Nickel-rich cathode material with damascene thermally stable nanoparticles

Abstract

A cathode electrode includes a cathode current collector and a cathode active material layer including a plurality of nickel-containing cathode active material particles and a plurality of nanoparticles mechanically inlaid on an outer surface of the plurality of cathode active material particles to form inlaid cathode active material particles.

Description

Technical Field

[0001] The present disclosure relates to cathode materials for battery cells, and more particularly to nickel-rich cathode materials having embedded thermally stable nanoparticles. Background Art

[0002] The information provided in this section is intended to generally introduce the background of the present disclosure. To the extent that work currently named as inventors is described in this section, and aspects of the specification that may not have been otherwise identified as prior art at the time of filing, are not admitted, either explicitly or implicitly, as prior art to the present disclosure.

[0003] The present disclosure relates to cathode materials for battery cells, and more particularly to nickel-rich cathode materials having embedded thermally stable nanoparticles.

[0004] Electric vehicles (EVs), such as battery electric vehicles (BEVs), hybrid vehicles, and / or fuel cell vehicles, include one or more motors and a battery system including one or more battery cells, modules, and / or battery packs. A power control system is used to control the charging and / or discharging of the battery system during charging and / or driving.

[0005] The battery cell includes a cathode electrode, an anode electrode, a separator and an electrolyte arranged in a housing. The cathode electrode includes a cathode active material layer (including cathode active material) arranged on a cathode current collector. The anode electrode includes an anode active material layer (including anode active material) arranged on an anode current collector. Summary of the invention

[0006] The cathode electrode includes a cathode current collector and a cathode active material layer, wherein the cathode active material layer comprises a plurality of cathode active material particles containing nickel and a plurality of nanoparticles, wherein the plurality of nanoparticles are mechanically embedded on the outer surfaces of the plurality of cathode active material particles to form a plurality of embedded cathode active material particles.

[0007] In other features, the plurality of cathode active material particles comprises a nickel-containing rock salt layered oxide. The plurality of cathode active material particles are selected from LiNi x Mn y Co 1-x-y O2、LiN x Co y Al 1-x-y O2、LiNi x Co y Mn z Al 1-x-y-z O2、LiNi x Mn y Al 1-x-y O2、LiNi x Mn1-x O2 and LiNiO2. The mass ratio of the plurality of nanoparticles to the mosaic cathode active material particles is 1% to 25%.

[0008] In other features, the plurality of nanoparticles are selected from olivine type, spinel type, MnNiO2 type and combinations thereof. The plurality of nanoparticles are selected from LiVOPO4, LMFP, AlPO4, CoPO4, LiTi2(PO4)3, LMO, LNMO, LiMn 0.7 Ni 0.3 O2 and combinations thereof. The plurality of nanoparticles comprises a selected from LiMn x Fe 1-x PO4、LiMn 0.7 Fe 0.3 PO4、LiMn 0.6 Fe 0.4 PO4、LiMn 0.8 Fe 0.2 PO4、LiMn 0.75 Fe 0.25 PO4, and LMFP in combination thereof. The plurality of nanoparticles includes doped LMFP.

[0009] In other features, the plurality of nanoparticles include LMFP and the particle size of the LMFP is 10 nm to 1000 nm. The plurality of nanoparticles include LMFP and the tap density of the LMFP is 0.3 g / cc to 2.0 g / cc. The plurality of nanoparticles include LMFP and the specific surface area of ​​the LMFP is 3 m 2 / g to 50m 2 / g.

[0010] In other features, a carbon coating is disposed on the outer surface of the plurality of embedded cathode active material particles. The carbon coating comprises at least one of carbon and N-doped carbon. The carbon coating accounts for 0.5 wt % to 10 wt % of the embedded cathode active material particles.

[0011] A method for manufacturing a cathode electrode for a battery includes providing a plurality of cathode active material particles containing nickel; and mechanically embedding a plurality of nanoparticles on the outer surface of the cathode active material particles to form embedded cathode active material particles.

[0012] In other features, the method includes creating a mixture including mosaic cathode active material particles, a conductive additive, and a binder; and coating a cathode current collector with the mixture.

[0013] In other features, the method includes forming a carbon coating on the mosaic cathode active material particles.

