POSITIVE ELECTRODE MATERIAL, POSITIVE ELECTRODE PLATE AND BATTERY

Abstract

A positive electrode material includes a first lithium manganese iron phosphate material in an aggregate form, a second and third lithium manganese iron phosphate materials in an aggregate and/or single-crystal-like form, and a fourth and fifth lithium manganese iron phosphate materials in a single-crystal-like form. A particle quantity ratio of the first to fifth lithium manganese iron phosphate materials is (0.8 to 1.2):(0.8 to 1.2):(1.6 to 2.4):(6.4 to 9.6):(6.4 to 9.6), and particle size D.sub.50 relationships satisfy: D.sub.50.sup.5<D.sub.50.sup.4<D.sub.50.sup.3<D.sub.50.sup.2<D.sub.50.sup.1, D.sub.50.sup.2=aD.sub.50.sup.1, D.sub.50.sup.3=bD.sub.50.sup.1, D.sub.50.sup.4=cD.sub.50.sup.1, D.sub.50.sup.5=dD.sub.50.sup.1, and 5 μm≤D.sub.50.sup.1≤15 μm, where 0.35≤a≤0.5, 0.2≤b≤0.27, 0.17≤c≤0.18, and 0.15≤d≤0.16.

Claims

1. A positive electrode material, comprising: a first lithium manganese iron phosphate material, a second lithium manganese iron phosphate material, a third lithium manganese iron phosphate material, a fourth lithium manganese iron phosphate material and a fifth lithium manganese iron phosphate material, wherein a particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material, and the fifth lithium manganese iron phosphate material is (0.8 to 1.2):(0.8 to 1.2):(1.6 to 2.4):(6.4 to 9.6):(6.4 to 9.6), the first lithium manganese iron phosphate material is an aggregate, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material are single-crystal-like, the second lithium manganese iron phosphate material and the third lithium manganese iron phosphate material are aggregates and/or single-crystal-like, and particle size relationships thereof satisfy: D.sub.50.sup.5<D.sub.50.sup.4<D.sub.50.sup.3<D.sub.50.sup.2<D.sub.50.sup.1, D.sub.50.sup.2=aD.sub.50.sup.1, D.sub.50.sup.3=bD.sub.50.sup.1, D.sub.50.sup.4=cD.sub.50.sup.1, D.sub.50.sup.5=dD.sub.50.sup.1, and 5 μm≤D.sub.50.sup.1≤15 μm, wherein, D.sub.50.sup.1 to D.sub.50.sup.5 represent particle sizes D.sub.50 of the first lithium manganese iron phosphate material to the fifth lithium manganese iron phosphate material, a is in a range of 0.35 to 0.5 inclusive, b is in a range of 0.2 to 0.27 inclusive, c is in a range of 0.17 to 0.18 inclusive, and d is in a range of 0.15 to 0.16 inclusive.

2. The positive electrode material according to claim 1, wherein a is in a range of 0.41 to 0.45 inclusive; and b is in a range of 0.21 to 0.23 inclusive.

3. The positive electrode material according to claim 1, wherein a is 0.41, b is 0.23, c is 0.18, and dis 0.16.

4. The positive electrode material according to claim 1, wherein the particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material, and the fifth lithium manganese iron phosphate material is 1:1:2:8:8.

5. The positive electrode material according to claim 1, wherein a median particle size of primary particles of the aggregate is in a range of 100 nm to 500 nm inclusive.

6. The positive electrode material according to claim 1, wherein a particle size of the single-crystal-like primary particle is in a range of 0.5 m to 2.5 m inclusive.

