Patent Application
20230207783
The present disclosure relates to a cathode material and a preparation method thereof, and more particularly to a carbon-coated cathode material and a preparation method thereof for improving a discharge performance of a secondary battery.
In recent years, with blooming development of electronic products, the demand for portable and reusable secondary batteries is gradually increasing. Among different types of secondary batteries, lithium-ion secondary batteries have great development potential with characteristics of high energy density, light weight, high charge/discharge cycle life, and no memory effect.
As a cathode material for a lithium-ion secondary battery, lithium metal phosphate material with olivine structure has advantages of high structural stability, high cycle life and high safety. However, the olivine structure also leads to disadvantages of low electrical conductivity and low lithium ion diffusion coefficient. With the disadvantages, the electrode polarization of the lithium ion secondary battery occurs during high-current charging and discharging, and the battery performance is reduced.
Therefore, there is a need to provide a carbon-coated cathode material and a preparation method thereof for improving a discharge performance of a secondary battery.
An object of the present disclosure is to provide a carbon-coated cathode material and a preparation method thereof for improving a discharge performance of a secondary battery. The carbon-coated cathode material includes a lithium metal phosphate particle and a carbon coating layer, and the carbon coating layer is coated on the lithium metal phosphate particle. The carbon coating layer is formed by, for example, two heat treatments. Two carbon sources such as carbohydrate are added in the two heat treatments, respectively. A first carbon coating portion is formed on the lithium metal phosphate particle by adding the first carbon source in the first heat treatment. With the first carbon coating portion, the second carbon source added in the second heat treatment is easily adhered on the surface of the particle through the cohesive force between the same substances, and the uniform carbon coating layer is formed after the second heat treatment. Preferably but not exclusively, the weight of the first carbon source is equal to or less than the weight of the second carbon source. The first carbon source has a first weight percentage relative to the lithium metal phosphate particle, and the first weight percentage of the first carbon source is equal to or less than 0.5 wt %. The second carbon source has a second weight percentage relative to the lithium metal phosphate particle, and the second weight percentage of the second carbon source is ranged from 0.4 wt % to 2 wt %. By adding less carbon in the first heat treatment, the first carbon coating portion with a dot-like structure is formed. The dot-like structure facilitates the adherence of the second carbon source added later. Each carbon dot of the dot-like structure has a median diameter ranged from 10 nm to 50 nm. The median diameter is obtained by an analysis of a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Furthermore, by controlling the weight of added carbon, the problem of decreased lithium-ion transfer rate due to excessive addition of carbon is prevented, and the discharge performance of the secondary battery is ensured. Preferably but not exclusively, the first heat treatment has a first highest temperature ranged from 500° C. to 700° C., so as to facilitate the nucleation of lithium metal phosphate particles and the cracking of the first carbon source. The preparation method of the carbon-coated cathode material of the present disclosure is simple, and the carbon-coated cathode material formed thereby has good discharge performance. Specifically, the carbon-coated cathode material maintains high capacity at different charge and discharge rates (C-rate).
In accordance with an aspect of the present disclosure, a carbon-coated cathode material with two carbon coating portions added in two heat treatments and incrementally is provided. The carbon-coated cathode material includes a lithium metal phosphate particle and a carbon coating layer. The carbon coating layer is coated on the lithium metal phosphate particle. The carbon coating layer is formed by a first heat treatment and a second heat treatment. A first carbon source is added in the first treatment, and a second carbon source is added in the second heat treatment. The first carbon source has a first weight percentage relative to the lithium metal phosphate particle. The second carbon source has a second weight percentage relative to the lithium metal phosphate particle. The first weight percentage of the first carbon source is equal to or less than the second weight percentage of the second carbon source.
In an embodiment, the lithium metal phosphate particle includes a Li-M-O based material, and M is one selected from a group consisting of nickel, cobalt, manganese, magnesium, titanium, aluminum, tin, chromium, vanadium, molybdenum and a combination thereof.
