PARTICLE STRUCTURE OF CATHODE MATERIAL AND PREPARATION METHOD THEREOF
20220255073 · 2022-08-11
Inventors
Cpc classification
H01M4/62
ELECTRICITY
C01P2004/61
CHEMISTRY; METALLURGY
C01P2004/80
CHEMISTRY; METALLURGY
H01M4/525
ELECTRICITY
C01G53/50
CHEMISTRY; METALLURGY
H01M4/131
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M2004/021
ELECTRICITY
H01M10/0525
ELECTRICITY
International classification
H01M4/525
ELECTRICITY
H01M10/0525
ELECTRICITY
H01M4/131
ELECTRICITY
Abstract
A particle structure of cathode material and a preparation method thereof is provided. Firstly, a precursor for forming a core is provided. The precursor includes at least nickel, cobalt and manganese. Secondly, a metal salt and a lithium ion compound are provided. The metal salt includes at least potassium, aluminum and sulfur. After that, the metal salt, the lithium ion compound and the precursor are mixed, and a mixture is formed. Finally, the mixture is subjected to a heat treatment step, and a cathode material particle structure is formed to include the core, a first coating layer coated on the core and a second coating layer coated on the first coating layer. The core includes potassium, aluminum and a Li—M—O based material. The first coating layer includes potassium and aluminum, and a potassium content of the first coating layer is higher than a potassium content of the core. The second coating layer includes sulfur.
Claims
1. A preparation method of a particle structure of cathode material, comprising steps of: (a) providing a precursor configured to form a core, wherein the precursor comprises at least nickel, cobalt and manganese; (b) providing a metal salt and a lithium ion compound, wherein the metal salt comprises at least potassium, aluminum and sulfur; (c) mixing the metal salt, the lithium ion compound and the precursor to form a mixture; and (d) subjecting the mixture to a heat treatment step to form the particle structure of cathode material, wherein the particle structure of cathode material comprises the core, a first coating layer and a second coating layer, wherein the core comprises potassium, aluminum and a Li—M—O based material, wherein M is one selected from the group consisting of nickel, cobalt, manganese, magnesium, titanium, aluminum, tin, chromium, vanadium, molybdenum and a combination thereof, wherein the first coating layer is coated on the core, and the second coating layer is coated on the first coating layer, wherein the first coating layer comprises potassium and aluminum, and a potassium content of the first coating layer is higher than a potassium content of the core, wherein the second coating layer comprises sulfur.
2. The preparation method according to claim 1, wherein the Li—M—O based material is a lithium nickel manganese cobalt oxide.
3. The preparation method according to claim 1, wherein the particle structure of cathode material has a particle size ranged from 3 μm to 10 μm.
4. The preparation method according to claim 1, wherein the particle structure of cathode material has a potassium content ranged from 0.01 mol % to 0.2 mol %, wherein the particle structure of cathode material has an aluminum content ranged from 0.01 mol % to 0.2 mol %.
5. The preparation method according to claim 1, wherein the first coating layer has a first thickness, and the second coating layer has a second thickness, wherein the first thickness is greater than the second thickness.
6. The preparation method according to claim 5, wherein the first thickness is ranged from 12 nm to 70 nm, and the second thickness is ranged from 1 nm to 3 nm, wherein the first thickness and the second thickness are obtained through analysis results of an X-ray photoelectron spectroscopy and a time-of-flight secondary ion mass spectrometer.
7. The preparation method according to claim 1, wherein the precursor is formed by a co-precipitation of a first solution and a second solution, wherein the first solution comprises at least nickel, cobalt and manganese, and the second solution comprises at least oxalic acid.
8. The preparation method according to claim 1, wherein the step (b) further comprises a step: (b1) dissolving the metal salt and the lithium ion compound in a water to form a third solution.
9. The preparation method according to claim 1, wherein the metal salt has a weight percentage relative to the precursor, and the weight percentage is ranged from 0.1 wt % to 2 wt %.
10. The preparation method according to claim 1, wherein the heat treatment step comprises a temperature-holding step, and the temperature-holding step has a temperature greater than or equal to 700° C.
11. The preparation method according to claim 1, wherein the heat treatment step further comprises a first heat treatment step and a second heat treatment step, wherein a maximum temperature of the second heat treatment step is greater than a maximum temperature of the first heat treatment step.
12. The preparation method according to claim 1, wherein the metal salt is a potassium alum.
13. A particle structure of cathode material, comprising: a core comprising potassium, aluminum and a Li—M—O based material, wherein M is one selected from the group consisting of nickel, cobalt, manganese, magnesium, titanium, aluminum, tin, chromium, vanadium, molybdenum and a combination thereof; a first coating layer coated on the core, wherein the first coating layer comprises potassium and aluminum, and a potassium content of the first coating layer is higher than a potassium content of the core; and a second coating layer coated on the first coating layer, wherein the second coating layer comprises sulfur.
