CN111403741A - Nano SiO-C composite material and application thereof in preparation of lithium ion battery cathode material - Google Patents

Nano SiO-C composite material and application thereof in preparation of lithium ion battery cathode material Download PDF

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CN111403741A
CN111403741A CN202010212153.8A CN202010212153A CN111403741A CN 111403741 A CN111403741 A CN 111403741A CN 202010212153 A CN202010212153 A CN 202010212153A CN 111403741 A CN111403741 A CN 111403741A
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sio
composite material
reaction solution
heating
lithium ion
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范智宇
杨洪
杜雄伟
梁晶晶
周鼎
孙延先
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Huading Guolian Sichuan Power Battery Co ltd
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Huading Guolian Sichuan Power Battery Co ltd
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Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nano SiO-C composite material and application thereof in preparing a lithium ion battery, in particular to a negative electrode material of a SiOx/CNTs lithium ion battery. The nano SiO-C composite material is prepared by taking SiO as CaO as a raw material, and Si and SiO are obtained by utilizing disproportionation reaction of SiO at high temperature2And further based on SiO at high temperatures2Reacting with CaO, and further applying an electrostatic spinning method to obtain SiO-CaSiO3The Si particles are coated in the carbon nanotube, so that the ion coating performance is more complete, the controllability on the structural morphology of the material is stronger, the agglomeration phenomenon of small particles is reduced, the coulombic efficiency of the material is improved, the cycle performance and the first-effect performance are improved, and the electrochemical performance of the material is better.

Description

Nano SiO-C composite material and application thereof in preparation of lithium ion battery cathode material
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a nano SiO-C composite material and application thereof in preparing a lithium ion battery, in particular to a negative electrode material of a SiOx/CNTs lithium ion battery.
Background
With the development of new energy technology, lithium ion batteries have become a main energy product due to the advantages of large energy density, long cycle life, good rate capability and safety performance and environmental protection. With the rapid development of electronic technology, electronic and power products tend to be more and more miniaturized and light-weighted, and the performance requirements of lithium ion batteries are higher and higher, especially the energy density requirements of the lithium ion batteries, and the lithium ion batteries are expected to have higher energy density without affecting the service performance. Therefore, researchers continuously seek and improve the specific capacity of the positive electrode and the specific capacity of the negative electrode to improve the energy density of the lithium ion battery.
The graphite negative electrode material has the advantages of good cycle performance and the like, and is widely applied, but the graphite negative electrode material has low lithium storage capacity, the lithium intercalation potential is close to the metallic lithium potential, and the graphite negative electrode material has the defect of difficult high-rate charging and certain potential safety hazard. The appearance of the high-capacity silicon-based negative electrode material (4200mAh/g, which is far higher than the theoretical specific capacity 372mAh/g of the graphite negative electrode material) provides a material foundation for the research of the high-specific-energy lithium ion battery. However, the crystalline silicon has a volume change of up to 310% during the lithium intercalation and deintercalation processes, and such a large volume change may cause structural damage and mechanical pulverization of the material, resulting in separation between active materials and between the active materials and a current collector, which in turn may lose electrical contact, resulting in capacity fade and deterioration of cycle performance. In recent years, researchers introduce silicon oxide, metal, graphite and the like as buffer materials to buffer and limit tension caused by volume change of crystalline silicon in the lithium insertion and removal processes, further inhibit the breakage of silicon, and greatly improve the electrochemical cycling stability of the silicon-based negative electrode material. However, since the silicon oxide used as the buffer material reacts with lithium ions during the lithium intercalation process to generate lithium oxide and other irreversible substances, the first irreversible capacity of the silicon-based negative electrode material is increased and the first coulombic efficiency is reduced, thereby limiting the application of the silicon-based negative electrode material. In contrast, researchers have proposed that SiO nanostructures improve the electrochemical performance of SiO by, for example, compounding with carbon materials.
