CN111082063B - Flexible conductive carbon/metal composite nanofiber membrane, preparation method and application thereof, and lithium-sulfur battery - Google Patents
Flexible conductive carbon/metal composite nanofiber membrane, preparation method and application thereof, and lithium-sulfur battery Download PDFInfo
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Abstract
The invention provides a flexible conductive carbon/metal composite nanofiber membrane, a preparation method and application thereof, and a lithium-sulfur battery, and belongs to the field of lithium-sulfur batteries. The invention reasonably designs the conductive nanofiber membrane reactor, and combines the chemical adsorption, the electrocatalysis and the ion (Li) of the lithium-sulfur battery membrane reactor + ) Diffusion, confining polysulfides on nanoscale surfaces and accelerating their reversible conversion kinetics, leading to high sulfur utilization and good rate capability and capacity retention at high discharge/charge current densities in rapid rechargeable, high-energy and high-power future lithium sulfur battery technologies, further driving lithium sulfur batteries towards high capacity and long cycle life.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a flexible conductive carbon/metal composite nanofiber membrane, a preparation method and application thereof, and a lithium-sulfur battery.
Background
Conversion chemistry is the primary electron and energy storage process for lithium/sulfur (Li/S) batteries, involving sulfur (S) from the solid state 8 ) To soluble lithium polysulphides (LipS, li) 2 S x X is 4-8) to solid Li 2 Multi-step chemical transformations and phase transitions of S. S 8 To Li 2 S 8 The conversion of (b) is a spontaneous process from the thermodynamic point of view, and polysulfides are essential for maintaining high capacity of lithium-sulfur batteries, from long-chain Li 2 S 8 To short chain Li 2 Redox conversion of two electrons/lithium ion during the progressive sulfur (S-S) bond cleavage of S (2 Li) + +2e - +xS→Li 2 S x (1≤x≤8))。Li 2 S x The binding interaction between the electrolyte and the electrolyte is stronger than S 8 Binding to itself, resulting in Li 2 S x Readily dissolved in the electrolyte and gradually diffused into the lithium negative electrode, resulting in a so-called "shuttle effect". However, severe shuttling, slow reaction kinetics, and discharge/charge at high current densities of polysulfidesPoor electron/Li during electrical cycling + Transport, resulting in lower effective sulfur utilization, dramatic capacity fade and shorter cycle life, makes it difficult to achieve theoretical capacity (1675 mAh g) -1 ) And energy density (2600 Wh kg) -1 ) The requirements of (2).
By designing a material having high conductivity and catalytic activity as a sulfur carrier, it is a recently developed strategy to restrict polysulfides while accelerating the redox conversion kinetics of polysulfides, which anchors polysulfides by strong chemisorption, inhibits shuttle of polysulfides, and accelerates the redox reaction kinetics by lowering the activation energy of the reaction through electrocatalysis; compared with the rapid development of sulfur carrier improvement and diaphragm improvement, the new structure of the lithium/sulfur battery provides another convenient method and battery assembly for the middle layer, so as to solve the problems and challenges of electrochemical dynamics in the lithium/S battery caused by slow substance conversion of polysulfide under the conditions of high current density and high sulfur load, such as the use of microporous carbon paper, porous carbon film and electron transport carbon film as the middle layer, and the like.
Disclosure of Invention
In view of the above, the present invention provides a flexible conductive carbon/metal composite nanofiber membrane, a preparation method and an application thereof, and a lithium-sulfur battery. The flexible conductive carbon/metal composite nanofiber membrane provided by the invention combines chemical adsorption, electrocatalysis and ion (Li) + ) Diffusion, confining polysulfides to nanoscale surfaces and accelerating their reversible conversion kinetics, achieves high sulfur utilization.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a flexible conductive carbon/metal composite nanofiber membrane which has a one-dimensional core-shell structure, wherein a core is carbon fiber, a shell layer is a carbon-bonded metal composite, the metal composite comprises two or three of metal oxide, metal nitride and metal carbide, the constituent elements of the flexible conductive carbon/metal composite nanofiber membrane are oxygen, nitrogen, carbon and metal elements, and the metal elements comprise titanium, zirconium or niobium.
Preferably, the atom percentage content of oxygen element in the flexible conductive carbon/metal composite nanofiber membrane is 4-15%, the atom percentage content of nitrogen element is 3-18%, and the atom percentage content of metal element is 50-80%.
Preferably, the flexible conductive carbon/metal composite nanofiber membrane comprises carbon-carbon double bonds, carbon-oxygen bonds, metal-oxygen bonds and metal-nitrogen bonds.
Preferably, the specific surface area of the flexible conductive carbon/metal composite nanofiber membrane is 30-300 m 2 /g。
The invention also provides a preparation method of the flexible conductive carbon/metal composite nanofiber membrane in the technical scheme, which comprises the following steps:
mixing a high molecular polymer, a metal organic precursor and a solvent to obtain a spinning solution, wherein the high molecular polymer is polyacrylonitrile or polyvinylpyrrolidone, and the metal organic precursor comprises n-butyl titanate, n-butyl zirconate or niobite;
carrying out electrostatic spinning on the spinning solution to obtain fibers;
and carbonizing the fibers to obtain the flexible conductive carbon/metal composite nanofiber membrane.
