CN113745477B - Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material - Google Patents
Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a sulfur-doped polyacrylonitrile-chlorella derivative carbon composite potassium ion battery anode material. The preparation process is simple; the chlorella is widely distributed, is a high-quality and low-cost carbon raw material, and derived carbon of the chlorella contains abundant heterogeneous elements (N, P); the sulfur-doped polyacrylonitrile has good three-dimensional network structure and structural stability. The technical proposal is as follows: and (3) blending and stirring a tin source, polyacrylonitrile, chlorella and N-N dimethylformamide to obtain a spinning solution, and then electrospinning and vulcanizing to obtain the sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material. The cathode material of the potassium ion battery has excellent electrochemical performance, and the specific capacity of the cathode material is up to 550 mAh/g after 50 cycles of charge and discharge under the current density of 0.1A/g; the specific capacity of the battery is up to 427 mAh/g at the current density of 1A/g after more than 1200 circles of charge-discharge cycles.
Description
Technical Field
The invention belongs to the field of potassium ion battery materials, and particularly relates to a preparation method and application of a sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material.
Background
In recent years, development of high-performance potassium ion batteries with alternative lithium ion battery prospects has been the focus of researchers due to the abundance of potassium, lower redox potential, and rapid migration kinetics of potassium ions in the electrolyte. However, many materials having higher electrochemical performance in lithium ion batteries are not suitable for potassium ion batteries, and due to the large radius of potassium ions, the diffusion of solids is slow, causing a huge volume expansion, resulting in unstable cycle performance and rate performance. Thus, it is imperative to design a negative electrode material with good kinetics and a suitable potassium ion diffusion path.
Hitherto, anode materials studied for potassium ion batteries include carbonaceous materials, chalcogenides, pure elements, organic substances, and the like. Among the materials, tin sulfide having a two-dimensional layered structure is of great interest because of its higher theoretical capacity and larger interlayer spacing. The larger interlayer spacing (0.59 nm) and the open structure between the layers provide the desired structural arrangement to accommodate more potassium ions and provide a shorter diffusion path for them. However, problems such as poor conductivity and large volume expansion prevent improvement of reversible capacity and cycle stability of the tin sulfide anode. In this regard, strategies such as doping modification, compounding with carbonaceous materials, rational design of novel nanostructures, and the like are considered as effective methods for improving the electrochemical performance of tin sulfide.
The invention utilizes various modification strategy coupling to achieve the purpose of improving the electrochemical performance of tin sulfide. On one hand, the biomass carbon-based material has the advantages of high conductivity, good stability and the like, and is widely used as a main body or a matrix material of a battery anode. The chlorella is widely distributed and contains rich N, P elements, and can be calcined to generate the nitrogen and phosphorus co-doped carbon-based composite material in situ, so that the conductivity and electrochemical storage performance of the material are improved. On the other hand, the tin source and the polyacrylonitrile are vulcanized synchronously through calcination, and the tin sulfide is limited in the sulfur-doped polyacrylonitrile fiber, so that the dissolution of an intermediate product can be inhibited, and the volume expansion is relieved. It is worth mentioning that the coupling of multiple modification strategies of heteroatom doping, carbon material compounding and novel structure reasonable design can be realized through electrospinning and calcining, the process is simple and convenient, the operability is strong, and related literature reports are rare. The result shows that the synthesized sulfur-doped polyacrylonitrile-chlorella derivative carbon compound has excellent potassium storage performance and application prospect.
Disclosure of Invention
The invention aims to provide a sulfur-doped polyacrylonitrile-chlorella derivative carbon composite potassium ion battery anode material, and a preparation method and application thereof, wherein the preparation process is simple, the composite can be obtained by combining electrospinning with calcination, equipment is easy to obtain, the cost is low, and the environment requirements are met. In order to achieve the above purpose, the invention adopts the following technical scheme:
(1) Blending 0.5-60 g tin source, 0.5-60 g polyacrylonitrile, 0.23-40 g chlorella and 10-150 mL N-N dimethylformamide, magnetically stirring 12-24 h to obtain uniform spinning solution for standby;
(2) Placing the above spinning solution into an injector, setting spinning voltage 20-25 kV, plug flow rate 0.2-10 mL/h, receiving distance 10-18 cm, and temperature 30-90 o C, preparing PAN/SnCl by electrospinning 2 Carbon composite fibers;
(3) The PAN/SnCl is prepared 2 Placing the carbon composite fiber and a certain amount of sulfur powder into a tube furnace, and under Ar atmosphere, controlling the gas flow to be 50-100 mL/min and 2-8 oC Heating at a rate of 400-600 a/min o Calcining for 1-2 h to obtain sulfur-doped polyacrylonitrile-chlorellaDerivatizing the carbon composite;
(4) The sulfur-doped polyacrylonitrile-chlorella derivative carbon composite is used as a negative electrode of a sodium ion battery, mixed and ground with conductive agent super P carbon and binder CMC according to the mass ratio of 8:1:1, then uniformly coated on copper foil to be used as a working electrode, a metal potassium sheet is used as a counter electrode, and 7M KFSI in DME=100% is used as electrolyte to be assembled into the button type 2025 battery.