Reyurong et al SiO/CNTs: the novel lithium ion battery cathode material prepares the SiO/CNTs composite material coated by the carbon nano tube by a chemical deposition method (CVD). The method utilizes methane as a carbon source, SiO powder as a matrix and nickel as a catalyst to prepare the SiO/CNTs composite material. The composite material used as the lithium ion battery cathode material shows better cycle performance than SiO, the coulombic efficiency is determined to be 67.4%, and the capacity is maintained to be 63.4% after 80 cycles. According to the method, the CNT is grown on the surface of the SiO through the CVD method and is coated, compared with the traditional SiO material, the cycle performance of the material is improved to a certain extent, but the problems of low first effect and the like are not improved. In addition, the coating is not complete, and the structure of the CNTs cannot be controlled randomly in the catalytic synthesis process by using a CVD method.
Therefore, the development of the SiO-C composite material which has better electrochemical performance, more complete ion coating and stronger controllability of material structure morphology and can be used for the lithium ion battery cathode material has positive significance for improving the performance of the lithium ion battery.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a nano SiO-C composite material which has better electrochemical performance, more complete ion coating and stronger controllability on the structural morphology of the material;
the second technical problem to be solved by the invention is to provide a preparation method of the nano SiO-C composite material;
the third technical problem to be solved by the invention is to provide the application of the nano SiO-C composite material in preparing the negative electrode material of the lithium ion battery, in particular to the SiOx/CNTs lithium ion battery.
In order to solve the technical problems, the preparation method of the nano SiO-C composite material comprises the following steps:
(1) taking SiO and CaO as raw materials, fully dispersing in absolute ethyl alcohol, carrying out ball milling treatment, and then carrying out spray drying to obtain SiO-CaO composite nano particles;
(2) dissolving Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) in N, N-Dimethylformamide (DMF) to prepare a first reaction solution, heating and preserving heat for later use; dissolving polymethyl methacrylate (PMMA) and the prepared SiO-CaO composite nano particles in N, N-Dimethylformamide (DMF) to prepare a second reaction solution, and heating and preserving heat for later use;
(3) respectively taking the first reaction solution and the second reaction solution as a spinning shell solution and a core solution to carry out electrostatic spinning preparation, so as to obtain carbon nanotube-coated spinning;
(4) and carrying out two-stage heating treatment on the obtained spinning to obtain the required nano SiO-C composite material with the chemical composition of SiO-CaSiO 3-Si-CNFs.
Specifically, in the step (1), the molar ratio of SiO to CaO is 8-9: 1-2.
Specifically, in the step (1), the ball milling step preferably adopts 0.2mm zirconia balls, and the ball-to-material ratio is controlled to be 20: 1, performing ball milling for 3 hours at the rotating speed of 2800 rpm/min.
Specifically, in the step (2):
in the first reaction solution, the mass ratio of the PAN, the PMMA and the DMF is 0.4-0.8: 0.2-0.6: 8-10;
in the second reaction solution, the mass ratio of PMMA, SiO-CaO composite nano particles to DMF is 2-3: 1-2: 4-8.
Specifically, in the step (2), the heating step is heating to 50-80 ℃.
Specifically, in the step (3), the electrospinning preparation step includes:
controlling the distance between the needle head and the aluminum foil receiving scroll to be 8-12m, and adjusting the voltage to be 12-15 KV;
controlling the feeding speed of the first reaction solution to be 0.6-1 ml/h;
the feeding speed of the second reaction solution is controlled to be 1.5-2.5 ml/h.
Specifically, in the step (4), the two-stage heating step includes a first heating step at 300 ℃ under an air atmosphere, and a second heating step at 1000 ℃ under an inert atmosphere.
Specifically, in the step (4):
controlling the temperature rise speed of the first heating step to be 0.5-1.5 ℃/min;
and controlling the temperature rise speed of the second heating step to be 2.5-3.5 ℃/min.
The invention also discloses the nano SiO-C composite material prepared by the method.
The invention also discloses application of the nano SiO-C composite material in preparing a lithium ion battery cathode material.
The invention also discloses a lithium ion battery cathode prepared from the nano SiO-C composite material and a lithium ion battery. Specifically, the lithium ion battery is a SiOx/CNTs lithium ion battery.
