CN110323464B - Potassium air battery comprising polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane - Google Patents
Potassium air battery comprising polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
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Abstract
A polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite diaphragm potassium air battery comprises a battery cathode, a first diaphragm, electrolyte, a second micro diaphragm, a battery anode, an argon chamber and an air chamber, wherein a PCSP composite nanofiber diaphragm is arranged on one side, close to the electrolyte, of the first diaphragm; the preparation steps are as follows: adding polyacrylonitrile into a solvent, stirring to obtain colloidal liquid, adding aniline and camphorsulfonic acid into the colloidal liquid, stirring, adding ammonium persulfate, stirring, refrigerating the solution in a refrigerating chamber of a refrigerator at 5 ℃, dissolving carbon nanotubes and tin oxide in the solution which is kept stand in the refrigerating chamber to obtain a spinning solution, and preparing the PCSP composite nanofiber membrane by electrostatic spinning. The advantages are that: the potassium air battery can selectively permeate potassium ions in electrolyte, and inhibit other ions, water and oxygen from permeating to the negative electrode side, so that the corrosion and failure of the negative electrode are slowed down, and the discharge capacity and the cycle performance of the potassium air battery are improved.
Description
Technical Field
The invention relates to a polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite diaphragm potassium air battery.
Background
A potassium air cell is a cell that uses potassium metal as the anode and oxygen provided in the air as the cathode reactant. During the discharging process of the potassium air battery, potassium metal anode releases electrons to become potassium ions, the potassium ions pass through the electrolyte, and are combined with oxygen and electrons flowing from an external circuit at the cathode to generate potassium oxide or potassium peroxide, and the potassium oxide or potassium peroxide is remained at the cathode. And (3) charging process: the electrons are supplied through the lead, potassium ions pass through the organic electrolyte to reach the surface of the anode, the potassium ions react on the surface of the anode to generate metal potassium, the potassium ions react on the cathode side to generate oxygen, and the generated electrons are supplied to the lead. However, during the operation of the potassium-air battery, the metal potassium anode is easy to react chemically with oxygen or water, which causes corrosion failure of the anode and finally leads to the termination of the discharge of the potassium-air battery.
Carbon Nanotubes (CNTs) are promising as graphite materials for lithium ion batteries because of their uniform one-dimensional tubular structure, large specific surface area, and nano-scale hollow channels, but research has shown that their charge-discharge processes are irreversible for the first time and have too large capacity to be practical. Polyaniline (PANI) is used as a conductive polymer material, has adjustable conductivity, is easy to synthesize, has special redox performance, can be used on a battery and a super capacitor material, and can effectively improve the energy storage performance of a potassium-air battery.
Disclosure of Invention
The invention aims to provide a polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite diaphragm potassium air battery, which can selectively permeate potassium ions in electrolyte and inhibit the permeation of other ions, water and oxygen to the negative electrode side, so that the corrosion and the failure of the negative electrode are slowed down, and the discharge capacity and the cycle performance of the potassium air battery are improved.
