CN114229807B - Si@SiOx-TiN/C composite anode material, preparation method and lithium ion battery - Google Patents
Si@SiOx-TiN/C composite anode material, preparation method and lithium ion battery Download PDFInfo
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Abstract
The invention provides a Si@SiOx-TiN/C composite anode material, a preparation method and a lithium ion battery, and relates to the technical field of sodium ion batteries, wherein the preparation method comprises the following steps: adding nano silicon into an alcohol solvent containing a surfactant to obtain a stable suspension; dropwise adding a titanium source into the suspension to obtain a mixture A; transferring the mixture A into a hydrothermal kettle for hydrothermal reaction to obtain a Si@TiO2 composite anode material; ball-milling and mixing the Si@TiO2 composite anode material with a cracking carbon precursor or high-conductivity carbon to obtain a mixture B; and (3) heating the mixture B under the protection of nitrogen, and cooling to room temperature to obtain the Si@SiOx-TiN/C composite anode material. Compared with the prior art, the Si@SiOx-TiN/C composite anode material provided by the invention has good charge-discharge rate performance and cycle stability when being used as an anode material of a lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a Si@SiOx-TiN/C composite anode material, a preparation method and a lithium ion battery.
Background
Lithium ion batteries have been widely used in the fields of portable electronic products, new energy automobiles and energy storage. In recent years, with the rapid development of the new energy automobile industry, higher requirements are put on the capacity, service life, multiplying power performance, safety and reliability performance and the like of lithium ion batteries.
Silicon negative electrode materials are attracting attention because of having a high theoretical specific capacity, low cost, environmental friendliness and higher charge-discharge voltage than lithium dendrite formation. However, the silicon negative electrode has poor conductivity, and serious volume expansion and shrinkage can occur in the charge and discharge process, pulverization of silicon can be caused in the volume change process, and an SEI film is continuously formed, so that the capacity of the battery is rapidly attenuated, and the cycle performance is deteriorated.
At present, the Si/C composite anode material prepared by taking the carbon material as the coating material is used for a lithium ion battery, so that the performance of the silicon-based anode material can be effectively improved. However, the mechanical strength of the carbon material is low, and the cracking of the coated carbon layer is easily caused by the stress generated by the volume expansion of silicon during long circulation. In the prior art, transition metal nitride (TiN) is introduced into the Si/C composite anode material, so that the strength of a coating layer on the surface of silicon particles can be improved, and the electrochemical performance of the Si-based composite anode material is improved, but in the process of preparing the Si/TiN/C composite anode material, tiN powder cannot form a good coating shell layer on the surface of the silicon particles, and the silicon particles are in physical contact with the surface coating layer, so that the silicon particles cannot be effectively protected in a long-cycle process, the performance of the material is influenced, and the application of the Si/TiN/C composite anode material in the aspect of lithium ion batteries is limited.
In view of the above drawbacks, the present inventors have finally achieved the present invention through long-time studies and practices.
Disclosure of Invention
The invention solves the problems that the TiN powder in the prior art cannot form a good coating shell layer on the surface of the silicon particles, cannot form effective protection in a long-cycle process, and limits the application of the lithium ion battery.
In order to solve the problems, the invention provides a preparation method of a Si@SiOx-TiN/C composite anode material, which comprises the following steps:
step S1, adding nano silicon into an alcohol solvent containing a surfactant, and performing ultrasonic dispersion to obtain a stable suspension;
step S2, dropwise adding a titanium source into the suspension in a stirring state to obtain a mixture A;
s3, transferring the mixture A into a hydrothermal kettle for hydrothermal reaction to obtain a Si@TiO2 composite anode material;
step S4, ball-milling and mixing the Si@TiO2 composite anode material with a cracking carbon precursor or high-conductivity carbon to obtain a mixture B;
and S5, heating the mixture B under the protection of nitrogen, and cooling to room temperature to obtain the Si@SiOx-TiN/C composite anode material.
Preferably, the mass ratio of the nano silicon to the surfactant is 1 (0.5-1).
Preferably, the surfactant comprises polyvinylpyrrolidone, F127 or P123.
Preferably, in step S2, the molar ratio of the titanium source to the nano-silicon ranges from (0.1 to 1): 1.
preferably, the titanium source comprises a chloride of titanium, a sulfate of titanium or an alkoxide of titanium.
Preferably, the temperature range in the hydrothermal reaction is 150-230 ℃, and the time range of the hydrothermal reaction is 12-36h.
Preferably, the addition mass percentage range of the cracking carbon precursor or the highly conductive carbon includes 5wt.% to 40wt.%.