7. A positive electrode plate, comprising a current collector and a positive electrode material layer disposed on the current collector, wherein the positive electrode material layer comprises a positive electrode material, and the positive electrode material comprises: a first lithium manganese iron phosphate material, a second lithium manganese iron phosphate material, a third lithium manganese iron phosphate material, a fourth lithium manganese iron phosphate material and a fifth lithium manganese iron phosphate material, a particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material, and the fifth lithium manganese iron phosphate material is (0.8 to 1.2):(0.8 to 1.2):(1.6 to 2.4):(6.4 to 9.6):(6.4 to 9.6), the first lithium manganese iron phosphate material is an aggregate, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material are single-crystal-like, the second lithium manganese iron phosphate material and the third lithium manganese iron phosphate material are aggregates and/or single-crystal-like, and particle size relationships thereof satisfy: D.sub.50.sup.5<D.sub.50.sup.4<D.sub.50.sup.3<D.sub.50.sup.2<D.sub.50.sup.1, D.sub.50.sup.2=aD.sub.50.sup.1, D.sub.50.sup.3=bD.sub.50.sup.1, D.sub.50.sup.4=cD.sub.50.sup.1, D.sub.50.sup.5=dD.sub.50.sup.1, and 5 μm D.sub.50.sup.1<15 μm, wherein, D.sub.50.sup.1 to D.sub.50.sup.5 represent particle sizes D.sub.50 of the first lithium manganese iron phosphate material to the fifth lithium manganese iron phosphate material, a is in a range of 0.35 to 0.5 inclusive, b is in a range of 0.2 to 0.27 inclusive, c is in a range of 0.17 to 0.18 inclusive, and d is in a range of 0.15 to 0.16 inclusive.

8. The positive electrode plate according to claim 7, wherein a is in a range of 0.41 to 0.45 inclusive; and b is in a range of 0.21 to 0.23 inclusive.

9. The positive electrode plate according to claim 7, wherein a is 0.41, b is 0.23, c is 0.18, and d is 0.16.

10. The positive electrode plate according to claim 7, wherein the particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material, and the fifth lithium manganese iron phosphate material is 1:1:2:8:8.

11. The positive electrode plate according to claim 7, wherein a median particle size of primary particles of the aggregate is in a range of 100 nm to 500 nm inclusive.

12. The positive electrode plate according to claim 7, wherein a particle size of the single-crystal-like primary particle is in a range of 0.5 m to 2.5 m inclusive.

13. A battery, comprising a positive electrode plate comprising a current collector and a positive electrode material layer disposed on the current collector, wherein the positive electrode material layer comprises a positive electrode material, and the positive electrode material comprises: a first lithium manganese iron phosphate material, a second lithium manganese iron phosphate material, a third lithium manganese iron phosphate material, a fourth lithium manganese iron phosphate material and a fifth lithium manganese iron phosphate material, a particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material, and the fifth lithium manganese iron phosphate material is (0.8 to 1.2):(0.8 to 1.2):(1.6 to 2.4):(6.4 to 9.6):(6.4 to 9.6), the first lithium manganese iron phosphate material is an aggregate, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material are single-crystal-like, the second lithium manganese iron phosphate material and the third lithium manganese iron phosphate material are aggregates and/or single-crystal-like, and particle size relationships thereof satisfy: D.sub.50.sup.5<D.sub.50.sup.4<D.sub.50.sup.3<D.sub.50.sup.2<D.sub.50.sup.1, D.sub.50.sup.2=aD.sub.50.sup.1, D.sub.50.sup.3=bD.sub.50.sup.1, D.sub.50.sup.4=cD.sub.50.sup.1, D.sub.50.sup.5=dD.sub.50.sup.1, and 5 μm D.sub.50.sup.1<15 μm, wherein, D.sub.50.sup.1 to D.sub.50.sup.5 represent particle sizes D.sub.50 of the first lithium manganese iron phosphate material to the fifth lithium manganese iron phosphate material, a is in a range of 0.35 to 0.5 inclusive, b is in a range of 0.2 to 0.27 inclusive, c is in a range of 0.17 to 0.18 inclusive, and d is in a range of 0.15 to 0.16 inclusive.

14. The battery according to claim 13, wherein a is in a range of 0.41 to 0.45 inclusive; and b is in a range of 0.21 to 0.23 inclusive.

15. The battery according to claim 13, wherein a is 0.41, b is 0.23, c is 0.18, and d is 0.16.

16. The battery according to claim 13, wherein the particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material, and the fifth lithium manganese iron phosphate material is 1:1:2:8:8.

17. The battery according to claim 13, wherein a median particle size of primary particles of the aggregate is in a range of 100 nm to 500 nm inclusive.

18. The battery according to claim 13, wherein a particle size of the single-crystal-like primary particle is in a range of 0.5 m to 2.5 m inclusive.

Description

DETAILED DESCRIPTION

[0014] While example embodiments of the present disclosure have been described above, the present disclosure is not limited thereto. It should be appreciated that some improvements and modifications can be made by those skilled in the art without departing from the technical principles of the present disclosure, which are also contemplated to be within the scope of the present disclosure.

