CN115117552B - Titanic acid-carbon nanofiber composite membrane and preparation method and application thereof - Google Patents
Titanic acid-carbon nanofiber composite membrane and preparation method and application thereof Download PDFInfo
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- CN115117552B CN115117552B CN202210933194.5A CN202210933194A CN115117552B CN 115117552 B CN115117552 B CN 115117552B CN 202210933194 A CN202210933194 A CN 202210933194A CN 115117552 B CN115117552 B CN 115117552B
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- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011229 interlayer Substances 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002127 nanobelt Substances 0.000 claims abstract description 9
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002149 hierarchical pore Substances 0.000 claims 1
- 239000005077 polysulfide Substances 0.000 abstract description 9
- 229920001021 polysulfide Polymers 0.000 abstract description 9
- 150000008117 polysulfides Polymers 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the technical field of lithium sulfur battery diaphragm materials, relates to a preparation method of a lithium sulfur battery diaphragm interlayer material, and in particular relates to a novel lithium sulfur battery diaphragm modification layer material titanic acid-carbon nanofiber composite film, a preparation method and application. The invention constructs a composite fiber membrane by an electrostatic spinning method, and then combines high-temperature carbonization and normal-temperature alkaline hydrothermal in-situ construction of a membrane modification layer material of layered titanic acid (H 2Ti2O5) nanobelts wound with carbon nanofibers to inhibit the shuttle effect of polysulfide in a lithium-sulfur battery. The preparation process is simple, the controllability is high, and when the titanic acid-carbon nanofiber composite film is used as the interlayer of the lithium-sulfur battery, the electrochemical cycling stability of the lithium-sulfur battery can be greatly optimized.
Description
Technical Field
The invention belongs to the technical field of lithium sulfur battery diaphragm materials, relates to a preparation method of a lithium sulfur battery diaphragm interlayer material, and in particular relates to a novel lithium sulfur battery diaphragm modification layer material titanic acid-carbon nanofiber composite film, a preparation method and application.
Background
Lithium is a minimum atomic number alkali metal, has a very low density (0.53 g cm -1), and has a very high specific lithium storage capacity (38362 mA h g -1). While its electrode potential is the lowest among all metals, only-3.04V (relative to standard hydrogen electrodes). These characteristics determine that lithium metal has a high energy density when used as a negative electrode of a battery, so that lithium metal batteries are becoming an important research point in the field of energy storage in recent years. In order to realize the practical application of the metal lithium battery, it is critical to find and research and develop a positive electrode material with high capacity and a proper charge and discharge platform. The lithium-sulfur battery is considered as a next-generation secondary battery with great development potential and application prospect because the sulfur anode has very high theoretical lithium storage specific capacity (1600 mA h g -1), and the characteristics of abundant sulfur storage, low price, environmental friendliness and the like. However, the poor conductivity of the active S and the discharge end products, the low utilization rate of active materials, rapid capacity decay and electrode structural damage caused by the dissolution and shuttling of soluble polysulfides, the volume expansion/contraction of electrodes during charge and discharge, and the like, seriously hamper the practical application of lithium-sulfur batteries.
In the prior art: the sulfur anode is blended with a porous carbon material or a polar metal oxide material to form an anode composite material, or a new electrolyte additive and other electrode protection strategies are developed, so that the performance of the lithium-sulfur battery can be effectively improved. However, the shuttle effect of polysulfides still exists. On the other hand, the original method has the problems of high cost, complex electrode process construction and the like, and the industrialization of the lithium-sulfur battery is difficult to realize.
In view of this, the present invention has been made.
Disclosure of Invention
In order to solve the problems faced by the lithium sulfur battery in the prior art, the invention provides a titanic acid-carbon nanofiber membrane composite membrane and a preparation method thereof, and provides application of the titanic acid-carbon nanofiber membrane composite membrane as a novel lithium sulfur battery membrane modification layer material.
In order to solve the technical problems, the invention adopts the following technical scheme:
The titanic acid-carbon nanofiber membrane composite membrane is characterized in that the material is a composite nanofiber membrane, the nanofiber membrane is composed of layered titanic acid nanobelts and carbon nanofibers, the diameter of the titanic acid nanobelts is between 15 and nm, and the diameter of the carbon nanofibers is between 200 and 400 and nm.
In addition, the invention also provides a preparation method of the titanic acid-carbon nanofiber membrane composite membrane, which comprises the following steps:
(1) And (3) electrostatic spinning: dissolving titanium salt, tetraethyl silicate and a polymer in N, N-Dimethylformamide (DMF) to obtain a spinning solution, and preparing a composite fiber membrane by an electrostatic spinning technology;
(2) Carbonizing: performing carbonization heat treatment on the composite fiber in the step (1) in an inert atmosphere to carbonize the polymer into carbon nanofibers, and finally obtaining a TiO 2-SiO2 -carbon nanofiber membrane;
(3) Alkali liquor treatment: and (3) placing the TiO 2-SiO2 -carbon nanofiber membrane in the step (2) in alkali liquor, dissolving SiO 2, converting nano TiO 2 into H 2Ti2O5 nano-belts, and finally obtaining the titanic acid-carbon nanofiber composite membrane.
