Patent Application
20140004421
The present invention relates to a cathode material, and more particularly to a cathode material with double carbon coatings.
With the diversified development of electronic products, the demands on portable energy sources are gradually increased. For example, consumer electronic devices, medical instruments, electric bicycles, electric vehicles or electric hand tools use portable power sources as sources of electric power. Among these portable power sources, rechargeable batteries (also referred as secondary cells) are widely used because the electrochemical reactions thereof are electrically reversible. Moreover, among the conventional secondary cells, lithium-ion secondary cells have high volumetric capacitance, low pollution, good charge and discharge cycle characteristics, and no memory effect. Consequently, the lithium-ion secondary cells are more potential for development.
As known, the performance of the secondary cell is influenced by many factors. Generally, the material for producing a positive electrode (also referred as a cathode) is more critical to the performance of the secondary cell. Because of good electrochemical characteristics, low environmental pollution, better security, abundant raw material sources, high specific capacity, good cycle performance, good thermal stability and high charge/discharge efficiency, the lithium iron phosphate-based compound having an olivine structure or a NASICON structure is considered to be the potential lithium-ion battery cathode material.
On the other hand, with increasing environmental awareness, electric vehicle technologies have received considerable attention in recent years. Generally, electric vehicles use rechargeable batteries (i.e. secondary cells) as the power sources. The economic benefits of the secondary cells not only depend on the electrical properties but also depend on the cycle life.
Therefore, there is a need of providing a cathode material of a secondary cell with enhanced cycle life.
The present invention provides a cathode material with double carbon coatings. By combining two types of carbon layers together to increase the adhesion of carbon on the lithium metal phosphate matrix, the problem of causing reduction of the material performance during the charging and discharging process will be avoided. Due to the double carbon coatings, the overall structural strength of the cathode material is enhanced, the influence on the structural flexibility during the charging and discharging process is reduced, and the structural damage caused by the acidic substance of the electrolyte is reduced. As a consequence, the use life of the cathode material is prolonged.
In accordance with an aspect of the present invention, there is provided a cathode material with double carbon coatings. The cathode material includes a lithium metal phosphate matrix, a first carbon coating, and a second carbon coating. The first carbon coating is coated on the lithium metal phosphate matrix. The second carbon coating is coated on the first carbon coating. A carbon source of the first carbon coating is a carbohydrate or a water-soluble macromolecule compound having relatively smaller molecular weight. A carbon source of the second carbon coating is a macromolecule compound having relatively higher molecular weight.
In accordance with another aspect of the present invention, there is provided a process of manufacturing a cathode material with double carbon coatings. Firstly, a lithium metal phosphate matrix and a carbon source of a first carbon coating are provided, and the mixture of the lithium metal phosphate matrix and the carbon source of the first carbon coating are thermally treated by sintering. Consequently, a cathode material with a single carbon coating is obtained. Meanwhile, the first carbon coating is coated on the lithium metal phosphate matrix. Then, a carbon source of a second carbon coating is added to the cathode material with the single carbon coating, and the mixture of the carbon source of the second carbon coating and the cathode material with the single carbon coating are thermally treated by sintering. Consequently, the cathode material with the double carbon coatings is obtained. The carbon source of the first carbon coating is a carbohydrate or a water-soluble macromolecule compound having relatively smaller molecular weight. The carbon source of the second carbon coating is a macromolecule compound having relatively higher molecular weight.
The above contents of the present invention will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed description and accompanying drawings, in which:
The present invention 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.
The present invention provides a cathode material with double carbon coatings. The cathode material comprises a lithium metal phosphate matrix and two carbon coatings coated on the lithium metal phosphate matrix. Due to the double carbon coatings, the overall structural strength of the cathode material is enhanced, the influence on the structural flexibility during the charging and discharging process is reduced, and the structural damage caused by the acidic substance of the electrolyte is reduced. As a consequence, the use life of the cathode material is prolonged.
In accordance with the present invention, the cathode material with double carbon coatings is produced by firstly providing a cathode material with a single carbon coating and then another carbon coating is coated thereon.