14. The particle structure of cathode material according to claim 13, wherein the Li—M—O based material is a lithium nickel manganese cobalt oxide.
15. The particle structure of cathode material according to claim 13, wherein the particle structure of cathode material has a particle size ranged from 3 μm to 10 μm.
16. The particle structure of cathode material according to claim 13, wherein the particle structure of cathode material has a potassium content ranged from 0.01 mol % to 0.2 mol %, wherein the particle structure of cathode material has an aluminum content ranged from 0.01 mol % to 0.2 mol %.
17. The particle structure of cathode material according to claim 13, wherein the first coating layer has a first thickness, and the second coating layer has a second thickness, wherein the first thickness is greater than the second thickness.
18. The particle structure of cathode material according to claim 17, wherein the first thickness is ranged from 12 nm to 70 nm, and the second thickness is ranged from 1 nm to 3 nm, wherein the first thickness and the second thickness are obtained through analysis results of an X-ray photoelectron spectroscopy and a time-of-flight secondary ion mass spectrometer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0028]
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[0031]
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[0039]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0040] The present disclosure will now be described more specifically with reference to the following embodiments. It is to be noted that the following descriptions of preferred embodiments of the disclosure are presented herein for purpose of illustration and description only. It is not intended to be exhaustive or to be limited to the precise form disclosed.
[0041] Refer to
[0042] Refer to
[0043] In the embodiment, the first coating layer 20 has a first thickness H1, and the second coating layer 30 has a second thickness H2. The first thickness H1 is greater than the second thickness H2. The first thickness H1 is ranged from 12 nm to 70 nm. The second thickness H2 is ranged from 1 nm to 3 nm. Preferably but not exclusively, the first thickness H1 and the second thickness H2 are obtained through a surface analysis of an X-ray photoelectron spectroscopy (XPS) and a depth profiling analysis of a time-of-flight secondary ion mass spectrometer (TOF-SIMS). It is noted that any instrument that can perform surface analysis and depth profiling analysis, such as an Auger electron spectroscopy (AES), is suitable for obtaining the thicknesses, and the present disclosure is not limited thereto.
[0044] Refer to
[0045] Secondly, a metal salt and a lithium ion compound are provided, as shown in step S2. In the embodiment, the metal salt includes at least potassium, aluminum and sulfur. Preferably but not exclusively, the metal salt is a potassium alum (KAl(SO.sub.4).sub.2.12H.sub.2O), and the lithium ion compound is a lithium hydroxide monohydrate (LiOH.H.sub.2O).
[0046] After that, the metal salt, the lithium ion compound and the precursor are mixed, and a mixture is formed. In the embodiment, a third solution is formed by dissolving the metal salt and the lithium ion compound in a water before being mixed with the precursor, so as to improve the uniformity of the mixture. In the embodiment, the metal salt has a weight percentage relative to the precursor, and the weight percentage is ranged from 0.1 wt % to 2 wt %.
[0047] Finally, the mixture is subjected to a heat treatment step, such as calcination, and the particle structure of cathode material 1 is formed. In the embodiment, the heat treatment step further includes a temperature-holding step and a cooling step. The temperature-holding step has a temperature greater than or equal to 700° C. Preferably but not exclusively, holding the temperature at 700° C. facilitates the formation of an orderly layered structure of the particle structure of cathode material 1. The cooling step facilitates the reduction of the oxygen vacancies in the particle structure of cathode material 1. Thus, the battery performance is improved. In the embodiment, the heat treatment step further includes a first heat treatment step and a second heat treatment step. A maximum temperature of the second heat treatment step is greater than a maximum temperature of the first heat treatment step. Preferably but not exclusively, the maximum temperature of the first heat treatment step is 700° C., and the maximum temperature of the second heat treatment step is 775° C. With two-step high-temperature calcination, cation disorder degree of the particle structure of cathode material 1 is further reduced, and a better orderly layered structure is formed. Thus, the battery performance is further improved.
[0048] The following examples illustrate the preparation method and efficacy of the present disclosure.
EXAMPLE 1
[0049] A first solution and a second solution are mixed for co-precipitation, and a precursor is formed. The first solution is a solution including metal ions, which is mixed by a 0.24 M nickel sulfate hexahydrate (NiSO.sub.4.6H.sub.2O) solution, a 0.03 M cobalt sulfate heptahydrate (COSO.sub.4.7H.sub.2O) solution and a 0.03 M hydrated manganese sulfate (MnSO.sub.4.H.sub.2O) solution. The second solution is a solution including oxalic acid, which is mixed by a 0.33 M oxalic acid (H.sub.2C.sub.2O.sub.4) solution, a 0.3 M sodium hydroxide (NaOH) solution and a 0.075 M ammonia (NH.sub.4OH) solution. Preferably but not exclusively, the precursor is
Ni.sub.0.8Co.sub.0.1Mn.sub.0.1C.sub.2O.sub.4. 2H.sub.2O.
