Patent Application
20240304810
This non-provisional application claims priority under 35 U.S.C. § 119(a) on Patent Application No(s). 112108791 filed in Taiwan, R.O.C. on Mar. 9, 2023, the entire contents of which are hereby incorporated by reference.
The present disclosure relates to a preparation method of soft carbon, and more particularly to a preparation method of soft carbon and a lithium-ion secondary battery containing the soft carbon as an anode.
In recent years, lithium-ion secondary batteries have been widely used in various electronic products because of their high working voltage, fast charging and discharging rate, and long life. In general, a cathode material of the lithium-ion secondary battery can be selected from lithium cobalt oxide, lithium iron phosphate, ternary lithium, lithium manganate, etc., while an anode material thereof can be selected from soft carbon and the like.
Next, as far as the production method of soft carbon is concerned, it mainly includes a front-end process and a back-end process. The front-end process refers to a process of converting heavy oil into a precursor structure (such as raw coke), while the back-end process refers to a process of pre-firing and carbonizing the precursor structure, sequentially followed by grinding and grading, high-temperature carbonization, modification and carbonization, and finally obtaining a soft carbon finished product.
However, the inventors have found that the traditional preparation method of soft carbon still has room for improvement in further improving the characteristics of lithium-ion secondary batteries such as capacity retention ratio and fast charging cycle life.
The specific content of the preparation method of soft carbon can refer to the prior application with application number TW111142065(unpublished) filed by the applicant in the Republic of China, the full text of which is introduced into the specification of the present disclosure. In the application, a soft carbon anode material that can improve the fast charging and discharging capability and cycle life of the battery can be provided by specific manufacturing steps.
In order to solve the disadvantageous of the prior art, an aspect of the preparation method of soft carbon of the present disclosure includes: step (A), heating heavy oil to raw coke under a condition of 480° C.-550° C.; step (B), heating the raw coke to 850° C.-900° C. at a first heating rate of 3° C./min to 5° C./min and holding the temperature for 4 hours or more to obtain a carbon-containing material; step (C), grinding and grading the carbon-containing material to obtain a carbon-containing powder, wherein a particle size distribution D50 of the carbon-containing powder is 8 μm-12 μm, and a cumulative amount of the powder with a particle size below 5 μm is 1.0% or less by weight of the overall carbon-containing powder; step (D), heating the carbon-containing powder to 1030° C.-1220° C. at a second heating rate of 3° C./min to 10° C./min and holding the temperature for 4 hours or more to obtain a carbon material powder; and step (E), adding pitch to the carbon material powder, and then heating it to 1030° C.-1220° C. at a third heating rate of 0.90° C./min to 1.25° C./min and holding the temperature for 5 hours or more to obtain soft carbon. The soft carbon can be used to prepare a first-type lithium-ion secondary battery.
In an embodiment, in step (E), the amount of pitch added is 5-8% by weight of the carbon material powder. The soft carbon of this embodiment may be used to prepare a second-type lithium-ion secondary battery.
In an embodiment, step (F) is further included, carrying out smoothing before the step (C) to reduce BET specific surface area of the carbon-containing material by 20% or more; or carrying out smoothing after the step (C) to reduce BET specific surface area of the carbon-containing powder by 20% or more. The soft carbon of this embodiment may be used to prepare a third-type lithium-ion secondary battery.
An aspect of the first-type lithium-ion secondary battery of the present disclosure comprises: a housing; an anode, which is disposed within the housing, and the anode contains the soft carbon as made above; a cathode, which is disposed within the housing, and separated from each other by the anode; a separator, which is disposed between the anode and the cathode; and an electrolyte, which is filled in the housing.
In an embodiment, a first cycle irreversible capacity of the first-type lithium-ion secondary battery is 40-45 mAh/g.
An aspect of the second-type lithium-ion secondary battery of the present disclosure comprises: a housing; an anode, which is disposed within the housing, and the anode contains the soft carbon as made above; a cathode, which is disposed within the housing, and separated from each other by the anode; a separator, which is disposed between the anode and the cathode; and an electrolyte, which is filled in the housing.
In an embodiment, under a condition of 12-minute fast charging of 5C, a capacity retention ratio of the second-type lithium-ion secondary battery is increased by 40% or more relative to a capacity retention ratio of the first-type lithium-ion secondary battery.