The tin source in the step (1) may be a series of tin-containing salts, including but not limited to anhydrous tin dichloride, stannous sulfate, tin sulfate, etc.; the mass ratio of the tin source to the polyacrylonitrile to the chlorella is 1:1:0.4-5, wherein the stirring time is 12-24 h.
The electrospinning conditions in the step (2) are voltage 20-25 kV, plug flow rate 0.2-10 mL/h, receiving distance 10-18 cm and temperature 30-90 o C。
PAN/SnCl described in the above step (3) 2 The mass fraction ratio of the carbon composite fiber to the sulfur powder is 1:5, the calcination condition is that the gas flow is 50-100 mL/min, and the mass fraction ratio is 2-8 oC Heating at a rate of 400-600 a/min o C calcining 1-2 h.
The sodium storage performance test result in the step (4) shows that when the voltage is 0.01-3.0V, the charge and discharge cycle is 50 under the current density of 0.1A/g, and the specific capacity is up to 550 mAh/g; the specific capacity is stabilized at 427 mAh/g under the current density of 1A/g and the charge-discharge cycle of more than 1200 circles.
Compared with the prior art, the invention has the following specific advantages:
(1) The chlorella is widely distributed, is a high-quality and low-cost carbon raw material, and derived carbon is amorphous carbon and contains abundant heterogeneous elements (N, P), so that more defects and active sites can be introduced; meanwhile, the chlorella-derived carbon material has the advantages of high conductivity, good stability and the like.
(2) The tin source and the polyacrylonitrile are vulcanized synchronously through calcination, and the tin sulfide is limited in the sulfur-doped polyacrylonitrile fiber, so that the dissolution of an intermediate product can be inhibited, and the volume expansion is relieved.
(3) The coupling of multiple modification strategies of the reasonable design of the heteroatom doping, the compounding with the carbon material and the novel structure can be realized through electrospinning and calcining, the process is simple and convenient, and the operability is strong.
(4) The negative electrode material prepared by the invention can be obtained through electrospinning and calcining, and the device is easy to obtain, the process is simple and the conditions are controllable.
(5) As a negative electrode material of a potassium ion battery, excellent electrochemical performance is exhibited. The specific capacity of the battery is up to 550 mAh/g for 50 times under the current density of 0.1A/g in the voltage range of 0.01-3V; the specific capacity is stabilized at 427 mAh/g at a current density of 1A/g for more than 1200 times.
Drawings
FIG. 1 is an XRD pattern of the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1.
FIG. 2 is an SEM/TEM image of sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1.
FIG. 3 is a Raman diagram of the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1.
FIG. 4 is a FTIR image of the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1.
FIG. 5 is a graph showing the cycle performance at a current density of 0.1A/g when the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1 was used as a negative electrode material for a potassium ion battery.
FIG. 6 is a graph showing charge and discharge at a current density of 0.1A/g when the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1 was used as a negative electrode material for a potassium ion battery.
FIG. 7 is a graph showing the cycle performance at a current density of 1A/g when the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1 was used as a negative electrode material for a potassium ion battery.
Detailed Description
Example 1
(1) Weighing 0.5 g anhydrous tin dichloride, 0.5 g polyacrylonitrile and 0.23 g chlorella to dissolve in 10 mL of N-N dimethylformamide, and magnetically stirring for 24 h to obtain uniform spinning solution for later use;
(2) Taking standby spinningThe spinning voltage of 23 kV, the plug flow rate of 0.3 mL/h, the receiving distance of 15 cm and the temperature of 40 are set in a syringe o C, preparing PAN/SnCl by electrospinning 2 Carbon composite fibers;
(3) PAN/SnCl 2 Placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 1:5, and under Ar atmosphere, placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 5, and placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 5 in an Ar atmosphere at a gas flow rate of 80 mL/min oC Heating rate per min to 470 o Calcining for 1 h to obtain sulfur-doped polyacrylonitrile-chlorella derivative carbon compound;
FIG. 1 is an XRD pattern of a sulfur-doped polyacrylonitrile-chlorella-derived carbon complex, wherein diffraction peaks appear in the pattern and are consistent with the standard spectrum of tin sulfide (JCPDS: 900-9121). FIG. 2 is an SEM/TEM image of sulfur-doped polyacrylonitrile-chlorella-derived carbon complex, and the bead-like structure is apparent from both (a, b) in FIG. 2. FIG. 3 is a Raman diagram of a sulfur-doped polyacrylonitrile-chlorella-derived carbon complex, wherein the C-S bond and the S-S bond in the diagram indicate the existence of SPAN; FTIR (as in fig. 4) gives similar results.