Preferably, the ratio of the amount of the high molecular polymer, the solvent and the metal organic precursor is 0.6-1.2 g: 6-15 mL:2 to 6mL.
Preferably, the carbonization environment is high-purity nitrogen or high-purity argon, the carbonization temperature is 800-1200 ℃, and the carbonization time is 1-3 h.
The invention also provides application of the flexible conductive carbon/metal composite nanofiber membrane in the technical scheme as a membrane reactor in the field of lithium-sulfur batteries.
The invention also provides a lithium-sulfur battery, and the flexible conductive carbon/metal composite nanofiber membrane in the technical scheme is a lithium-sulfur battery membrane reactor.
The invention provides a flexible conductive carbon/metal composite nanofiber membrane which has a one-dimensional core-shell structure, wherein a core is carbon fiber, a shell layer is a carbon-bonded metal composite, the metal composite comprises two or three of metal oxide, metal nitride and metal carbide, the constituent elements of the flexible conductive carbon/metal composite nanofiber membrane are oxygen, nitrogen, carbon and metal elements, and the metal elements comprise titanium, zirconium or niobium. The invention reasonably designs the conductive nano-fiber membrane reactor, and combines the chemical adsorption, the electric catalysis and the ion (Li) of the membrane reactor + ) Diffusion, confining polysulfides to nanoscale surfaces and accelerating their reversible conversion kinetics, thereby achieving high sulfur utilization and good rate capability and capacity retention at high discharge/charge current densities in the fast rechargeable, high energy and high power future lithium sulfur battery technologies, further driving lithium sulfur batteries toward high capacity and long cycle life. The flexible conductive carbon/metal composite nanofiber membrane provided by the invention serves as a reactor between a positive electrode and a diaphragm in a lithium sulfur battery, metal elements are bonded by carbon and embedded in carbon fibers to form a shell structure, the shell structure is composed of a carbon-bonded metal composite, the core part is the carbon fibers, the shell structure has a strong bonding effect, and the problem that metal particles on the surface of the existing carbon fibers are easy to fall off during reaction to cause material inactivation is solved.
The invention also provides a preparation method of the flexible conductive carbon/metal composite nanofiber membrane, and the preparation method provided by the invention is convenient to operate, high in yield, suitable for large-scale application and capable of ensuring future production practice application.
The invention also provides a high-performance lithium-sulfur batteryThe flexible conductive carbon/metal composite nanofiber membrane is used as a lithium-sulfur battery membrane reactor to construct a high-performance lithium-sulfur battery, so that a way is provided for the application of the carbon nanofiber membrane reactor in the high-performance lithium-sulfur battery, and the rate capability and the cycle performance of the battery can be effectively improved; combines strong chemical adsorption, electric catalysis and ion (Li) of a nano fiber membrane reactor + ) Diffusion, confining polysulfides on nanoscale surfaces and accelerating their reversible conversion kinetics, thus enabling high sulfur utilization, as well as rapid rechargeability, and in the case of rapid rechargeability, high energy and power for lithium sulfur batteries, with good rate capability and capacity retention at high discharge/charge current densities. The results of the examples show that a lithium sulfur battery using a conductive titanium (Ti) -containing flexible conductive carbon/metal composite nanofiber membrane (TiNOC) as a membrane reactor can achieve bifunctional confinement separation and electrocatalysis for LiPS, and n-butyl titanate (IV)/PAN molecules in the flexible conductive carbon/metal composite nanofiber membrane are converted into TiN and magneli phase Ti during carbonization 4 O 7 (p-TiN-Ti 4 O 7 ) From cyclic voltammetry tests, it was found that the overpotential of both cathodic peaks at 0.1C was reduced by 53.9mV (C1) and 65.7mV (C2), the current was increased by 1.87 and 3.63 times, and the corresponding discharge plateau was extended by 228.5mAh g -1 (C1) And 655.7mAh g -1 (C2) (ii) a Reversibly, there occurs a small overpotential of 55.7mV (A1) and 46.4mV (A2) and a 2.02 and 1.20 times higher current in the anodic process; the polarization controlled by electron transfer and ion diffusion is also obviously improved, the charge transfer resistance is shortened by 7.55 times, and the diffusion of Li ions is improved by 2.42 times (C1), 1.87 times (C2) and 2.87 times (A1), which are higher than that of the sulfur anode taking pure SuperP as a host material. By constructing a module with a sulfur anode-TiNOC membrane, a Li/S battery with a TiNOC membrane reactor module can provide 869.1mAh g at 5C -1 The capacity of the super P body is 6.10 times that of the super P body, and after 200 cycles, the capacity retention rate is up to 92.48%. Stacking the modules to a sulfur area loading of 12mg cm -2 It was found that 14.40mAh · cm was provided at 2.26mA -2 Initial capacity, capacity retention after 60 cyclesThe content was 89.3%. Two Li/S batteries can output 2.3V working voltage and 30mA current and supply power for 60 LED bulbs for 1 hour.