Preferably, the temperature range of the heating treatment in the step S5 is 1100-1500 ℃, and the time of the heating treatment is in the range of 0.5-6h.
Compared with the prior art, the preparation method of the Si@SiOx-TiN/C composite anode material disclosed by the invention is characterized in that Si@TiO is adopted 2 The composite anode material is ball-milled and mixed with cracking carbon precursor or high-conductivity carbon, and in the heating treatment, under the condition that silicon and carbon are simultaneously used as reducing agents, tiO 2 Is reduced to Ti 2 O 3 ，Ti 2 O 3 The SiOx layer is connected with the TiN through chemical bonds, so that the combination between the coating layer and the silicon particles is tighter; in the Si@SiOx-TiN/C composite anode material prepared by the method, the TiN can form a relatively complete rigid protective layer on the surface of the silicon particles, and due to the synergistic effect of the TiN and the C, the inert layer on the surface of the silicon particles not only has relatively high conduction characteristic, but also has high strength, and can effectively relieve the volume effect of silicon in the lithium intercalation process. Therefore, when the composite anode material is used as the anode material of a lithium ion battery, the composite anode material has good charge-discharge rate performance and cycle stability.
In order to solve the technical problems, the invention also provides the Si@SiOx-TiN/C composite anode material, which is prepared according to the preparation method of the Si@SiOx-TiN/C composite anode material.
The preparation method of the Si@SiOx-TiN/C composite anode material and the Si@SiOx-TiN/C composite anode material has the same advantages as those of the prior art, and is not repeated herein.
In order to solve the technical problems, the invention also provides a lithium ion battery, which comprises the Si@SiOx-TiN/C composite anode material prepared by the preparation method of the Si@SiOx-TiN/C composite anode material or the Si@SiOx-TiN/C composite anode material.
The preparation method of the lithium ion battery and the Si@SiOx-TiN/C composite anode material or the Si@SiOx-TiN/C composite anode material has the same advantages as those of the prior art, and is not repeated herein.
Drawings
FIG. 1 is a flow chart of a preparation method of a Si@SiOx-TiN/C composite anode material in an embodiment of the invention;
FIG. 2 is an XRD plot of a Si@SiOx-TiN/C composite anode material according to an embodiment of the invention;
FIG. 3 is a schematic diagram of an electron microscope of a Si@SiOx-TiN/C composite anode material according to an embodiment of the invention;
FIG. 4 is a transmission electron microscope image II of the Si@SiOx-TiN/C composite anode material and an EDS analysis image of Si, ti, N, O and C elements in the embodiment of the invention;
FIG. 5 is a graph showing the cycle performance of a Si@SiOx-TiN/C composite anode material according to an embodiment of the invention at a current density of 1A/g.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the description of embodiments of the present application, the term "description of some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same implementations or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
As shown in fig. 1, the embodiment of the invention provides a preparation method of a si@siox-TiN/C composite anode material, which comprises the following steps:
step S1, adding nano silicon into an alcohol solvent containing a surfactant, and performing ultrasonic dispersion to obtain a stable suspension;
step S2, dropwise adding a titanium source into the suspension in a stirring state to obtain a mixture A;
s3, transferring the mixture A into a hydrothermal kettle for hydrothermal reaction to obtain a Si@TiO2 composite anode material;
step S4, ball-milling and mixing the Si@TiO2 composite anode material with a cracking carbon precursor or high-conductivity carbon to obtain a mixture B;
and S5, heating the mixture B under the protection of nitrogen, and cooling to room temperature to obtain the Si@SiOx-TiN/C composite anode material.
The preparation method of the Si@SiOx-TiN/C composite anode material comprises the steps of 2 Ball milling and mixing the composite anode material with cracking carbon precursor or high-conductivity carbon, and under the condition that silicon and carbon are simultaneously used as reducing agents in heating treatment, tiO 2 Is reduced to Ti 2 O 3 ，Ti 2 O 3 And the SiOx layer is connected with the TiN through chemical bonds, so that the combination between the coating layer and the silicon particles is tighter, and the electrochemical performance of the material is improved.
In the step S1, the addition of the surfactant is beneficial to the uniform dispersion of the silicon particles and the formation of a uniform titanium dioxide coating layer on the surfaces of the silicon particles.
In some embodiments, the mass ratio of the nanosilicon to the surfactant ranges from 1 (0.5-1). Therefore, the silicon particles can be uniformly dispersed in the surfactant, and the subsequent formation of a uniform titanium dioxide coating layer on the surfaces of the silicon particles is facilitated.
