Patent Application
20230037323
The subject matter herein generally relates to batteries, and more particularly, to a composite anode material of micrometer-sized carbon-coated silicon, a preparation method of the composite anode material, an anode, and a lithium-ion battery.
As a new generation of anode material for lithium-ion batteries, silicon has rich reserves, and its theoretical specific capacity of lithium storage is the highest among all alloy-type elements that can store lithium. Therefore, silicon has a great potential to replace graphite as the anode material for commercial lithium-ion batteries. Nowadays, significant achievements have been made in the research of silicon anodes. However, applications of nanotechnology, including the use of nano-sized silicon as an active material to prepare electrode materials, reduce a tap density of the electrode materials and an electrode density. Thus, nano-sized silicon limits the improvement of volumetric performances of the silicon anodes.
Micrometer-sized silicon, which has an average particle size of 3 μm to 5 μm, has the characteristics of a low cost and a high tap density. Thus, micrometer-sized silicon can effectively avoid the inherent defects of nano-sized silicon. However, with the increase of particle size, the ability of the active particles to effectively=buffer internal stress decreases. Studies have shown that the silicon active particles. When having a particle size exceeding 150 nm, will break into smaller nanoparticles under the internal stress during charging and discharging processes. Thus, some active particles may lose electrical contact therebetween. Also, a specific surface area of the active particles increases, and fresh particle surfaces of silicon are exposed outside. Thus, an SEI film may repeatedly grow on the exposed surface, which seriously restricts the cycle stability.
Furthermore, an existing carbon coating cannot effectively ensure the cycle stability of the micrometer-sized silicon anode. This is because the volume of silicon greatly expands during the cycle process. On the one hand, the expansion of silicon is anisotropic. For the micrometer-sized silicon particles with different sizes, it is difficult to accurately design the space for buffering the volume expansion of each particle. On the other hand, the above space causes the silicon material difficult to maintain structural integrity during a calendering of the electrode.
Therefore, the present application provides a preparation method of a composite anode material of micrometer-sized carbon-coated silicon. The composite anode material prepared by the above method not only can effectively buffer the volume expansion of internal micrometer-sized silicon particles, but also can bear the pressure of an external calendering.
In addition, the present application also provides a composite anode material prepared by the above method.
In addition, the present application also provides an anode including the composite anode material.
In addition, the present application also provides a lithium-ion battery including the anode.
The present application provides a preparation method of a composite anode material, the preparation method includes the following steps:
subjecting micrometer-sized silicon particles to a chemical vapor deposition reaction under a gas atmosphere containing carbon to obtain carbon-coated first micrometer-sized silicon particles, wherein a mass ratio of carbon in the carbon-coated first micrometer-sized silicon particles is 7% to 38%;
dispersing the carbon-coated first micrometer-sized silicon particles in a first mixed solvent to obtain a dispersed solution;
adding alkali into the dispersed solution and heating the dispersed solution, causing the alkali to etch a portion of the micrometer-sized silicon particles inside the carbon-coated first micrometer-sized silicon particles to obtain carbon-coated second micrometer-sized silicon particles;
dispersing the carbon-coated second micrometer-sized silicon particles and graphene oxide in a second mixed solvent to obtain a mixed solution, and subjecting the mixed solution to a hydrothermal reaction to obtain a composite hydrogel of reduced graphene oxide, carbon, and silicon: and heating the composite hydrogel to remove water from the composite hydrogel, thereby obtaining the composite anode material.
The present application also provides a composite anode material prepared by the above-described preparation method. A density of the composite anode material is 0.8 g/cm3 to 1.2 g/cm3.
The present application also provides an anode, which includes the above composite anode material.
The present application also provides a lithium on battery, which includes a cathode and the above anode.
The composite anode material prepared by the above method of the present application has a multilayered buffer structure. The composite anode material not only can effectively buffer the volume expansion of the internal micrometer-sized silicon particles, but also can bear the pressure of external calendering. Thus, the anode and the lithium-ion battery prepared by the composite anode material have a long cycle life.