Preferably, the titanium salt in the step (1) is one or a mixture of more of titanium dichloride, titanium isopropoxide, tetrabutyl titanate and titanium tetrachloride.
Preferably, the polymer in step (1) is one or more of polyvinylpyrrolidone, polyacrylonitrile and polyethylene oxide.
Preferably, the amount of the titanium salt in the step (1) is 1-5 mmol, the amount of the tetraethyl silicate is 5-20 mmol, more preferably, the molar ratio of the titanium salt to the tetraethyl silicate is 1:2, the amount of the polymer is 0.5-2 g, and the amount of the azomethide is 7-15 ml.
Preferably, the process parameters of the electrospinning in the step (1) are as follows: the electrostatic spinning voltage is 15-25 kV; the receiving distance is 16-20cm; the liquid pushing speed is 0.4-2 ml h -1.
Preferably, the temperature of the carbonization heat treatment in the step (2) is 500-600 ℃, the time of the carbonization heat treatment is 30-120 min, and the heating rate of the carbonization heat treatment is 3-15 ℃/min.
Preferably, the alkali liquor in the step (3) is one or more of KOH aqueous solution, ammonia water, sodium carbonate aqueous solution and the like.
Preferably, the concentration of the alkali liquor in the step (3) is 1-10 mol L -1.
Preferably, the temperature of the alkali liquor treatment in the step (3) is 20-60 ℃, and the treatment time is 24-48 h.
The invention also provides application of the titanic acid-carbon nanofiber membrane composite membrane in lithium-sulfur batteries. The titanic acid-carbon nanofiber membrane composite membrane can be directly used as a diaphragm interlayer of a lithium-sulfur battery, and is clamped between a commercial diaphragm and a sulfur-carbon positive electrode sheet in the lithium-sulfur battery assembling process.
The invention has the following beneficial effects: (1) The invention directly utilizes alkali liquor for treatment, can form a composite film of titanic acid nanobelt wound carbon nanofiber in situ at a lower temperature, and compared with the traditional method for preparing nano oxide by high-temperature hydrothermal method, the process is simple and controllable, and the uniformity of the obtained material is good; (2) The invention utilizes the layered structure and the surface activity of the titanic acid to adsorb polysulfide, and combines the excellent conductivity of the carbon nanofiber, thereby being capable of synergistically enhancing the cycle stability of the lithium-sulfur battery. (3) According to the invention, a composite fiber membrane is constructed by an electrostatic spinning method, and then a diaphragm modification layer material of which layered titanic acid (H 2Ti2O5) nanobelts are wound around carbon nanofibers is constructed in situ by combining high-temperature carbonization and normal-temperature alkaline water heating, so that the shuttle effect of polysulfide in a lithium-sulfur battery is inhibited. (4) The preparation process is simple, the controllability is high, and when the titanic acid-carbon nanofiber composite film is used as the interlayer of the lithium-sulfur battery, the electrochemical cycling stability of the lithium-sulfur battery can be greatly optimized.
Drawings
FIG. 1 is a scanning electron microscope photograph of a composite film of a titanic acid-carbon nanofiber film in example 1 of the present invention;
FIG. 2 is a graph showing the cycle performance of a lithium sulfur battery assembled with a composite membrane of a titanic acid-carbon nanofiber membrane as a separator interlayer in example 1 of the present invention;
Fig. 3 is a graph showing cycle performance of a lithium sulfur battery assembled with a carbon nanofiber membrane as a separator interlayer in comparative example 1 of the present invention.
Detailed Description
The titanic acid-carbon nanofiber membrane composite membrane prepared by the invention is further described below with reference to the accompanying drawings and the preparation method of the invention:
Example 1
The preparation method of the titanic acid-carbon nanofiber composite membrane in the embodiment is as follows:
(1) Weighing 5 mmol tetrabutyl titanate, 10 mmol tetraethyl silicate and 0.8 g polyacrylonitrile, dissolving in 7 ml DMF, mechanically stirring to obtain a homogeneous spinning solution, and preparing the composite fiber by an electrostatic spinning method, wherein the specific parameters of an electrostatic spinning device are as follows: 16 A kV; reception distance: 16 cm; pushing feed liquid speed: 1 ml h -1;
(2) Placing the composite fiber in a nitrogen atmosphere furnace for heat treatment, wherein the heating rate of the heat treatment is 3 ℃/min, the heat treatment temperature is 500 ℃, the heat treatment time is 120 min, and naturally cooling to obtain a TiO 2-SiO2 -carbon nanofiber membrane;
(3) The TiO 2-SiO2 -carbon nanofiber membrane is soaked in 5 mol/L sodium hydroxide aqueous solution at 30 ℃ to be treated for 24 h, and the titanic acid-carbon nanofiber composite membrane is prepared.