[0014] In other features, the cathode active material particles are selected from LiNi x Mn y Co 1-x-y O2、LiN x Co y Al 1-x-y O2、LiNi x Co y Mn z Al 1-x-y-z O2、LiNi x Mn y Al 1-x-y O2、LiNi x Mn 1-x O2 and LiNiO2. The plurality of nanoparticles are selected from olivine type, spinel type, MnNiO2 type and combinations thereof. The plurality of nanoparticles are selected from LiVOPO4, LMFP, AlPO4, CoPO4, LiTi2(PO4)3, LMO, LNMO, LiMn 0.7 Ni 0.3 O2 and its combinations.

[0015] In other features, the plurality of nanoparticles comprises doped LMFP.

[0016] The present invention provides the following solutions:

[0017] Solution 1. A cathode electrode, comprising:

[0018] a cathode current collector; and

[0019] The cathode active material layer includes a plurality of cathode active material particles containing nickel and a plurality of nanoparticles, wherein the plurality of nanoparticles are mechanically embedded on the outer surfaces of the plurality of cathode active material particles to form a plurality of embedded cathode active material particles.

[0020] Option 2. A cathode electrode according to Option 1, wherein the plurality of cathode active material particles comprise a nickel-containing rock salt layered oxide.

[0021] Option 3. The cathode electrode according to Option 1, wherein the plurality of cathode active material particles are selected from LiNi x Mn y Co 1-x-y O2、LiN x Co y Al 1-x-y O2、LiNi x Co y Mn z Al 1-x-y-z O2、LiNi x Mn y Al 1-x-yO2、LiNi x Mn 1-x O2 and LiNiO2.

[0022] Option 4. The cathode electrode according to Option 1, wherein the mass ratio of the plurality of nanoparticles to the embedded cathode active material particles is 1% to 25%.

[0023] Option 5. A cathode electrode according to Option 1, wherein the plurality of nanoparticles are selected from olivine type, spinel type, MnNiO2 type and combinations thereof.

[0024] Scheme 6. The cathode electrode according to Scheme 1, wherein the plurality of nanoparticles are selected from LiVOPO4, LMFP, AlPO4, CoPO4, LiTi2(PO4)3, LMO, LNMO, LiMn 0.7 Ni 0.3 O2 and its combinations.

[0025] Option 7. The cathode electrode according to Option 1, wherein the plurality of nanoparticles comprises a selected from LiMn x Fe 1- x PO4、LiMn 0.7 Fe 0.3 PO4、LiMn 0.6 Fe 0.4 PO4、LiMn 0.8 Fe 0.2 PO4、LiMn 0.75 Fe 0.25 PO4, and LMFP in their combinations.

[0026] Option 8. A cathode electrode according to Option 1, wherein the plurality of nanoparticles comprise doped LMFP.

[0027] Option 9. The cathode electrode according to Option 1, wherein the plurality of nanoparticles comprises LMFP, and the particle size of the LMFP is 10 nm to 1000 nm.

[0028] Embodiment 10. The cathode electrode according to Embodiment 1, wherein the plurality of nanoparticles comprises LMFP, and the tap density of the LMFP is 0.3 g / cc to 2.0 g / cc.

[0029] Solution 11. The cathode electrode according to Solution 1, wherein the plurality of nanoparticles comprises LMFP, and the specific surface area of ​​the LMFP is 3 m 2 / g to 50m 2 / g.

[0030] Option 12. The cathode electrode according to Option 1 further includes a carbon coating arranged on the outer surface of the plurality of mosaic cathode active material particles.

[0031] Option 13. A cathode electrode according to Option 12, wherein the carbon coating comprises at least one of carbon and N-doped carbon.

[0032] Option 14. A cathode electrode according to Option 12, wherein the mass ratio of the carbon coating to the mosaic cathode active material particles is 0.5 wt% to 10 wt%.

[0033] Embodiment 15. A method for manufacturing a cathode electrode for a battery, comprising:

[0034] providing a plurality of cathode active material particles comprising nickel; and

[0035] A plurality of nanoparticles are mechanically embedded on the outer surface of the cathode active material particles to form embedded cathode active material particles.

[0036] Solution 16. The method according to Solution 15 further includes:

[0037] producing a mixture comprising the mosaic cathode active material particles, a conductive additive, and a binder; and

[0038] The cathode current collector is coated with the mixture.