The nano SiO-C composite material is prepared by taking SiO as CaO as a raw material, and Si and SiO are obtained by utilizing disproportionation reaction of SiO at high temperature2And further based on SiO at high temperatures2Reacting with CaO to obtain SiO-CaSiO3Si particles, effectively reducing SiO in the charging and discharging process2And L i+Formed L iSiO4、Li2Si2O5Equal irreversible substance pair L i+Thereby improving the coulomb efficiency of the material; further using an electrostatic spinning method to obtain SiO-CaSiO3Si particles are coated in the carbon nanotube, so that the coating property of the carbon nanotube on ions is more complete, the controllability of the structural morphology of the material is stronger, the agglomeration phenomenon of small particles is reduced, and the cycle performance and the first-effect performance are improved; the good conductivity of the carbon nano tube and the buffer space provided by the carbon nano tube solve the problem of poor conductivity of the silicon-based material to a certain extent, reduce the volume expansion of the material and ensure that the electrochemical performance of the material is better.
Figure BDA0002423193210000041
Figure BDA0002423193210000042
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a diagram illustrating the preparation of SiO-CaSiO in example 13-a schematic structural representation of Si/CNTs composites;
FIG. 2 is a schematic structural diagram of a CVD method for coating SiO in the prior art.
Detailed Description
Example 1
The preparation method of the nano SiO-C composite material comprises the following steps:
(1) according to the weight ratio of 8.5: 1.5, uniformly dispersing SiO and CaO in absolute ethyl alcohol according to a molar ratio, performing ball milling treatment, selecting a zirconia ball with the diameter of 0.2mm, and controlling a ball material ratio to be 20: 1, ball milling for 3h at the rotating speed of 2800rpm/min to form nano particles; spray drying the obtained solution containing the SiO/CaO nano-particles to obtain SiO-CaO composite nano-particles for later use; .
(2) According to the weight ratio of 0.6: 0.4: 9, dissolving PAN and PMMA in DMF to prepare a first reaction solution for later use; according to the weight ratio of 2.5: 1.5: 6, taking PMMA to prepare SiO-CaO composite nano particles, placing the SiO-CaO composite nano particles in DMF, and preparing to obtain a second reaction solution for later use;
respectively placing the first reaction solution and the second reaction solution on a magnetic stirrer, controlling the temperature to be 60 ℃ and the rotating speed to be 400rpm, and carrying out magnetic stirring for 6 hours to fully disperse;
(3) respectively placing the first reaction solution and the second reaction solution into two 10ml injectors as a spinning shell solution and a core solution, and performing electrostatic spinning preparation; the needle head is used with the model of 17-23G, the distance between the needle head and the aluminum foil receiving scroll is adjusted to be 10cm, the voltage is adjusted to be 14KV, the feeding speed of the first reaction solution is controlled to be 0.8ml/h, the feeding speed of the second reaction solution is controlled to be 2ml/h, and the spinning is obtained through preparation;
(4) placing the obtained spinning in a tubular furnace, heating to 280 ℃ at a heating speed of 1 ℃/min for 2h in an air atmosphere; heating to 900 ℃ at a heating rate of 3 ℃/min for 3h in an Ar gas environment to obtain the SiO-CaSiO with the required chemical composition3-SiO-C composites of Si-CNTs.
The material obtained in this example was examined by scanning electron microscope (FE-SEM, Hitachi, S-5500), and the structure of the material was as shown in FIG. 1. As can be seen, this example produced SiO-CaSiO3-Si particles are encapsulated in tubular CNTs.