The sulfur-doped polyacrylonitrile-chlorella derivative carbon compound prepared in the embodiment is adopted as an active ingredient of a negative electrode of a potassium ion battery, and is uniformly coated on a copper foil to serve as a working electrode after being mixed and ground with a conductive agent super P carbon and a binder CMC according to the mass ratio of 8:1:1, a metal potassium sheet serves as a counter electrode, and 7M KFSI in DME=100% is taken as electrolyte to assemble a button 2025 type battery; all the assembly was performed in an inert atmosphere glove box. When the sulfur-doped polyacrylonitrile-chlorella derivative carbon composite is used as a cathode material of a potassium ion battery, the specific capacity of the sulfur-doped polyacrylonitrile-chlorella derivative carbon composite is up to 550 mAh/g after 50 cycles of charge and discharge under the current density of 0.1A/g in the voltage range of 0.01-3.0V as shown in figure 5; fig. 6 is a corresponding charge-discharge graph, and it can be seen from the graph that the remaining curves are highly coincident except for the first circle, which shows that the material has excellent cycle stability. As shown in figure 7, the specific capacity of the material can still be stabilized at 427 mAh/g after charge and discharge cycles are performed for more than 1200 times under the current density of 1A/g, which proves that the material has stable long-cycle performance.
Example 2
(1) Weighing 1 g stannous sulfate, 1 g polyacrylonitrile and 0.4 g chlorella to dissolve in 25 mL of N-N dimethylformamide, and magnetically stirring 24 h to obtain uniform spinning solution for later use;
(2) Placing the spinning solution in a syringe, setting spinning voltage 23 kV, plug flow rate 0.4 mL/h, receiving distance 15 cm, and temperature 35 o C, preparing PAN/SnCl by electrospinning 2 Carbon composite fibers;
(3) PAN/SnCl 2 Placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 1:5, and under Ar atmosphere, placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 5, and placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 5 in an Ar atmosphere at a gas flow rate of 80 mL/min oC Heating rate per min to 450 o Calcining for 1 h to obtain sulfur-doped polyacrylonitrile-chlorella derivative carbon compound;
the sulfur-doped polyacrylonitrile-chlorella derivative carbon compound prepared in the embodiment is adopted as an active ingredient of a negative electrode of a potassium ion battery, and is uniformly coated on a copper foil to serve as a working electrode after being mixed and ground with a conductive agent super P carbon and a binder CMC according to the mass ratio of 8:1:1, a metal potassium sheet serves as a counter electrode, and 7M KFSI in DME=100% is taken as electrolyte to assemble a button 2025 type battery; all the assembly was performed in an inert atmosphere glove box.
Example 3
(1) Weighing 5 g tin sulfate, 5 g polyacrylonitrile and 3 g chlorella to dissolve in 50 mL N-N dimethylformamide, and magnetically stirring 24 h to obtain uniform spinning solution for later use;
(2) Placing spinning solution in injector, setting spinning voltage 25 kV, plug flow rate 0.6 mL/h, receiving distance 18 cm, and temperature 40 o C, preparing PAN/SnCl by electrospinning 2 Carbon composite fibers;
(3) PAN/SnCl 2 Placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 1:5, and under Ar atmosphere, setting the gas flow rate at 80 mL/min at 8 oC The temperature rise rate per min is 500 o Calcining for 1 h to obtain sulfur-doped polyacrylonitrile-chlorella derivative carbon compound;
the sulfur-doped polyacrylonitrile-chlorella derivative carbon compound prepared in the embodiment is adopted as an active ingredient of a negative electrode of a potassium ion battery, and is uniformly coated on a copper foil to serve as a working electrode after being mixed and ground with a conductive agent super P carbon and a binder CMC according to the mass ratio of 8:1:1, a metal potassium sheet serves as a counter electrode, and 7M KFSI in DME=100% is taken as electrolyte to assemble a button 2025 type battery; all the assembly was performed in an inert atmosphere glove box.