[0050] A metal salt and a lithium ion compound are dissolved in a water, and a third solution is formed. The metal salt includes at least potassium, aluminum and sulfur, Preferably but not exclusively, the metal salt is a potassium alum (KAl(SO.sub.4).sub.2.12H.sub.2O). The lithium ion compound is a lithium hydroxide monohydrate (LiOH.H.sub.2O). The weight percentage of the potassium alum relative to the precursor is 0.3 wt %.
[0051] Refer to
EXAMPLE 2
[0052] Preferably but not exclusively, a preparation method of the example 2 is similar to that of the example 1. However, in the preparation method of the example 2, the weight percentage of the potassium alum relative to the precursor is 0.5 wt %.
EXAMPLE 3
[0053] Preferably but not exclusively, a preparation method of the example 3 is similar to that of the example 1. However, in the preparation method of the example 3, the weight percentage of the potassium alum relative to the precursor is 1 wt %.
COMPARATIVE EXAMPLE
[0054] Preferably but not exclusively, potassium alum is not added in a preparation method of the comparative example.
[0055] Refer to
[0056] Refer to
[0057] Refer to
[0058] Refer to
TABLE-US-00001 TABLE 1 Capacity after 1 Capacity after 100 Capacity retention cycle (mAh/g) cycles (mAh/g) after 100 cycles Comparative 181 143 79% example Example 1 182 150 82% (0.3 wt % potassium alum) Example 2 188 162 86% (0.5 wt % potassium alum) Example 3 183 147 80% (1 wt % potassium alum)
[0059]
TABLE-US-00002 TABLE 2 Capacity after 1 Capacity after 100 Capacity retention cycle (mAh/g) cycles (mAh/g) after 100 cycles Comparative 190 142 75% example Example 1 199 160 80% (0.3 wt % potassium alum) Example 2 198 172 87% (0.5 wt % potassium alum) Example 3 198 159 80% (1 wt % potassium alum)
[0060]
[0061] As shown in table 3 below, the capacity of the comparative example after 100 cycles is 119 mAh/g, and the capacity retention is 66%. In contrast, the capacity of the example 2 after 100 cycles is 151 mAh/g, and the capacity retention is 82%. It can be concluded from the above results that the particle structure of cathode material 1 of the present disclosure facilitates the migration of lithium ions with an inner coating layer including potassium and aluminum, and avoid the reaction between the cathode material and the electrolyte with an outer coating layer including sulfur. Accordingly, the purpose of improving cycle life, capacity and stability of battery is achieved.
TABLE-US-00003 TABLE 3 Capacity after 1 Capacity after 100 Capacity retention cycle (mAh/g) cycles (mAh/g) after 100 cycles Comparative 180 119 66% example Example 1 181 132 73% (0.3 wt % potassium alum) Example 2 184 151 82% (0.5 wt % potassium alum) Example 3 177 126 71% (1 wt % potassium alum)
[0062] As stated above, a particle structure of cathode material and a preparation method thereof for improving a working voltage and a cycle life of a battery formed thereby is provided in the present disclosure. The particle structure of cathode material includes at least two coating layers, and each of the different coating layers has different element composition. Preferably but not exclusively, the at least two coating layers are a first coating layer as an inner coating layer and a second coating layer as an outer coating layer. Since the first coating layer contains potassium and aluminum, it is conducive to the migration of lithium ions. Moreover, the second coating layer contains sulfur, so that the reaction between the cathode material and the electrolyte during charging and discharging is avoided. Accordingly, the purpose of improving battery performances, such as cycle life, capacity and stability, is achieved. Preferably but not exclusively, a metal salt and a lithium ion compound are mixed and added to a precursor, and a mixture is formed. The metal salt includes potassium, aluminum and sulfur. The precursor includes nickel, cobalt and manganese. After that, the mixture is subjected to a heat treatment, and the particle structure of cathode material is formed. The particle structure of cathode material has at least two coating layers. Thicknesses and compositions of the at least two coating layers are obtained through analysis results of an X-ray photoelectron spectroscopy (XPS) and a time-of-flight secondary ion mass spectrometer (TOF-SIMS). With at least two coating layers having different compositions, such as potassium, aluminum and sulfur, respectively, the migration of lithium ions is improved, and the reaction between the cathode material and the electrolyte during charging and discharging is avoided. Preferably but not exclusively, a potassium alum in a specific ratio range is added into a precursor, and a mixture is formed. The mixture is subjected to two heat treatment steps, and the particle structure of cathode material is formed to have at least two coating layers. The particle structure of cathode material has low cation disorder degree and orderly layered structure Moreover, the preparation method of the particle structure of cathode material is simple and low costing. It is helpful of enhancing the product competitiveness of the battery formed by the particle structure of cathode material.
[0063] While the disclosure has been described in terms of what is presently considered to be the most practical and preferred embodiments, it is to be understood that the disclosure needs not be limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.