[0039] Option 17. The method according to Option 15 also includes forming a carbon coating on the embedded cathode active material particles.

[0040] Scheme 18. The method according to Scheme 15, wherein:

[0041] The cathode active material particles are selected from LiNi x Mn y Co 1-x-y O2、LiN x Co y Al 1-x-y O2、LiNi x Co y Mn z Al 1-x-y-z O2、LiNi x Mn y Al 1-x-y O2、LiNi x Mn 1-x O2 and LiNiO2; and

[0042] The plurality of nanoparticles are selected from olivine type, spinel type, MnNiO2 type and combinations thereof.

[0043] Scheme 19. The method according to Scheme 15, wherein the plurality of nanoparticles are selected from LiVOPO4, LMFP, AlPO4, CoPO4, LiTi2(PO4)3, LMO, LNMO, LiMn 0.7 Ni 0.3 O2 and its combinations.

[0044] Option 20. A method according to Option 19, wherein the plurality of nanoparticles comprise doped LMFP.

[0045] Further areas of applicability of the present disclosure will become apparent from the detailed description, claims and drawings.The detailed description and specific examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The present disclosure will be more fully understood through the detailed description and accompanying drawings, in which:

[0047] Figure 1 is a side cross-sectional view of an example of a battery cell according to the present disclosure, the battery cell including a cathode electrode having a nickel-rich cathode active material including mosaic nanoparticles, an anode electrode, and a separator disposed in a battery cell housing;

[0048] Figure 2 is a graph illustrating the heat flow of a Ni-rich cathode active material such as NMCA as a function of temperature;

[0049] Figure 3 is a graph illustrating the variation of cell temperature and cell voltage over time for an NMCA cathode electrode and a graphite anode;

[0050] Figure 4 is a side cross-sectional view of a nickel-rich particle of a cathode active material including embedded thermally stable nanoparticles according to the present disclosure;

[0051] Figure 5 is a side cross-sectional view of a nickel-rich particle of a cathode active material including mosaic thermally stable nanoparticles and a carbon coating according to the present disclosure;

[0052] Figure 6 is a side cross-sectional view of a portion of a mechanical fusion machine for embedding thermally stable nanoparticles on the outer surface of nickel-rich particles of a cathode active material according to the present disclosure;

[0053] Figure 7 is a flow chart of a method for embedding thermally stable nanoparticles into nickel-rich particles of a cathode active material according to the present disclosure;

[0054] FIG. 8A to FIG. 8Cis a scanning electron microscope (SEM) image showing the outer surface of nickel-rich particles, nanoparticles, and / or nanoparticles embedded in nickel-rich particles of cathode active material according to the present disclosure; and

[0055] Fig. 9 is a graph showing an example of heat flow as a function of temperature for a nickel-rich cathode active material having embedded nanoparticles according to the present disclosure.

[0056] Among the drawings, reference numerals may be repeated to identify similar and / or identical elements. DETAILED DESCRIPTION

[0057] Although battery cells according to the present disclosure are shown in the context of an electric vehicle, the battery cells may be used in stationary applications and / or other applications.

[0058] As described above, the battery cell includes a cathode electrode, an anode electrode, a separator, and an electrolyte arranged in a housing. The cathode electrode includes a cathode active material layer (including a cathode active material) arranged on a cathode current collector. In some examples, the cathode active material includes a nickel-rich (Ni-rich) cathode material. Nickel-rich cathode active materials such as NCMA, NCA, and NMC811 are thermally stable because they decompose below 300°C and produce molecular oxygen (O2). When O2 is released, it reacts with flammable battery contents and increases the likelihood of thermal events such as thermal runaway.

[0059] The present disclosure relates to nickel-rich cathode active materials, which include thermally stable nanoparticles (e.g., LMFP) mechanically embedded on the outer surface of the nickel-rich cathode active material to enhance the thermal performance of the battery. The interface between the nanoparticles and the outer surface of the nickel-rich cathode active material exhibits a strong fusion force to mechanically maintain the structure. The nanoparticles improve thermal stability and will not peel off during electrode manufacturing or cycling. For example, a cathode active material including a Ni-rich cathode material having 5 wt% nanoparticles (e.g., LMFP) provides a 9% reduction in heat generation when in contact with an electrolyte during differential scanning calorimetry (DSC) testing.