[0015] According to an aspect of the present disclosure, an embodiment of the present disclosure provides a positive electrode material, including: a first lithium manganese iron phosphate material, a second lithium manganese iron phosphate material, a third lithium manganese iron phosphate material, a fourth lithium manganese iron phosphate material and a fifth lithium manganese iron phosphate material. A particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material is (0.8 to 1.2):(0.8 to 1.2):(1.6 to 2.4):(6.4 to 9.6):(6.4 to 9.6). The first lithium manganese iron phosphate material is an aggregate, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material are single-crystal-like, the second lithium manganese iron phosphate material and the third lithium manganese iron phosphate material are aggregates and/or single-crystal-like, and following particle size relationships thereof satisfy:

[0016] D.sub.50.sup.5<D.sub.50.sup.4<D.sub.50.sup.3<D.sub.50.sup.2<D.sub.50.sup.1, D.sub.50.sup.2=aD.sub.50.sup.1, D.sub.50.sup.3=bD.sub.50.sup.1, D.sub.50.sup.4=cD.sub.50.sup.1, D.sub.50.sup.5=dD.sub.50.sup.1, and 5 μm≤D.sub.50.sup.1≤15 μm,

[0017] Where, D.sub.50.sup.1 to D.sub.50.sup.5 represent values of particle sizes D.sub.50 of the first lithium manganese iron phosphate material to the fifth lithium manganese iron phosphate material, a value range of a is 0.35 to 0.5, a value range of b is 0.2 to 0.27, a value range of c is 0.17 to 0.18, and a value range of d is 0.15 to 0.16. The above ranges and any other ranges disclosed in this application include the boundary values unless explicitly disclaimed.

[0018] In the present disclosure, the above D.sub.50.sup.1 to D.sub.50.sup.5 can be regarded as respective particle sizes of secondary particles (if an LMFP single-crystal-like material is composed of one primary particle, it can also be regarded as a “secondary particle”). Different morphology and different particle size D.sub.50 values of LMFP materials affect the length of path for diffusion of lithium ions in the materials, the amount of dissolved Mn and the cycle stability. The first lithium manganese iron phosphate material in the aggregate form has many grain boundaries, indicating a large energy barrier for diffusion of lithium ions therein. However, the particle size of primary particles of the material is small, indicating a short path for diffusion of lithium ions. The fourth and fifth lithium manganese iron phosphate materials in the single-crystal-like form have fewer grain boundaries and a small diffusion energy barrier, and have a large primary particle size, indicating a long path for diffusion of lithium ions therein. Therefore, under the joint action of the above morphology requirements and D.sub.50 particle size requirements, the above-mentioned five lithium manganese iron phosphate materials have basically consistent charge and discharge capabilities.

[0019] In the present disclosure, if the D.sub.50.sup.1 of the first lithium manganese iron phosphate material is too small, the compaction density of the positive electrode plate may still be low even when the above particles with different sizes are used in combination. In addition, if the D.sub.50.sup.1 of the first lithium manganese iron phosphate material is too small, the particle size of the primary particle is lower, and the specific surface area of the first lithium manganese iron phosphate material increases, increasing the side reactions between the first lithium manganese iron phosphate material and the electrolyte solution, affecting the structural stability of the first lithium manganese iron phosphate material during the cycle process, and resulting in an increased dissolved Mn content. If the D.sub.50.sup.1 of the first lithium manganese iron phosphate material is too large, the compaction density of the positive electrode plate is decreased to a certain extent. In addition, according to the relationship between the particle sizes of the particles, the particle sizes of the fourth and fifth lithium manganese iron phosphate materials in the single-crystal-like form are also very large, which leads to a longer path for the diffusion of lithium ions in these two materials, resulting in degraded rate performance of the battery.

[0020] If the values of a, b, c and d are not in the above ranges, the particle sizes of the five lithium manganese iron phosphate materials may not be well distinguished from each other, and the compaction density of the positive electrode plate manufactured with these materials may not be increased by multiple filling of LMFP materials with different particle size levels.

[0021] According to an embodiment of the present disclosure, the value range of a is 0.41≤a≤0.45, and the value range of b is 0.21≤b≤0.23. According to another embodiment of the present disclosure, a is 0.41, b is 0.23, c is 0.18, and d is 0.16.

[0022] It should be noted that, “the second lithium manganese iron phosphate material and the third lithium manganese iron phosphate material are aggregates and/or single-crystal-like respectively” can be understood as that the second lithium manganese iron phosphate material is in the aggregate or single-crystal-like or contains both aggregate and single-crystal-like materials, and similarly, the third lithium manganese iron phosphate material is in the aggregate or single-crystal-like or contains both aggregate and single-crystal-like materials.