The titanic acid-carbon nanofiber membrane composite membrane prepared in the example 1 is used as a lithium sulfur battery diaphragm interlayer material, a polypropylene porous membrane is used as a battery diaphragm, a sulfur-carbon composite material is used as a positive electrode material, metal lithium is used as a counter electrode, a lithium sulfur electrolyte is added, and a CR2025 button cell is assembled in a glove box filled with argon.
FIG. 1 is a scanning electron micrograph of a composite membrane of a titanic acid-carbon nanofiber membrane obtained in example 1. It can be observed from fig. 1 that the titanic acid nanobelt is wound on the surface of the carbon nanofiber to form a multi-level pore structure, and on the other hand, the titanic acid nanobelt has extremely strong adsorption capacity on polysulfide, which can effectively inhibit the shuttle effect of polysulfide in a lithium sulfur battery.
Fig. 2 is a graph showing capacity fade at 0.5C cycles for a lithium-sulfur battery employing a composite film of titanic acid-carbon nanofiber membrane as a separator interlayer in example 1. As can be seen from fig. 2, when the composite film of the titanate-carbon nanofiber film is used as a separator interlayer material of a lithium-sulfur battery, the capacity fade after 50 cycles is 851 mA h g -1. From this, it can be seen that: the titanic acid-carbon nanofiber membrane composite membrane interlayer can inhibit the shuttle of polysulfide, and improves the cycle charge and discharge performance of the lithium-sulfur battery.
Example 2
The preparation method of the titanic acid-carbon nanofiber composite membrane in the embodiment is as follows:
(1) Weighing 3 mmol tetrabutyl titanate, 6 mmol tetraethyl silicate and 1g polyvinylpyrrolidone, dissolving in 10ml DMF, mechanically stirring to obtain a homogeneous spinning solution, and preparing the composite fiber by an electrostatic spinning method, wherein the specific parameters of the electrostatic spinning device are as follows: 20 A kV; reception distance: 19 cm; pushing feed liquid speed: 2ml h -1;
(2) Placing the composite fiber in a nitrogen atmosphere furnace for heat treatment, wherein the heating rate of the heat treatment is 3 ℃/min, the heat treatment temperature is 600 ℃, the heat treatment time is 120 min, and naturally cooling to obtain a TiO 2-SiO2 -carbon nanofiber membrane;
(3) The TiO 2-SiO2 -carbon nanofiber membrane is soaked in a3 mol/L sodium hydroxide aqueous solution at 50 ℃ to be treated for 24h, and the titanic acid-carbon nanofiber membrane composite membrane is prepared.
The titanic acid-carbon nanofiber membrane composite membrane prepared in example 2 is used as a lithium-sulfur battery diaphragm interlayer material, a polypropylene porous membrane is used as a battery diaphragm, a sulfur-carbon composite material is used as a positive electrode material, metallic lithium is used as a counter electrode, a lithium-sulfur electrolyte is added, and a CR2025 button cell is assembled in a glove box filled with argon.
Example 3
The preparation method of the titanic acid-carbon nanofiber composite membrane in the embodiment is as follows:
(1) Weighing 4 mmol tetrabutyl titanate, 8 mmol tetraethyl silicate and 1.2 g polyvinylidene fluoride, dissolving in 10 ml DMF, mechanically stirring to obtain a homogeneous spinning solution, and preparing the composite fiber by an electrostatic spinning method, wherein the specific parameters of the electrostatic spinning device are as follows: 18A kV; reception distance: 17 cm; pushing feed liquid speed: 1.5 ml h -1;
(2) Placing the composite fiber in a nitrogen atmosphere furnace for heat treatment, wherein the heating rate of the heat treatment is 3 ℃/min, the heat treatment temperature is 550 ℃, the heat treatment time is 60 min, and naturally cooling to obtain a TiO 2-SiO2 -carbon nanofiber membrane;
(3) And soaking the TiO 2-SiO2 -carbon nanofiber membrane in 5 mol/L ammonia water solution at 40 ℃ for 24-h to prepare the titanic acid-carbon nanofiber membrane composite membrane.
The titanic acid-carbon nanofiber membrane composite membrane prepared in example 3 is used as a lithium-sulfur battery diaphragm interlayer material, a polypropylene porous membrane is used as a battery diaphragm, a sulfur-carbon composite material is used as a positive electrode material, metallic lithium is used as a counter electrode, a lithium-sulfur electrolyte is added, and a CR2025 button cell is assembled in a glove box filled with argon.