In an embodiment, the first carbon source has a first median diameter ranged from 10 nm to 50 nm. The second carbon source has a second median diameter ranged from 10 nm to 50 nm. The first median diameter of the first carbon source and the second median diameter of the second carbon source are obtained by an analysis of a scanning electron microscope (SEM) or a transmission electron microscope (TEM).
In an embodiment, the lithium metal phosphate particle has a median diameter ranged from 0.05 μm to 2 μm.
In an embodiment, the first weight percentage of the first carbon source is equal to or less than 0.5 wt %.
In an embodiment, the second weight percentage of the second carbon source is ranged from 0.4 wt % to 2 wt %.
In an embodiment, a first secondary particle is formed by a lithium metal phosphate matrix and the first carbon source after the first heat treatment. The first secondary particle has a specific surface area ranged from 5 m2/g to 30 m2/g.
In an embodiment, the first secondary particle is subjected to a grinding process, and the first secondary particle has a median diameter ranged from 0.1 μm to 2 μm after the grinding process.
In an embodiment, the first heat treatment has a first highest temperature ranged from 500° C. to 700° C., and the first heat treatment has a first soaking time ranged from 1 hour to 5 hours at the first highest temperature of the first heat treatment. The second heat treatment has a second highest temperature ranged from 700° C. to 850° C., and the second heat treatment has a second soaking time ranged from 1 hour to 5 hours at the second highest temperature of the second heat treatment.
In accordance with another aspect of the present disclosure, a preparation method of a carbon-coated cathode material is provided. The preparation method of the carbon-coated cathode material includes steps of: (a) mixing a lithium metal phosphate matrix and a first carbon source and subjecting the lithium metal phosphate matrix and the first carbon source to a first heat treatment to form a first secondary particle, wherein the first secondary particle is formed by an aggregation of a plurality of first primary particles, wherein each one of the plurality of first primary particles includes a lithium metal phosphate particle and a first carbon coating portion, and the first carbon coating portion is coated on the lithium metal phosphate particle; (b) mixing the first secondary particle and a second carbon source to form a second secondary particle, wherein the second secondary particle is formed by an aggregation of a plurality of second primary particles, wherein each one of the second primary particles includes one of the first primary particles and a second carbon coating portion coated on the one of the first primary particles, wherein the first carbon source has a first weight percentage relative to the lithium metal phosphate particle, the second carbon source has a second weight percentage relative to the lithium metal phosphate particle, and the first weight percentage of the first carbon source is equal to or less than the second weight percentage of the second carbon source; and (c) subjecting the second secondary particle to a second heat treatment to form the carbon-coated cathode material, wherein the carbon-coated cathode material includes the lithium metal phosphate particle and a carbon coating layer, and the carbon coating layer is coated on the lithium metal phosphate particle, wherein the carbon coating layer is formed by the first carbon coating portion and the second carbon coating portion.
In an embodiment, the lithium metal phosphate particle includes a Li-M-O based material, and M is one selected from a group consisting of nickel, cobalt, manganese, magnesium, titanium, aluminum, tin, chromium, vanadium, molybdenum and a combination thereof.
In an embodiment, the first carbon source has a first median diameter ranged from 10 nm to 50 nm. The second carbon source has a second median diameter ranged from 10 nm to 50 nm. The first median diameter of the first carbon source and the second median diameter of the second carbon source are obtained by an analysis of a scanning electron microscope or a transmission electron microscope.
In an embodiment, the lithium metal phosphate particle has a median diameter ranged from 0.05 μm to 2 μm.
In an embodiment, the first weight percentage of the first carbon source is equal to or less than 0.5 wt %.
In an embodiment, the second weight percentage of the second carbon source is ranged from 0.4 wt % to 2 wt %.
In an embodiment, the first secondary particle has a specific surface area ranged from 5 m2/g to 30 m2/g.