In an embodiment, under a condition of 7.5-minute fast charging of 8C, the capacity retention ratio of the second-type lithium-ion secondary battery is increased by 40% or more relative to the capacity retention ratio of the first-type lithium-ion secondary battery.
An aspect of the third-type lithium-ion secondary battery of the present disclosure comprises: a housing; an anode, which is disposed within the housing, and the anode contains the soft carbon as made above; a cathode, which is disposed within the housing, and separated from each other by the anode; a separator, which is disposed between the anode and the cathode; and an electrolyte, which is filled in the housing.
In an embodiment, under a condition of 12-minute fast charging of 5C, a capacity retention ratio of the third-type lithium-ion secondary battery is increased by 10% or more relative to a capacity retention ratio of the first-type or the second-type lithium-ion secondary battery.
In an embodiment, under a condition of 7.5-minute fast charging of 8C, the capacity retention ratio of the third-type lithium-ion secondary battery is increased by 20% or more relative to the capacity retention ratio of the first-type or the second-type lithium-ion secondary battery.
An aspect of the present disclosure provides a soft carbon material for an anode of a lithium-ion secondary battery. By using the aforementioned soft carbon material as the anode of the lithium-ion secondary battery, the characteristics of the lithium-ion secondary battery such as capacity retention ratio and fast charging cycle life can be improved.
The implementation of the present disclosure is illustrated by the specific embodiments as follows, so one skilled in the art may understand other advantages and effects of the present disclosure by the contents disclosed in the specification. The present disclosure may also be implemented or applied by other embodiments, and the details in the specification may also be modified and varied based on different views and applications without departing from the spirit of the present disclosure.
Unless otherwise specified herein, the term “A-B” used in the specification and the claims attached includes the meaning of “A or more and B or less”. For example, the term “10-40 wt %” includes the meaning of “10 wt % or more and 40 wt % or less”.
Refer to
As shown in
Step (A) is a step of heating heavy oil to raw coke under a condition of 480° C.-550° C. Specifically, the heavy oil can be transported to a reaction tank, and under a coking temperature of 480° C.-550° C. and a pressure of 0.2 MPa to 4 MPa, the heavy oil can be heated for 1-16 hours, so that the heavy oil sets off pyrolysis and a condensation polymerization to generate the raw coke.
Step (B) is a step of heating the raw coke obtained by Step (A) to 850° C.-900° C. at a first heating rate of 3° C./min to 5° C./min and holding the temperature for 4 hours or more to obtain a carbon-containing material. By Step (B), the raw coke can carry out at least one of a condensation polymerization, dehydrogenation reaction, and pyrolysis reaction, so that the raw coke begins to form a carbon-containing material with sp2 hybrid orbitals.
Step (C) is a step of grinding the carbon-containing material obtained by Step (B) to obtain a carbon-containing powder; wherein a particle size distribution D50 of the carbon-containing powder is 8 μm-12 μm, and a cumulative amount of the powder with a particle size below 5 μm is 1.0% or less by weight of the overall carbon-containing powder. In addition, the grinding of Step (C) can use a high-pressure air grinder, a collision plate grinder, or an impact grinder, etc., and the grading of Step (C) can use a cyclone grader or a vibration grader, etc., without special restrictions.
The first technical feature of the present disclosure compared with the prior art is that: by step (C), the proportion of fine powder (powder with a median particle size of 5 μm or less) in the carbon-containing powder is reduced, so that it can reduce the weight of a solid electrolyte interface (SEI) formed on a surface of an anode when the soft carbon material of the present disclosure is used to subsequently manufacture the anode of the lithium-ion secondary battery, thereby improving capacity retention ratio and fast charging cycle life of a lithium-ion secondary battery.
Step (D) is a step of heating the carbon-containing powder obtained by Step (C) to 1030° C.-1220° C. at a second heating rate of 3° C./min to 10° C./min and holding the temperature for 4 hours or more to obtain a carbon material powder. By Step (D), the residual raw coke in the carbon-containing powder can carry out at least one of a condensation polymerization, dehydrogenation reaction and pyrolysis reaction, so that carbon of the residual raw coke can be rearranged into sp2 hybrid orbitals to become a carbon material powder.