Drawings
FIG. 1 is a digital photograph of a flexible conductive carbon/metal composite nanofiber membrane containing titanium (Ti) prepared in example 1;
FIG. 2 is a graph of cyclic voltammetry measurements for a lithium sulfur cell prepared in example 1, with a scan rate of 0.1 mV/sec;
FIG. 3 is a graph showing cyclic voltammograms of the lithium sulfur cell prepared in example 1, at scan rates of 0.2 to 1.2 mV/s;
FIG. 4 is a graph of rate performance of a lithium sulfur battery prepared in example 1;
FIG. 5 is a graph showing electrical AC impedance measurements of the lithium sulfur battery prepared in example 1;
FIG. 6 is a 200 cycle test plot at 1C rate for a lithium sulfur battery prepared in example 1;
FIG. 7 is a 200 cycle test plot at 2C rate for a lithium sulfur battery prepared in example 1;
FIG. 8 is a 200 cycle test plot at 5C rate for a lithium sulfur battery prepared in example 1;
FIG. 9 is a 70-cycle test plot at 0.1C rate for a lithium sulfur battery prepared in example 2;
fig. 10 is a depiction of the power supply of 60 LED bulbs by the lithium sulfur battery prepared in example 2;
FIG. 11 is a 200 cycle test plot at 2C and 5C rates for a lithium sulfur battery prepared in example 3;
FIG. 12 is a 200 cycle test plot at 1C rate for a lithium sulfur battery prepared in example 4;
FIG. 13 is a 200 cycle test plot at 5C rate for a lithium sulfur battery prepared in example 5;
fig. 14 is a 200-cycle test plot at 5C rate for the lithium sulfur cell prepared in example 6.
Detailed Description
The invention provides a flexible conductive carbon/metal composite nanofiber membrane which has a one-dimensional core-shell structure, wherein a core is a carbon fiber, a shell layer is a carbon-bonded metal composite, the metal composite comprises two or three of metal oxides, metal nitrides and metal carbides, the constituent elements of the flexible conductive carbon/metal composite nanofiber membrane are oxygen, nitrogen, carbon and metal elements, and the metal elements comprise titanium, zirconium or niobium.
In the invention, the atomic percentage of oxygen element in the flexible conductive carbon/metal composite nanofiber membrane is preferably 4-15%, the atomic percentage of nitrogen element is preferably 3-18%, and the atomic percentage of metal element is preferably 50-80%. In the invention, the flexible conductive carbon/metal composite nanofiber membrane further comprises carbon elements.
In the present invention, the flexible conductive carbon/metal composite nanofiber membrane preferably includes a carbon-carbon double bond, a carbon-oxygen bond, a metal-oxygen bond, and a metal-nitrogen bond.
In the present invention, the flexible conductive carbon/metal composite nanofiber membrane preferably includes a micro mesoporous structure, and the pore diameter of the micro mesoporous structure is preferably 0.5nm to 20nm.
In the present invention, the specific surface area of the flexible conductive carbon/metal composite nanofiber membrane is preferably 30 to 300m 2 /g。
The invention also provides a preparation method of the flexible conductive carbon/metal composite nanofiber membrane in the technical scheme, which comprises the following steps:
mixing a high molecular polymer, a metal organic precursor and a solvent to obtain a spinning solution, wherein the high molecular polymer is polyacrylonitrile or polyvinylpyrrolidone, and the metal organic precursor comprises n-butyl titanate, n-butyl zirconate or nionol;
carrying out electrostatic spinning on the spinning solution to obtain fibers;
and carbonizing the fibers to obtain the flexible conductive carbon/metal composite nanofiber membrane.
The spinning solution is obtained by mixing a high molecular polymer, a metal organic precursor and a solvent, wherein the high molecular polymer is polyacrylonitrile or polyvinylpyrrolidone, and the metal organic precursor comprises n-butyl titanate, n-butyl zirconate or niobium alcohol. In the present invention, the ratio of the amount of the high molecular polymer, the solvent and the metal-organic precursor is preferably 0.6 to 1.2g: 6-15 mL:2 to 6mL, more preferably 0.6 to 1.0g: 6-12 mL:2 to 5mL, more preferably 0.7 to 0.9g: 8-11 mL: 3-5 mL; the volume ratio of the solvent to the metal-organic precursor is preferably 10. In the present invention, the solvent is preferably N, N-Dimethylformamide (DMF), nitromethylpyrrolidone (NMP), or ethanol. The mixing method of the present invention is not particularly limited, and a mixing method known to those skilled in the art may be used.
After the spinning solution is obtained, the spinning solution is subjected to electrostatic spinning to obtain the fiber.