In an embodiment, the step (a) further includes a step of: (a1) grinding the first secondary particle, wherein the first secondary particle has a median diameter ranged from 0.1 μm to 2 μm after grinding.
In an embodiment, the first secondary particle and the second carbon source are ground before mixing. The first secondary particle has a median diameter ranged from 0.05 μm to 2 μm after grinding. The second carbon source has a median diameter ranged from 0.05 μm to 2 μm after grinding.
In an embodiment, the first secondary particle and the second carbon source are mixed to form the second secondary particle through a spray drying process. The second secondary particle has a median diameter ranged from 2 μm to 50 μm.
In an embodiment, the first heat treatment has a first highest temperature ranged from 500° C. to 700° C., and the first heat treatment has a first soaking time ranged from 1 hour to 5 hours at the first highest temperature of the first heat treatment. The second heat treatment has a second highest temperature ranged from 700° C. to 850° C., and the second heat treatment has a second soaking time ranged from 1 hour to 5 hours at the second highest temperature of the second heat treatment.
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 this invention 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. Although the wide numerical ranges and parameters of the present disclosure are approximations, numerical values are set forth in the specific examples as precisely as possible. In addition, although the “first,” “second,” “third,” and the like terms in the claims be used to describe the various elements can be appreciated, these elements should not be limited by these terms, and these elements are described in the respective embodiments are used to express the different reference numerals, these terms are only used to distinguish one element from another element. For example, a first element could be termed a second element, and, similarly, a second element could be termed a first element, without departing from the scope of example embodiments. Besides, “and/or” and the like may be used herein for including any or all combinations of one or more of the associated listed items. Alternatively, the word “about” means within an acceptable standard error of ordinary skill in the art-recognized average. In addition to the operation/working examples, or unless otherwise specifically stated otherwise, in all cases, all of the numerical ranges, amounts, values and percentages, such as the number for the herein disclosed materials, time duration, temperature, operating conditions, the ratio of the amount, and the like, should be understood as the word “about” decorator. Accordingly, unless otherwise indicated, the numerical parameters of the present invention and scope of the appended patent proposed is to follow changes in the desired approximations. At least, the number of significant digits for each numerical parameter should at least be reported and explained by conventional rounding technique is applied. Herein, it can be expressed as a range between from one endpoint to the other or both endpoints. Unless otherwise specified, all ranges disclosed herein are inclusive.
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In the embodiment, the lithium metal phosphate particle P includes a Li-M-O based material, and M is one selected from a group consisting of nickel, cobalt, manganese, magnesium, titanium, aluminum, tin, chromium, vanadium, molybdenum and a combination thereof. In the embodiment, the first carbon source has a first median diameter ranged from 10 nm to 50 nm. The second carbon source has a second median diameter (D50) ranged from 10 nm to 50 nm. The first median diameter of the first carbon source and the second median diameter of the second carbon source are obtained by an analysis of a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Certainly, the present disclosure is not limited thereto. Other instruments that can perform surface analysis are suitable for detecting the first median diameter of the first carbon source and the second median diameter of the second carbon source. In the embodiment, the lithium metal phosphate particle has a median diameter ranged from 0.05 μm to 2 μm.
In the embodiment, the first weight percentage of the first carbon source is equal to or less than 0.5 wt %, and the second weight percentage of the second carbon source is ranged from 0.4 wt % to 2 wt %. By adding less carbon in the first heat treatment, a dot-like structure facilitating the adherence of the second carbon source added later is formed. Thereby, the problem of decreased lithium ion transfer rate due to excessive addition of carbon is prevented, and the discharge performance of the secondary battery is ensured.
In the embodiment, the first secondary particle 1 has a specific surface area ranged from 5 m2/g to 30 m2/g. Preferably but not exclusively, the specific surface area of the first secondary particle 1 is detected by a BET surface area analysis. The first secondary particle 1 is, for example, subjected to a grinding process, and the first secondary particle 1 has a median diameter ranged from 0.1 μm to 2 μm after the grinding process.