[0023] According to an embodiment of the present disclosure, in the positive electrode material, a median particle size of primary particles of the aggregate is in a range of 100 nm to 500 nm. That is, a median particle size of the primary particles of the first lithium manganese iron phosphate material is in the range of 100 nm to 500 nm, a median particle size of the primary particles of the second lithium manganese iron phosphate material in the aggregate form is in the range of 100 nm to 500 nm, and a median particle size of the primary particles of the third lithium manganese iron phosphate material in the aggregate form is in the range of 100 nm to 500 nm.

[0024] With the design of the same particle size of secondary particles, the aggregates of which the median particle sizes are in the above range can avoid the increase of specific surface area of secondary particles caused by the increase of the number of primary particles constituting secondary particles of the LMFP material, thereby avoiding the increase of area where side reactions occur. Meanwhile, in the compression process of the positive electrode plate, the breakage rate of secondary particles can be reduced, thereby avoiding the problem of formation of new interfaces to degrade the battery performance. In addition, the aggregates of which the median particle sizes are in the above range can shorten the diffusion path of lithium ions in the secondary particle materials, thereby avoiding the problems of low capacity of LMFP materials as well as increased impedance and reduced power performance of the battery. Also, the aggregates of which the median particle sizes are in the above range can prevent the primary particles of the aggregates from being too small to increase side reactions between the aggregates and the electrolyte solution, thereby avoiding the deterioration of the structural stability of the aggregates and the increase of the dissolved Mn content. In addition, the diffusion path of lithium ions in the aggregates is more appropriate, achieving good rate performance of the battery.

[0025] According to an embodiment of the present disclosure, the particle size of the single-crystal-like primary particle is in a range of 0.5 m to 2.5 m. This can prevent the single-crystal-like primary particle from being too large to lengthen the diffusion path of lithium ions and degrade the rate performance of the battery. According to an embodiment of the present disclosure, the particle size of the primary particles of the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material can both be in a range of 1.5 m to 2.5 m, the median particle size of the primary particles of the third lithium manganese iron phosphate material in the single-crystal-like form is in a range of 1.0 m to 1.5 m, and the median particle size of the primary particles of the second lithium manganese iron phosphate material in the single-crystal-like form is in a range of 0.5 m to 1.0 km. In this way, the five lithium manganese iron phosphate materials can have more consistent charge and discharge capabilities.

[0026] In the present disclosure, a particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material may be (0.8 to 1.2):(0.8 to 1.2):(1.6 to 2.4):(6.4 to 9.6):(6.4 to 9.6). When the particle quantity ratio of the above five lithium manganese iron phosphate materials is in the above range, the positive electrode plate manufactured with the above positive electrode material can have a higher compaction density (2.55 g/cm.sup.3 or more). According to an embodiment of the present disclosure, the particle quantity ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material is 1:1:2:8:8. In this way, the positive electrode plate can have an extremely high compaction density (e.g., about 2.9 g/cm.sup.3). Further, a mass ratio between the first lithium manganese iron phosphate material, the second lithium manganese iron phosphate material, the third lithium manganese iron phosphate material, the fourth lithium manganese iron phosphate material and the fifth lithium manganese iron phosphate material may be 100:14:2.5:0.5:0.3.

[0027] According to an embodiment of the present disclosure, the surfaces of the first to fifth lithium manganese iron phosphate materials may further be provided with a carbon cladding layer, so as to improve the electrical conductivity of the lithium manganese iron phosphate materials.

[0028] According to an embodiment of the present disclosure, molar ratios of manganese to iron (Mn/Fe ratios) in the first lithium manganese iron phosphate material to the fifth lithium manganese iron phosphate material are in a range of 1.0 to 7.4. The Mn/Fe ratios in the five lithium manganese iron phosphate materials can be equal or not equal, which is not specifically limited.

[0029] The LMFP material in the aggregate form can be prepared by the following method:

[0030] (1) Raw materials (i.e., manganese source, iron source, phosphorus source, lithium source, and carbon source) for synthesizing LMFP are mixed according to a certain mass ratio, and the mixed materials are wet ground with water to a particle size of 40 nm to 60 nm.

[0031] (2) The ground wet material is spray dried to obtain a dry powder.