The technical solution of the invention is as follows:
the utility model provides a polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) compound diaphragm potassium-air battery, includes stainless steel casing and the insulating cover plate of setting at the top and the bottom of stainless steel casing, is equipped with potassium-air battery negative pole, first diaphragm, electrolyte, second diaphragm, potassium-air battery positive pole in proper order at the middle part of insulating cover plate in the stainless steel casing, leave the argon gas cavity between potassium-air battery negative pole and the stainless steel casing that is close to potassium-air battery negative pole to be equipped with the argon gas valve on the stainless steel casing of argon gas cavity one side, leave the air cavity between potassium-air battery positive pole and the stainless steel casing that is close to potassium-air battery positive pole, and be equipped with the air valve on the stainless steel casing of air cavity one side, its special character is then: the first diaphragm and the second diaphragm are both made of microporous polyolefin diaphragms, and one side of the first diaphragm, which is close to the electrolyte, is provided with a polyaniline-carbon nano tube-tin oxide-polyacrylonitrile composite diaphragm;
the preparation method of the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile composite membrane comprises the following steps:
(1) preparing spinning solution
Adding polyacrylonitrile into a solvent, stirring for 2-4 h at room temperature to obtain uniform colloidal liquid, adding aniline and camphorsulfonic acid into the colloidal liquid according to the mass ratio of 1:1.2, wherein the mass ratio of aniline to polyacrylonitrile is 0.3:1, stirring for 2-4 h, adding ammonium persulfate according to the mass ratio of polyacrylonitrile to ammonium persulfate of 4:3, stirring for 30-60 min at room temperature, putting the solution into a refrigerator refrigerating chamber at 5 ℃ for 24-48 h, and then adding Carbon Nano Tubes (CNT) and tin oxide (SnO) according to the mass ratio of 1:12) Dissolving the carbon nano tube into a solution which is kept stand in a refrigerating chamber, wherein the mass ratio of the carbon nano tube to the polyacrylonitrile is 1:6, and stirring the mixture for 12 to 24 hours at room temperature to obtain a spinning solution;
(2) preparation of PCSP Membrane
Carrying out electrostatic spinning on the spinning solution, wherein the electrostatic spinning parameters are as follows: the spinning voltage is 6kV to 10kV, the spinning receiving distance is 10cm to 18cm, the ambient temperature is 20 ℃ to 28 ℃, the relative humidity is 20 percent to 30 percent, and the polyaniline-carbon nano tube-tin oxide-polyacrylonitrile (PCSP) composite nanofiber membrane is obtained after the spinning solution is exhausted.
Further, the solvent is a mixed solvent of chloroform and N, N-dimethylformamide.
Further, the mass ratio of the chloroform to the N, N-dimethylformamide is 1: 6.5.
Further, the mass ratio of the chloroform to the polyacrylonitrile is 5: 3.
Furthermore, the addition amount of the spinning solution in the electrostatic spinning injector is 3mL, and the area of the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile composite nanofiber membrane is 8 multiplied by 8cm2～10×10cm2。
Further, the electrostatic spinning adopts a 1mL plastic spray gun head.
Furthermore, 3-6 parts of bis (trifluoromethyl) sulfonyl imide (LiTFSI) is dissolved in 7-15 parts of imidazole ionic liquid by weight, and then 0.2-0.5 part of spiro quaternary ammonium tetrafluoroborate is added into the electrolyte and uniformly mixed under the auxiliary condition of ultrasonic waves, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 1-3 h.
Further, the imidazole ionic liquid is 1-ethyl-3-butylimidazole hexafluorophosphate.
The invention has the beneficial effects that:
the potassium-air battery has a simple and reasonable structure, the PCSP diaphragm is arranged between the two layers of microporous polyolefin diaphragms, and the composite material formed by the tin oxide and the CNT of the PCSP diaphragm layer not only has higher potassium storage capacity, but also shows excellent electrochemical activity. The PCSP diaphragm has the structural characteristics of a three-dimensional void structure, small size, large specific surface area, high porosity and the like, can reduce the size effect of the potassium-air battery material in the charging and discharging process, and effectively improves the battery performance, thereby improving the safety performance and the service life of the potassium-air battery material. In addition, the PCSP membrane can promote the uniform migration of potassium ions at the interface of the electrolyte and the electrode, selectively permeate the potassium ions in the electrolyte, inhibit the permeation of other ions, water and oxygen to the negative electrode side, and slow down the corrosion and failure of the negative electrode. The potassium-air battery has high rate performance and good cycle performance, the first discharge capacity of the battery is more than or equal to 490 mAh/g, and the cycle frequency can reach 52 times.
Drawings
Fig. 1 is a schematic structural diagram of a passive potassium-air battery.
In the figure: the composite membrane comprises a 1-potassium air battery cathode, a 2-first microporous polyolefin membrane, a 3-electrolyte, a 4-second microporous polyolefin membrane, a 5-potassium air battery anode, a 6-insulating cover plate, a 7-stainless steel shell, an 8-argon valve, a 9-air valve, a 10-spring and an 11-PCSP composite nanofiber membrane.
FIG. 2 is a PANI/CNT/SnO sample of the present invention2Structural mechanism diagram of the/PAN composite nanofiber membrane.
