-3.5.
In some embodiments of the present disclosure, the mixing weight ratio of the first lithium iron phosphate material and the second lithium iron phosphate material is in the range of 1:(1-9).
In some embodiments of the present disclosure, at least one surface of the first lithium iron phosphate material and the second lithium iron phosphate material has a carbon coating layer.
In a second aspect, the present disclosure provides a positive electrode sheet. The positive electrode sheet includes a lithium iron phosphate positive electrode active material according to the first aspect of the present disclosure.
In some embodiments of the present disclosure, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on a surface of the positive electrode current collector. The positive electrode active material layer includes the lithium iron phosphate positive electrode active material, a binder, and a conductive agent.
In some embodiments of the present disclosure, the positive electrode active material layer is formed by coating a positive electrode paste including the lithium iron phosphate positive electrode active material, the conductive agent, the binder and a solvent on the positive electrode current collector.
In a third aspect, the present disclosure provides a lithium ion battery. The lithium ion battery includes a positive electrode sheet according to the second aspect of the present disclosure.
In some embodiments of the present disclosure, the lithium ion battery further includes a negative electrode sheet, and an electrolyte solution, and a separator between the positive electrode sheet and the negative electrode sheet.
The foregoing descriptions are some implementations of the present disclosure. It should be noted that several modifications and variations can be made by those of ordinary skill in the art without departing from the principle of the present disclosure, which shall fall within the protection scope of the present disclosure.
The present disclosure provides a lithium iron phosphate positive electrode active material, which has an increased compaction density, and enables a battery prepared therewith to have good electrochemical performances.
In a first aspect, the present disclosure provides a lithium iron phosphate positive electrode active material, which includes:
In the present disclosure, two lithium iron phosphate materials having different particle sizes are used, and the particle size of the obtained positive electrode active material is made to meet a certain relation formula, to obtain that the positive electrode active material has a high compaction density (2.55 g/cm3 or higher). This promotes the improvement of the energy density of a battery prepared with this positive electrode active material. In addition, the battery prepared with this positive electrode active material has excellent electrochemical performances, particularly the cycle performance.
In some embodiments of the present disclosure, the maximum compaction density of the lithium iron phosphate positive electrode active material is 2.55 g/cm3 or higher. In some embodiments of the present disclosure, the maximum compaction density is 2.55-2.85 g/cm3. It is to be understood that the maximum compaction density of a certain material mentioned in the present disclosure refers to the maximum compaction density obtained by testing the material with a powder compaction densitometer, or the maximum available compaction density of a positive electrode sheet prepared with this material. The maximum compaction density of the positive electrode sheet refers to the corresponding compaction density of the electrode sheet when the active material particles in the positive electrode sheet are crushed under a certain pressure.
The D1v50 value of the first lithium iron phosphate material and D2v50 value of the second lithium iron phosphate material can be obtained from their respective laser particle size distribution diagrams. In an embodiment, the test instrument is a laser particle size analyzer (such as Malvern 3000). The test method can be found in GB/T 19077-2016/ISO 13320:2009 Particle size analysis-Laser diffraction methods. When the cumulative volume distribution percentage of a material is at 50%, the corresponding particle size is referred to as median particle size of the material. Similarly, the values of the particle size Dn50, Dv90, Dv10, and Dv50 of the lithium iron phosphate positive electrode active material can be obtained by determining the laser particle size distribution of a mixed powder obtained by mixing the first lithium iron phosphate material and the second lithium iron phosphate material.
In the present disclosure, D1v50<D2v50. When D1v50 of the lithium iron phosphate material is small, the lithium ion diffusion path is relatively short, and the prepared battery has a good electrical performance. When D2v50 of the lithium iron phosphate material is large, the compaction density of the positive electrode active material can be increased. When the particle sizes Dv50 of the two materials are in the above ranges, it allows that the two lithium iron phosphate materials can form a dense mass by mixing the two materials, thus improving the compaction density of the obtained positive electrode active material without compromising the cycle performance of the battery.
In some embodiments of the present disclosure, D1v50 of the first lithium iron phosphate material is in the range of 0.4-0.85, and D2v50 of the second lithium iron phosphate material is in the range of 1.2-3.0. In this case, the use of the positive electrode active material obtained by mixing the two lithium iron phosphate materials can obtain the high compaction density of the positive electrode sheet and the good electrochemical performance of the battery.
In some embodiments of the present disclosure,
is in the range of 0.2-31. In some embodiments,
In some embodiments of the present disclosure, Dv50×Dn50 is in the range of 0.05-4.9. In this case, the compaction density of the positive electrode active material is high, and the electrochemical performance is excellent. In some embodiments, Dv50×Dn50 may be in the range of 0.1-4.5. In some embodiments, Dv50×Dv50 may be in the range of 0.6-4.
In some embodiments of the present disclosure, Dv50 of the lithium iron phosphate positive electrode active material is in the range of 0.25-3.5. Dv50 represents the corresponding particle size when the cumulative volume distribution percentage of the positive electrode active material is at 50%. If the Dv50 value of the positive electrode active material obtained after mixing is in the above range, it allows that the positive electrode active material particles can be properly piled up, the polarization intensity of the electrode sheet is low, the lithium ion transmission speed is high during the cycle process of the battery, and the energy density of the secondary battery is high.