The raw materials for synthesizing the lithium iron phosphate material comprise iron powder or iron-containing compound, phosphoric acid or phosphate compound, and lithium carbonate or lithium hydroxide. After the above materials and the carbon source of the first carbon coating are subject to a dry processing reaction or a wet processing reaction, the mixture is spray-dried and granulated to form a carbon-containing lithium iron phosphate precursor. Under a protective atmosphere such as nitrogen or argon gas, the precursor is thermally treated by sintering. Consequently, a cathode material with a single carbon coating is produced. The carbon source of the first carbon coating is a carbohydrate or a water-soluble macromolecule compound having relatively smaller molecular weight. For example, the carbohydrate having relatively smaller molecular weight is a monosaccharide, a disaccharide or a polysaccharide. An example of the water-soluble macromolecule compound includes but is not limited to polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP).
Then, a second carbon coating formation process is performed. The carbon source of the second carbon coating is a macromolecule compound having relatively higher molecular weight. Preferably, the carbon source of the second carbon coating is an aromatic compound such as coal tar pitch or petroleum pitch. The carbon source of the second carbon coating is dissolved in an organic solvent. Then, the cathode material with a single carbon coating is added and uniformly mixed. Under a protective atmosphere such as nitrogen or argon gas, the mixture is thermally treated by sintering. Consequently, a cathode material with double carbon coatings is produced.
The preparation process and efficacy of the cathode material with double carbon coatings will be illustrated in the following examples.
Phosphoric acid (85%, 2 moles) was dissolved in deionized water (600 ml) to form an acidic solution. Then, iron powder (99%, 2 moles) was added to the acidic solution. After reaction, a product containing iron and phosphorous is formed. This solution was continuously stirred for 24 hours to provide complete dispersion. Triton X-100 (10 ml), a non-ionic surfactant, was then added to the dispersed solution. Lithium hydroxide monohydrate (1 mole) was added to the resulting solution while it was thoroughly stirred. Lithium carbonate (1 mole) was then added. Consequently, a precursor containing iron, phosphorous and lithium at a molar ratio of 1:1:1 was produced. The precursor was analyzed and identified by inductively coupled plasma atomic emission spectrometry (ICP/AES).
Then, vanadium pentoxide (0.04 mole, V2O5) and fructose (0.07 mole) were added to the resulting precursor. A wet dispersion process was performed to form a semicrystalline nanoscale particle mixture in solution. The mixture was spray-dried to form a powdery precursor. Then, the powdery precursor was placed in an aluminum oxide crucible. Under a protective atmosphere such as nitrogen or argon gas, the powdery precursor was sintered at high temperature up to 800° C. and maintained at this temperature for at least five hours. Under this circumstance, a cathode material covered with a single carbon coating (also referred as an “M product powder”) was produced. The content of carbon in the M product powder was 1˜1.5%.
The cathode material covered with the single carbon coating (i.e. the M product powder), which was prepared in Example 1, was further subject to a second carbon coating formation process. Firstly, several coal tar pitch solutions (0.4˜1%) were prepared. These coal tar pitch solutions were obtained by dissolving different amounts of coal tar pitch (0.4 g, 0.6 g, 0.8 g and 1 g) into different amounts of xylene (99.6 g, 99.4 g, 99.2 g and 99 g). After the coal tar pitch was completely dissolved, 20 g of the M product powder was added and uniformly mixed. The obtained mixture solution was subject to a suction vacuum treatment in order to remove air from pores of the powder. The mixture solution was then stirred by a homogenizer and mixed by a ball mill jar. Consequently, the coal tar pitch was coated on the surface of the M product powder more uniformly. The mixture was heated to 150° C. to remove xylene. Consequently, a uniform mixture, i.e. coal tar pitch coated on the M product powder, was produced. Then, the mixture was sintered in a furnace under a nitrogen or argon atmosphere. The furnace was raised to 550° C. at a ramp rate of 5° C/min and maintained at 550° C. for 4 hours, then raised to 750° C. and maintained at 750° C. for 4 hours, and finally reduced to room temperature. Consequently, a cathode material with double carbon coatings was produced.