And after obtaining the fibers, carbonizing the fibers to obtain the flexible conductive carbon/metal composite nanofiber membrane. In the invention, the carbonization environment is preferably high-purity nitrogen or high-purity argon, so that the original appearance of the fiber can be maintained and the overall flexibility can be realized; the carbonization temperature is preferably 800-1200 ℃, more preferably 900-1200 ℃, further preferably 1000-1100 ℃, and the time is preferably 1-3 h.
After the carbonization is completed, the present invention preferably cuts the obtained carbonized product into a practically required size for use.
The invention also provides application of the flexible conductive carbon/metal composite nanofiber membrane in the technical scheme as a membrane reactor in the field of lithium-sulfur batteries.
The invention also provides a lithium-sulfur battery, wherein the flexible conductive carbon/metal composite nanofiber membrane in the technical scheme is a lithium-sulfur battery membrane reactor, and has the functions of electrocatalytic conversion of sulfur and lithium polysulfide, reduction of overpotential and improvement of current density, and the thermodynamic reversibility of conversion chemistry can be improved by active sulfur-sulfur bonds and lithium-sulfur bonds; the charge transfer and substance transfer impedance can be reduced, and the lithium ion transmission dynamics is improved; the function of strongly and chemically adsorbing soluble lithium polysulfide is strengthened, and the shuttle effect of the lithium polysulfide is inhibited.
In the present invention, the flexible conductive carbon/metal composite nanofiber membrane preferably constitutes a module of a positive electrode-flexible conductive carbon/metal composite nanofiber membrane in a lithium sulfur battery.
In the present invention, the preferred structure of the lithium sulfur battery comprises a module/separator/lithium sheet/gasket or spring sheet of positive electrode-flexible conductive carbon/metal composite nanofiber membrane.
In the present invention, the separator is preferably a Celgard 2400 separator, and the thickness of the Celgard 2400 separator is preferably 16 to 25 μm, and more preferably 20 to 25 μm.
In the present invention, the lithium sulfur battery preferably uses commercial activated carbon, supp, as a host material of activated sulfur, and the electrolyte is 1M LiTFSI { lithium bis (trifluoromethanesulfonic acid) imide } and 1% LiNO in a solution of DOL (1, 3-dioxolane) and DME (ethylene glycol dimethyl ether) (volume ratio 1 3 (lithium nitrate) or 1M LiTFSI { lithium bis (trifluoromethanesulfonate) imide) }, 0.5M LiCF dissolved in a solution of DOL (1, 3-dioxolane) and DME (ethylene glycol dimethyl ether) (volume ratio 1 3 SO 3 (lithium trifluoromethanesulfonate) and 0.5M LiNO 3 (lithium nitrate).
The specific structure of the lithium-sulfur battery is not particularly limited, and specifically includes a button-type lithium-sulfur battery, a soft-package-type lithium-sulfur battery or a column-type lithium-sulfur battery. In the invention, when the lithium-sulfur battery is a button type, button battery cases with different diameters and different heights are selected according to the size of a sulfur positive electrode, the quality of an electrode and the size of a flexible conductive carbon/metal composite nanofiber membrane, such as CR 3032, CR 2430, CR 2335, CR2032, CR 2025, CR 2016, CR 1632, CR 1620, CR 1616, CR1225, CR 1216, CR 1220 and the like; when the lithium-sulfur battery is in a soft package type, assembling according to the size of an electrode, the quality of a sulfur positive electrode and the size of a flexible conductive carbon/metal composite nanofiber membrane to form a large soft package type super capacitor, wherein the size preferably comprises 1cm multiplied by 1cm to 10cm multiplied by 10cm; when the lithium-sulfur battery is a column type, column type battery cases with different diameters and different heights are selected according to the size of a sulfur positive electrode, the quality of the electrode and the size of the flexible conductive carbon/metal composite nanofiber membrane, such as 26650, AA, CR 123, 18650 and 32650.
In the present invention, the lithium sulfur battery preferably includes a normal temperature lithium sulfur battery and a high and low temperature (-40 to 70 ℃) lithium sulfur battery.
The flexible conductive carbon/metal composite nanofiber membrane provided by the invention is used as a membrane reactor of a lithium-sulfur battery, provides a reaction space for mutual transformation of polysulfide in the charging and discharging processes, and can effectively inhibit the shuttle effect by strong chemical adsorption of metal nanoparticles in the fiber on the polysulfide; the high conductivity of the nano-fiber can accelerate the transfer of electrons, and shows higher effective utilization rate of sulfur and better rate performance; the excellent pore size distribution of the fiber not only can adsorb polysulfide, but also provides convenience for ion diffusion and shows higher ion diffusion capacity. Therefore, the capacity, energy and power output of the lithium-sulfur battery can be effectively improved by the characteristics, and beneficial help is provided for commercialization of the lithium-sulfur battery.