Implementations of the disclosure will now be described, by way of embodiments only, with reference to the drawings. The disclosure is illustrative only, and changes may be made in the detail within the principles of the present application. It will, therefore, be appreciated that the embodiments may be modified within the scope of the claims.
Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The technical terms used herein are not to be considered as limiting the scope of the embodiments.
Implementations of the disclosure will now be described, by way of embodiments only, with reference to the drawings.
Referring to
In step S11, micrometer-sized silicon particles are subjected to a chemical vapor deposition reaction under a gas atmosphere containing carbon. Then, carbon-coated first micrometer-sized silicon particles are obtained. A mass ratio of carbon in the carbon-coated first micrometer-sized silicon particles is 7% to 18%.
Specifically, the micrometer-sized silicon particles that have a particle size ranging from 3 μm to 5 μm are placed in a container. The container containing the micrometer-sized silicon particles is placed in a reaction receptacle, in which the micrometer-sized silicon particles are subjected to the chemical vapor deposition reaction under the gas atmosphere containing carbon. Thus, the carbon-coated first micrometer-sized silicon particles are obtained.
In some embodiments, the gas atmosphere containing carbon is methane.
In some embodiments, the container is a crucible.
In some embodiments, the reaction receptacle is a tubular furnace.
In some embodiments, the chemical vapor deposition reaction includes the following three stages:
A heating stage, which is performed under an argon atmosphere. A flow rate of argon is 30 ml/min to 50 ml/min, and a heating rate is 5° C./min to 10° C./min.
A constant temperature stage, which is performed under a mixed atmosphere of methane and argon. A flow rate of methane is 30 ml/min to 50 ml/min, and a flow rate of argon is 30 ml/min to 50 ml/min. The constant temperature is 900° C. to 1000° C., and a period for the constant temperature stage is 40 min to 60 min.
A cooling stage, which is performed under an argon atmosphere. A flow rate of argon is 30 ml/min to 50 ml/min. A cooling rate is 5° C./min to 10° C./min. A natural cooling is followed. In the cooling stage, the natural cooling is performed after the temperature is cooled to 400° C.
Compared with a carbon coating obtained by a polymer pyrolysis process, a carbon coating obtained by chemical vapor deposition (i.e., the carbon of the carbon-coated first micrometer-sized silicon particles) has a higher degree of graphitization, so that the conductivity and mechanical properties are better.
In step S12, the carbon-coated first micrometer-sized silicon particles are dispersed in a first mixed solvent to obtain a dispersed solution.
Specifically, the carbon-coated first micrometer-sized silicon particles are ultrasonically dispersed in the first mixed solvent. Thus, the dispersed solution is uniform.
In some embodiments, the first mixed solvent is a mixture of water and ethanol. In the first mixed solvent, a volume ratio of water to ethanol can be in a range of 0.8:1 to 1:1. The ethanol in the first mixed solvent can disperse the carbon-coated first micrometer-sized silicon particles, and the water in the first mixed solvent can dissolve the alkali subsequently added.
In the dispersed solution, a concentration of the carbon-coated first micrometer-sized silicon particles is 1 mg/ml to 3 mg/min.
In step S13, alkali is added to the dispersed solution and heated, so that the alkali etches a portion of the micrometer-sized silicon particles inside the carbon-coated first micrometer-sized silicon particles. Then, carbon-coated second micrometer-sized silicon particles are obtained.
Specifically, the alkali is added to the dispersed solution, and the dispersed solution is heated to allow the alkali to etch a portion of the micrometer-sized silicon particles. Hydrogen generated during the etching escapes from the dispersed solution. The micrometer-sized silicon particles may be etched by different etching degrees when a period of the reaction is adjusted. Then, the dispersed solution is ultrasonically treated and filtered. The filtered residue is washed and dried, thereby obtaining the carbon-coated second micrometer-sized silicon particles.
The etching process can generate gaps between the carbon coating and the micrometer-sized silicon particles. That is, a suitable space generates between the carbon coating and the micrometer-sized silicon particles. The space can buffer the volume expansion of the micrometer-sized silicon particles.
In some embodiments, the alkali includes at least one of sodium hydroxide and potassium hydroxide. A concentration of the alkali in the dispersed solution is 0.5 mol/l to 1 mol/l.