In the embodiment, the first heat treatment has a first highest temperature ranged from 500° C. to 700° C., and the first heat treatment has a first soaking time ranged from 1 hour to 5 hours at the first highest temperature of the first heat treatment. The second heat treatment has a second highest temperature ranged from 700° C. to 850° C., and the second heat treatment has a second soaking time ranged from 1 hour to 5 hours at the second highest temperature of the second heat treatment. In the embodiment, the first heat treatment has a first heating rate of 3° C./min, and the second heat treatment has a second heating rate of 3° C./min.
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Secondly, the first secondary particle 1 and the second carbon source are mixed, and the second secondary particle 2 is formed, as shown in a step S2. The second secondary particle 2 is formed by an aggregation of a plurality of second primary particles 20. Each one of the second primary particles 20 includes one of the first primary particles 10 and a second carbon coating portion C2 coated on the one of the first primary particles 10. The first carbon source has a first weight percentage relative to the lithium metal phosphate particle P. The second carbon source has a second weight percentage relative to the lithium metal phosphate particle P. The first weight percentage of the first carbon source is equal to or less than the second weight percentage of the second carbon source.
Finally, the second secondary particle 2 is subjected to the second heat treatment, and the carbon-coated cathode material 3 is formed, as shown in a step S3. The carbon-coated cathode material 3 includes the lithium metal phosphate particle P and the carbon coating layer C. The carbon coating layer C is coated on the lithium metal phosphate particle P. The carbon coating layer C is formed by the first carbon coating portion C1 and the second carbon coating portion C2.
In the embodiment, a lithium matrix of the lithium metal phosphate matrix is a lithium hydroxide (LiOH), a lithium carbonate (Li2CO3), a lithium phosphate (Li3PO4), a lithium hydrogen phosphate (Li2HPO4), or a lithium dihydrogen phosphate (LiH2PO4). A phosphorus matrix of the lithium metal phosphate matrix is a phosphoric acid (H3PO4), a ammonium dihydrogen phosphate (NH4H2PO4) or ammonium hydrogen phosphate ((NH4)2HPO4). A metal matrix of the lithium metal phosphate matrix is a metal oxide (M2O3, MO2), a phosphate (MPO4), a carbonate (MCO3), a sulfate (MSO4), a nitrate (MNO3) or a metal (M). In the embodiment, the first carbon source is a fructose. In other embodiment, the first carbon source is a carbon compound such as a carbohydrate other than fructose or an aromatic compound. The present disclosure is not limited thereto. In the embodiment, the lithium metal phosphate matrix and the first carbon source are subjected to a grinding process and a mixing process. The mixing process is, for example, a spray drying process. Preferably but not exclusively, the grinding process of the lithium metal phosphate matrix and the first carbon source is ball milling the lithium metal phosphate matrix, the first carbon source and a surfactant. The surfactant is a non-ionic surfactant.
In the embodiment, the lithium metal phosphate particle P includes a Li-M-O based material, and M is one selected from a group consisting of nickel, cobalt, manganese, magnesium, titanium, aluminum, tin, chromium, vanadium, molybdenum and a combination thereof. In the embodiment, the first carbon source has a first median diameter (D50) ranged from 10 nm to 50 nm. The second carbon source has a second median diameter ranged from 10 nm to 50 nm. The first median diameter of the first carbon source and the second median diameter of the second carbon source are obtained by an analysis of a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Certainly, the present disclosure is not limited thereto. Other instruments that can perform surface analysis are suitable for detecting the first median diameter of the first carbon source and the second median diameter of the second carbon source. In the embodiment, the lithium metal phosphate particle has a median diameter ranged from 0.05 μm to 2 μm.
