CN113745477A - 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 PDF

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CN113745477A
CN113745477A CN202110984446.2A CN202110984446A CN113745477A CN 113745477 A CN113745477 A CN 113745477A CN 202110984446 A CN202110984446 A CN 202110984446A CN 113745477 A CN113745477 A CN 113745477A
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sulfur
chlorella
polyacrylonitrile
carbon composite
ion battery
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CN113745477B (en
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曾令兴
汪依依
康碧玉
陈庆华
钱庆荣
黄宝铨
肖荔人
薛珲
夏新曙
汤营茂
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Fujian Normal University
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Abstract

The invention discloses a preparation method and application of a sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery cathode material. The preparation process is simple; the chlorella is widely distributed, is a cheap and good carbon raw material, and the derived carbon contains rich heterogeneous elements (N, P); the sulfur-doped polyacrylonitrile has a good three-dimensional network structure and structural stability. The technical scheme is as follows: blending and stirring a tin source, polyacrylonitrile, chlorella and N-N dimethylformamide to obtain a spinning solution, and then carrying out electrospinning and vulcanization to obtain the sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery negative electrode material. The potassium ion battery cathode material has excellent electrochemical performance, and the specific capacity of 50 cycles of charge-discharge circulation under the current density of 0.1A/g is up to 550 mAh/g; the specific capacity of over 1200 circles of charge-discharge cycle under the current density of 1A/g is up to 427 mAh/g.

Description

Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material
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 negative electrode material.
Background
In recent years, due to the abundance of potassium, the low oxidation-reduction potential and the rapid migration kinetics of potassium ions in electrolytes, the development of high-performance potassium ion batteries with the prospect of replacing lithium ion batteries has become the focus of attention of researchers. However, many materials having higher electrochemical properties in lithium ion batteries are not suitable for potassium ion batteries, and in addition, the potassium ions have large radii, so that the solid diffusion thereof is slow, causing huge volume expansion, resulting in instability of cycle performance and rate performance. Therefore, it is imperative to design a negative electrode material with good kinetics and suitable diffusion paths for potassium ions.
Negative electrode materials studied for potassium ion batteries so far include carbonaceous materials, chalcogenides, pure elements, organic substances, and the like. Among the numerous 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 an ideal structural arrangement that can accommodate more potassium ions and provide a shorter diffusion path for them. However, poor conductivity and large volume expansion have hindered the improvement of reversible capacity and cycling stability of tin sulfide negative electrodes. In this regard, strategies such as doping modification, compounding with carbonaceous materials, and rational design of novel nanostructures are considered to be effective methods for improving electrochemical performance of tin sulfide.
The invention utilizes a plurality of modification strategies to achieve the aim of improving the electrochemical performance of tin sulfide. On the other hand, biomass carbon-based materials are widely used as main bodies or base materials of battery cathodes because of their advantages of high conductivity, good stability, and the like. The chlorella is widely distributed, contains abundant N, P elements, and can be calcined to generate a nitrogen-phosphorus co-doped carbon-based composite material in situ, so that the conductivity and the electrochemical storage performance of the material are improved. On the other hand, the tin source and polyacrylonitrile are vulcanized synchronously through calcination, and tin sulfide is confined 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 various modification strategies of heteroatom doping, compounding with carbon materials and reasonable design of a novel structure 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 derived carbon compound has excellent potassium storage performance and application prospect.
Disclosure of Invention
The invention aims to provide a sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery cathode material, a preparation method and application thereof, the preparation process is simple, the composite can be obtained by combining electrospinning and calcining, the equipment is easy to obtain, the cost is low, and the environment requirements are met. In order to achieve the purpose, the invention adopts the following technical scheme:
(1) mixing 0.5-60 g of tin source, 0.5-60 g of polyacrylonitrile, 0.23-40 g of chlorella and 10-150 mL of N-N dimethylformamide, and magnetically stirring for 12-24 h to obtain a uniform spinning solution for later use;
(2) placing the spinning solution in an injector, setting spinning voltage of 20-25 kV, plug flow rate of 0.2-10 mL/h, receiving distance of 10-18 cm, and temperature of 30-90oC, preparing PAN/SnCl by electrospinning2A carbon composite fiber;
(3) mixing the above PAN/SnCl2Placing carbon composite fiber and a certain amount of sulfur powder in a tube furnace, and in Ar atmosphere, at a gas flow rate of 50-100 mL/min, 2-8 oCThe temperature rises to 400℃ and 600℃ at the/min rateoCalcining for 1-2 h to obtain a sulfur-doped polyacrylonitrile-chlorella derived carbon compound;
(4) the sulfur-doped polyacrylonitrile-chlorella derived carbon composite is used as a cathode of a sodium ion battery, mixed and ground with super P carbon serving as a conductive agent and CMC (carboxy methyl cellulose) serving as a binder according to the mass ratio of 8: 1: 1, and then uniformly coated on a 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 assemble a button type 2025 battery.