In order to further illustrate the present invention, the flexible conductive carbon/metal composite nanofiber membrane provided by the present invention, the preparation method and application thereof, and the lithium sulfur battery are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 4mL of n-butyl titanate, 10mL of N, N-dimethylformamide and 800mg of polyacrylonitrile, stirring for 12 hours in a 50mL beaker at the same time, spinning for 4 hours under the conditions that positive high pressure and negative high pressure are +15KV and-3 KV when the solution is completely dissolved, then carbonizing the spun fibers for 1 hour under the conditions of high temperature of 1000 ℃ and high purity nitrogen, and finally obtaining the carbonized product, namely the flexible conductive carbon/metal composite nanofiber membrane containing titanium (Ti) nanoparticles, wherein the metal titanium atom percentage content of the fiber membrane is 74 percent, the oxygen atom percentage content of the fiber membrane is 14 percent, the nitrogen atom percentage content of the fiber membrane is 4 percent, the balance is carbon elements, and the specific surface area of the fiber membrane is 149.8m 2 In terms of a/g, the mean pore diameter is 3.18nm. The nanofiber membrane was then cut into equal sized (12 mm diameter) circles as a lithium sulfur battery membrane reactor.
1M LiTFSI and 1% LiNO dissolved in DOL and DME (1 volume to volume) 3 Selecting Celgard 2400 as a diaphragm and a button cell mould as electrolyteCR2032, commercial activated carbon SuperP as host material for activated sulfur, coated at 2mg/cm 2 The electrode is used as a sulfur positive electrode, a module of a positive electrode-flexible conductive carbon/metal composite nanofiber membrane reactor and a lithium sheet are used as a negative electrode, the modules/a diaphragm/the lithium sheet/a gasket and a spring sheet are arranged in a button cell shell in sequence, and a certain amount of electrolyte is dripped to assemble the high-performance lithium-sulfur battery with the titanium (Ti) -nanoparticle-containing high-conductivity flexible nanofiber membrane as the lithium-sulfur battery membrane reactor.
Fig. 1 is a digital photograph of the flexible conductive carbon/metal composite nanofiber film containing titanium (Ti) prepared in example 1, and it can be seen from fig. 1 that the flexible conductive carbon/metal composite nanofiber film prepared in this example has good flexibility.
Fig. 2 is a cyclic voltammogram test chart of the lithium sulfur cell prepared in example 1, with a scan rate of 0.1 mv/sec, and it can be seen that, when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium sulfur cell membrane reactor, strong kinetics of electrochemical reaction and small overpotential are exhibited, and as the number of cycles increases, the oxidation peak and the reduction peak respectively have a tendency to shift to the left and right, representing the catalytic action of the metal nanoparticles on polysulfides; the overpotential of both cathodic peaks at 0.1C was reduced by 53.9mV (C1) and 65.7mV (C2), the current increased by 1.87 and 3.63 times, and the corresponding discharge plateau was extended by 228.5mAh g -1 (C1) And 655.7mAh g -1 (C2) (ii) a Reversibly, a small overpotential of 55.7mV (A1) and 46.4mV (A2) and a high current of 2.02 and 1.20 times during the anodic process; the polarization controlled by electron transfer and ion diffusion is also obviously improved, the charge transfer resistance is shortened by 7.55 times, and the diffusion of Li ions is improved by 2.42 times (C1), 1.87 times (C2) and 2.87 times (A1), which are higher than that of a pure SuperP main body.
Fig. 3 is a test chart of cyclic voltammetry curves of the lithium-sulfur battery prepared in example 1, where the scanning rate is 0.2 to 1.2 mv/sec, and it can be seen that when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with a lithium-sulfur battery membrane reactor, the intrinsic characteristics of charge and discharge of the lithium-sulfur battery can be maintained at different scanning rates, strong electrochemical reaction kinetics and good rate performance are shown, and as the scanning rate increases, the current potential thereof also increases with a positive proportion, and shows strong ion diffusion capability.
FIG. 4 is a graph of rate performance of the lithium sulfur cell prepared in example 1, showing that the membrane reactor of the lithium sulfur cell is combined with conventional commercial carbon SuperP as a sulfur carrier, and the membrane reactor is still operated at different current densities (rates)
The lithium-sulfur battery can maintain good charge-discharge rate capacity, particularly shows stronger electrochemical reaction kinetics and better rate performance under the condition of high rate 5C, obtains higher capacity under the condition of low rate to realize effective utilization of active sulfur, and can provide 869.1 mAh.g at the time of 5C -1 The capacity of (a) to achieve good rate capability is 6.10 times that of the SuperP body.
Fig. 5 is a graph of electrical ac impedance test of the lithium-sulfur battery prepared in example 1, and it can be seen that the membrane reactor of the lithium-sulfur battery exhibits smaller resistance and better rate capability when the conventional commercial carbon SuperP is used as a sulfur carrier, compared with the battery without the membrane reactor.
Fig. 6 is a 200-cycle test chart of the lithium sulfur battery prepared in example 1 at a rate of 1C, and it can be seen that, when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium sulfur battery membrane reactor, under a current condition of a high rate of 1C, the capacity is maintained at 89.96% after 200 cycles, which shows that the carbon nanofiber membrane effectively controls polysulfides, and long cycle of the lithium sulfur battery at a high rate and a high capacity is realized.