In the embodiment, the first weight percentage of the first carbon source is equal to or less than 0.5 wt %, and the second weight percentage of the second carbon source is ranged from 0.4 wt % to 2 wt %. By adding less carbon in the first heat treatment, a dot-like structure facilitating the adherence of the second carbon source added later is formed. Thereby, the problem of decreased lithium ion transfer rate due to excessive addition of carbon is prevented, and the discharge performance of the secondary battery is ensured.
In the embodiment, the first secondary particle 1 has a specific surface area ranged from 5 m2/g to 30 m2/g. Preferably but not exclusively, the specific surface area of the first secondary particle 1 is detected by a BET surface area analysis. In the embodiment, the preparation method of the carbon-coated cathode material further includes a step of grinding the first secondary particle. The first secondary particle 1 has a median diameter ranged from 0.1 μm to 2 μm after grinding.
In the embodiment, the first secondary particle 1 and the second carbon source further subjected to a grinding process before mixing. The first secondary particle 1 has a median diameter ranged from 0.5 μm to 1.5 μm after the grinding process. The second carbon source has a median diameter ranged from 0.5 μm to 1.5 μm after the grinding process. Preferably but not exclusively, the grinding process of the first secondary particle 1 and the second carbon source is ball milling the first secondary particle 1, the second carbon source and a surfactant. The surfactant is a non-ionic surfactant. The first secondary particle 1 and the second carbon source are mixed to form the second secondary particle 2 through a spray drying process. The second secondary particle 2 has a median diameter ranged from 2 μm to 50 μm.
In the embodiment, the first heat treatment has a first highest temperature ranged from 500° C. to 700° C., and the first heat treatment has a first soaking time ranged from 1 hour to 5 hours at the first highest temperature of the first heat treatment. The second heat treatment has a second highest temperature ranged from 700° C. to 850° C., and the second heat treatment has a second soaking time ranged from 1 hour to 5 hours at the second highest temperature of the second heat treatment. In the embodiment, the first heat treatment has a first heating rate of 3° C./min, and the second heat treatment has a second heating rate of 3° C./min.
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The following examples illustrate the preparation method and efficacy of the present disclosure.
A lithium metal phosphate matrix, a first carbon source and a surfactant are subjected to a grinding process. After that, the lithium metal phosphate matrix, the first carbon source and the surfactant and mixed through a spray drying process. The surfactant is an alkyl polyglycoside (APG), which is a non-ionic surfactant. The grinding process of the lithium metal phosphate matrix, the first carbon source and the surfactant is a ball milling through zirconia balls. The ratio of a total weight of the lithium metal phosphate matrix, the first carbon source and the surfactant to a total weight of the zirconia balls is ranged from 1:0.45 to 1:1.31. The grinding process has a rotating speed between 250 rpm to 650 rpm and an operating time between 1 to 4 hours. The product of the grinding process is subjected to a sintering process, and a first secondary particle is formed. The sintering process is to increase the temperature to 550° C. at a heating rate of 3° C./min and then hold the temperature for 4 hours. The first secondary particle of the demonstrative example includes a lithium metal phosphate particle and a first carbon coating portion formed by the first carbon source. With an analysis of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), it is detected that the first carbon coating portion has a dot-like structure. Each carbon dot of the dot-like structure has a median diameter ranged from 10 nm to 50 nm. The first carbon source has a first weight percentage of 0.20 wt % relative to the lithium metal phosphate particle. The first secondary particle has a specific surface area ranged of 12.8 m2/g. The specific surface area of the first secondary particle is detected by a BET surface area analysis.
The first secondary particle is ground by ball milling, and the first secondary particle has a median diameter ranged from 0.1 μm to 2 μm after grinding. After that, the first secondary particle, a second carbon source and another surfactant are ground by ball milling and mixed through a spray drying process, and a second secondary particle is formed. The median diameter of the first secondary particle is ranged from 0.5 μm to 1.5 μm after being ground for the second time. The second carbon is a fructose. The another surfactant is a polyvinylpyrrolidone (PVP-K30), which is an non-ionic surfactant. The second carbon source has a second weight percentage of 1.05 wt % relative to the lithium metal phosphate particle. The second secondary particle has a median diameter ranged from 2 μm to 50 μm.