[0032] (3) The dry powder is sintered in an atmosphere with an oxygen concentration less than 150 ppm. The sintering process includes a first heating stage, a first constant temperature stage, a second heating stage, a second constant temperature stage, and a cooling stage in sequence. In the first heating stage, the temperature is raised from the room temperature to a first constant temperature (e.g., 400° C.), where the heating time can be 2.5 h to 3.5 h. The holding time of the first constant temperature is 3.5 h to 5.5 h. In the second heating stage, the temperature is raised from the first constant temperature (e.g., 400° C.) to a second constant temperature (e.g., 700° C.), where the heating time can be 2.5 h to 4.0 h. The holding time of the second constant temperature can be 2.5 h to 4.5 h. In the cooling stage, the temperature is lowed from the second constant temperature (such as 750° C.) to about 50° C., where the cooling time is 5.5 h to 7.5 h.

[0033] (4) The sintered material is crushed by airflow. The pressure of airflow crushing can be 3 MPa to 5 MPa, and the time of airflow crushing can be 2 h to 3 h. Then, screening and grading are carried out to obtain a material with the required particle size D.sub.50.

[0034] According to an embodiment of the present disclosure, in the step (1), the mixing time may be 0.5 h to 1.5 h. According to another embodiment of the present disclosure, the mixing time in the step (1) may be 0.75 h to 1.2 h.

[0035] According to an embodiment of the present disclosure, in the step (1), manganese iron phosphate can be used as the manganese source, iron source and phosphorus source at the same time. The lithium source may include, but is not limited to, at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, and lithium acetate. The carbon source includes, but is not limited to, at least one of glucose, sucrose, starch, fructose, citric acid, ascorbic acid, and polyethylene glycol.

[0036] According to an embodiment of the present disclosure, in the step (1), the material may be ground using a grinding medium with a diameter of 0.6 mm to 0.8 mm to a particle size of 50 m or below, and then ground using a grinding medium with a diameter of 0.1 mm to 0.3 mm to a particle size of 40 nm to 60 nm.

[0037] According to an embodiment of the present disclosure, in the step (2), the inlet temperature during the spray drying may be 150° C. to 200° C. According to another embodiment of the present disclosure, the inlet temperature during the spray drying is 160° C. to 180° C.

[0038] The preparation methods of the LMFP materials in the single-crystal-like form are different from those of the LMFP materials in the aggregate form in the first constant temperature and the second constant temperature during sintering and the pressure during airflow crushing.

[0039] For the preparation of the LMFP material in the single-crystal-like form, in the sintering process, in the first heating stage, the temperature is raised from the room temperature to a first constant temperature (e.g., 450° C.), where the heating time can be 2.5 h to 3.5 h. The holding time of the first constant temperature is 3.5 h to 5.5 h. In the second heating stage, the temperature is raised from the first constant temperature (e.g., 450° C.) to a second constant temperature (e.g., 750° C.), where the heating time can be 2.5 h to 4.0 h. The holding time of the second constant temperature can be 2.5 h to 4.5 h. In the cooling stage, the temperature is lowed from the second constant temperature (such as 750° C.) to about 50° C., where the cooling time is 6.5 h to 8.5 h. In addition, for the preparation of the LMFP material in the single crystal-like form, after the sintering, the airflow crushing can be carried out at a pressure of 5 MPa to 8 MPa for 2 h to 3 h. Then, screening and grading are carried out to obtain a material with the required particle size.

[0040] According to a second aspect of the present disclosure, an embodiment of the present disclosure further provides a positive electrode slurry, including the positive electrode material, a conductive agent, a binder, and a solvent.

[0041] According to an embodiment of the present disclosure, a mass ratio of the positive electrode material, the conductive agent and the binder is 100:(0.5 to 5):(0.5 to 5). According to another embodiment of the present disclosure, the solid content in the positive electrode slurry is 10 wt % to 80 wt %.

[0042] The conductive agent includes at least one of carbon nanotubes, conductive carbon black and graphene. According to another embodiment of the present disclosure, the conductive agent includes carbon nanotubes, conductive carbon black and graphene. The conductive agent of three dimensions can make the positive electrode material layer formed by the positive electrode slurry have good electrical conductivity. Further, a mass ratio of carbon nanotubes, conductive carbon black and graphene can be 6:5:2.