In some embodiments, a heating temperature of the dispersed solution is 70 CC to 80° C.
In some embodiments, a period for the ultrasonic treatment is 4 min to 10 min.
In some embodiments, water and ethanol are alternately used during the washing procedure.
In some embodiments, a drying temperature is 70°V to 80° C.
In step S14, the carbon-coated second micrometer-sized silicon particles and a graphene oxide are dispersed in a second mixed solvent, so that a mixed solution is obtained. The mixed solution is subjected to a hydrothermal reaction to obtain a composite hydrogel of reduced graphene oxide, silicon, and carbon.
In detail, the carbon-coated second micrometer-sized silicon particles and the graphene oxide are ultrasonically dispersed in the second mixed solvent to obtain the mixed solution. Then, the mixed solution is added into a hydrothermal reactor, and the hydrothermal reaction is performed therein. The graphene oxide is reduced to obtain the composite hydrogel.
In some embodiments, a mass ratio of the carbon-coated second micrometer-sized silicon particles to the graphene oxide is 2:1 to 3:1.
In the mixed solution, a concentration of graphene oxide is 1.5 mol/l to mol/l.
In some embodiments, the second mixed solvent is a mixture of water and ethanol. A volume ratio of water to ethanol in the second mixed solvent can be 0.8:1 to 1:1.
In some embodiments, a temperature of the hydrothermal reaction is 180° C. to 200° C. A period of the hydrothermal reaction is 6 h to 10 h.
In step S15, the composite hydrogel is heated to remove water from the composite hydrogel, so as to obtain the composite anode material.
During the water removal process, the reduced graphene oxide in the composite hydrogel is compacted to form a dense three-dimensional network. The carbon-coated second micrometer-sized silicon particles are dispersed in the three-dimensional network of the reduced graphene oxide.
In some embodiments, a temperature for removing water is 60° C. to 80° C., and a period for removing water is 24 h to 48 h.
A composite anode material prepared by the above-described method is also provided according to some embodiments of the present application. A density of the composite anode material is 0.8 g/cm3 to 1.2 g/cm3.
A micrometer-scale area on the composite anode material is selected. Mechanical properties of the composite anode material within the micrometer-scale area are then measured. Test results show that within the micrometer-scale area, the composite anode material shows a high yield strength greater than 150 MPa and a yield strain of 8.6%. Similarly, in the nano-scale area, the composite anode material exhibits a strength higher than 1.7 GPa and a high plasticity of 15%.
An anode is also provided according to some embodiments of the present application, which includes the composite anode material.
A lithium-ion battery is also provided according to some embodiments of the present application, which includes a cathode and the above anode.
The present application will be described in detail in combination with specific examples and comparative examples.
At a first step, micrometer-sized silicon particles (SiMP) of 1.0 g were placed in a crucible. The micrometer-sized silicon particles had a particle size ranging from 3 μm to 5 μm. The crucible containing the micrometer-sized silicon particles was transferred to a tubular furnace. The tubular furnace was heated to 1000° C. at a heating rate of 10° C./min. A flow rate of argon was 50 mL/min. Then, methane gas was introduced into the tubular furnace at this temperature, with a flow rate of 50 ml/min. The period for the reaction time was 60 min. After the reaction, the introduction of the methane gas was stopped, and the flow rate of argon was remained unchanged. The tubular furnace was then cooled to 400° C. at the rate of 10° C./min, and then naturally cooled to the room temperature to obtain carbon-coated first micrometer-sized silicon particles.
At a second step, the carbon-coated first micrometer-sized silicon particles of 500 mg were ultrasonically dispersed in a mixed solvent of 100 ml water and 100 ml ethanol. Then, a uniform dispersed solution was obtained.
At a third step, sodium hydroxide of 6 g was added to the dispersed solution. The dispersed solution was heated to a temperature of 80° C., and the temperature was maintained for 15 min. When there were bubbles in the dispersed solution, the dispersed solution was ultrasonically treated for 5 min and filtered, washed alternately by water and ethanol, and dried at 70° C. Then, carbon-coated second micrometer-sized silicon particles (SiMP@C) were obtained.