Finally, the second secondary particle is subjected to a sintering process, and a carbon-coated cathode material is formed. The temperature of the sintering process is increased to 550° C. at a heating rate of 3° C./min, and is held at 550° C. for 4 hours. After that, the temperature of the sintering process is increased to 650° C. at a heating rate of 3° C./min, and is held at 650° C. for 4 hours. Finally, the temperature of the sintering process is increased to 750° C. at a heating rate of 3° C./min, and is held at 750° C. for 3 hours. The carbon-coated cathode material of the demonstrative example has a median diameter of 30.46 μm. The carbon-coated cathode material of the demonstrative example has a specific surface area of 11.80 m2/g. The specific surface area of the carbon-coated cathode material is detected by a BET surface area analysis.
A preparation method of the comparative example and the demonstrative example thereof are roughly the same. However, a first carbon source of the comparative example has a first weight percentage of 1.01% relative to a lithium metal phosphate particle of the comparative example. A second carbon source of the comparative example has a second weight percentage of 0.28% relative to the lithium metal phosphate particle of the comparative example. A first secondary particle of the comparative example has a specific surface area of 18.24 m2/g. The specific surface area of the first secondary particle is detected by a BET surface area analysis. In other words, the total weight of the first carbon source and the second carbon source of the comparative example is approximately the same as the total weight of the first carbon source and the second carbon source of the demonstrative example. However, the first weight of the first carbon source of the comparative example is greater than the first weight of the first carbon source of the demonstrative example.
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As stated above, a carbon-coated cathode material and a preparation method thereof for improving a discharge performance of a secondary battery is provided. The carbon-coated cathode material includes a lithium metal phosphate particle and a carbon coating layer, and the carbon coating layer is coated on the lithium metal phosphate particle. The carbon coating layer is formed by, for example, two heat treatments. Two carbon sources such as carbohydrate are added in the two heat treatments, respectively. A first carbon coating portion is formed on the lithium metal phosphate particle by adding the first carbon source in the first heat treatment. With the first carbon coating portion, the second carbon source added in the second heat treatment is easily adhered on the surface of the particle through the cohesive force between the same substances, and the uniform carbon coating layer is formed after the second heat treatment. Preferably but not exclusively, the weight of the first carbon source is equal to or less than the weight of the second carbon source. The first carbon source has a first weight percentage relative to the lithium metal phosphate particle, and the first weight percentage of the first carbon source is equal to or less than 0.5 wt %. The second carbon source has a second weight percentage relative to the lithium metal phosphate particle, and the second weight percentage of the second carbon source is ranged from 0.4 wt % to 2 wt %. By adding less carbon in the first heat treatment, a first carbon coating portion with a dot-like structure is formed. The dot-like structure facilitates the adherence of the second carbon source added later. Each carbon dot of the dot-like structure has a median diameter ranged from 10 nm to 50 nm. The median diameter is obtained by an analysis of a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Furthermore, by controlling the weight of added carbon, the problem of decreased lithium ion transfer rate due to excessive addition of carbon is prevented, and the discharge performance of the secondary battery is ensured. Preferably but not exclusively, the first heat treatment has a first highest temperature ranged from 500° C. to 700° C., so as to facilitate the nucleation of lithium metal phosphate particles and the cracking of the first carbon source. The preparation method of the carbon-coated cathode material of the present disclosure is simple, and the carbon-coated cathode material formed thereby has good discharge performance. Specifically, the carbon-coated cathode material maintains high capacity at different charge and discharge rates (C-rate).
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.
| Number | Date | Country | Kind |
|---|---|---|---|
| 110148959 | Dec 2021 | TW | national |
