The entire contents of Taiwan Patent Application No. 098131582, filed on Sep. 18, 2009, from which this application claims priority, are incorporated herein by reference.
1. Field of the Invention
The present invention relates to an electrode material, and more particularly, to an electrode material of a lithium secondary cell, along with its construct, formation, and application.
2. Description of Related Art
The capacity of an electrochemical cell, such as a lithium secondary cell, should be high and very much depends on the capacitances per unit weight of its positive electrode and negative electrode materials. Taking the lithium secondary cell as example, most prior-art techniques employ crystalline metal oxide, such as LiCoO2, LiNiO2, LiMn2O4, and LiFePO4, as the positive electrode material. In these electrodes, the numbers of lithium ions intercalated in and deintercalated from the structure of the electrode material are limited; when the electrode contains too many or too few ions, the crystalline structure is easily collapsed and/or altered irreversibly, resulting in a decrease of the electrode's electroactivity thereby undesirably decreasing the capacity of the electrochemical cell.
A few prior-art approaches have employed amorphous metal oxide as the positive electrode material. By doing so, although the lithium-ion diffusion is faster, cycle-ability is superior, with the capacity of the electrochemical cell being increased as well. Generally, manufacturing costs of cells fabricated with amorphous metal oxides are significantly increased. Furthermore, considerable binder and conductive materials are required for the manufacture of such electrodes. Therefore, electrode materials of pure amorphous metal oxides have not been commercially adopted.
Accordingly, a novel electrode material with excellent electrochemical properties and less manufacturing costs is needed, or at least worthwhile of pursuit, for the commercial electrochemical cells.
An object of the present invention is to provide an electrode of novel material, forming method, and application, which has excellent electrochemical properties and a reduced manufacturing cost.
According to the object, the present invention provides an electrode material that comprises a particle-shaped crystalline metal oxide and a particle-shaped amorphous metal oxide, wherein the amorphous metal oxide is a porous material with a pore volume greater than or equal to about 0.5 cm3/g.
According to the object, the present invention provides a lithium secondary cell that comprises a first electrode, a second electrode, and an electrolyte arranged between the first electrode and the second electrode. The first electrode comprises a particle-shaped crystalline metal oxide and further comprises a particle-shaped amorphous metal oxide that is porous with a pore volume greater than or equal to about 0.5 cm3/g, and the second electrode is electrically opposite to (e.g., has an opposite electrode polarity relative to) the first electrode.
According to the object, the present invention also provides a method for forming an electrode material. The method comprises: providing a metal oxide precursor; performing a sol-gel reaction on the metal oxide precursor, the sol-gel reaction comprising an ionic liquid and a solvent and employing the ionic liquid as a template to form an amorphous metal oxide aerogel; drying the amorphous metal oxide aerogel to form a particle-shaped amorphous metal oxide; and physically mixing a particle-shaped crystalline metal oxide with the particle-shaped amorphous metal oxide to form an electrode material.
Reference will now be made in detail to specific embodiments of the invention. Examples of these embodiments are illustrated in the accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to these embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well-known components and process operations have not been described in detail in order not to obscure unnecessarily the present invention. While the drawings are illustrated in detail, it is to be appreciated that the quantity of the disclosed components may be greater or less than that disclosed, except for instances expressly restricting the amount of the components.
The present invention provides a composite material (also referred to as an “electrode material” in this text) applied to an electrode. In contrast to prior-art implementations, the composite (e.g., electrode) material of the invention is mixed from a crystalline metal oxide and an amorphous metal oxide. According to the present invention, mixing of the crystalline metal oxide and the amorphous metal oxide provides much better and more stable paths for the intercalation and deintercalation of the electrolyte ions. Accordingly, the embodiments of the present invention physically mix the particle-shaped crystalline metal oxide (being nearly 100% crystalline) with the particle-shaped amorphous metal oxide in predetermined percentages, and may further mix with binder, conductive material, and optional dopants or fillers to form the composite material. Later in this description, the composite material is used to form electrodes followed by structures and properties of the resulting electrodes being discussed.
As shown in
Because the above-mentioned method employs two different precursors and two different solvents, a total of four different vanadium pentoxide aerogels can be produced. The abbreviations, A, B, C, and D, are used to distinguish them, as shown below in Table 1, along with the crystalline vanadium pentoxide, Cm, which can be obtained from commercial products.
Then,
Uniformly mixing the particle-shaped crystalline metal oxide 21 and the particle-shaped amorphous metal oxide 22 can obtain a composite material 25, wherein the ratio of the weight of the amorphous metal oxide particle 22 to the weight of the crystalline metal oxide particle 21 is equal to or smaller than 3:7, and in one embodiment, the ratio is about 1:9. Simultaneously or later, a (electrical) conductive material 23 such as conductive carbon and a binder 24 such as polyvinylidene difluoride (PVDF), which is dissolved in a solvent such as N-Methyl-2-Pyrrolidone (NMP), may be added into the composite material 25. In this example, the weight percentage of the crystalline metal oxide 21, the amorphous metal oxide 22, the conductive material 23, and the binder 24 is about 63 wt %, 7 wt %, 20 wt %, 10 wt %, respectively, but this should not be limited. The composite material 25 is mixed uniformly for about 1 day and then coated on a substrate 26, which is made of metal or other material having a metal surface. The coating area is about 1 cm2; then, the substrate 26 may be placed in a vacuum oven to be heated at 100° C. for 6 hours to vaporize the remaining solvent from the substrate 26, and an electrode 20 is then obtained.