In some preferred embodiments, the surfactant comprises polyvinylpyrrolidone, F127, or P123. The materials are easy to obtain, and the dispersing effect is good.
In some preferred embodiments, the alcohol solvent in step S1 is ethanol, which is inexpensive, and the material is easy to obtain, and can be used to disperse nano silicon together with the surfactant, so that the dispersing effect is good.
In some embodiments, in step S2, the molar ratio of the titanium source to the nano-silicon ranges from (0.1-1): 1. is beneficial to the formation of subsequent TiO2 coating layers.
Optionally, the titanium source comprises titanium chloride, titanium sulfate or titanium alkoxide, and in some preferred embodiments, the titanium source comprises tetrabutyl titanate or isopropyl titanate, which is readily available.
In some embodiments, the temperature in the hydrothermal reaction ranges from 150 ℃ to 230 ℃ and the time range of the hydrothermal reaction ranges from 12 to 36 hours. Thus, a uniform titanium dioxide coating layer can be formed on the surface of the silicon particles.
In some preferred embodiments, the addition mass percent range of the cracking carbon precursor or highly conductive carbon includes 5wt.% to 40wt.%. The method is beneficial to the formation of TiN as a reducing agent in the follow-up process, and saves the cost.
In some embodiments, the si@tio2 composite anode material is ball milled with a cracking carbon precursor or highly conductive carbon, wherein the purpose of the ball milling is to let the cracking carbon precursor or highly conductive carbon and si@tio 2 The compound is uniformly mixed, thereby being beneficial to the subsequent reduction of Si and carbon and TiO 2 Reduction to Ti 2 O 3 Then is favorable to Ti 2 O 3 And nitrogen gas to produce TiN.
In some preferred embodiments, the temperature range of the heat treatment in step S5 comprises 1100 ℃ to 1500 ℃ and the time of the heat treatment is in the range of 0.5 to 6 hours. Therefore, the Si@SiOx-TiN/C composite anode material is easier to form, and the efficiency is improved.
In step S5 of this embodiment, the nitrogen gas is used not only as a protective atmosphere but also for introducing N element, and in the heating treatment, tiO is used under the condition that silicon and carbon are used as reducing agents simultaneously 2 Is reduced to Ti 2 O 3 ，Ti 2 O 3 And reacting with nitrogen to form TiN, and finally forming the Si@SiOx-TiN/C composite anode material.
According to the preparation method of the Si@SiOx-TiN/C composite anode material, inert components with strength are introduced into the carbon coating layer, and the synergistic effect among different inert components is fully utilized, so that the coating layer on the surface of the silicon particle has high strength and high electronic and ion conduction, and the electrochemical performance of the silicon-based composite anode material is effectively improved. Specifically, in the embodiment, the Si@TiO2 composite anode material is mixed with a cracking carbon precursor or high-conductivity carbon in a ball milling way, and the mixture is heatedIn the condition of silicon and carbon being simultaneously used as reducing agent, tiO 2 Is reduced to Ti 2 O 3 ，Ti 2 O 3 Reacting with nitrogen to form TiN, forming an SiOx layer on the surface of the silicon particles through oxidation-reduction reaction, and connecting the SiOx layer with the TiN through chemical bonds to enable the combination between the coating layer and the silicon particles to be tighter; in the Si@SiOx-TiN/C composite anode material prepared by the method, the TiN can form a relatively complete rigid protective layer on the surface of the silicon particles, and due to the synergistic effect of the TiN and the C, the inert layer on the surface of the silicon particles not only has relatively high conduction characteristic, but also has high strength, and can effectively relieve the volume effect of silicon in the lithium intercalation process. Therefore, when the composite anode material is used as the anode material of a lithium ion battery, the composite anode material has good charge-discharge rate performance and cycle stability.
The invention also provides a Si@SiOx-TiN/C composite anode material, which is prepared according to the preparation method of the Si@SiOx-TiN/C composite anode material.
The preparation methods of the Si@SiOx-TiN/C composite anode material and the Si@SiOx-TiN/C composite anode material in the embodiment have the same advantages as those of the preparation methods in the prior art, and are not repeated here.
The invention also provides a lithium ion battery, which comprises the Si@SiOx-TiN/C composite anode material prepared by the preparation method of the Si@SiOx-TiN/C composite anode material or the Si@SiOx-TiN/C composite anode material.
The preparation method of the lithium ion battery and the Si@SiOx-TiN/C composite anode material or the Si@SiOx-TiN/C composite anode material in the embodiment has the same advantages as those of the preparation method of the Si@SiOx-TiN/C composite anode material in the prior art, and is not repeated herein.