Detailed Description
Example 1
As shown in the figure, the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite membrane potassium-air battery comprises a stainless steel shell 7 and insulating cover plates 6 arranged at the top and the bottom of the stainless steel shell 7, wherein a potassium battery cathode 1, a first microporous polyolefin membrane 2, an electrolyte 3, a second microporous polyolefin membrane 4 and a potassium battery anode 5 are sequentially arranged in the middle of the insulating cover plate 6 in the stainless steel shell 7, an argon chamber is reserved between the potassium-air battery cathode 1 and the stainless steel shell 7 close to the potassium-air battery cathode 1, an argon valve 8 is arranged on the stainless steel shell 7 at one side of the argon chamber, an air chamber is reserved between the potassium-air battery anode 5 and the stainless steel shell 7 close to the potassium-air battery anode 5, an air valve 9 is arranged on the stainless steel shell 7 at one side of the air chamber, and a PCSP composite nanofiber membrane 11 is arranged at one side of the first microporous polyolefin membrane 2 close to the electrolyte 3;
the preparation method of the PCSP composite membrane comprises the following steps:
(1) preparing spinning solution
Adding 0.6g of Polyacrylonitrile (PAN) into a mixed solvent of 1g of chloroform and 6.5g of 6.5g N, N-Dimethylformamide (DMF), and stirring at room temperature for 3 hours to obtain uniform colloidal liquid; adding 0.1800g aniline and 0.216g camphorsulfonic acid into the colloidal solution, stirring at room temperature for 3h, adding 0.45g ammonium persulfate, stirring at room temperature for 45min, placing the solution in the refrigerator compartment at 5 deg.C for 36h, and adding 0.1g Carbon Nanotube (CNT) and 0.1g SnO2Dissolving in the above solution, stirring for 18 hr to obtain spinning solutionA solution;
(2) preparation of PCSP Membrane
A1 mL plastic spray gun is sleeved on a 5mL injector, 3mL of spinning solution is injected into the injector, a receiving device is a horizontally placed iron wire mesh, electrostatic spinning is carried out, and electrostatic spinning parameters are as follows: spinning voltage is 10kV, the distance between the needle point of the plastic spray gun head and the wire gauze is 18cm, the environmental temperature is 20-28 ℃, the relative humidity is 20-30%, and PANI/CNT/SnO is obtained after the spinning solution is exhausted2/PAN composite nanofiber membrane (PCSP membrane), and PANI/CNT/SnO prepared from the membrane2The area of the/PAN composite nanofiber membrane is 9 multiplied by 9cm2From PANI/CNT/SnO2The composite nano-fiber comprises composite nano-fibers, wherein the diameter of each composite nano-fiber is 200nm-600nm, and the gaps among the fibers are 20nm-100 nm;
preparing the positive electrode of the potassium-air battery:
adding 8g of Ketjen black and 2g of manganese dioxide into an organic solvent to prepare a mixture, and coating the mixture on foamed nickel to prepare a potassium-air battery anode;
preparing a potassium air battery cathode:
pressing the hydrophobic metal potassium sheet and the current-collecting nickel net into a potassium-air battery cathode;
preparing a potassium air battery electrolyte:
dissolving 4.5g of bis (trifluoromethyl) sulfimide (LiTFSI) in 12g of 1-ethyl-3-butylimidazole hexafluorophosphate, fully dissolving, adding 0.3g of spiro quaternary ammonium tetrafluoroborate, and uniformly mixing under the auxiliary condition of ultrasonic waves, wherein the ultrasonic wave power is 400W, the ultrasonic wave time is 2h, and the electrolyte of the potassium-air battery is prepared;
when the potassium-air battery positive electrode assembly works, the negative electrode of the potassium-air battery, the first microporous polyolefin diaphragm, the PCSP diaphragm, the electrolyte, the second microporous polyolefin diaphragm and the positive electrode of the potassium-air battery are arranged in a stainless steel shell to be assembled into the PCSP composite diaphragm potassium-air battery, argon is filled in an argon chamber through an argon valve, air is filled in the air chamber through an air valve, and the filling pressure of the argon and the air is 0.1 MPa. Through detection, the electrochemical performance of the PCSP composite diaphragm potassium-air battery is shown in Table 1.
Example 2
As shown in the figure, the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite membrane potassium air battery has the same structure as that in example 1.