The powders obtained in Example 1 and Example 2 were analyzed by an X-ray diffractometer (XRD) and observed by a scanning electron microscope (SEM). The XRD result and the SEM photograph are shown in
The powders obtained in Example 1 and Example 2 were coated on aluminum substrates in order to form a cathode element and assemble coin-type cells. The electric properties of the coin-type cells were tested. The test results are listed in Table 1. As shown in Table 1, the capacity of the cathode material with the double carbon coatings is slightly reduced. It is inferred that the thicker carbon coatings may hinder passage of ions. On the other hand, the double carbon coatings may smooth the surfaces of the particles and reduce the specific surface area (S.A.). Moreover, the ratio of the carbon percentage of the first carbon coating to the carbon percentage of the second carbon coating is in the range between 1:1 and 1:2.
As shown in
Iron phosphate hydrate (2 mole) was added to pure water (600 ml). Polyvinylpyrrolidone (PVP K30, 10 ml) was added to a dispersed solution. While stirring, a wet dispersion process (e.g. a ball mill process or an ultrasonic dispersion process) was performed to form a nanoscale particle mixture in solution. Lithium hydroxide monohydrate (2 mole) and fructose (0.07 mole) were added. After the solution was uniformly stirred, the solution was spray-dried to form a powdery precursor.
Then, the powdery precursor was placed in an aluminum oxide crucible. Under a protective atmosphere such as nitrogen or argon gas, the powdery precursor was sintered at high temperature up to 800° C. and maintained at this temperature for at least five hours. Consequently, the carbon coating was subject to excellent carbonation. Under this circumstance, a cathode material covered with a single carbon coating (also referred as an “A product powder”) was produced. The content of carbon in the A product powder was 2˜2.5%.
The cathode material covered with the single carbon coating (i.e. the A product powder), which was prepared in Example 3, was further subject to a second carbon coating formation process. Firstly, several coal tar pitch solutions (0.6˜1%) were prepared. These coal tar pitch solutions were obtained by dissolving different amount of coal tar pitch (0.6 g, 0.8 g and 1 g) into different amount of xylene (99.4 g, 99.2 g and 99 g). After the coal tar pitch was completely dissolved, 20 g of the A product powder was added and uniformly mixed. The subsequent procedures are identical to those of Example 2, and are not redundantly described herein.
The physical data of the powders obtained in Example 3 and Example 4 are shown in Table 2 as follows. As shown in Table 2, the double carbon coatings may reduce the specific surface area. Moreover, the ratio of the carbon percentage of the first carbon coating to the carbon percentage of the second carbon coating is in the range between 4:3 and 1:1.
The cathode material covered with the single carbon coating (i.e. the M product powder), which was prepared in Example 1, was further subjected to a second carbon coating formation process. The subsequent sintering conditions of this example were different from those of Example 2. In Example 2, the sintering procedure was performed by maintaining at 550° C. for 4 hours and then maintaining at 750° C. for 4 hours. In Example 5, the sintering procedure was performed by maintaining at 260° C. for 2 hours and then maintaining at 900° C. for 2 hours.
The cathode material covered with the single carbon coating (i.e. the M product powder), which was prepared in Example 1, was further subjected to a second carbon coating formation process. The subsequent sintering conditions of this example were different from those of Example 2. In Example 2, the sintering procedure was performed by maintaining at 550° C. for 4 hours and then maintaining at 750° C. for 4 hours. In Example 6, the sintering procedure was performed by maintaining at 550° C. for 4 hours and then maintaining at 650° C. for 4 hours.
The comparisons between the physical properties and electrical properties of the powders obtained in Example 1, Example 2, Example 5 and Example 6 are shown in Table 3. As shown in Table 3, the sintering conditions of Example 5 and Example 6 can increase the specified surface area of the powder and effectively avoid reduction of the capacity when compared with the sintering condition of Example 2 (i.e. maintaining at 550° C. for 4 hours and then maintaining at 750° C. for 4 hours). The obtained capacity (0.1C:147˜153/2C:106˜114) is close to the M product powder with the single carbon coating (0.1C:155/2C:114).