[0060] Reference now Figure 1The battery cell 10 includes C cathode electrodes 20, A anode electrodes 40, and S separators 32 arranged in a predetermined order in a battery cell stack 12 located in a housing 50, wherein C, S, and A are integers greater than zero. The C cathode electrodes 20-1, 20-2, ..., and 20-C include a cathode active material layer 24 arranged on one or both sides of a cathode current collector 26. The cathode active material layer 24 includes a Ni-rich cathode active material with embedded thermally stable nanoparticles and / or a nickel-rich cathode active material with embedded thermally stable nanoparticles and a carbon coating, as will be further described below.

[0061] A anode electrodes 40-1, 40-2, ... and 40-A include an anode active material layer 42 disposed on one or both sides of an anode current collector 46. In some examples, the anode active material layer 42 and / or the cathode active material layer 24 are free-standing electrodes that are disposed adjacent to (or attached to) the cathode current collector 26 and / or the anode current collector 46, respectively. In some examples, the anode active material layer 42 and / or the cathode active material layer 24 include a coating that includes one or more active materials, one or more conductive fillers / additives, and / or one or more binder materials applied to the current collector.

[0062] In some examples, the cathode current collector 26 and / or the anode current collector 46 include metal foil, metal mesh and / or expanded metal. In some examples, the cathode current collector 26 and / or the anode current collector 46 are made of one or more materials selected from copper, stainless steel, brass, bronze, zinc, aluminum and / or their alloys. The external tabs 28 and 48 are connected to the current collectors of the cathode electrode and the anode electrode, respectively, and can be arranged on the same side or opposite sides of the battery stack 12. The external tabs 28 and 48 are connected to the terminals of the battery cells.

[0063] Reference now Figure 2 and Figure 3 , showing the thermal performance of nickel-rich cathode active materials such as NMCA (without embedded thermally stable nanoparticles). Figure 2 In the , heat flow is shown as a function of temperature of the nickel-rich cathode active material during the DSC test (as shown by the solid line S). In this example, the NCMA cathode was tested at 100% SOC in the presence of an electrolyte. The temperature was increased to 300°C at a rate of 5°C / min. At temperatures between 200°C and 230°C, significant heat flow occurred with the release of O2. In contrast, LMFP was thermally stable during the test up to 300°C (as shown by the dashed line D). Figure 3 In FIG. 5 , the cell temperature and the cell voltage are shown as a function of time for a NMCA cathode electrode and a graphite anode.

[0064] Reference now Figure 4 and Figure 5 , showing an example of a cathode active material with mechanically embedded thermally stable nanoparticles. Figure 4 In the embodiment, the embedded cathode active material 100 includes Ni-rich particles 110 of the cathode active material and mechanical embedded nanoparticles 114 on the outer surface thereof. Figure 5 In the embodiment, the intercalated cathode active material 110 includes Ni-rich particles 110 of cathode active material containing mechanical intercalated nanoparticles 114 and a carbon coating 118 disposed on an outer surface thereof.

[0065] Reference now Figure 6 , the mechanical fusion machine 200 can be used to mechanically embed thermally stable nanoparticles on the outer surface of the nickel-rich particles of the cathode active material. The mechanical fusion machine 200 includes a rotor 216 that rotates (e.g., in a direction 224). The mechanical fusion machine 200 includes an inner surface and a pressure head 208, and the pressure head 208 includes a shaft 210 connected to the head 214. When the rotor 216 rotates, a mixture 217 of nickel-rich cathode active material and nanoparticles is pressed against the inner surface of the rotor 216 by centrifugal force 220. The head 214 of the pressure head 208 presses the mixture 217 against the inner surface of the rotor 216 to mechanically fuse the nanoparticles into the nickel-rich cathode active material. In some examples, the rotor 216 rotates at a speed of 2000rpm to 4000rpm (e.g., 3000rpm) for a predetermined time period of 3 to 10 minutes (e.g., 5 minutes).

[0066] Reference now Figure 7 , a method 300 for embedding thermally stable nanoparticles into Ni-rich particles of a cathode active material is shown. At 310, the method includes placing a mixture of nickel-rich cathode active material and thermally stable nanoparticles into a mechanical fusion machine. At 314, the thermally stable nanoparticles are pressed into the nickel-rich cathode active material (e.g., in a mechanical fusion machine).