Preparation of PCSP composite diaphragm
(1) Preparing spinning solution
Adding 0.6g of Polyacrylonitrile (PAN) into a mixed solvent of 1g of chloroform and 6.5g of N, N-Dimethylformamide (DMF), and stirring at room temperature for 4 hours to obtain uniform colloidal liquid; 0.1800g of aniline and 0.216g of camphorsulfonic acid were added to the jelly and stirred at room temperature for 4 hours, 0.45g of ammonium persulfate was added and stirred at room temperature for 60 minutes, the solution was placed in the refrigerator compartment at 5 ℃ for 48 hours, and then 0.1g of Carbon Nanotubes (CNT) and 0.1g of SnO were added2Dissolving in the solution, and stirring for 24h to obtain a spinning solution;
(2) preparation of PCSP Membrane
A1 mL plastic spray gun is sleeved on a 5mL injector, 3mL of spinning solution is injected into the injector, a receiving device is a horizontally placed iron wire mesh, electrostatic spinning is carried out, and electrostatic spinning parameters are as follows: spinning voltage is 8kV, the distance between the needle point of the plastic spray gun head and the wire gauze is 10cm, the environmental temperature is 20-28 ℃, the relative humidity is 20-30%, and PANI/CNT/SnO is obtained after the spinning solution is exhausted2/PAN composite nanofiber membrane (PCSP membrane), and PANI/CNT/SnO prepared from the membrane2The area of the/PAN composite nanofiber membrane is 10 multiplied by 10cm2From PANI/CNT/SnO2The composite nanometer fiber consists of composite nanometer fiber of 200-600 nm diameter and 20-100 nm interval.
2. Preparing a potassium air battery electrolyte:
dissolving 4.5g of bis (trifluoromethyl) sulfimide (LiTFSI) in 12g of 1-ethyl-3-butylimidazole hexafluorophosphate, fully dissolving, adding 0.3g of spiro quaternary ammonium tetrafluoroborate, and uniformly mixing under the auxiliary condition of ultrasonic waves, wherein the ultrasonic wave power is 400W, the ultrasonic wave time is 2h, and the electrolyte of the potassium-air battery is prepared;
the potassium-air battery positive electrode and the potassium-air battery negative electrode used were the same as in example 1.
When the potassium-air battery works, the negative electrode of the potassium-air battery, the first microporous polyolefin diaphragm, the PCSP diaphragm, the electrolyte, the second microporous polyolefin diaphragm and the positive electrode of the potassium-air battery are arranged in a stainless steel shell to be assembled into the PCSP composite diaphragm potassium-air battery, argon is filled in an argon chamber through an argon valve, air is filled in the air chamber through an air valve, and the filling pressure of the argon and the air is 0.1 MPa. Through detection, the electrochemical performance of the PCSP composite diaphragm potassium-air battery is shown in Table 1.
Example 3
As shown in the figure, the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite membrane potassium-air battery has the same structure as that of example 1.
Preparation of PCSP composite diaphragm
(1) Preparing spinning solution
Adding 0.6g of Polyacrylonitrile (PAN) into a mixed solvent of 1g of chloroform and 6.5g of 6.5g N, N-Dimethylformamide (DMF), and stirring at room temperature for 2 hours to obtain uniform colloidal liquid; 0.1800g of aniline and 0.216g of camphorsulfonic acid were added to the jelly and stirred at room temperature for 2 hours, 0.45g of ammonium persulfate was added and stirred at room temperature for 30 minutes, the solution was placed in the refrigerator compartment at 5 ℃ for 24 hours, and then 0.1g of Carbon Nanotubes (CNT) and 0.1g of SnO were added2Dissolving the mixture in the solution, and stirring for 12 hours to obtain a spinning solution;
(2) preparation of PCSP Membrane
A1 mL plastic spray gun is sleeved on a 5mL injector, 3mL of spinning solution is injected into the injector, a receiving device is a horizontally placed iron wire mesh, electrostatic spinning is carried out, and electrostatic spinning parameters are as follows: spinning voltage is 6kV, the distance between the needle point of the plastic spray gun head and the wire gauze is 12cm, the environmental temperature is 20-28 ℃, the relative humidity is 20-30%, and PANI/CNT/SnO is obtained after the spinning solution is exhausted2/PAN composite nanofiber membrane (PCSP membrane), and PANI/CNT/SnO prepared from the membrane2The area of the/PAN composite nanofiber membrane is 8 multiplied by 8cm2From PANI/CNT/SnO2The composite nano-fiber comprises composite nano-fibers, wherein the diameter of each composite nano-fiber is 200nm-600nm, and the gaps among the fibers are 20nm-100 nm;
2. preparing a potassium air battery electrolyte:
dissolving 4.5g of bis (trifluoromethyl) sulfimide (LiTFSI) in 12g of 1-ethyl-3-butylimidazole hexafluorophosphate, fully dissolving, adding 0.3g of tetrafluoroboric acid spiro quaternary ammonium salt, and uniformly mixing under the ultrasonic-assisted condition, wherein the ultrasonic power is 400W, the ultrasonic time is 2h, and the electrolyte of the potassium-air battery is prepared;
the potassium-air battery positive electrode and the potassium-air battery negative electrode used were the same as in example 1.