In this example, a scale-up test was performed. The cathode material covered with the single carbon coating (i.e. the M product powder), which was prepared in Example 1, was further subjected to a second carbon coating formation process. In Example 2, 20 g of the M product powder was mixed with 0.4 g coal tar pitch/100 g (0.4%) and 1 g coal tar pitch/100 g (1%). In this example (Example 7), 50 g of the M product powder was mixed with 1 g coal tar pitch/100 g and 2.5 g coal tar pitch/100 g. Consequently, the carbon content of Example 7 was controlled to be equal to the carbon content of Example 2. Moreover, in Example 7, the sintering procedure was performed by maintaining at 550° C. for 4 hours and then maintaining at 650° C. for 4 hours. The subsequent procedures are identical to those of Example 2, and are not redundantly described herein. The physical data of the powders obtained in Example 7 are shown in Table 4 as follows. As shown in Table 4, in the powder obtained by mixing 50 g of the M product powder with 1 g coal tar pitch/100 g, the ratio of the carbon percentage of the first carbon coating to the carbon percentage of the second carbon coating is about 1:1. Moreover, in the powder obtained by mixing 50 g of the M product powder with 2.5 g coal tar pitch/100 g, the ratio of the carbon percentage of the first carbon coating to the carbon percentage of the second carbon coating is close to 1:2.
From the above embodiments, it is found that the cell produced from the cathode material with the double carbon coatings has obviously longer cycle life. For example, the cell produced from the cathode material with the double carbon coatings has a cycle life of up to 500 charge/discharge cycles at 100% of life cycle retention. As known, the conventional coin-type cell has a life cycle of about 100˜200 cycles. In comparison with the conventional coin-type cell, the cycle life of the cell produced from the cathode material with the double carbon coatings has been increased at least two times. Although the capacity of the cathode material with the double carbon coatings is slightly reduced, the adjustment of the sintering temperature can restore the capacity to be close to the capacity of the cathode material with the single carbon coating. Moreover, the electrical properties and the physical properties of the cathode material with the double carbon coatings are related to the carbon content of the second carbon coating. In accordance with the optimal conditions, the satisfactory cycle life is achieved when the ratio of the carbon percentage of the first carbon coating to the carbon percentage of the second carbon coating is close to 1:1 or 1:2.
From the above descriptions, the present invention provides a cathode material with double carbon coatings. The cathode material comprises a lithium metal phosphate matrix and two carbon coatings coated on the lithium metal phosphate matrix. The carbon source of the first carbon coating is a carbohydrate or a water-soluble macromolecule compound having relatively smaller molecular weight. Consequently, the first carbon coating has a looser structure, and a space is retained in the first carbon coating for allowing expansion and contraction of the structure during the charging and discharging process. Under this circumstance, the possibility of peeling off the carbon structure will be minimized. The carbon source of the second carbon coating is a macromolecule compound having relatively higher molecular weight. Preferably, the carbon source of the second carbon coating is an aromatic compound such as coal tar pitch or petroleum pitch. Consequently, the second carbon coating has a denser structure in order to reduce the structural damage of the lithium metal phosphate matrix by the acidic substance of the electrolyte. By combining two types of carbon layers together to increase the adhesion of carbon on the lithium metal phosphate matrix, the problem of causing reduction of the material performance during the charging and discharging process will be avoided. Due to the double carbon coatings, the overall structural strength of the cathode material is enhanced, the influence on the structural flexibility during the charging and discharging process is reduced, and the structural damage caused by the acidic substance of the electrolyte is reduced. As a consequence, the use life of the cathode material is prolonged.
While the invention 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 invention needs not be limited to the disclosed embodiment. 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.
This application is the National Stage of International Application No. PCT/CN2012/072472, filed Mar. 16, 2012, which claims the benefit of U.S. Provisional Application No. 61/453,298, filed Mar. 16, 2011, and entitled “LITHIUM METAL PHOSPHATE HAVING DOUBLE CARBON COATINGS”, the disclosures of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN2012/072472 | 3/16/2012 | WO | 00 | 9/16/2013 |
| Number | Date | Country | |
|---|---|---|---|
| 61453298 | Mar 2011 | US |