At a fourth step, the SiMP@C of 300 mg and graphene oxide of 150 mg were ultrasonically dispersed in a mixed solvent of 50 ml water and ethanol of 50 ml. Then, a mixed solution was obtained. The mixed solution was added into a hydrothermal reactor, and subjected to a hydrothermal reaction at 180° C. for 6 h. Then, a composite Hydrogel of reduced grapheme oxide, silicon, and carbon was obtained.
At a fifth step, the obtained composite hydrogel was dried at 70° C. for 24 h. Then, a composite anode material of micrometer-sized carbon-coated silicon (SiMP@C-GN) was obtained.
A difference between example 2 and example 1 is that the flow rate of methane was 30 ml/min.
A difference between example 3 and example 1 is that at the first step, the tubular furnace was heated to 950° C. at a heating rate of 7° C./min. A flow rate of argon was 40 Then, methane gas was introduced at this temperature at a flow rate of 50 ml/min. The period for the reaction was 40 min. After the reaction, the introduction of methane gas was stopped, and the flow rate of argon was remained unchanged. The tubular furnace was cooled to 400° C. at a rate of 7° C./min, and then naturally cooled to the room temperature.
A difference between example 4 and example 1 is that the amount of SiMP@C used at the fourth step was 400 mg. The amount of water was 40 ml, and the amount of ethanol was 60 ml.
A difference between example 5 and example 1 is that the amount of sodium hydroxide used at the third step was 4 g.
A difference between example 6 and example 1 is that the sodium hydroxide was replaced with potassium hydroxide at the third step.
A difference between example 7 and example 1 is that when bubbles were generated in the dispersed solution, the ultrasonic treatment was performed for 8 min.
A difference between example 8 and example 1 is that the amount of SiMP@C used at the fourth step was 250 ma. The amount of water was 60 ml, and the amount of ethanol was 40 ml.
A difference between example 9 and example 1 is that the amount of graphene oxide used at the fourth step is 170 mg.
A difference between example 10 and example 1 is that the drying temperature at the fifth step is 80° C.
The carbon-coated first micrometer-sized silicon particles, which were obtained at the first step of example 1, were directly used as an anode material.
The carbon-coated second micrometer-sized silicon particles (SiMP@C), which were obtained at the third step of example 1, were directly used as an anode material.
At a first step, micrometer-sized silicon particles of 1.0 g were placed in a crucible. The micrometer-sized silicon particles had a particle size ranging from 3 μm to 5 μm. The crucible containing the micrometer-sized silicon particles was transferred to a tubular furnace. The tubular furnace was heated to 1000° C. at a heating rate of 10° C./min. A flow rate of argon was 50 ml/min. Then, methane gas was introduced into the tubular furnace at this temperature, with a flow rate of 50 ml/min. The period for the reaction time was 60 min. After the reaction, the introduction of the methane gas was stopped, and the flow rate of argon was remained unchanged. The tubular furnace was then cooled to 400° C. at the rate of 10° C./min, and then naturally cooled to the room temperature to obtain carbon-coated first micrometer-sized silicon particles.
At a second step, the carbon-coated first micrometer-sized silicon particles of 300 mg and graphene oxide of 150 mg were ultrasonically dispersed into a mixed solution of 50 ml water and 50 ml ethanol. Thus, the mixed solution was obtained. Then, the mixed solution was added to a hydrothermal reactor, and subjected to a hydrothermal reaction at 180° C. for 6 h. Then, a composite hydrogel was obtained.
At a third step, the obtained composite hydrogel was dried at 70° C. for 24 h. Then, a composite anode material (SiMP@;C-GN) was obtained.
A difference between comparative example 4 and example 1 is that the silicon particles, which had a particle size ranging from 3 μm to 5 μm used at the first step, was replaced with nano-sized silicon particles.
The first to third steps in comparative example 5 were the same as those in example 1. Such detail steps were shown at example 1.