Example 1
The embodiment provides a preparation method of a Si@SiOx-TiN/C composite anode material, which comprises the following steps:
1) Adding 0.5g of nano silicon into ethanol containing 0.5g of polyvinylpyrrolidone, and performing ultrasonic dispersion for 2 hours to obtain a stable suspension;
2) Dropwise adding 3mL of tetrabutyl titanate titanium source into the suspension in the step 1) under stirring to obtain a mixture A;
3) Transferring the mixture A obtained in the step 2) into a hydrothermal kettle, and keeping the temperature at 230 ℃ for 12 hours to obtain a Si@TiO2 compound;
4) Ball-milling and mixing the Si@TiO2 compound obtained in the step 3) with SuperP to obtain a mixture B, wherein the adding mass percentage of the SuperP is 30%;
5) Transferring the mixture B obtained in the step 4) into a tube furnace, treating for 3 hours at 1200 ℃ under the protection of nitrogen, and obtaining the Si@SiOx-TiN/C compound after the temperature of the tube furnace is reduced to room temperature.
As shown in fig. 2-4, fig. 2 is an XRD graph of the si@siox-TiN/C composite negative electrode material of the present example, and it can be seen from the graph that characteristic peaks at 28.5 °, 47.4 °, 56.2 °, 69.2 °, 76.4 ° and 88.1 ° are completely coincident with standard cards of Si (pdf#99-0092), while characteristic peaks at 36.7 °, 42.6 °, 61.9 °, 74.2 ° and 78.0 ° are completely coincident with standard cards of TiN (pdf#87-0632), indicating successful preparation of TiN crystal structure in the si@siox-TiN/C composite negative electrode material. As can be seen from fig. 3 and 4, the surface of the silicon particles is coated with a uniform SiOx layer, and the SiOx layer is an amorphous layer, and the TiN layer is uniformly coated on the surface of the silicon particles, and at the same time, the carbon layer is uniformly distributed around the si@siox-TiN particles, indicating successful preparation of the si@siox-TiN/C composite.
Therefore, the Si@SiOx-TiN/C composite anode material prepared in the embodiment comprises silicon particles, a silicon oxide layer and a titanium nitride layer on the surfaces of the silicon particles, and a carbon layer coated on the surfaces of the silicon oxide layer and the titanium nitride layer. Therefore, the SiOx layer is connected with the TiN through chemical bonds, so that the combination between the coating layer and the silicon particles is tighter, in the Si@SiOx-TiN/C composite anode material prepared by the embodiment, the TiN can form a complete rigid protective layer on the surface of the silicon particles, and due to the synergistic effect of the TiN and the C, the inert layer on the surface of the silicon particles not only has higher conduction characteristics, but also has high strength, and the volume effect of silicon in the lithium removal and intercalation process can be effectively relieved. Therefore, when the composite anode material is used as the anode material of a lithium ion battery, the composite anode material has good charge-discharge rate performance and cycle stability.
Example 2
The embodiment provides a lithium ion battery, which comprises the Si@SiOx-TiN/C composite anode material obtained in the embodiment 1, wherein the preparation process of the lithium ion battery comprises the following steps:
the Si@SiOx-TiN/C composite anode material obtained in the example 1, acetylene black serving as a conductive agent and CMC serving as a binder are mixed according to a mass ratio of 70:10:20, the mixture is prepared into slurry by distilled water, the slurry is uniformly coated on a copper foil, and the slurry is dried in vacuum at 60 ℃ for 8 hours to prepare the electrode plate for the experimental battery.
And then, a lithium sheet is used as a counter electrode, an EC+DEC solution of 1mol/L LiPF6 (volume ratio is 1:1, and the proportion of FEC additives is 5%) is used as an electrolyte, a Celgard 2400 film is used as a diaphragm, and the LIR2430 button cell is assembled in a glove box filled with argon atmosphere.
The specific capacities of the battery at 0.1,0.5,1.0 and 5.0A/g current densities are 1537mAh/g,1280mAh/g,1185mAh/g and 817mAh/g respectively, the specific capacities of the battery are 1154mAh/g and 94.3% after 50 circles at 500mAh/g current densities, and the specific capacities still reach 910mAh/g after 200 circles at 1A/g current densities. Exhibiting good cycle performance.