Fig. 7 is a 200-cycle test chart of the lithium-sulfur battery prepared in example 1 at a rate of 2C, and it can be seen that when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium-sulfur battery membrane reactor, under a current condition of a high rate of 2C, the capacity is maintained at 87.17% after 200 cycles, and long cycles of the lithium-sulfur battery under the conditions of the high rate and the high capacity are realized.
Fig. 8 is a 200-cycle test chart of the lithium-sulfur battery prepared in example 1 at 5C rate, and it can be seen from the chart that when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium-sulfur battery membrane reactor, under a high-rate 5C current condition, the capacity is maintained at 92.48% after 200 cycles, and a long cycle of the lithium-sulfur battery under a high-rate and high-capacity condition is realized, so that a selective help is provided for the future commercial development of the lithium-sulfur battery.
Example 2
Weighing 4mL of n-butyl titanate, 10mL of N, N-dimethylformamide and 800mg of polyacrylonitrile, stirring for 12 hours in a 50mL beaker at the same time, spinning for 4 hours under the conditions that positive high pressure and negative high pressure are +15KV and-3 KV after the solution is completely dissolved, carbonizing the spun fibers for 2 hours under the conditions of high temperature of 1000 ℃ and high purity nitrogen, and finally obtaining the carbonized product flexible conductive carbon/metal composite nanofiber membrane containing titanium (Ti) nanoparticles, wherein the metal titanium atom percentage of the fiber membrane is 74%, the oxygen atom percentage of the fiber membrane is 14%, the nitrogen atom percentage of the fiber membrane is 4%, the balance is carbon elements, and the specific surface area of the fiber membrane is 149.8m 2 In terms of/g, the mean pore diameter is 3.18nm. The nanofiber membrane was then cut into equal sized (12 mm diameter) circles as a lithium sulfur battery membrane reactor.
1M LiTFSI and 1% LiNO dissolved in DOL and DME (1 volume ratio) 3 Selecting Celgard 2400 as a diaphragm, selecting a die CR2032 of a button cell, using commercial activated carbon SuperP as a host material of active sulfur, and coating the host material to be 2mg/cm 2 The electrode is used as a sulfur anode, a module of the sulfur anode-flexible conductive carbon/metal composite nano fiber membrane reactor is constructed, and the unit surface capacity is 12mg/cm through layer-by-layer stacking and assembling 2 The lithium sulfur battery takes a lithium sheet as a negative electrode, the lithium sheet is arranged in a button battery shell according to the sequence of a stacking module/a diaphragm/the lithium sheet/a gasket and a spring plate, and a certain amount of electrolyte is dripped to assemble the high-performance lithium sulfur battery taking a high-conductivity flexible nanofiber membrane containing titanium (Ti) nano particles as a membrane reactor.
FIG. 9 is 12mg/cm prepared in example 2 2 60-cycle cycling test chart for high-capacity lithium-sulfur battery and 12mg/cm prepared in example 2 in FIG. 10 2 A demonstration of 60 LED bulbs powered by high-capacity lithium-sulfur batteries is shown in FIG. 9, which provides 14.40mAh cm at a current of 2.26mA -2 After 60 cycles, the capacity retention was 89.3%. Two Li/S batteries can output 2.3V working voltage and 30mA current and supply power for 60 LED bulbs for 1 hour.
Example 3
Weighing 4mL of n-butyl titanate, 10mL of N, N-dimethylformamide and 800mg of polyacrylonitrile, stirring for 12 hours in a 50mL beaker at the same time, spinning for 4 hours under the conditions that positive high pressure and negative high pressure are +15KV and-3 KV when the solution is completely dissolved, then carbonizing the spun fibers for 2 hours under the conditions of high temperature of 1200 ℃ and high purity nitrogen, and finally obtaining the carbonized product, namely the flexible conductive carbon/metal composite nanofiber membrane containing titanium (Ti) nanoparticles, wherein the metal titanium atom percentage content of the fiber membrane is 72 percent, the oxygen atom percentage content of the fiber membrane is 12 percent, the nitrogen atom percentage content of the fiber membrane is 3.5 percent, the balance is carbon elements, and the specific surface area of the fiber membrane is 161.4m 2 In terms of a/g, the mean pore diameter is 3.48nm. The nanofiber membrane was then cut into equal sized (12 mm diameter) circles as a lithium sulfur battery membrane reactor.
1M LiTFSI and 1% LiNO dissolved in DOL and DME (1 volume to volume) 3 Celgard 2400 was used as separator for the electrolyte, die CR2032 for button cells, commercial carbon nitride (g-C) 3 N 4 ) Is host material of active sulfur, and is coated at 2mg/cm 2 The electrode is used as a sulfur anode, a module of the sulfur anode-flexible conductive carbon/metal composite nano fiber membrane reactor is constructed, and the unit surface capacity is 12mg/cm through layer-by-layer stacking and assembling 2 According to the lithium-sulfur battery, a lithium sheet is used as a negative electrode, the lithium sheet is placed in a button battery shell according to the sequence of a stacking module/diaphragm/lithium sheet/gasket and a spring plate, and a certain amount of electrolyte is dripped to assemble the high-performance lithium-sulfur battery with the titanium (Ti) -nanoparticle-containing high-conductivity flexible nanofiber membrane as a membrane reactor.