At a fourth step, the SiMP@C of 300 mg and graphene oxide of 150 mg were ultrasonically dispersed in a mixed solvent of 50 ml water and 50 ml ethanol. Then, the mixture was filtered by vacuum extraction, and then dried at 70° C. to obtain a composite material.
At a fifth step, the composite material was heated at 800° C. for 2 h, at a flow rate of argon of 50 ml/min. The heating rate was 5° C./min. Then, a composite anode material was obtained.
Referring to
Referring to
Referring to
The micrometer-sized silicon particles (SiMP), the carbon-coated second micrometer-sized silicon particles (SIMP@C), and the composite anode material (SiMP@C-GN) prepared in different steps in example 1 were further respectively used to manufacture anodes of lithium-ion batteries. The cycle performances were tested.
Referring to
Other anodes were prepared by mixing the materials of examples 1-10 and comparative examples 1-4 together with conductive carbon and binder SBR according to a mass ratio of 96:2:2. A lithium sheet was used as a counter electrode to assemble a half cell. Electrolyte was also used, including vinyl carbonate/diethyl carbonate (EC/DEC, 1:1, v/v) containing 10 vol % fluoroethylene carbonate (FEC) and 1 vol % vinylene carbonate (VC) additives. The performance results tested under a current density of 1 A/g current density are shown in Table 1 below.
Table 1 shows;
1. By comparing example 1 with examples 2 and 3, when the amount of the carbon coating formed by the chemical vapor deposition decreases, the internal silicon active particles cannot be effectively protected, and the cycle stability of the material decreases.
2. By comparing example 1 with examples 8 and 9 and with comparative examples 1 and 2, when the reduced graphene oxide at the outside layer decreases in amount or even disappears in the composite material, the stress buffer function is weakened, and the cycle stability of the material is reduced.
3. By comparing example 1 with example 7 and comparative example 3, when the etching degree increases, the overall cycle stability of the material is improved, but the capacity decreases since the amount of active material decreases.
4. By comparing example 1 with comparative example 4, when nano-sized silicon is used as source material, although the cycle performance of the material is slightly improved, its density is much lower than that of the composite material prepared by micrometer-sized silicon. Therefore, the multilayer buffer structure in the application can obtain a higher volumetric performance when applied to the micrometer-sized silicon anode.
The composite anode material prepared by the method in the present application has a strong and tough multilayer buffer structure. The buffer structure stabilizes the micrometer-sized silicon particles that crushed during the cycle process and can resist the pressure during the calendering of the electrode.
Specifically, the inner carbon coating that is highly graphitized and the appropriate space have excellent mechanical flexibility; which can effectively stabilize the internal micrometer-sized silicon particles, and protect the exposed fresh surface when the micrometer-sized silicon particles are broken. The outer network formed by the reduced graphene oxide that is dense and contracted closely connects the internal carbon-coated second micrometer-sized silicon particles (SiMP@C) together as a whole of a mechanic and electric. Thus, the strength and toughness of the electrode increase, so as to realize effective mechanical buffer and continuous and rapid electron transfer in the process of lithiation/dilithiation. At the same time, the dense network with high-strength and high modulus formed by the assembling and stacking of the reduced graphene oxide, can maintain the structural integrity of the internal silicon-carbon active particles to a greatest extent during the calendering.
In addition, the micrometer-sized silicon anode (with a compacted density of 1.0 g/cm3), when manufactured by the composite anode material prepared in the present application, can obtain a long cycle life of 1000 cycles and maintain a high capacity (750 mAh/g). Thus, the composite anode material has a great significance for the practicability of the micrometer-sized silicon anode.
The embodiments shown and described above are only examples. Therefore, many commonly-known features and details are neither shown nor described. Even though numerous characteristics and advantages of the present technology have been set forth in the foregoing description, together with details of the structure and function of the present application, the disclosure is illustrative only, and changes may be made in the detail, including in matters of shape, size, and arrangement of the parts within the principles of the present application, up to and including the full extent established by the broad general meaning of the terms used in the claims. It will, therefore, be appreciated that the embodiments described above may be modified within the scope of the claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202010052236.5 | Jan 2020 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/072182 | 1/15/2021 | WO |