The composite material prepared in the embodiment is assembled and subjected to a power-on test, the obtained composite material, Super P and CMC are mixed according to a mass ratio of 85: 5: 10, a proper amount of deionized water is added to prepare a slurry, then the slurry is coated on a circular copper foil with the diameter of 10mm to prepare a pole piece, the pole piece is put into a glove box filled with argon after being subjected to vacuum drying at 80 ℃ for 12 hours to be assembled into a CR2032 button cell, metal lithium is used as a counter electrode, a diaphragm is Celgard2500 polypropylene porous membrane, an electrolyte is 1 mol/L L iPF6/EC (ethylene carbonate) + DMC (dimethyl carbonate) + EMC (methyl ethyl carbonate) (the volume ratio is 1: 1: l) containing 2% VC (vinylene carbonate), and the test conditions are that the voltage range is 0.01-1.5V and the current is 100 mA/g.
The test result shows that the specific capacity of the material reaches 1602mAh/g, the coulombic efficiency is 76.2%, and the specific capacity is 693mAh/g after 200 cycles. As can be seen, the SiO-CaSiO solution described in this example3the-Si-CNTs composite material has better electrochemical performance.
Example 2
The preparation method of the nano SiO-C composite material comprises the following steps:
(1) according to the following steps of 8: 2, uniformly dispersing SiO and CaO in absolute ethyl alcohol according to a molar ratio, performing ball milling treatment, selecting 0.2mm zirconia balls, and controlling a ball-to-feed ratio to be 20: 1, ball milling for 3h at the rotating speed of 2800rpm/min to form nano particles; spray drying the obtained solution containing the SiO/CaO nano-particles to obtain SiO-CaO composite nano-particles for later use;
(2) according to the weight ratio of 0.6: 0.4: 9, dissolving PAN and PMMA in DMF to prepare a first reaction solution for later use; according to the weight ratio of 2.5: 1.5: 6, taking PMMA to prepare SiO-CaO composite nano particles, placing the SiO-CaO composite nano particles in DMF, and preparing to obtain a second reaction solution for later use;
respectively placing the first reaction solution and the second reaction solution on a magnetic stirrer, controlling the temperature to be 60 ℃ and the rotating speed to be 500rpm, and carrying out magnetic stirring for 6 hours to fully disperse;
(3) respectively placing the first reaction solution and the second reaction solution into two 10ml injectors as a spinning shell solution and a core solution, and performing electrostatic spinning preparation; the needle head is used with the model of 17-23G, the distance between the needle head and the aluminum foil receiving scroll is adjusted to be 10cm, the voltage is adjusted to be 14KV, the feeding speed of the first reaction solution is controlled to be 1ml/h, the feeding speed of the second reaction solution is controlled to be 2ml/h, and the spinning is obtained through preparation;
(4) placing the obtained spinning in a tubular furnace, heating to 280 ℃ at a heating speed of 1 ℃/min for 2h in an air atmosphere; heating to 1000 deg.C at a heating rate of 3 deg.C/min for 3 hr in Ar gas environment to obtain SiO-CaSiO3-SiO-C composites of Si-CNTs.
The composite material prepared by the embodiment is assembled and subjected to a power-on test (same as embodiment 1), and the test result shows that the specific capacity of the material reaches 1548mAh/g, the coulombic efficiency is 78.1%, and after 200 cycles, the specific capacity is 682 mAh/g. As can be seen, the SiO-CaSiO solution described in this example3the-Si-CNTs composite material has better electrochemical performance.
Example 3
The preparation method of the nano SiO-C composite material comprises the following steps:
(1) according to the following steps of 9: 2, uniformly dispersing SiO and CaO in absolute ethyl alcohol according to a molar ratio, performing ball milling treatment, selecting 0.2mm zirconia balls, and controlling a ball-to-feed ratio to be 20: 1, ball milling for 3h at the rotating speed of 2800rpm/min to form nano particles; spray drying the obtained solution containing the SiO/CaO nano-particles to obtain SiO-CaO composite nano-particles for later use;
(2) according to the weight ratio of 0.4: 0.2: 8, dissolving PAN and PMMA in DMF to prepare a first reaction solution for later use; according to the following steps: 1: 4, putting PMMA and prepared SiO-CaO composite nano particles into DMF (dimethyl formamide), and preparing a second reaction solution for later use;
respectively placing the first reaction solution and the second reaction solution on a magnetic stirrer, controlling the temperature to be 50 ℃ and the rotating speed to be 500rpm, and carrying out magnetic stirring for 6 hours to fully disperse;
(3) respectively placing the first reaction solution and the second reaction solution into two 10ml injectors as a spinning shell solution and a core solution, and performing electrostatic spinning preparation; the needle head is used with the model of 17-23G, the distance between the needle head and the aluminum foil receiving scroll is adjusted to be 8cm, the voltage is adjusted to be 12KV, the feeding speed of the first reaction solution is controlled to be 0.6ml/h, the feeding speed of the second reaction solution is controlled to be 1.5ml/h, and the spinning is obtained through preparation;
(4) placing the obtained spinning in a tubular furnace, heating to 250 ℃ at a heating rate of 0.5 ℃/min in an air atmosphere for 2 h; heating to 950 ℃ at a heating rate of 2.5 ℃/min for 3h in an Ar gas environment to obtain the SiO-CaSiO with the required chemical composition3-SiO-C composites of Si-CNTs.