[0043] The binder is a conventional choice in the battery field and may be, for example, selected from one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polyimide (PI), polyacrylic acid (PAA), polyacrylate, polyolefin, sodium carboxymethyl cellulose (CMC) and sodium alginate. The PVDF can refer to a copolymer obtained by copolymerizing vinylidene fluoride with an olefin compound containing a polar group. The polar group includes at least one of carboxyl group, epoxy group, hydroxyl group and sulfonic acid group. The existence of the polar group can enhance the peel strength between the positive electrode coating formed by the positive electrode slurry and the current collector.

[0044] The solvent is a conventional choice in the battery field, and is, for example, N-methylpyrrolidone (NMP).

[0045] According to an embodiment of the present disclosure, the positive electrode slurry can further contain a dispersant to better improve the dispersibility and stability of the positive electrode slurry. The dispersant can be polyvinylpyrrolidone (PVP), etc.

[0046] During the preparation of the positive electrode slurry, the first LMFP material, the second LMFP material and the third LMFP material with a larger particle size can be directly added in the form of powder, so as to prevent sedimentation during slurry mixing. The fourth LMFP material and the fifth LMFP material with a smaller particle size can be added in the form of powder or slurry. Each slurry includes an organic solvent, and may further includes a dispersant, such as PVP.

[0047] According to a third aspect of the present disclosure, an embodiment of the present disclosure further provides a positive electrode plate, including a current collector and a positive electrode material layer arranged on the current collector, where the positive electrode material layer includes the positive electrode material described in the first aspect of the present disclosure, or is obtained by coating the positive electrode slurry. Therefore, the positive electrode plate including the positive electrode material has a high compaction density.

[0048] The positive electrode material layer further includes a conductive agent and a binder. The positive electrode material layer can be formed by coating the positive electrode slurry on the current collector.

[0049] According to a fourth aspect of the present disclosure, an embodiment of the present disclosure further provides a battery, including the positive electrode plate. The battery has excellent electrical properties such as high capacity, low probability of manganese dissolution and high cycle stability.

[0050] The embodiments of the present disclosure are further described below with reference to a number of embodiments.

[0051] Preparation of Positive Electrode Material

[0052] The first LMFP material to the fifth LMFP material were respectively recorded as particle 1, particle 2, particle 3, particle 4 and particle 5. Five types of particles were respectively selected according to the particle size and the particle quantity ratio in Table 1 for subsequent mixing to obtain positive electrode materials corresponding to different examples. The chemical formula of LMFP in the particles 1 to 5 is LiMn.sub.0.65Fe.sub.0.35PO.sub.4.

[0053] A method for testing the particle size of each LMFP material was as follows. A laser particle size analyzer Malvern 2000/3000 was used as the test equipment. The LMFP materials were dispersed in deionized water for 10 min, where the refractive index of particles was 1.74. The particle size D.sub.50 of each LMFP material was obtained by testing.

[0054] A method for testing the particle quantities of LMFP materials with different particle sizes was as follows. LMFP materials with different particle sizes were approximately spherical. The mass of a single sphere was calculated according to the particle size Dso and a bulk density (about 3.6 g/cm.sup.3) of each particle. The particle quantities of the LMFP materials with different particle sizes were controlled by controlling the feeding mass of the LMFP materials with different particle sizes.

[0055] A method for testing the median particle size of primary particles of each LMFP material was as follows. Scanning electron microscope (SEM) images of the LMFP materials at magnification of 10000 times were taken. The sizes of about 300 primary particles were measured manually, and a quantity distribution was made to obtain the median particle size of primary particles.

[0056] Preparation of positive electrode slurry: An organic solvent NMP and a binder PVDF were added at a certain ratio into a mixer. After stirring for 1 h, a conductive agent (which is a mixture of carbon tubes, conductive carbon black and graphene at a mass ratio of 0.6:0.5:0.3) was added into the mixer. The mixture was stirred for 30 min, and then the particles 1, 2 and 3 were added in the form of powders. After stirring for 1.5 h, PVP-containing NMP slurries of the particles 4 and 5 were added. The mixture was stirred for 1.5 h, and sieved to obtain a positive electrode slurry. In the positive electrode slurry, the mass ratio of the positive electrode material composed of the particles 1 to 5, the conductive agent, the binder PVDF and the organic solvent NMP was 100:2:2:30.