When the potassium-air battery works, the negative electrode of the potassium-air battery, the first microporous polyolefin diaphragm, the PCSP diaphragm, the electrolyte, the second microporous polyolefin diaphragm and the positive electrode of the potassium-air battery are arranged in a stainless steel shell to be assembled into the PCSP composite diaphragm potassium-air battery, argon is filled in an argon chamber through an argon valve, air is filled in the air chamber through an air valve, and the filling pressure of the argon and the air is 0.1 MPa. Through detection, the electrochemical performance of the PCSP composite diaphragm potassium-air battery is shown in Table 1.
Comparative example
The potassium-air battery comprises a stainless steel shell and insulating cover plates arranged at the top and the bottom of the stainless steel shell, wherein a potassium-air battery cathode, a first diaphragm, electrolyte, a second diaphragm and a potassium-air battery anode are sequentially arranged in the middle of the insulating cover plate in the stainless steel shell, an argon chamber is reserved between the potassium-air battery cathode and the stainless steel shell close to the potassium-air battery cathode, an argon valve is arranged on the stainless steel shell on the side, an air chamber is reserved between the potassium-air battery anode and the stainless steel shell close to the potassium-air battery anode, and an air valve is arranged on the stainless steel shell on the side; the potassium-air battery positive electrode, the potassium-air battery negative electrode and the potassium-air battery electrolyte used were the same as in example 1. The electrochemical performance of the potassium-air battery is shown in table 1.
Table 1 electrochemical performance of potassium air cell of examples 1-3 of the invention, comparative examples
Example 4
As shown in the figure, the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite membrane potassium-air battery has the same structure as that of example 1.
Preparation of PCSP composite diaphragm
(1) Preparing spinning solution
Adding 0.6g of Polyacrylonitrile (PAN) into a mixed solvent of 1g of chloroform and 6.5g of 6.5g N, N-Dimethylformamide (DMF), and stirring at room temperature for 2 hours to obtain uniform colloidal liquid; adding 0.1800g aniline and 0.216g camphorsulfonic acid into the colloidal solution, stirring at room temperature for 2h, adding 0.45g ammonium persulfate, stirring at room temperature for 30min, placing the solution in the refrigerator cold room at 5 deg.C for 24h, and adding 0.1g Carbon Nanotube (CNT) and 0.1g SnO2Dissolving in the solution, and stirring for 12h to obtain a spinning solution;
(2) preparation of PCSP Membrane
A1 mL plastic spray gun is sleeved on a 5mL injector, 3mL of spinning solution is injected into the injector, a receiving device is a horizontally placed iron wire mesh, electrostatic spinning is carried out, and electrostatic spinning parameters are as follows: spinning voltage is 6kV, the distance between the needle point of the plastic spray gun head and the wire gauze is 12cm, the environmental temperature is 20-28 ℃, the relative humidity is 20-30%, and PANI/CNT/SnO is obtained after the spinning solution is exhausted2/PAN composite nanofiber membrane (PCSP membrane), and PANI/CNT/SnO prepared from the membrane2The area of the/PAN composite nanofiber membrane is 8 multiplied by 8cm2From PANI/CNT/SnO2The composite nano-fiber comprises composite nano-fibers, wherein the diameter of each composite nano-fiber is 200nm-600nm, and the gaps among the fibers are 20nm-100 nm;
2. preparing a potassium air battery electrolyte:
dissolving 3g of bis (trifluoromethyl) sulfimide (LiTFSI) in 15g of 1-ethyl-3-butylimidazole hexafluorophosphate, fully dissolving, adding 0.2g of spiro quaternary ammonium tetrafluoroborate, and uniformly mixing under the ultrasonic-assisted condition, wherein the ultrasonic power is 300W, the ultrasonic time is 3h, and the potassium-air battery electrolyte is prepared;
the potassium-air battery positive electrode and the potassium-air battery negative electrode used were the same as in example 1.