Example 3
The embodiment provides a preparation method of a Si@SiOx-TiN/C composite anode material, which comprises the following steps:
1) Adding 0.5g of nano silicon into ethanol containing 0.05g of polyvinylpyrrolidone, and performing ultrasonic dispersion for 2 hours to obtain a stable suspension;
2) Dropwise adding 1.2mL of tetrabutyl titanate titanium source into the suspension in the step 1) under stirring to obtain a mixture A;
3) Transferring the mixture A obtained in the step 2) into a hydrothermal kettle, and keeping the temperature at 180 ℃ for 24 hours to obtain a Si@TiO2 compound;
4) Ball-milling and mixing the Si@TiO2 compound obtained in the step 3) and conductive carbon black (SuperP) to obtain a mixture B, wherein the adding mass percentage of the SuperP is 30%;
5) Transferring the mixture B obtained in the step 4) into a tube furnace, treating for 3 hours at 1100 ℃ under the protection of nitrogen, and obtaining the Si@SiOx-TiN/C compound after the temperature of the tube furnace is reduced to room temperature.
Example 4
The embodiment provides a lithium ion battery, which comprises the Si@SiOx-TiN/C composite anode material obtained in the embodiment 3, wherein the preparation process of the lithium ion battery comprises the following steps:
the Si@SiOx-TiN/C composite anode material obtained in the example 3, acetylene black serving as a conductive agent and CMC serving as a binder are mixed according to a mass ratio of 70:10:20, the mixture is prepared into slurry by distilled water, the slurry is uniformly coated on a copper foil, and the slurry is dried in vacuum at 60 ℃ for 8 hours to prepare the electrode plate for the experimental battery.
And then taking a lithium sheet as a counter electrode, taking an EC+DEC solution (volume ratio is 1:1 and the proportion of FEC additives is 5%) of 1mol/L LiPF6 as an electrolyte, taking a Celgard 2400 membrane as a diaphragm, and assembling the lithium sheet into the LIR2430 button cell in a glove box filled with argon atmosphere.
The specific capacities of the battery at 0.1,0.5,1.0 and 5.0A/g current densities were 2072mAh/g, 1822mAh/g, 1639mAh/g and 1037mAh/g, respectively, and were measured 1550mAh/g by cycling 50 times at 500mAh/g current densities, with a capacity retention of 88.2%. As shown in FIG. 5, after 200 times of circulation at the current density of 1A/g, the specific capacity of the material is reduced from 1549mAh/g after 200 times of circulation, but the specific capacity still reaches 1166mAh/g, the capacity retention rate is 72%, the circulation efficiency is always maintained above 98%, and good circulation performance is shown.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (7)
1. The preparation method of the Si@SiOx-TiN/C composite anode material is characterized by comprising the following steps of:
step S1, adding nano silicon into an alcohol solvent containing a surfactant, and performing ultrasonic dispersion to obtain a stable suspension, wherein the mass ratio of the nano silicon to the surfactant is 1 (0.5-1);
step S2, dropwise adding a titanium source into the suspension in a stirring state to obtain a mixture A;
s3, transferring the mixture A into a hydrothermal kettle for hydrothermal reaction to obtain the Si@TiO2 composite anode material, wherein the temperature in the hydrothermal reaction is 150-230 ℃, and the time of the hydrothermal reaction is 12-36h;
step S4, ball-milling and mixing the Si@TiO2 composite anode material with a cracking carbon precursor or high-conductivity carbon to obtain a mixture B;
and S5, heating the mixture B under the protection of nitrogen, and cooling to room temperature to obtain the Si@SiOx-TiN/C composite anode material, wherein the temperature of the heating treatment is 1100-1500 ℃, and the time of the heating treatment is 0.5-6h.
2. The method for preparing the si@siox-TiN/C composite negative electrode material according to claim 1, wherein the surfactant comprises polyvinylpyrrolidone, F127 or P123.
3. The method for preparing the si@siox-TiN/C composite negative electrode material according to claim 1, wherein in step S2, the molar ratio of the titanium source to the nano-silicon is (0.1-1): 1.
4. the method for producing a si@siox-TiN/C composite negative electrode material according to claim 1 or 3, wherein the titanium source comprises a chloride of titanium, a sulfate of titanium or an alkoxide of titanium.
5. The method for preparing the si@siox-TiN/C composite negative electrode material according to claim 1, wherein in step S4, the addition mass percentage of the cracking carbon precursor or the highly conductive carbon is 5 wt% -40 wt%.
6. A si@siox-TiN/C composite negative electrode material, characterized by being prepared according to the preparation method of the si@siox-TiN/C composite negative electrode material according to any one of claims 1-5.
7. A lithium ion battery, characterized by comprising the si@siox-TiN/C composite anode material prepared by the preparation method of the si@siox-TiN/C composite anode material according to any one of claims 1 to 5 or the si@siox-TiN/C composite anode material according to claim 6.
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