[0057] Preparation of positive electrode plate: Each of the positive electrode slurries corresponding to the examples was coated on two side surfaces of an aluminum foil. After drying, a positive electrode material layer is formed on the aluminum foil to obtain an uncompressed positive electrode plate. The uncompressed positive electrode plate is made into a size of 40*100 mm, and then compressed by a large hydraulic press to obtain a compressed positive electrode plate. The compaction density of the positive electrode plate can be calculated according to the areal density of the positive electrode plate and the thickness after compression. The results are shown in Table 2.

[0058] Preparation of battery: First, the positive electrode slurry corresponding to each example was prepared into a single-sided positive electrode plate with an areal density of 2.0 g/dm.sup.2 and a compaction density of 2.65 g/cm.sup.3. Each single-sided positive electrode plate is manufactured into a 2025 button cell.

[0059] First, the positive electrode slurry corresponding to each example was prepared into a double-sided positive electrode plate with an areal density of 4.0 g/dm.sup.2 and a compaction density of 2.65 g/cm.sup.3. Then a double-sided negative electrode plate with an areal density of 2.1 g/dm.sup.2 and a compaction density of 1.60 g/cm.sup.3 was provided. A PP film is used as a separator to assemble a 053450 whole cell.

[0060] The specific capacity of each button cell was tested. The rate performance and the amount of Mn dissolved in the negative electrode during the cycle of each whole cell were tested. The results are shown in Table 2.

[0061] A method for testing the specific capacity was as follows. The button cell corresponding to each example was charged to a voltage of 4.3 V at a 0.1 C constant current and constant voltage, where the cut-off current was 0.05 C. Then the button cell is discharged to 2.5 V at a 0.1 C constant current and constant voltage. The charge and discharge cycles were carried out for three times. The specific capacity of the battery was calculated by dividing the discharge capacity after the third cycle by the dressing amount of the positive electrode material layer on the positive electrode plate.

[0062] A method for testing the rate performance is: At 25° C., the whole cell corresponding to each example was first charged to 4.2 V at a 0.2 C constant current, and then discharged to 2.5 V at 0.2 C and 5 C constant currents respectively. The ratio of the discharge capacity at 5 C to the discharge capacity at 0.2 C was calculated. The ratio is used to measure the rate performance of the battery.

[0063] A method for testing the amount Mn dissolved in the negative electrode was as follows. At 45° C., the whole cell corresponding to each example was charged to 4.3 V at a 1 C constant current, and then discharged to 2.5 V at a 1 C constant current. After the charge and discharge cycles were carried out for 500 times, the cell was dissembled and the Mn content in the negative electrode material of the negative electrode plate was tested. The content of Mn was measured by an inductively coupled plasma-emission spectrometer (ICP).

[0064] In addition, to make the beneficial effects of the technical solutions of the present disclosure prominent, positive electrode materials of comparative examples 1 to 10 were further provided, and the parameters of each LMFP material used in the positive electrode materials are shown in Table 1. The performance of the prepared electrode plates and batteries are shown in Table 2.

TABLE-US-00001 TABLE 1 Parameters of positive electrode materials in examples and comparative examples Median Particle Particle size of primary size D.sub.50 of Particle Particle Particle Particles in Experiment No. Particle/μm size ratio morphology quantity ratio aggregate Example 1 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 4.5 b = 0.23 Particle 2 = aggregate c = 0.18 Particle 3 = single crystal-like d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 2 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.23 Particle 2 = aggregate c = 0.18 Particle 3 = single crystal-like d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 3 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 13 b = 0.23 Particle 2 = aggregate c = 0.18 Particle 3 = single crystal-like d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 4 Particle a = 0.35 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.20 Particle 2 = aggregate c = 0.18 Particle 3 = single crystal-like d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 5 Particle a = 0.50 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.27 Particle 2 = aggregate c = 0.18 Particle 3 = single crystal-like d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 6 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.23 Particle 2 = aggregate c = 0.15 Particle 3 = aggregate d = 0.12 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 7 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.23 Particle 3 = single crystal-like d = 0.20 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 8 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 9 Particle a = 0.45 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 10 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.21 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 11 Particle a = 0.45 Particle 1 = aggregate 1:1:2:8:8 200 1 = 8 b = 0.21 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 12 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 450 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 13 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 100 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 14 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 500 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 15 Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 550 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 16 Particle a = 0.41 Particle 1 = aggregate 1.2:1.2:2.4:8:8 200 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 17 Particle a = 0.41 Particle 1 = aggregate 0.8:0.8:1.6:8:8 200 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Example 18 Particle a = 0.41 Particle 1 = aggregate 1:1:2:6.4:9.6 200 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 Example 1 1 = 2.5 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 Example 2 1 = 18 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.75 Particle 1 = aggregate 1:1:2:8:8 200 Example 3 1 = 8 b = 0.35 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.25 Particle 1 = aggregate 1:1:2:8:8 200 Example 4 1 = 8 b = 0.15 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 Example 5 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.28 Particle 3 = aggregate d = 0.23 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:1:2:8:8 200 Example 6 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.10 Particle 3 = aggregate d = 0.08 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:2:4:8:8 200 Example 7 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:1:2:12:15 200 Example 8 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:0.5:0.8:8:8 200 Example 9 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like Comparative Particle a = 0.41 Particle 1 = aggregate 1:1:2:4:3 200 Example 10 1 = 8 b = 0.23 Particle 2 = single crystal-like c = 0.18 Particle 3 = aggregate d = 0.16 Particle 4 = single crystal-like Particle 5 = single crystal-like