To highlight the outstanding advantages of the materials of the present invention, the following two comparative examples are provided.
Comparative example 1: and comparing the pure carbon nanofiber membrane with the titanic acid-carbon nanofiber membrane composite membrane.
Weighing 10 mmol tetraethyl silicate and 0.8 g polyacrylonitrile, dissolving in 7 ml DMF, mechanically stirring to obtain a homogeneous spinning solution, and preparing the composite fiber by an electrostatic spinning method, wherein the specific parameters of an electrostatic spinning device are as follows: 12 A kV; reception distance: 16 cm; pushing feed liquid speed: 1ml h -1;
Placing the composite fiber in a nitrogen atmosphere furnace for heat treatment, wherein the heating rate of the heat treatment is 3 ℃/min, the heat treatment temperature is 500 ℃, the heat treatment time is 120 min, and naturally cooling to obtain a SiO 2 -carbon nanofiber membrane;
Soaking the SiO 2 -carbon nanofiber membrane in 5 mol/L sodium hydroxide aqueous solution at 30 ℃ for 24-h to prepare a pure carbon nanofiber membrane composite membrane;
The pure carbon nanofiber membrane composite membrane prepared in comparative example 1 was used as a lithium sulfur battery separator interlayer material, a polypropylene porous membrane was used as a battery separator, a sulfur-carbon composite material was used as a positive electrode material, metallic lithium was used as a counter electrode, a lithium sulfur electrolyte was added, and a CR2025 button cell was assembled in a glove box filled with argon.
Fig. 3 is a graph showing capacity fade at 0.5C cycles for a lithium-sulfur battery of comparative example 1 in which a pure carbon nanofiber membrane composite membrane was sandwiched as a separator. As can be seen from fig. 3, when the pure carbon nanofiber membrane composite membrane is used as a lithium sulfur battery separator interlayer material, the capacity decays to only 618 mA h g -1 after 50 cycles. From this, it can be seen that: pure carbon nanofiber membranes are far less effective at inhibiting polysulfide shuttling than titanate-carbon nanofiber membrane composite membranes.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (1)
1. The application of the titanic acid-carbon nanofiber composite membrane as a lithium sulfur battery diaphragm modification layer material is characterized in that the titanic acid-carbon nanofiber composite membrane is directly used as a diaphragm interlayer of a lithium sulfur battery and is clamped between a commercial diaphragm and a sulfur-carbon positive plate in the lithium sulfur battery assembly process; the capacity attenuation of the lithium sulfur battery taking the titanic acid-carbon nanofiber membrane composite membrane as the diaphragm interlayer is 851 mA h g -1 after the lithium sulfur battery circulates for 50 times at the multiplying power of 0.5C; the preparation method of the titanic acid-carbon nanofiber composite membrane comprises the following steps:
(1) Weighing 5 mmol tetrabutyl titanate, 10 mmol tetraethyl silicate and 0.8 g polyacrylonitrile, dissolving in 7 ml DMF, mechanically stirring to obtain a homogeneous spinning solution, and preparing the composite fiber by an electrostatic spinning method, wherein the specific parameters of an electrostatic spinning device are as follows: 16 A kV; reception distance: 16 cm; pushing feed liquid speed: 1 ml h -1;
(2) Placing the composite fiber in a nitrogen atmosphere furnace for heat treatment, wherein the heating rate of the heat treatment is 3 ℃/min, the heat treatment temperature is 500 ℃, the heat treatment time is 120 min, and naturally cooling to obtain a TiO 2-SiO2 -carbon nanofiber membrane;
(3) Soaking the TiO 2-SiO2 -carbon nanofiber membrane in 5 mol/L sodium hydroxide aqueous solution at 30 ℃ for 24-h to prepare a titanic acid-carbon nanofiber composite membrane;
The titanic acid nanobelt in the titanic acid-carbon nanofiber composite film is wound on the surface of the carbon nanofiber, so that a hierarchical pore structure is formed.
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| CN202210933194.5A CN115117552B (en) | 2022-08-04 | Titanic acid-carbon nanofiber composite membrane and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210933194.5A CN115117552B (en) | 2022-08-04 | Titanic acid-carbon nanofiber composite membrane and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN115117552A CN115117552A (en) | 2022-09-27 |
| CN115117552B true CN115117552B (en) | 2024-07-12 |
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Non-Patent Citations (1)
| Title |
|---|
| High-Performance Li-Ion Capacitor Based on an Activated Carbon Cathode and Well-Dispersed Ultrafine TiO2 Nanoparticles Embedded in Mesoporous Carbon Nanofibers Anode;Cheng Yang;ACS Appl Mater. Interfaces;第9卷(第22期);18710-18719 * |
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