The composite material prepared by the embodiment is assembled and subjected to a power-on test (same as embodiment 1), and the test result shows that the specific capacity of the material reaches 1576mAh/g, the coulombic efficiency is 76.4%, and after 200 cycles, the specific capacity is 693 mAh/g. As can be seen, the SiO-CaSiO solution described in this example3the-Si-CNTs composite material has better electrochemical performance.
Example 4
The preparation method of the nano SiO-C composite material comprises the following steps:
(1) according to the following steps of 8: 1, uniformly dispersing SiO and CaO in absolute ethyl alcohol according to a molar ratio of 1, performing ball milling treatment, selecting a zirconia ball with the diameter of 0.2mm, and controlling a ball-to-feed ratio to be 20: 1, ball milling for 3h at the rotating speed of 2800rpm/min to form nano particles; spray drying the obtained solution containing the SiO/CaO nano-particles to obtain SiO-CaO composite nano-particles for later use;
(2) according to the weight ratio of 0.8: 0.6: 10, dissolving PAN and PMMA in DMF to prepare a first reaction solution for later use; according to the following steps of 3: 2: 8, taking PMMA to prepare SiO-CaO composite nano particles, placing the SiO-CaO composite nano particles in DMF, and preparing to obtain a second reaction solution for later use;
respectively placing the first reaction solution and the second reaction solution on a magnetic stirrer, controlling the temperature to be 80 ℃ and the rotating speed to be 400rpm, and carrying out magnetic stirring for 6 hours to fully disperse;
(3) respectively placing the first reaction solution and the second reaction solution into two 10ml injectors as a spinning shell solution and a core solution, and performing electrostatic spinning preparation; the needle head is used with the model of 17-23G, the distance between the needle head and the aluminum foil receiving scroll is adjusted to be 12cm, the voltage is adjusted to be 15KV, the feeding speed of the first reaction solution is controlled to be 1ml/h, the feeding speed of the second reaction solution is controlled to be 2.5ml/h, and the spinning is obtained through preparation;
(4) placing the obtained spinning in a tubular furnace, heating to 300 ℃ at a heating rate of 1.5 ℃/min in an air atmosphere for 2 h; heating to 1000 deg.C at a temperature rise rate of 3.5 deg.C/min in Ar gas environment for 3 hr to obtain SiO-CaSiO3-SiO-C composites of Si-CNTs.
The composite material prepared in the embodiment is assembled and subjected to a power-on test (same as embodiment 1), and the test result shows that the specific capacity of the material reaches 1610mAh/g, the coulombic efficiency is 75%, and after 200 cycles, the specific capacity is 676 mAh/g. As can be seen, the SiO-CaSiO solution described in this example3the-Si-CNTs composite material has better electrochemical performance.