FIG. 11 is a graph of 200 cycles of the lithium sulfur battery prepared in example 3 at 2C and 5C rates, showing that commercial carbon nitride (g-C) is used 3 N 4 ) When the catalyst is used as a sulfur carrier, the catalyst is combined with a lithium-sulfur battery membrane reactor, under the current condition of high multiplying power of 2C and 5C, the capacity is kept at 93.91 percent and 100 percent after 200 cycles, and the lithium-sulfur battery is realizedLong cycle under high multiplying power and high capacity conditions.
Example 4
Weighing 3mL of n-butyl zirconate, 8mL of N, N-dimethylformamide and 600mg of polyacrylonitrile, stirring for 12 hours in a 50mL beaker, spinning for 4 hours under the conditions that positive high pressure and negative high pressure are +15KV and-3 KV after the solution is completely dissolved, carbonizing the spun film for 2 hours at the high temperature of 800 ℃ under the condition of high-purity nitrogen, and finally obtaining the carbonized product, namely the flexible conductive carbon/metal composite nanofiber film containing zirconium (Zr) nanoparticles, wherein the atom percentage of metal titanium of the fiber film is 74.6%, the atom percentage of oxygen of the fiber film is 12.9%, the atom percentage of nitrogen of the fiber film is 3.5%, the balance is carbon, and the specific surface area of the fiber film is 66.4m 2 In terms of/g, the mean pore diameter is 6.6nm. And then cutting the atomic percent into circles with equal sizes (the diameter is 12 mm) to obtain the lithium-sulfur battery membrane reactor containing the zirconium (Zr) nano particles.
1M LiTFSI and 1% LiNO dissolved in DOL and DME (1 volume to volume) 3 Selecting Celgard 2400 as a diaphragm for electrolyte, selecting a die CR2032 of a button cell, selecting commercial active carbon SuperP as a host material of active sulfur, and coating the host material to be 2mg/cm 2 The electrode is used as a sulfur anode, a module of the sulfur anode-flexible conductive carbon/metal composite nanofiber membrane reactor is constructed, a lithium sheet is used as a cathode, the module, a diaphragm, the lithium sheet, a gasket and a spring sheet are sequentially arranged in a button cell shell, and a certain amount of electrolyte is dripped to assemble the high-performance lithium sulfur cell with the high-conductive flexible nanofiber membrane containing zirconium (Zr) nano particles as the membrane reactor
Fig. 12 is a 200-cycle test chart of the lithium sulfur battery prepared in example 4 at a rate of 1C, and it can be seen that, when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium sulfur battery membrane reactor, under a current condition of a high rate of 1C, the capacity is maintained at 89.3% after 200 cycles, and long cycle of the lithium sulfur battery under a high rate and high capacity condition can still be achieved.
Example 5
6mL of n-butyl titanate, 10mL of N, N-dimethylformamide and 800mg of polyacrylonitrile were weighed while stirring in a 50mL beakerSpinning for 4 hours under the conditions that positive high pressure and negative high pressure are +15KV and-3 KV after the solution is completely dissolved, then carbonizing the spun membrane for 2 hours at the high temperature of 1000 ℃ and under the condition of high-purity nitrogen, and finally obtaining a carbonized product, namely the flexible conductive carbon/metal composite nanofiber membrane containing titanium (Ti) nano particles, wherein the atom percentage of metal titanium in the fiber membrane is 79 percent, the atom percentage of oxygen in the fiber membrane is 11 percent, the atom percentage of nitrogen in the fiber membrane is 3.4 percent, the balance is carbon elements, and the specific surface area is 114.7m 2 (ii)/g, average pore diameter was 3.07nm. The nanofiber membrane was then cut into equal-sized (12 mm diameter) circles to obtain a lithium sulfur battery membrane reactor.
1M LiTFSI and 1% LiNO dissolved in DOL and DME (1 volume ratio) 3 Selecting Celgard 2400 as a diaphragm, selecting a die CR2032 of a button cell, using commercial activated carbon SuperP as a host material of active sulfur, and coating the host material to be 2mg/cm 2 The electrode is used as a sulfur anode, a module of a sulfur anode-flexible conductive carbon/metal composite nanofiber membrane reactor is constructed, a lithium sheet is used as a cathode, the module/a diaphragm/the lithium sheet/a gasket and a spring sheet are arranged in a button cell shell in sequence, and a certain amount of electrolyte is dripped to assemble the high-performance lithium sulfur battery with the titanium (Ti) nanoparticle-containing high-conductivity flexible nanofiber membrane as the membrane reactor.