Step (E) is a step of adding pitch to the carbon material powder obtained by Step (D), and then heating it to 1030° C.-1220° C. at a third heating rate of 0.90° C./min to 1.25° C./min and holding the temperature for 5 hours or more to obtain soft carbon. By Step (E), a feature of the softening point of the pitch is used, so that the viscosity of the pitch in the carbon material powder added with the pitch can be reduced because of the temperature reaching the softening point of the pitch during the heating process of Step (E), and the pitch after the viscosity reduction can modify the tiny holes on a surface of the carbon material powder, so that the specific surface area of the carbon material powder is reduced, and then the soft carbon of the present disclosure is obtained.
The second technical feature of the present disclosure compared with prior art is that: the amount of pitch added in step (E) is set to 5-8% by weight of the carbon material powder. In general, as mentioned earlier, the addition of pitch will reduce the specific surface area of the carbon material powder, which is accompanied by a decrease in the charging capacity per unit time of the lithium-ion secondary battery. However, compared with the amount of pitch added as 4% by weight, if the amount of pitch added in Step (E) is set to 5-8% by weight of the carbon material powder (especially 5% by weight), the charging capacity fails to decrease but rises, and can also improve the capacity retention ratio and fast charging cycle life of a lithium-ion secondary battery.
In addition, in Step (E), it is preferable to add the pitch with a content of 5% by weight of the carbon material powder, and increase the temperature to 1100° C. at a heating rate of 1.22° C. per minute and hold the temperature for at least 5 hours.
The third technical feature of the present disclosure compared with the prior art is that: Step (F) is carrying out smoothing before the Step (C) to reduce BET specific surface area of the carbon-containing material by 20% or more; or carrying out smoothing after the Step (C) to reduce BET specific surface area of the carbon-containing powder by 20% or more.
Specifically, Step (F) can use a jet mill (for example, STJ200 made by SEISHIN) to grind the carbon-containing material or the carbon-containing powder to smooth the surface of the carbon-containing material or the carbon-containing powder and reduce the BET specific surface area by 20% or more. Further, Step (F) may also repeat the Step (C) five to ten times, by the carbon-containing material or the carbon-containing powder repeatedly colliding with the wall of the grinder and/or grader, or by allowing the carbon-containing material or the carbon-containing powder to collide with each other, so as to reduce the BET specific surface area by 20% or more, and achieve the effect of smoothing.
By Step (F), the capacity retention ratio and fast charging cycle life of a lithium-ion secondary battery can be further improved.
Below, although the present disclosure is specifically described by various embodiments and comparative examples, the present invention is not limited to such embodiments and comparative examples.
According to Step (A)-Step (E) above, and based on the conditions listed in Table 1 below, soft carbons of Comparative example 1 and Embodiments 1-2 are prepared. Further, in Step (C) of Comparative example 1 and Embodiments 1-2, a high-pressure air grinder and a cyclone grader are used.
Comparative example 2 is the same as Comparative example 1 except for the use of a collision plate grinder. Embodiment 3 is the same as Embodiment 2 except for the use of a collision plate grinder. Thus, soft carbons of Comparative example 2 and Embodiment 3 are prepared.
Embodiment 4 is the same as Comparative example 1 except that Step (F) is implemented after Step (C) (repeating Step (C) five times). Embodiment 5 is the same as Embodiment 4 except that the cumulative amount of the powder with a particle size below 5 μm is reduced to 0.75% by weight. Thus, soft carbons of Embodiments 4-5 are prepared.
Soft carbon anodes can be made by referring to the method of application number TW111142065. First, each the above soft carbon is disintegrated by a disintegrator, and then the soft carbon anode material is obtained by sieving through a screen (for example, mesh size of 38 μm). Next, 9.1 g of soft carbon anode material, 0.5 g of PVDF, 0.4 g of conductive carbon black and 12 g to 15 g of N-methylpyrrolidone (NMP) are evenly mixed to form a mixed solvent, which was coated on a copper foil with a thickness of 14 μm, and dried at 85° C. for 0.5 hours to remove NMP and moisture, and the soft carbon anodes of Comparative examples 1-2 and Embodiments 1-5 are formed.