TABLE-US-00002 TABLE 2 Performance parameters of positive electrode plates and batteries in examples and comparative examples C500-negative Positive electrode Specific Rate 5 electrode Experiment plate compaction capacity C/0.2 C manganese No. density g/cm.sup.3 mAh/g % content/ppm Example 1 2.75 165 91 390 Example 2 2.9 166 90 360 Example 3 2.8 165 89 320 Example 4 2.68 165 85 380 Example 5 2.71 165 92 340 Example 6 2.67 165 90 390 Example 7 2.73 165 85 380 Example 8 2.75 165 85 380 Example 9 2.73 166 87 320 Example 10 2.72 164 84 350 Example 11 2.69 161 85 360 Example 12 2.69 161 85 320 Example 13 2.65 164 89 420 Example 14 2.71 161 85 310 Example 15 2.7 160 84 320 Example 16 2.85 166 90 390 Example 17 2.81 164 87 370 Example 18 2.86 165 89 360 Comparative 2.2 164 88 1000 Example 1 Comparative 2.35 154 70 390 Example 2 Comparative 2.41 162 85 580 Example 3 Comparative 2.26 163 85 350 Example 4 Comparative 2.41 159 80 330 Example 5 Comparative 2.36 162 85 390 Example 6 Comparative 2.45 165 90 390 Example 7 Comparative 2.05 161 81 350 Example 8 Comparative 2.15 162 83 380 Example 9 Comparative 2.48 164 88 390 Example 10

[0065] As can be seen from Tables 1 and 2, when the positive electrode materials in Examples 1 to 18 satisfy the requirements on the particle morphology, particle size relationship and particle quantity ratio in the present disclosure, the compaction density of the positive electrode plate can be 2.65 g/cm.sup.3 or more, and can reach up to 2.9 g/cm.sup.3, and the specific capacity of the battery is not significantly reduced, enabling the battery to have a high energy density. In addition, the positive electrode materials of the above-mentioned examples can also make the battery have excellent rate performance, for example, the ratio of the discharge capacity at 5 C to the discharge capacity 0.2 C is 84% to 92%, and the amount of Mn dissolved in the negative electrode of the battery after 500 cycles at 45° C. is low, not exceeding 420 ppm.

[0066] In addition, it can be seen from the comparison between Comparative Examples 1 and 2 and Examples 1 to 3 that if the first LMFP material is too small, the compaction of the positive electrode plate is decreased even if multiple particle sizes are used in combination, and the dissolved Mn content of the negative electrode of the battery is greatly increased. If the first LMFP material is too large, the compaction density of the positive electrode plate is decreased to a certain extent, and the rate performance of the battery is significantly reduced.

[0067] It can be seen from the comparison between Comparative Examples 3 to 6 and Example 2 that if the ratios a, b, c, and d of the particle sizes Dso between the second LMFP material to the fifth LMFP material and the first LMFP material are not within the range defined above, the positive electrode plate manufactured with the materials does not have a high compaction density. It can be seen from the comparison between Comparative Examples 7 to 10 and Example 2 that if the particle number ratio of the five LMFP materials is not within the ranges defined above, the compaction density of the positive electrode plate is significantly reduced.

[0068] The above-described embodiments are merely illustrative of several implementations of the present disclosure, but does not limit the scope of the present disclosure. It should be pointed out that for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present disclosure, which are all falling within the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure is defined by the appended claims.