Example 4
(1) Weighing 20 g anhydrous tin dichloride, 20 g polyacrylonitrile and 10 g chlorella to dissolve in 100 mL of N-N dimethylformamide, and magnetically stirring 24 h to obtain uniform spinning solution for later use;
(2) Placing spinning solution into injector, setting spinning voltage 25 kV, plug flow rate 0.8 mL/h, receiving distance 18 cm, and temperature 50 o C, preparing PAN/SnCl by electrospinning 2 Carbon composite fibers;
(3) PAN/SnCl 2 Placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 1:5, and under Ar atmosphere, placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 5, and placing the carbon composite fiber and a certain amount of sulfur powder in a tubular furnace according to the mass ratio of 5 in an Ar atmosphere at a gas flow rate of 80 mL/min oC Heating rate per min to 600 o Calcining for 1 h to obtain sulfur-doped polyacrylonitrile-chlorella derivative carbon compound;
the sulfur-doped polyacrylonitrile-chlorella derivative carbon compound prepared in the embodiment is adopted as an active ingredient of a negative electrode of a potassium ion battery, and is uniformly coated on a copper foil to serve as a working electrode after being mixed and ground with a conductive agent super P carbon and a binder CMC according to the mass ratio of 8:1:1, a metal potassium sheet serves as a counter electrode, and 7M KFSI in DME=100% is taken as electrolyte to assemble a button 2025 type battery; all the assembly was performed in an inert atmosphere glove box.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. A preparation method of a sulfur-doped polyacrylonitrile-chlorella-derived carbon composite potassium ion battery anode material comprises the following steps:
(1) Mixing 0.5-60 g tin source, 0.5-60 g polyacrylonitrile, 0.23-40 g chlorella and 10-150-mL N-N dimethylformamide, magnetically stirring 12-24 h to obtain uniform spinning solution for later use;
(2) Placing the spinning solution prepared in the step (1) in an injector, setting spinning voltage 20-25 kV, plug flow rate 0.2-10 mL/h, receiving distance 10-18 cm, and temperature 30-90 o C, preparing PAN/SnCl by electrospinning 2 Carbon composite fibers;
(3) PAN/SnCl prepared in the step (2) is processed 2 Placing the carbon composite fiber and a certain amount of sulfur powder into a tube furnace, and under Ar atmosphere, controlling the gas flow to be 50-100 mL/min and 2-8 o Heating at a rate of C/min to 400-600 o Calcining for 1-2 h to obtain sulfur-doped polyacrylonitrile-chlorella derivative carbon compound;
(4) The sulfur-doped polyacrylonitrile-chlorella derivative carbon composite is used as a negative electrode of a potassium ion battery, mixed and ground with conductive agent super P carbon and binder CMC according to the mass ratio of 8:1:1, then uniformly coated on copper foil to be used as a working electrode, a metal potassium sheet is used as a counter electrode, and 7M KFSI and DME=100% are used as electrolyte to be assembled into the button type 2025 battery.
2. The method for preparing the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite potassium ion battery anode material according to claim 1, wherein the tin source in the step (1) is anhydrous stannous chloride, stannous sulfate or stannic sulfate; the mass ratio of the tin source to the polyacrylonitrile to the chlorella is 1:1:0.4-5, wherein the stirring time is 12-24 h.
3. The method for preparing the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite potassium ion battery anode material according to claim 1, wherein the electrospinning conditions in the step (2) are voltage 20-25 kV, plug flow rate 0.2-10 mL/h, receiving distance 10-18 cm and temperature 30-90 o C。
4. The method for preparing the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite potassium ion battery anode material according to claim 1, wherein the PAN/SnCl in the step (3) is characterized by 2 Mass fraction of carbon composite fiber and sulfur powderThe number ratio is 1:5, the calcination condition is that the gas flow is 50-100 mL/min,2-8 o Heating at a rate of C/min to 400-600 o C calcining 1-2 h.
5. The preparation method of the sulfur-doped polyacrylonitrile-chlorella derivative carbon composite potassium ion battery anode material is characterized in that the chlorella is widely distributed and is rich in N, P element, and the carbon derived from the chlorella is amorphous carbon.
6. A sulfur-doped polyacrylonitrile-chlorella-derived carbon composite is a high-performance potassium ion battery anode material prepared by the preparation method of any one of claims 1-5.
7. The use of a sulfur-doped polyacrylonitrile-chlorella-derived carbon compound as defined in claim 6 for preparing a battery negative electrode material.
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