By the method elucidated in
Table 3 is the BET surface area analysis result of the five vanadium pentoxides listed in Table 1. The BET analysis shows that the specific surface area and the pore volume of the four vanadium pentoxide aerogels are 27 to 89 and 40 to 197 times greater than that of the crystalline metal oxide, respectively. In addition, the vanadium pentoxide aerogel A and B, that use isopropanol as the solvent has larger specific surface and larger pore volume than the corresponding aerogel, that use acetone as the solvent, C and D, respectively, at the condition using the same precursor; and the vanadium pentoxide aerogel, A, that uses vanadium oxytriisopropoxide (vip) as the precursor and isopropanol as the solvent has the largest pore volume.
The specific capacitances of the electrodes can be calculated from the cycling area (area under curve) of the CV measurement.
Then, the capacities of the electrodes are measured by charge and discharge test with constant current. The test system used for the capacity measurement is the same three-electrode-electrochemical system used for the CV measurement, where the electrolyte is 1M LiClO4/(PC/EC), and the test condition is 2 to 3.5 V (charge) and 1 C (discharge). The discharging rate C is defined as the capacity discharged per hour (mA/hr). If the nominal capacity of one cell is 1000 mAhr−1, the discharging rate 1 C is 1000 mA per hour, and discharging rate C/10 is 100 mA per hour.
The cycle-abilities of the electrodes can be calculated from
The charge/discharge test results show that the electrode E-A produced by the embodiment of the present invention has better capacity, lower irreversible capacity, and better stability. This is ascribed to the large surface area and pore volume of the amorphous vanadium pentoxide aerogel that is mixed with the crystalline vanadium pentoxide in the electrode, suppressing the collapse or structure change of the crystalline vanadium pentoxide
In the above embodiment, the composite material that comprises crystalline vanadium pentoxide and vanadium pentoxide aerogel is used to produce the electrodes. The vanadium pentoxide aerogel not only has a large specific surface area and large pore volume, providing more intercalation sites for the electrolyte ions, but also has a smaller particle size than the crystalline vanadium pentoxide, filling in the voids between the crystalline vanadium pentoxide particles, whereby the capacity and cycle-ability of the electrode is enhanced, and the irreversible capacity of the electrode is reduced under fast charge/discharge rates.
In other embodiments of the present invention, properties of the electrode can be promoted by the same theory as mentioned above. For example, other metal oxides such as titanium dioxide (TiO2), manganese dioxide (MnO2), zinc oxide (ZnO) and tin dioxide (SnO2) can be employed, and the amorphous, porous metal oxide with large specific surface and pore volume can be produced by other methods in other embodiments of the present invention. Moreover, the crystalline metal oxide and amorphous metal oxide can be two or more different metal oxides. According to the inventive concept of the present invention, the particle size of the crystalline metal oxide is not limited; its average may be microscale, nanoscale, or a uniform distribution of microscale and nanoscale, because regardless of the size of the crystalline metal oxide particles the voids between the crystalline metal oxide particles can be filled by the amorphous metal oxide particles that have similar or smaller size. In one embodiment of the present invention, the average size of the crystalline metal oxide particles is about 2 to 3 μm. In addition, one inventive implementation of the present invention requires that the amorphous metal oxide particle be a porous material having a large specific surface area and a large pore volume wherein “large pore volume” means at least equal to or larger than 0.5 cm3/g (or, ≧about 0.5 cm3/g), and preferably equal to or larger than 1 cm3/g (or, ≧about 1 cm3/g); “large specific surface area” means at least equal to or larger than 50 m2/g (or, ≧about 50 m2/g), and preferably equal to or larger than 100 m2/g (or, ≧about 100 m2/g).
In addition, the mixing ratio of the crystalline metal oxide and the amorphous metal oxide is not limited to the above embodiments; it can be other ratios. In one embodiment of the present invention, the ratio of the weight of the crystalline metal oxide to the weight of the amorphous metal oxide is about 70 wt %:30 wt %. In another embodiment, the ratio of the weight of the crystalline metal oxide to the weight of the amorphous metal oxide is about 90 wt %:10 wt % whereby the composite material with this ratio can produce an electrode having excellent properties. Other experiments of the present invention show that, when the weight percentage of the amorphous metal oxide is less than 10 wt %, such as 7 wt %, 5 wt %, and 2 wt %, of the total weight of crystalline metal oxide and amorphous metal oxide, the electrodes also have good properties.
Although the composite material of the above embodiments is mainly employed to produce the positive electrode of an electrochemical cell, it can be used to match different negative electrodes as well. For example, electrodes produced from the composite material of the embodiments can be used as the positive electrode of a rocking chair lithium cell or a lithium cell. Hence, different dopants or fillers may be added into the composite material for adjusting the properties of the electrodes. For example, the dopants or fillers may comprise ionic liquid, metals, lithium ions, lithium salts, and other materials capable of being intercalated/deintercalated by the lithium ion, such as LiCoO2, LiNiO2, LiMn2O4, and LiFePO4. Further, other experiments of the present invention reveal that when the crystalline metal oxide or the amorphous metal oxide contains crystal water the properties of the electrode may be better.
The above disclosure shows that the properties of the electrode can be significantly improved by adding a little amorphous metal oxide with large pore volume into the electrode material, whereby the manufacturing cost is substantially reduced compared with that of an electrode produced from pure amorphous metal oxide; therefore, the electrode material and its application have potential as the best candidate for a new generation of electrode materials.
Although specific embodiments have been illustrated and described, it will be appreciated by those skilled in the art that various modifications may be made without departing from the scope of the present invention, which is intended to be limited solely by the appended claims.
Number | Date | Country | Kind |
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098131582 | Sep 2009 | TW | national |