In the present disclosure, the mixing weight ratio of the first lithium iron phosphate material and the second lithium iron phosphate material is not particularly limited, as long as it allows that the particle size of the positive electrode active material formed by mixing the two materials meet the above relation formula. In some embodiments of the present disclosure, the mixing weight ratio of the first lithium iron phosphate material and the second lithium iron phosphate material is in the range of 1:(1-9), and further in the range of 1:(1-4). In this case, the positive electrode active material formed by mixing the two lithium iron phosphate materials can well allow the high compaction density of the electrode sheet and the good cycle performance of the battery.
In some embodiments of the present disclosure, the first lithium iron phosphate material has a carbon coating layer on the surface and/or the second lithium iron phosphate material has a carbon coating layer on the surface. The carbon coating layer can be obtained by sequentially sanding, spray drying, and sintering a mixed slurry of a phosphorus source, an iron source, a lithium source, and a carbon source. In the present disclosure, the preparation method of the two lithium iron phosphate materials is not limited. The presence of the carbon coating layer allows the first and the second lithium iron phosphate material to have good electrical conductivity, and less side reactions with the electrolyte solution. The positive electrode active material obtained by mixing the two materials has a good electrical conductivity, and the cycle performance of the battery is good.
According to the lithium iron phosphate positive electrode active material provided in the first aspect of the present disclosure, by mixing two lithium iron phosphate materials meeting the requirements of the particle size parameters, it allows that the obtained positive electrode active material has a high compaction density, and a battery prepared with the positive electrode active material has a good cycle performance and a good rate performance. The preparation method has simple process, and is easy to operate, thus being suitable for use in the large-scale production.
In a second aspect, the present disclosure provides a positive electrode sheet. The positive electrode sheet includes a lithium iron phosphate positive electrode active material according to the first aspect of the present disclosure.
In some embodiments of the present disclosure, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer arranged/disposed on a surface of the positive electrode current collector. The positive electrode active material layer includes the lithium iron phosphate positive electrode active material, a binder, and a conductive agent.
The maximum compaction density of the positive electrode sheet is 2.55 g/cm3 or higher. In some embodiments, the maximum compaction density is 2.55-2.85 g/cm3.
In some embodiments of the present disclosure, the positive electrode active material layer is formed by coating a positive electrode paste including the lithium iron phosphate positive electrode active material, the conductive agent, the binder, and a solvent on the positive electrode current collector. The solvent can be one or more of N-methylpyrrolidone (NMP), acetone, and dimethyl acetamide (DMAC). The positive electrode current collector includes any one of an aluminum foil, a carbon-coated aluminum foil and a perforated aluminum foil. The conductive agent includes, but is not limited to, one or more of carbon nanotubes, graphene carbon black, carbon fiber, and the like. The binder includes, but is not limited to, one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyacrylate, polyacrylonitrile (PAN), sodium carboxymethyl cellulose (CMC), and sodium alginate.
In a third aspect, the present disclosure provides a lithium ion battery. The lithium ion battery includes a positive electrode sheet according to the second aspect of the present disclosure.
In some embodiments of the present disclosure, the lithium ion battery further includes a negative electrode sheet, an electrolyte solution, and a separator located between the positive electrode sheet and the negative electrode sheet.
The lithium ion battery using the positive electrode sheet has a high energy density and an excellent cycle performance.
In the following, the technical solution of the present disclosure will be described in combination with embodiments.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, where when the cumulative volume distribution percentage was at 50%, the corresponding particle size was determined to be 0.56 μm, that is, D1v50 was 0.56.
A second lithium iron phosphate material LFP-2 was used, where when the cumulative volume distribution percentage was at 50%, the corresponding particle size was determined to be 1.85 μm, that is, D2v50 was 1.85.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 2:8, to obtain a lithium iron phosphate positive electrode active material LFP-3. When the cumulative volume distribution percentages of the LFP-3 material were at 10%, 50%, and 90%, the corresponding particle sizes were respectively 0.31 μm, 0.74 μm, and 4.97 μm (that is, Dv10 was 0.31, Dv50 was 0.74, and Dv90 was 4.97). When the cumulative number distribution percentage was at 50%, the corresponding particle size is 0.84 μm (that is, Dv50 was 0.84). As calculated,
and Dv50×Dn50=0.6216.
The positive electrode active material LFP-3 was prepared into a positive electrode sheet, by mixing the LFP-3 material with a binder (e.g., polyvinylidene fluoride (PVDF)) and conductive carbon black at a weight ratio of 85:5:10, adding an appropriate amount of N-methyl pyrrolidone (NMP), and mixing uniformly, to obtain a positive electrode paste. The positive electrode paste was coated on two sides of a carbon-coated aluminum foil, and dried, to obtain a positive electrode sheet. The maximum compaction density of the positive electrode sheet without particle breakage was determined. The maximum compaction density of the positive electrode sheet was determined to be 2.63 g/cm3.