When the potassium-air battery positive electrode assembly works, the negative electrode of the potassium-air battery, the first microporous polyolefin diaphragm, the PCSP diaphragm, the electrolyte, the second microporous polyolefin diaphragm and the positive electrode of the potassium-air battery are arranged in a stainless steel shell to be assembled into the PCSP composite diaphragm potassium-air battery, argon is filled in an argon chamber through an argon valve, air is filled in the air chamber through an air valve, and the filling pressure of the argon and the air is 0.1 MPa. Through detection, the electrochemical performance of the PCSP composite diaphragm potassium-air battery is shown in Table 2.
Example 5
As shown in the figure, the polyaniline-carbon nanotube-tin oxide-polyacrylonitrile (PCSP) composite membrane potassium-air battery has the same structure as that of example 1.
Preparation of PCSP composite diaphragm
(1) Preparing spinning solution
Adding 0.6g of Polyacrylonitrile (PAN) into a mixed solvent of 1g of chloroform and 6.5g of 6.5g N, N-Dimethylformamide (DMF), and stirring at room temperature for 2 hours to obtain uniform colloidal liquid; adding 0.1800g aniline and 0.216g camphorsulfonic acid into the colloidal solution, stirring at room temperature for 2h, adding 0.45g ammonium persulfate, stirring at room temperature for 30min, placing the solution in the refrigerator cold room at 5 deg.C for 24h, and adding 0.1g Carbon Nanotube (CNT) and 0.1g SnO2Dissolving in the solution, and stirring for 12h to obtain a spinning solution;
(2) preparation of PCSP Membrane
A1 mL plastic spray gun is sleeved on a 5mL injector, 3mL of spinning solution is injected into the injector, a receiving device is a horizontally placed iron wire mesh, electrostatic spinning is carried out, and electrostatic spinning parameters are as follows: spinning voltage is 6kV, the distance between the needle point of the plastic spray gun head and the wire gauze is 12cm, the environmental temperature is 20-28 ℃, the relative humidity is 20-30%, and PANI/CNT/SnO is obtained after the spinning solution is exhausted2/PAN composite nanofiber membrane (PCSP membrane), and PANI/CNT/SnO prepared from the membrane2The area of the/PAN composite nanofiber membrane is 8 multiplied by 8cm2From PANI/CNT/SnO2The composite nanometer fiber consists of composite nanometer fiber with diameter of 200-600 nm and interval of 20-100 nmnm；
2. Preparing a potassium air battery electrolyte:
dissolving 6g of bis (trifluoromethyl) sulfimide (LiTFSI) in 7g of 1-ethyl-3-butylimidazole hexafluorophosphate, fully dissolving, adding 0.5g of spiro quaternary ammonium tetrafluoroborate, and uniformly mixing under the ultrasonic wave auxiliary condition, wherein the ultrasonic wave power is 600W, and the ultrasonic wave time is 1h to obtain the potassium-air battery electrolyte;
the potassium-air battery positive electrode and the potassium-air battery negative electrode used were the same as in example 1.
When the potassium-air battery positive electrode assembly works, the negative electrode of the potassium-air battery, the first microporous polyolefin diaphragm, the PCSP diaphragm, the electrolyte, the second microporous polyolefin diaphragm and the positive electrode of the potassium-air battery are arranged in a stainless steel shell to be assembled into the PCSP composite diaphragm potassium-air battery, argon is filled in an argon chamber through an argon valve, air is filled in the air chamber through an air valve, and the filling pressure of the argon and the air is 0.1 MPa. Through detection, the electrochemical performance of the PCSP composite diaphragm potassium-air battery is shown in Table 2.