The tin source in step (1) may be a series of tin-containing salts, including but not limited to anhydrous tin dichloride, stannous sulfate, stannic sulfate, etc.; the mass ratio of the tin source, polyacrylonitrile and chlorella is 1: 1: 0.4 to 5, and the stirring time is 12 to 24 hours.
The electrospinning conditions in the step (2) are that the voltage is 20-25 kV, the plug flow rate is 0.2-10 mL/h, the receiving distance is 10-18 cm, and the temperature is 30-90oC。
PAN/SnCl as defined in the step (3) above2The mass fraction ratio of the carbon composite fiber to the sulfur powder is 1: 5, the calcining condition is that the gas flow is 50-100 mL/min, and the calcining condition is 2-8 oCThe temperature rises to 400℃ and 600℃ at the/min rateoAnd C, calcining for 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-discharge cycle is 50 under the current density of 0.1A/g, and the specific capacity is up to 550 mAh/g; the charge-discharge cycle exceeds 1200 circles under the current density of 1A/g, and the specific capacity is stabilized at 427 mAh/g.
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 the derived carbon is amorphous carbon, contains rich heterogeneous elements (N, P), and can introduce more defects and active sites; meanwhile, the carbon material derived from the chlorella has the advantages of high conductivity, good stability and the like.
(2) The tin source and polyacrylonitrile are vulcanized synchronously through calcination, and tin sulfide is confined 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 various modification strategies of heteroatom doping, compounding with carbon materials and reasonable design of novel structures can be realized through electrospinning and calcining, the process is simple and convenient, and the operability is strong.
(4) The cathode material prepared by the invention can be obtained by electrospinning and calcining, the equipment is easy to obtain, the process is simple, and the conditions are controllable.
(5) The material is used as a negative electrode material of a potassium ion battery, and has excellent electrochemical performance. Within the voltage range of 0.01-3V, the specific capacity is up to 550 mAh/g after 50 times of charge-discharge circulation under the current density of 0.1A/g; the specific capacity is stabilized at 427 mAh/g after more than 1200 times of charge-discharge circulation under the current density of 1A/g.
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 the sulfur-doped polyacrylonitrile-chlorella-derived carbon composite obtained in example 1.
FIG. 3 is a Raman plot of the sulfur-doped polyacrylonitrile-chlorella derived carbon composite obtained in example 1.
FIG. 4 is an FTIR plot 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 polyacrylonitrile-chlorella derived carbon composite doped with sulfur obtained in example 1 is used as a negative electrode material of a potassium ion battery.
FIG. 6 is a graph showing charge and discharge curves at a current density of 0.1A/g when the polyacrylonitrile-chlorella derived carbon composite doped with sulfur obtained in example 1 is used as a negative electrode material of a potassium ion battery.
FIG. 7 is a graph showing the cycle performance at a current density of 1A/g when the polyacrylonitrile-chlorella derived carbon composite doped with sulfur obtained in example 1 is used as a negative electrode material of a potassium ion battery.