Comparative example 1
According to the prior art, the reference SiO/CNTs: the preparation method of the novel lithium ion battery negative electrode material recorded in the specification specifically comprises the following steps: dissolving 8g of nickel nitrate hexahydrate in a certain amount of deionized water, adding 100g of SiO powder, carrying out ball milling for 10 hours, controlling the particle size to be less than or equal to 3 mu m, uniformly mixing, and evaporating the solvent to obtain SiO nickel nitrate-loaded powder; placing the mixture in a quartz boat, heating the mixture for 1h at the constant temperature of 550 ℃ in the nitrogen atmosphere, introducing a mixed gas of methane (50%) and hydrogen (50%), cracking the mixture for 1h at the temperature of 550 ℃, growing CNTs on the surface of SiO, coating the SiO to form the SiO/CNTs composite material, and continuously cooling the SiO/CNTs composite material to the room temperature under the protection of nitrogen. The structure of the obtained material is shown in FIG. 2, and it can be seen that the coating of the material is not complete, and the structure of CNTs cannot be controlled freely. The coulombic efficiency of the composite material used as the lithium ion battery cathode material is 67.4 percent through tests, and the capacity is maintained to be 63.4 percent after 80 cycles.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A preparation method of a nano SiO-C composite material is characterized by comprising the following steps:
(1) taking SiO and CaO as raw materials, fully dispersing in absolute ethyl alcohol, carrying out ball milling treatment, and then carrying out spray drying to obtain SiO-CaO composite nano particles;
(2) dissolving Polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) in N, N-Dimethylformamide (DMF) to prepare a first reaction solution, heating and preserving heat for later use; dissolving polymethyl methacrylate (PMMA) and the prepared SiO-CaO composite nano particles in N, N-Dimethylformamide (DMF) to prepare a second reaction solution, and heating and preserving heat for later use;
(3) respectively taking the first reaction solution and the second reaction solution as a spinning shell solution and a core solution to carry out electrostatic spinning preparation, so as to obtain carbon nanotube-coated spinning;
(4) and carrying out two-stage heating treatment on the obtained spinning to obtain the required nano SiO-C composite material with the chemical composition of SiO-CaSiO 3-Si-CNFs.
2. The method for preparing nano SiO-C composite material according to claim 1, wherein in the step (1), the molar ratio of SiO to CaO is 8-9: 1-2.
3. The method for preparing nano SiO-C composite material according to claim 1 or 2, wherein in the step (2):
in the first reaction solution, the mass ratio of the PAN, the PMMA and the DMF is 0.4-0.8: 0.2-0.6: 8-10;
in the second reaction solution, the mass ratio of PMMA, SiO-CaO composite nano particles to DMF is 2-3: 1-2: 4-8.
4. The method for preparing nano SiO-C composite material according to claim 3, wherein in the step (2), the heating step is heating to 50 to 80 ℃.
5. The method for preparing nano SiO-C composite material according to any of claims 1 to 4, wherein in the step (3), the electrospinning preparation step comprises:
controlling the distance between the needle head and the aluminum foil receiving scroll to be 8-12m, and adjusting the voltage to be 12-15 KV;
controlling the feeding speed of the first reaction solution to be 0.6-1 ml/h;
the feeding speed of the second reaction solution is controlled to be 1.5-2.5 ml/h.
6. The method for preparing nano SiO-C composite material as claimed in any of claims 1 to 5, wherein in the step (4), the two-stage heat treatment step comprises a step of performing a first heating at 300 ℃ under an air atmosphere and a step of performing a second heating at 1000 ℃ under an inert atmosphere and 900-.
7. The method for preparing nano SiO-C composite material according to any of claims 1 to 5, wherein in the step (4):
controlling the temperature rise speed of the first heating step to be 0.5-1.5 ℃/min;
and controlling the temperature rise speed of the second heating step to be 2.5-3.5 ℃/min.
8. A nano SiO-C composite material prepared by the method of any one of claims 1 to 7.
9. Use of the nano SiO-C composite material according to claim 8 for the preparation of negative electrode materials for lithium ion batteries.
10. A lithium ion battery cathode and a lithium ion battery prepared from the nano SiO-C composite material of claim 8.
CN202010212153.8A 2020-03-24 2020-03-24 Nano SiO-C composite material and application thereof in preparation of lithium ion battery cathode material Pending CN111403741A (en)

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