Table 2 electrochemical performance of potassium air cell of examples 4 and 5 of the present invention
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The utility model provides a potassium air battery including polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber diaphragm, includes stainless steel casing and the insulating cover plate of setting at stainless steel casing's top and bottom, is equipped with potassium air battery negative pole, first diaphragm, electrolyte, second diaphragm, potassium air battery positive pole in proper order at stainless steel casing's internal insulation cover plate's middle part, leave the argon gas cavity between potassium air battery negative pole and the stainless steel casing that is close to potassium air battery negative pole to be equipped with the argon gas valve on the stainless steel casing of argon gas cavity one side, leave the air cavity between potassium air battery positive pole and the stainless steel casing that is close to potassium air battery positive pole, and be equipped with the air valve on the stainless steel casing of air cavity one side, characterized by: the first diaphragm and the second diaphragm are both made of microporous polyolefin diaphragms, and one side of the first diaphragm, which is close to the electrolyte, is provided with a polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber diaphragm;
the preparation method of the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane comprises the following steps:
(1) preparing spinning solution
Adding polyacrylonitrile into a solvent, stirring for 2-4 h at room temperature to obtain uniform colloidal liquid, adding aniline and camphorsulfonic acid into the colloidal liquid according to the mass ratio of 1:1.2, wherein the mass ratio of aniline to polyacrylonitrile is 0.3:1, stirring for 2-4 h, adding ammonium persulfate according to the mass ratio of polyacrylonitrile to ammonium persulfate of 4:3, stirring for 30-60 min at room temperature, placing the solution into a refrigerator refrigerating chamber at 5 ℃ for 24-48 h, and then adding Carbon Nano Tubes (CNT) and tin dioxide (SnO) according to the mass ratio of 1:12) Dissolving the carbon nano tube into a solution which is kept stand in a refrigerating chamber, wherein the mass ratio of the carbon nano tube to the polyacrylonitrile is 1:6, and stirring the mixture for 12 to 24 hours at room temperature to obtain a spinning solution;
(2) preparation of polyaniline-carbon nanotube-stannic oxide-polyacrylonitrile (PCSP) composite nanofiber membrane
Carrying out electrostatic spinning on the spinning solution, wherein the electrostatic spinning parameters are as follows: the spinning voltage is 6kV to 10kV, the spinning receiving distance is 10cm to 18cm, the environmental temperature is 20 ℃ to 28 ℃, the relative humidity is 20 percent to 30 percent, and the polyaniline-carbon nanotube-stannic oxide-polyacrylonitrile (PCSP) composite nanofiber membrane is obtained after the spinning solution is exhausted.
2. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 1, wherein: the solvent is a mixed solvent of chloroform and N, N-dimethylformamide.
3. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 2, wherein: the mass ratio of the chloroform to the N, N-dimethylformamide is 1: 6.5.
4. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 3, wherein: the mass ratio of chloroform to polyacrylonitrile is 5: 3.
5. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 1, wherein: the adding amount of the spinning solution in the electrostatic spinning injector is 3mL, and the area of the polyaniline-carbon nano tube-stannic oxide-polyacrylonitrile composite nano fiber diaphragm is 8 multiplied by 8cm2～10×10cm2。
6. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 1, wherein: the electrostatic spinning was carried out using a 1mL plastic spray gun head.
7. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 1, wherein: according to parts by weight, 3-6 parts of lithium bistrifluoromethylsulfonyl imide (LiTFSI) are dissolved in 7-15 parts of imidazole ionic liquid, fully dissolved, 0.2-0.5 part of spiro quaternary ammonium tetrafluoroborate is added, and the mixture is uniformly mixed under the auxiliary condition of ultrasonic waves, wherein the ultrasonic power is 300-600W, and the ultrasonic time is 1-3 h.