Among them, the soft carbon anode includes a copper foil and a conductive film formed on the copper foil. Moreover, when a thickness of the conductive film is 20-30 μm, it is a high-power type anode, which can be used as a high-power type half-cell; when the thickness of the conductive film is 50 μm, it is a high-energy type anode, which can be used as a high-energy type half-cell.
Half-cells can be made by referring to the method of application number TW111142065. First, the anodes made by the soft carbons of Comparative examples 1-2 and Embodiments 1-5 (hereinafter referred to as the anodes of Comparative examples 1-2 and Embodiments 1-5), a lithium metal sheet as a cathode, an electrolyte, and a separator [for example, manufacturer: Celgard, material: polypropylene (PP) and polyethylene (PE)] are assembled into half-cells (hereinafter referred to as the half-cells of Comparative examples 1-2 and Embodiments 1-5). Among them, the electrolyte contains 99 wt % 1M LiPF6 solution and 1 wt % vinylene carbonate. The LiPF6 solution contains LiPF6, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC), and the volume ratio of EC:EMC:DMC is 1:1:1.
Among them, Comparative example 1 and Embodiment 1 make a high-power type half-cell and a high-energy type half-cell; Comparative example 2 makes a high-power type half-cell; Embodiments 2-3 make high-power type half-cells; Embodiments 4-5 make high-energy type half-cells.
A charging and discharging machine (for example, manufacturer: Arbin, model: BT2043) is used to measure the first cycle charging capacity and the first circle discharging capacity of the half-cells of Comparative examples 1-2 and Embodiments 1, 4-5; among them, the test conditions are a temperature of 25° C., a charging and discharging rate (C-rate) of 0.2C, a charging cut-off voltage of 0V, and a discharging cut-off voltage of 1.8V, and the first cycle irreversible capacity of the half-cell is calculated by the following formula. The first cycle irreversible capacity=(the first cycle charging capacity−the first cycle discharging capacity). Further, the above measurement results are summarized in Table 2 below.
A BET specific surface area measuring instrument (for example, model: ASAP2020plus, brand: Micromeritics) is used to measure BET specific surface area of the soft carbons of Comparative examples 1-2 and Embodiments 1, 4-5, and the measurement results are summarized in Table 2 below.
TGA tests are performed on the high-energy type half-cell of Comparative example 1 and the high-energy type half-cell of Embodiment 1. Specifically, after the half-cell of Comparative example 1 and the half-cell of Embodiment 1 have passed their respective cycle lives, 7.76 mg of anode material on the half-cell electrode plate of Comparative example 1 and 10.58 mg of anode material on the half-cell electrode plate of Embodiment 1 are respectively scraped for TGA testing, and the anode material is heated for one hour at an oxygen environment of 1100° C. to burn carbon off. As can be seen from Table 3 below, the residual weight (i.e., the weight of SEI) of Comparative example 1 after the TGA test is 0.29 mg, while the residual weight (i.e., the weight of SEI) of Embodiment 1 after the test is 0.20 mg. It can be seen that by making the cumulative amount of the powder with a particle size below 5 μm to be 1.0% or less by weight of the overall carbon-containing powder in Step (C), the weight of the high-impedance SEI can be reduced, thereby improving the fast charging cycle life.
A charging and discharging machine (for example, manufacturer: Maccor, model: Series 4000) is used to measure the capacity retention ratio of the half-cells in Comparative example 1-2 and Example 1 and 4-5 respectively at a charging rate/discharging rate of 5C/5C (charging and discharging time is 12 minutes) and 8C/8C (charging and discharging time is 7.5 minutes) relative to different charging and discharging cycles. In addition, the charging rate/discharging rate of 5C/5C and the charging and discharging time of 12 minutes are referred to as “12-minute fast charging of 5C”; the charging rate/discharging rate of 8C/8C and the charging rate/discharging time of 7.5 minutes are referred to as “7.5-minute fast charging of 8C”. The results of fast charging performance detection of the half-cells in the above Comparative example 1-2 and Example 1 and 4-5 are shown in
Refer to
Also, as shown in
Then, as shown in
It can be seen that whether under the condition of 12-minute fast charging of 5C or 7.5-minute fast charging of 8C, by the technical feature of the present disclosure of “by Step (C), the proportion of powder with D50 below 5 μm in the carbon-containing powder is reduced to 1% or less by weight of the overall carbon-containing powder”, the capacity retention ratio and fast charging cycle life of the lithium-ion secondary battery can be improved.