Detailed Description
Example 1
(1) Weighing 0.5 g of anhydrous stannic chloride, 0.5 g of polyacrylonitrile and 0.23 g of chlorella, dissolving in 10 mL of N-N dimethylformamide, and magnetically stirring for 24 hours to obtain a uniform spinning solution for later use;
(2) taking the spinning solution for later use in an injector, setting the spinning voltage of 23 kV, the plug flow rate of 0.3 mL/h, the receiving distance of 15 cm and the temperature of 40oC, preparing PAN/SnCl by electrospinning2A carbon composite fiber;
(3) mixing PAN/SnCl2Placing 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 the Ar atmosphere, at the gas flow rate of 80 mL/min, 5 oCHeating rate to 470/minoC, calcining for 1 h to obtain a sulfur-doped polyacrylonitrile-chlorella derived carbon compound;
FIG. 1 is an XRD pattern of a sulfur-doped polyacrylonitrile-chlorella derived carbon composite, wherein diffraction peaks appear in the pattern which are consistent with a standard pattern of tin sulfide (JCPDS: 900-9121). FIG. 2 is an SEM/TEM image of a sulfur-doped polyacrylonitrile-chlorella-derived carbon composite, and a similar beaded structure is evident from both (a, b) in FIG. 2. FIG. 3 is a Raman diagram of a sulfur-doped polyacrylonitrile-chlorella derived carbon composite, in which the C-S bond and S-S bond indicate the presence of SPAN; similar results are given by FTIR plots (FIG. 4).
The sulfur-doped polyacrylonitrile-chlorella derived carbon compound prepared in the embodiment is used as an active ingredient of a negative electrode of a potassium ion battery, is mixed and ground with a conductive agent super P carbon and a binder CMC according to a mass ratio of 8: 1: 1, and is uniformly coated on a 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 an electrolyte to assemble a button 2025 type battery; all assembly was carried out in an inert atmosphere glove box. When the sulfur-doped polyacrylonitrile-chlorella derived carbon composite is used as a potassium ion battery cathode material, the specific capacity is up to 550 mAh/g after 50 cycles of charge-discharge under the current density of 0.1A/g within the voltage range of 0.01-3.0V as shown in figure 5; fig. 6 is a corresponding charge-discharge curve diagram, and it can be seen from the diagram that the remaining curves are highly overlapped 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 the charge-discharge cycle exceeds 1200 times under the current density of 1A/g, which indicates that the material has more stable long cycle performance.
Example 2
(1) Weighing 1 g of stannous sulfate, 1 g of polyacrylonitrile and 0.4 g of chlorella, dissolving the stannous sulfate, the polyacrylonitrile and the chlorella in 25 mL of N-N dimethylformamide, and magnetically stirring the solution for 24 hours to obtain a uniform spinning solution for later use;
(2) taking the spinning solution for later use in an injector, setting the spinning voltage of 23 kV, the plug flow rate of 0.4 mL/h, the receiving distance of 15 cm and the temperature of 35oC, preparing PAN/SnCl by electrospinning2A carbon composite fiber;
(3) mixing PAN/SnCl2Placing 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 the Ar atmosphere, at the gas flow rate of 80 mL/min, 5 oCHeating rate to 450/minoC, calcining for 1 h to obtain a sulfur-doped polyacrylonitrile-chlorella derived carbon compound;
the sulfur-doped polyacrylonitrile-chlorella derived carbon compound prepared in the embodiment is used as an active ingredient of a negative electrode of a potassium ion battery, is mixed and ground with a conductive agent super P carbon and a binder CMC according to a mass ratio of 8: 1: 1, and is uniformly coated on a 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 an electrolyte to assemble a button 2025 type battery; all assembly was carried out in an inert atmosphere glove box.
Example 3
(1) Weighing 5 g of tin sulfate, 5 g of polyacrylonitrile and 3 g of chlorella, dissolving the tin sulfate, the polyacrylonitrile and the chlorella in 50 mL of N-N dimethylformamide, and magnetically stirring for 24 hours to obtain a uniform spinning solution for later use;
(2) taking the spinning solution for later use in an injector, and arranging a spinning electrode25 kV pressure, 0.6 mL/h plug flow rate, 18 cm receiving distance and 40 ℃ temperatureoC, preparing PAN/SnCl by electrospinning2A carbon composite fiber;
(3) mixing PAN/SnCl2Placing 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 the Ar atmosphere, controlling the gas flow rate at 80 mL/min to be 8 oCHeating rate to 500/minoC, calcining for 1 h to obtain a sulfur-doped polyacrylonitrile-chlorella derived carbon compound;
the sulfur-doped polyacrylonitrile-chlorella derived carbon compound prepared in the embodiment is used as an active ingredient of a negative electrode of a potassium ion battery, is mixed and ground with a conductive agent super P carbon and a binder CMC according to a mass ratio of 8: 1: 1, and is uniformly coated on a 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 an electrolyte to assemble a button 2025 type battery; all assembly was carried out in an inert atmosphere glove box.