Preparation of pouch lithium ion battery: The positive electrode sheet prepared with the positive electrode active material LFP-3 in Example 1 was used as a positive electrode. A graphite electrode sheet was used as a negative electrode. A polypropylene film was used as a separator. A solution containing 1.0 mol/L LiPF6 in ethylene carbonate (EC): dimethyl carbonate (DMC)=1:1 (volume ratio) was used as an electrolyte solution. After assembly, a pouch battery was obtained.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 (the concept was as described in Example 1, and would not be repeated here, hereinafter) was determined to be 0.65.
A second lithium iron phosphate material LFP-2 was used, and D2v50 (the concept was as described in Example 1, and would not be repeated here, hereinafter) was determined to be 2.5.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 3:7, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.19, Dv50 was 1.15, Dn90 was 4.97, Dn50 was 1.89,
and Dv50×Dn50=2.1735.
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Example 2 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Example 2 was determined to be 2.67 g/cm3.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 was determined to be 0.92.
A second lithium iron phosphate material LFP-2 was used, and D2v50 was determined to be 3.43.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 4:6, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.31, Dv50 was 0.89, Dv90 was 6.67, Dv50 was 4.31,
and Dv50×Dn50=3.8359.
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Example 3 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Example 3 was determined to be 2.60 g/cm3.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 was determined to be 0.15.
A second lithium iron phosphate material LFP-2 was used, and D2v50 was determined to be 1.15.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 3:7, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.17, Dv50 was 0.25, Dv90 was 6.7, Dn50 was 2.77, Dv90−Dv10/Dv50+Dv50×Dn50=26.81, and Dv50×Dn50=0.6925.
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Example 4 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Example 4 was determined to be 2.79 g/cm3.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 was determined to be 0.92.
A second lithium iron phosphate material LFP-2 was used, and D2v50 was determined to be 1.23.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 1:9, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.25, Dv50 was 0.67, Dv90 was 5.79, Dn50 was 1.32,
and Dv50×Dn50=0.8844.
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Example 5 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Example 5 was determined to be 2.83 g/cm3.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 was determined to be 0.90.
A second lithium iron phosphate material LFP-2 was used, and D2v50 was determined to be 1.12.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 1:9, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.8, Dv50 was 3.5, Dv90 was 4.23, Dv50 was 0.23,
and Dv50×Dn50=0.805.
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Example 6 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Example 6 was determined to be 2.62 g/cm3.
To highlight the beneficial effects of the present disclosure, the following comparative examples are provided.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 was determined to be 0.95.
A second lithium iron phosphate material LFP-2 was used, and D2v50 was determined to be 3.45.
The LFP-1 material and the LFP-2 material were mixed at a weight ratio of 1:9, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.94, Dv50 was 4.55, Dv90 was 7.89, Dv50 was 6.78, and
which fell outside the range of 0.16-31.1 defined in the present disclosure.
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Comparative Example 1 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Comparative Example 1 was determined to be 2.49 g/cm3.
A method for preparing a lithium iron phosphate positive electrode active material includes the following steps:
A first lithium iron phosphate material LFP-1 was used, and D1v50 was determined to be 1.24, which fell outside the range of 0.3-0.95 defined in the present disclosure.
A second lithium iron phosphate material LFP-2 was used, and D2v50 was determined to be 4.2, which fell outside the range of 1.0-3.5 defined in the present disclosure.
The LFP-1 material and the LFP-2 material were mixed at a certain weight ratio, to obtain a lithium iron phosphate positive electrode active material LFP-3. For the LFP-3 material, Dv10 was 0.87, Dv50 was 3.21, Dv90 was 8.32, Dv50 was 3.65, and
Following the method described in Example 1, the positive electrode active material LFP-3 obtained in Comparative Example 2 was prepared into a positive electrode sheet, and assembled into a pouch battery. The maximum compaction density of the positive electrode sheet in Comparative Example 2 was determined to be 2.35 g/cm3.
To provide powerful support for the beneficial effects of the present disclosure, the pouch battery of each example and comparative example were tested for the following electrochemical performance.
As can be seen from
The foregoing embodiments show only several implementations of the present disclosure and are described in detail, which, however, are not to be construed as a limitation to the scope of the present disclosure. It is to be understood that several variations and improvements can be made by those of ordinary skill in the art without departing from the idea of the present disclosure, which are all contemplated in the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be defined by the appended claims.
Number | Date | Country | Kind |
---|---|---|---|
202210139348.3 | Feb 2022 | CN | national |
This application is a continuation application of International Patent Application No. PCT/CN2023/074706, filed on Feb. 7, 2023, which is based on and claims priority to and benefits of Chinese Patent Application No. 202210139348.3 filed on Feb. 15, 2022. The entire content of all of the above-referenced applications is incorporated herein by reference.
Number | Date | Country | |
---|---|---|---|
Parent | PCT/CN2023/074706 | Feb 2023 | WO |
Child | 18802786 | US |