Fig. 13 is a 200-cycle test chart of the lithium sulfur battery prepared in example 5 at a rate of 5C, and it can be seen that, when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium sulfur battery membrane reactor, under a current condition of a high rate of 5C, the capacity is maintained at 86.0% after 200 cycles, and long cycle of the lithium sulfur battery under the conditions of the high rate and the high capacity can still be achieved.
Example 6
Weighing 4mL of n-butyl titanate, 10mL of N, N-dimethylformamide and 1000mg of polyacrylonitrile, stirring for 12 hours in a 50mL beaker at the same time, spinning for 4 hours under the conditions that positive high pressure and negative high pressure are +15KV and-3 KV after the solution is completely dissolved, carbonizing the spun film for 2 hours at the high temperature of 1000 ℃ under the condition of high-purity nitrogen, and finally carbonizing the obtained carbonized product, namely the flexible conductive carbon containing titanium (Ti) nano particlesThe metal composite nano fiber membrane comprises 69% of metal titanium atoms, 14.6% of oxygen atoms, 5.4% of nitrogen atoms and 162.6m of specific surface area 2 In terms of a/g, the mean pore diameter is 4.25nm. The nanofiber membrane was then cut into equal-sized (12 mm diameter) circles to obtain a lithium sulfur battery membrane reactor.
1M LiTFSI and 1% LiNO dissolved in DOL and DME (1 volume to volume) 3 Selecting Celgard 2400 as a diaphragm, selecting a die CR2032 of a button cell, using commercial activated carbon SuperP as a host material of active sulfur, and coating the host material to be 2mg/cm 2 The electrode is used as a sulfur anode, a module of a sulfur anode-flexible conductive carbon/metal composite nanofiber membrane reactor is constructed, a lithium sheet is used as a cathode, the module/a diaphragm/the lithium sheet/a gasket and a spring sheet are arranged in a button cell shell in sequence, and a certain amount of electrolyte is dripped to assemble the high-performance lithium sulfur battery with the titanium (Ti) nanoparticle-containing high-conductivity flexible nanofiber membrane as the membrane reactor.
Fig. 14 is a 200-cycle test chart of the lithium sulfur battery prepared in example 6 at a rate of 5C, and it can be seen that, when a conventional commercial carbon SuperP is used as a sulfur carrier, in combination with the lithium sulfur battery membrane reactor, under a current condition of a high rate of 5C, the capacity is maintained at 84.2% after 200 cycles, and long cycle of the lithium sulfur battery under the conditions of the high rate and the high capacity can still be achieved.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. The flexible conductive carbon/metal composite nanofiber membrane is characterized by having a one-dimensional core-shell structure, wherein the core is carbon fiber, the shell is a carbon-bonded metal composite, the metal composite is two or three of metal oxide, metal nitride and metal carbide, the constituent elements of the flexible conductive carbon/metal composite nanofiber membrane are oxygen, nitrogen, carbon and metal elements, and the metal elements are titanium, zirconium or niobium;
the atom percentage content of oxygen element in the flexible conductive carbon/metal composite nanofiber membrane is 4-15%, the atom percentage content of nitrogen element is 3-18%, and the atom percentage content of metal element is 50-80%.
2. The flexible conductive carbon/metal composite nanofiber membrane according to claim 1, wherein the flexible conductive carbon/metal composite nanofiber membrane comprises carbon-carbon double bonds, carbon-oxygen bonds, metal-oxygen bonds, and metal-nitrogen bonds.
3. The flexible conductive carbon/metal composite nanofiber membrane according to claim 1, wherein the specific surface area of the flexible conductive carbon/metal composite nanofiber membrane is 30 to 300m 2 /g。
4. The method for preparing the flexible conductive carbon/metal composite nanofiber membrane as claimed in any one of claims 1 to 3, comprising the steps of:
mixing a high molecular polymer, a metal organic precursor and a solvent to obtain a spinning solution, wherein the high molecular polymer is polyacrylonitrile or polyvinylpyrrolidone, and the metal organic precursor comprises n-butyl titanate, n-butyl zirconate or nionol;
carrying out electrostatic spinning on the spinning solution to obtain fibers;
and carbonizing the fibers to obtain the flexible conductive carbon/metal composite nanofiber membrane.
5. The preparation method according to claim 4, wherein the ratio of the amount of the high molecular polymer, the solvent and the metal-organic precursor is 0.6 to 1.2g: 6-15 mL:2 to 6mL.
6. The preparation method according to claim 4, wherein the carbonization environment is high-purity nitrogen or high-purity argon, and the carbonization temperature is 800-1200 ℃ and the carbonization time is 1-3 h.
7. Use of the flexible conductive carbon/metal composite nanofiber membrane of any one of claims 1 to 3 as a membrane reactor in the field of lithium sulfur batteries.
8. A lithium-sulfur battery, characterized in that the flexible conductive carbon/metal composite nanofiber membrane of any one of claims 1-3 is used as a lithium-sulfur battery membrane reactor.
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