Example 4
(1) Weighing 20 g of anhydrous tin dichloride, 20 g of polyacrylonitrile and 10 g of chlorella, dissolving the anhydrous tin dichloride, the 20 g of polyacrylonitrile and the 10 g of chlorella in 100 mL of N-N dimethylformamide, and magnetically stirring for 24 hours to obtain a uniform spinning solution for later use;
(2) taking the spinning solution for later use in an injector, setting the spinning voltage to be 25 kV, the plug flow rate to be 0.8 mL/h, the receiving distance to be 18 cm and the temperature to be 50oC, preparing PAN/SnCl by electrospinning2A carbon composite fiber;
(3) mixing PAN/SnCl2Placing 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 the Ar atmosphere, at the gas flow rate of 80 mL/min, 5 oCHeating rate to 600/minoC, calcining for 1 h to obtain a sulfur-doped polyacrylonitrile-chlorella derived carbon compound;
the sulfur-doped polyacrylonitrile-chlorella derived carbon compound prepared in the embodiment is used as an active ingredient of a negative electrode of a potassium ion battery, is mixed and ground with a conductive agent super P carbon and a binder CMC according to a mass ratio of 8: 1: 1, and is uniformly coated on a 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 an electrolyte to assemble a button 2025 type battery; all assembly was carried out in an inert atmosphere glove box.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (7)

1. A preparation method of a sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery negative electrode material comprises the following steps:
(1) mixing 0.5-60 g of tin source, 0.5-60 g of polyacrylonitrile, 0.23-40 g of chlorella and 10-150 mL of N-N dimethylformamide, and magnetically stirring for 12-24 h to obtain a uniform spinning solution for later use;
(2) putting the spinning solution prepared in the step (1) into an injector, setting the spinning voltage to be 20-25 kV, the plug flow rate to be 0.2-10 mL/h, the receiving distance to be 10-18 cm and the temperature to be 30-90oC, preparing PAN/SnCl by electrospinning2A carbon composite fiber;
(3) PAN/SnCl prepared in the step (2)2Placing carbon composite fiber and a certain amount of sulfur powder in a tube furnace, and in Ar atmosphere, at a gas flow rate of 50-100 mL/min, 2-8 oCThe temperature rises to 400℃ and 600℃ at the/min rateoCalcining for 1-2 h to obtain a sulfur-doped polyacrylonitrile-chlorella derived carbon compound;
(4) the sulfur-doped polyacrylonitrile-chlorella derived carbon composite is used as a cathode of a sodium ion battery, mixed and ground with super P carbon serving as a conductive agent and CMC (carboxy methyl cellulose) serving as a binder according to the mass ratio of 8: 1: 1, and then uniformly coated on a 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 assemble a button type 2025 battery.
2. The method for preparing the sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material as claimed in claim 1, wherein the tin source in step (1) is a series of tin-containing salts including but not limited to anhydrous tin dichloride, stannous sulfate, and stannic sulfate; the mass ratio of the tin source, polyacrylonitrile and chlorella is 1: 1: 0.4 to 5, and the stirring time is 12 to 24 hours.
3. The method for preparing the sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material as claimed in claim 1, wherein the electrospinning conditions in the step (2) are voltage of 20-25 kV, plug flow rate of 0.2-10 mL/h, receiving distance of 10-18 cm, and temperature of 30-90oC。
4. The method for preparing the sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material as claimed in claim 1, wherein the PAN/SnCl in the step (3) is2The mass fraction ratio of the carbon composite fiber to the sulfur powder is 1: 5, the calcining condition is that the gas flow is 50-100 mL/min, and the calcining condition is 2-8 oCThe temperature rises to 400℃ and 600℃ at the/min rateoAnd C, calcining for 1-2 h.
5. The method for preparing the sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material as claimed in claim 1, wherein the chlorella is widely distributed and rich in N, P elements, and the derived carbon is amorphous carbon.
6. The high-performance potassium ion battery negative electrode material prepared by the preparation method of any one of claims 1 to 5 is a sulfur-doped polyacrylonitrile-chlorella derived carbon composite.
7. The use of the polyacrylonitrile-chlorella derived carbon composite doped with sulfur as claimed in claim 6 in the preparation of negative electrode materials for batteries.
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