8. The potassium air battery comprising the polyaniline-carbon nanotube-tin dioxide-polyacrylonitrile composite nanofiber membrane as claimed in claim 7, wherein: the imidazole ionic liquid is 1-ethyl-3-butylimidazole hexafluorophosphate.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5832354A (en) * | 1981-07-27 | 1983-02-25 | Toshiba Battery Co Ltd | Battery |
| CN104201437A (en) * | 2014-07-26 | 2014-12-10 | 渤海大学 | Passive potassium air battery |
| CN105679983A (en) * | 2016-03-11 | 2016-06-15 | 中南大学 | Modified diaphragm and preparation method and application therefor |
| CN106480529A (en) * | 2015-08-24 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of organic inorganic hybridization Process of Antistatic PAN Fiber |
| CN106784552A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of lithium ion battery coating barrier film and preparation method thereof |
| CN106935410A (en) * | 2016-12-08 | 2017-07-07 | 常州大学 | A kind of preparation method of the self-supporting flexible super capacitor based on graphitized ordered arrangement spinning fibre |
| CN108539207A (en) * | 2018-04-04 | 2018-09-14 | 江南大学 | A kind of nanofiber air battery cathode and preparation method thereof |
| KR20190012123A (en) * | 2017-07-26 | 2019-02-08 | 주식회사 엘지화학 | Polymer electrolyte for secondary battery and lithium secondary battery comprising the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040224233A1 (en) * | 2003-05-05 | 2004-11-11 | Show -An Chen | Method for preparation of chemically crosslinked polyacrylonitrile polymer electrolyte as separator for secondary battery |
| WO2015061383A1 (en) * | 2013-10-22 | 2015-04-30 | Cornell University | Nanostructures for lithium air batteries |
| CN103647104B (en) * | 2013-12-18 | 2017-01-25 | 中国科学院上海硅酸盐研究所 | Lithium-sulfur battery |
| CN104151588B (en) * | 2014-07-14 | 2017-02-22 | 浙江大学 | Diaphragm for lithium-sulfur batteries and preparation method of lithium-sulfur batteries |
| CN106548877B (en) * | 2015-09-22 | 2018-07-17 | 南京绿索电子科技有限公司 | Carbon nano pipe array/polyaniline/ceria composite electrode and its preparation method and application |
| CN105938100A (en) * | 2016-04-14 | 2016-09-14 | 福建师范大学 | New luminol cathode electrochemiluminescence excitation method based on ordered mesoporous carbon and polyaniline |
| US10211455B2 (en) * | 2017-02-20 | 2019-02-19 | Nanotek Instruments, Inc. | Lithium secondary batteries containing protected particles of anode active materials and method of manufacturing |
| CN106935916A (en) * | 2017-03-01 | 2017-07-07 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of high-performance zinc Polyaniline Secondary Battery |
-
2019
- 2019-06-27 CN CN201910567988.2A patent/CN110323464B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5832354A (en) * | 1981-07-27 | 1983-02-25 | Toshiba Battery Co Ltd | Battery |
| CN104201437A (en) * | 2014-07-26 | 2014-12-10 | 渤海大学 | Passive potassium air battery |
| CN106480529A (en) * | 2015-08-24 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of organic inorganic hybridization Process of Antistatic PAN Fiber |
| CN105679983A (en) * | 2016-03-11 | 2016-06-15 | 中南大学 | Modified diaphragm and preparation method and application therefor |
| CN106935410A (en) * | 2016-12-08 | 2017-07-07 | 常州大学 | A kind of preparation method of the self-supporting flexible super capacitor based on graphitized ordered arrangement spinning fibre |
| CN106784552A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of lithium ion battery coating barrier film and preparation method thereof |
| KR20190012123A (en) * | 2017-07-26 | 2019-02-08 | 주식회사 엘지화학 | Polymer electrolyte for secondary battery and lithium secondary battery comprising the same |
| CN108539207A (en) * | 2018-04-04 | 2018-09-14 | 江南大学 | A kind of nanofiber air battery cathode and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Polyacrylonitrile Separator for High-Performance Aluminum Batteries with Improved Interface Stability;Giuseppe, at al.;《ACS APPLIED MATERIALS & INTERFACES》;20171018;第9卷(第44期);全文 * |
| 静电纺丝制备聚苯胺及其复合导电纳米纤维的研究进展;许菲菲等;《高分子通报》;20141015(第10期);全文 * |
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