[0067] At 318, the nickel-rich cathode active material with the mosaic nanoparticles is optionally coated with a carbon coating. In some examples, the carbon coating comprises carbon or N-doped carbon. In some embodiments, the nickel-rich cathode active material with the mosaic thermally stable nanoparticles is annealed at a temperature of 550° C. to 750° C. for a predetermined period of 1 to 3 hours in the presence of a carbon source. In some examples, the carbon source is an organic carbon source. In some examples, the carbon source is selected from sucrose, glucose and / or citric acid.

[0068] Reference now FIG. 8A to FIG. 8C, showing a scanning electron microscope (SEM) view of the outer surface of nickel-rich particles of a cathode active material, thermally stable nanoparticles, and thermally stable nanoparticles embedded in the nickel-rich particles of the cathode active material. The thermally stable embedded nanoparticles are uniformly embedded on the outer surface of the cathode active material.

[0069] Reference now Fig. 9 , during DSC testing, the heat flow of a nickel-rich cathode active material with embedded thermally stable nanoparticles (at 520) is shown as a function of temperature compared to the same cathode active material without embedded nanoparticles (at 510). In this example, the embedded particles comprise 5 wt % LMFP embedded in 95 wt % NCMA (e.g., a loading of about 5 mAh / cm 2 NCMA active material, conductive additive and PVDF binder). In this example, the cathode electrode was tested at 100% SOC with electrolyte. The temperature was increased to 300°C at a rate of 5°C / min. It can be seen that the NCMA cathode with embedded nanoparticles has a heat flow reduction of about 9% at a temperature of 200°C to 230°C compared to the NCMA cathode without embedded nanoparticles.

[0070] In some examples, the cathode active material includes a nickel-rich rock salt layered oxide. Examples of nickel-rich rock salt layered oxides include LiNi x Mn y Co 1-x-y O2(NMC)811、LiN x Co y Al 1-x-y O2(NCA), LiNi x Co y Mn z Al 1-x-y-z O2(NCMA), LiNi x Mn y Al 1-x-y O2(NMA), LiNi x Mn 1-x O2(NM) and Li 1x NiO2 (LNO). In some examples, the nickel-rich cathode active material includes primary and secondary single-sized particles or bimodal nickel-rich cathode materials. In some examples, the primary particles have a D of 1 μm to 20 μm (e.g., 3 μm to 6 μm). 50 size, and the secondary particles have a D of 3 μm to 15 μm 50 size.

[0071] In some examples, the cathode electrode is manufactured using a dry process. In some examples, the cathode active material layer includes a mosaic cathode active material combined with a conductive additive and a binder. In some examples, the mixture is sheared, pressed and / or heated, and then coated on a cathode current collector.

[0072] In some examples, the ratio of the mosaic nanoparticles on the nickel-rich cathode active material is 1% to 25% by weight. In some examples, the ratio of the mosaic nanoparticles on the nickel-rich cathode active material is 2% to 15% by weight. In some examples, the calculation of the ratio is shown in Table 1 below:

[0073]

[0074] In some examples, the nanoparticles are selected from olivine type, spinel type, MnNiO2 type or a combination thereof. Examples of olivine type include LiVOPO4, LMFP, AlPO4, CoPO4 and LiTi2(PO4)3. Examples of spinel type include LMO and LNMO. Examples of MnNiO2 type include LiMn 0.7 Ni 0.3 O2.

[0075] In some examples, LMFP may include LiMn x Fe 1-x PO4(0<x≤1), LiMn 0.7 Fe 0.3 PO4、LiMn 0.6 Fe 0.4 PO4、LiMn 0.8 Fe 0.2 PO4、LiMn 0.75 Fe 0.25 PO4. In some examples, the LMFP particles are doped. Examples of doped LMFP particles include LiMn 0.7 Mg 0.05 Fe 0.25 PO4 and LiMn 0.75 Al 0.05 Fe 0.2 PO4.

[0076] In some examples, the LMFP particle size is 10 nm to 1000 nm. In some examples, the LMFP particle size is 50 nm to 300 nm. In some examples, the LMFP tap density is 0.3 g / cc to 2.0 g / cc. In some examples, the LMFP tap density is 0.4 g / cc to 0.9 g / cc. In some examples, the LMFP specific surface area is 3 m 2 / g to 50m 2 / g. In some examples, the LMFP has a specific surface area of ​​15m2 / g to 35m 2 / g. In some examples, the coating accounts for 0.5 wt% to 10 wt%. In some examples, the coating accounts for 1.5 wt% to 3 wt%.