Further, referring to
In addition, the first cycle irreversible capacity of the high-energy type half-cell in Embodiment 1 is 43 mAh/g, which is still within the acceptable range (40-45 mAh/g). Further, from the results of
First, the difference between Embodiment 2 and Comparative example 1 is that the amount of pitch added in Step (E) is increased from 4% by weight of the carbon material powder to 5% by weight of the carbon material powder (second technical feature of the present disclosure). Next, referring to
In addition, the charging capacity per unit time of Comparative example 1 are respectively 59% (5C fast charging) and 50% (8C fast charging), and the charging capacity per unit time of Embodiment 2 are 60% (5C fast charging) and 50% (8C fast charging). It can be seen that by virtue of the technical feature of the present disclosure, the capacity retention ratio and fast charging cycle life of the lithium-ion secondary battery can be further improved under the condition that the charging capacity fails to decrease but rises.
Embodiment 3 and Comparative example 2 are intended to show that the method of the present disclosure (e.g., a second technical feature) can also be applied to soft carbon materials with characteristic deviations. First, as shown in Table 2, the first cycle irreversible capacity of Comparative example 2 is 51 mAh/g, which is slightly higher than the acceptable range (40-45 mAh/g). Next, referring to
In addition, the charging capacity per unit time of Comparative example 2 are 62% (5C fast charging) and 58% (8C fast charging), and the charging capacity per unit time of Embodiment 3 are 65% (5C fast charging) and 62% (8C fast charging). It can be seen that even if the characteristics of the soft carbon material deviate, the capacity retention ratio of the lithium-ion secondary battery can be improved by the present disclosure.
First, the difference between Embodiment 4 and Comparative example 1 is that smoothing of Step (F) is further carried out (technical feature of the present disclosure). Further, as shown in Table 2, the BET specific surface area in Comparative example 1 is 2.3 m2/g, and the BET specific surface area in Embodiment 4 is 1.5 m2/g, that is, the specific surface area of Comparative example 1 is reduced by about 30% by smoothing. Next, referring to
It can be seen that by the technical feature of the present disclosure, the capacity retention ratio and fast charging cycle life of the lithium-ion secondary battery can also be further improved.
First, the difference between Embodiment 5 and Embodiment 4 is that Embodiment 5 is based on Embodiment 4, further reducing the cumulative amount of the powder with a particle size below 5 μm to 0.75% by weight (the technical feature of the present disclosure). That is, Embodiment 5 simultaneously implements the technical features of the present disclosure, while Embodiment 4 only implements a technical feature of the present disclosure. Next, referring to
Herein, as described in the section of the preceding
In other words, even if one of the technical features of the present disclosure (Embodiment 4) is applied, another technical feature (Embodiment 5) is further applied, and the same improvement effect of capacity retention ratio can be obtained as “from without applying technical features of the present disclosure (Comparative example 1) to applying one of the technical features of the present disclosure (Embodiment 1)”.
In summary, the present disclosure can be applied to various lithium-ion secondary batteries such as high-power type lithium batteries or high-energy type lithium batteries, and can also be applied to soft carbon materials with characteristic deviations. Further, each technical feature of the present disclosure has the effect of improving the capacity retention ratio and fast charging cycle life, and even if one of the technical features of the present disclosure is applied, another technical feature or more is further applied, a further cumulative effect of improving the capacity retention ratio can also be obtained.
By the preparation method of the present disclosure, a soft carbon material for an anode of a lithium-ion secondary battery can be provided. In addition, by using the aforementioned soft carbon material as the anode of the lithium-ion secondary battery, the characteristics of the lithium-ion secondary battery such as capacity retention ratio and fast charging cycle life can be improved.
The present invention is not limited to the above embodiments, various changes may be made within the scope indicated in the claims, and the embodiments obtained by the appropriate combination of technical means disclosed in different embodiments are also included in the technical scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 112108791 | Mar 2023 | TW | national |