[0077] The foregoing description is essentially only exemplary and is absolutely not intended to limit the present disclosure, its application or use. The broad teachings of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be limited thereto, because after studying the drawings, the specification and the following claims, other modifications will become apparent. It should be understood that one or more steps in the method may be implemented in different orders (or simultaneously) without changing the principles of the present disclosure. In addition, although each embodiment is described above as having certain features, any one or more features described with respect to any embodiment of the present disclosure may be implemented in any other embodiment and / or combined with the features of any other embodiment, even if the combination is not explicitly described. In other words, the embodiments are not mutually exclusive, and the mutual replacement of one or more embodiments is still within the scope of the present disclosure.

[0078] Various terms are used to describe the spatial and functional relationships between elements (e.g., between modules, circuit elements, semiconductor layers, etc.), including "connected," "engaged," "coupled," "adjacent," "next to," "on top of," "on," "under," and "disposed." Unless explicitly described as "directly," when describing the relationship between a first element and a second element in the above disclosure, the relationship can be a direct relationship in which no other intervening elements exist between the first element and the second element, or an indirect relationship in which one or more intervening elements exist between the first element and the second element (spatially or functionally). The phrase "at least one of A, B, and C" as used herein should be interpreted to mean a logical (A or B or C) using a non-exclusive logical OR, and should not be interpreted to mean "at least one A, at least one B, and at least one C."

[0079] In the drawings, the direction of the arrows, as shown by arrows, generally demonstrates the flow of information (such as data or instructions) related to the diagram. For example, when component A and component B exchange various information but the information transmitted from component A to component B is related to the diagram, the arrow may point from component A to component B. Such a unidirectional arrow does not mean that no other information is transmitted from component B to component A. In addition, for the information transmitted from component A to component B, component B may send a request for the information to component A or a receipt of the information.

Claims

1. A cathode electrode, comprising: cathode current collector; and The cathode active material layer includes a plurality of cathode active material particles containing nickel and a plurality of nanoparticles, wherein the plurality of nanoparticles are mechanically embedded on the outer surfaces of the plurality of cathode active material particles to form a plurality of embedded cathode active material particles. 2 . The cathode electrode according to claim 1 , wherein the plurality of cathode active material particles comprise a nickel-containing rock-salt layered oxide.

3. The cathode electrode according to claim 1, wherein the plurality of cathode active material particles are selected from LiNi x Mn y Co 1-x-y O2、LiN x Co y Al 1-x-y O2、LiNi x Co y Mn z Al 1-x-y-z O2、LiNi x Mn y Al 1-x-y O2、LiNi x Mn 1-x O2 and LiNiO2. 4 . The cathode electrode according to claim 1 , wherein the mass ratio of the plurality of nanoparticles to the mosaic cathode active material particles is 1% to 25%.

5. The cathode electrode according to claim 1, wherein the plurality of nanoparticles are selected from olivine type, spinel type, MnNiO2 type and combinations thereof.

6. The cathode electrode according to claim 1, wherein the plurality of nanoparticles are selected from the group consisting of LiVOPO4, LMFP, AlPO4, CoPO4, LiTi2(PO4)3, LMO, LNMO, LiMn 0.7 Ni 0.3 O2 and its combinations.

7. The cathode electrode according to claim 1, wherein the plurality of nanoparticles comprises a x Fe 1-x PO4、LiMn 0.7 Fe 0.3 PO4、LiMn 0.6 Fe 0.4 PO4、LiMn 0.8 Fe 0.2 PO4、LiMn 0.75 Fe 0.25 PO4, and LMFP in their combinations.

8. The cathode electrode of claim 1, wherein the plurality of nanoparticles comprises doped LMFP. 9 . The cathode electrode according to claim 1 , wherein the plurality of nanoparticles comprises LMFP, and a particle size of the LMFP is 10 nm to 1000 nm.

10. The cathode electrode of claim 1, wherein the plurality of nanoparticles comprises LMFP, and the tap density of the LMFP is 0.3 g / cc to 2.0 g / cc.

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