CN112421044A - Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery - Google Patents
Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery Download PDFInfo
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Abstract
The invention discloses a core-shell structure sulfur positive electrode material, a preparation method and application in a lithium sulfur battery, wherein the core-shell structure nano-cage adopts a one-step method to directly generate metal complex gel from transition metal salt and organic ligand, the metal complex gel is used as a skeleton, and after freeze drying and high-temperature calcination treatment, a coating material of C @ Fe is obtained3O4In order to make the active material uniformly distributed and fully exert the structural advantages, part of Fe is etched by acid3O4Obtaining a core-shell structure (YCF) using the carbon shell and Fe3O4The gaps between the S and the C encapsulate sulfur to obtain the S/YCF material. The carbon shell and the polar inner core can effectively inhibit the shuttle effect of polysulfide by exerting the synergistic effect of a physical barrier and a chemical adsorbent, and Fe is regulated and controlled3O4The content of the polar spheres balances the maximum sulfur carrying amount, inhibits the shuttle of polysulfide and accommodates the expansion of volume, and realizes the preparation of the anode with high coulombic efficiency and long service life.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a core-shell structure sulfur positive electrode material, a preparation method and application in a lithium-sulfur battery.
Background
The problem of energy shortage is increasingly apparent as the reserves of petrochemical fuels are greatly reduced due to the high intensity dependence on the petrochemical fuels in the past. Electric energy is one of clean energy, and meets the requirement of sustainable development of human beings, so that the storage of the electric energy is also important. Since the first commercialization of sony in 1991, secondary batteries have been a hot spot of research. However, the theoretical capacity of lithium ions is relatively low, and it is difficult to meet the demand of portable electronic devices and electric vehicles in the rapid development of the electronic devices and the electric vehicles. Therefore, attention has been directed to lithium sulfur batteries with higher specific energy, which is considered as one of the most promising next-generation energy storage batteries.
The theoretical specific capacity of the lithium-sulfur battery is 1675mAh g < -1 > and the theoretical mass energy density is 2600Wh kg < -1 >, which is 5 times of that of the traditional lithium ion battery. Meanwhile, the active substance sulfur element of the anode has the advantages of abundant reserves, environmental friendliness and low cost. However, several key challenges still exist to prevent commercial application of lithium sulfur batteries: 1) the ion/electron insulativity of sulfur and a discharge product Li2S/Li2S2 thereof, wherein the conductivity of the sulfur at room temperature is only 5m 10 < -3 > S cm < -1 >, so that the electrochemical activity and the utilization rate of an active substance are both lower; 2) the density difference between the charged elemental sulfur density (2.07g cm-3) and the discharged elemental sulfur density (1.66g cm-3) is about 80% of volume change in the charging and discharging process, which is easy to crush the electrode to cause rapid attenuation of the battery performance; 3) the shuttling effect of soluble polysulfides, on the one hand, causes loss of active species and, on the other hand, diffusion into the lithium negative electrode is accompanied by side reactions. Therefore, the lithium-sulfur battery has problems of rapid capacity fade, short cycle life, and severe self-discharge.
In order to improve the electrochemical utilization rate of sulfur, various host materials are currently applied to the research of lithium-sulfur batteries, such as graphene materials, Metal Organic Framework (MOF) materials, and emerging materials MXene, and meanwhile, the modification of the existing materials, such as coating, heteroatom doping and the like, is derived. Among them, a carbon material having good electrical conductivity, a rich specific surface area, and a developed pore structure is considered as one of the most potential host materials. It is well documented that nucleation of Li2S deposition, which plays a critical role, can only occur on a conductive substrate during the conversion of Li2S4, which occupies three-quarters of the theoretical specific capacity of a lithium sulfur battery. Hollow carbon spheres, one of the porous carbon materials, have a high sulfur loading and a strong ability to adapt to volume expansion, but cannot ensure sufficient contact between the active material and the carbon while a large number of cavities inside the hollow carbon spheres will result in a lower volumetric energy density. Meanwhile, due to the weak nonpolar interaction between nonpolar carbon and sulfur, only simple physical blocking can be achieved, and the shuttle effect of polysulfide cannot be completely eliminated, so an ideal sulfur host material is usually designed by integrating a carbon material and a polar material, and the defect of few active attachment points of the polar material is overcome. The commonly used polar materials comprise metal oxides, metal phosphides, metal nitrides and the like, and the chemical barrier of polysulfide is realized by virtue of polar bonds, so that the aim of effectively inhibiting the shuttle effect can be achieved. But most metal composites are poorly conductive, which in turn reduces the overall conductivity.
Disclosure of Invention
The first invention of the present invention is directed to: aiming at the problems of the existing host material, the YCF nanometer cage host material is provided, the host material is high in coating degree, a space is reserved for carrying sulfur by etching part of the inner core, the balance among sulfur carrying amount, chemical adsorption and conductivity is realized, the excellent battery charge and discharge performance is ensured while the shuttle effect is inhibited, the catalytic action is ensured to the maximum extent, the conductivity of the anode is ensured, the multiplying power performance is improved, and the defects of the existing host material are overcome.
The technical scheme adopted by the invention is as follows: a YCF nanocage host material, wherein said YCF nanocage host material is composed of a carbon shell and Fe3O4The YCF nano cage host material is made of Fe coated with carbon obtained after drying and annealing iron-based hydrogel3O4Nanospheres, then partially etched with an acid, said carbon shell having a three-dimensional skeletal structure.
Because the surface of the carbon shell has certain mesopores and micropores, the YCF nano cage host material directly carries sulfur, so that most of sulfur is attached to the surface of the carbon shell and can not be contacted with the Fe core3O4Effective contact also weakens the chemical adsorption and chemical catalysis of the electrolyte, and the carbon shell with a three-dimensional skeleton structure obtained by acid partial etching is adopted, so that on the premise of not damaging the carbon shell, a space is reserved for carrying sulfur, the balance among sulfur carrying amount, chemical adsorption and conductivity is realized, and the excellent charge and discharge performance of the battery is ensured while the shuttle effect is inhibited. And the catalytic action is ensured to the maximum extent, and the conductivity of the anode material is ensured, so that the rate capability is improved. Furthermore, the preparation method omits complex steps such as high-temperature aging, in-situ coating and the like, obtains the carbon host material with excellent performance by adopting an etching mode, and provides possibility for forming a high-performance lithium-sulfur battery.
The invention also discloses a preparation method of the YCF nano cage host material, which is characterized by comprising the following steps:
s2.1, dissolving water-soluble iron salt and trimesic acid in a polar organic solvent, reacting to prepare iron-based hydrogel, and aging at normal temperature for 20-48 h;
s2.2, washing the hydrogel by using a polar organic solvent and water, freezing the hydrogel for 2-3 days at the temperature of minus 10- (-40) DEG C after washing, then transferring the hydrogel to a freeze drier, and freeze-drying the hydrogel at the temperature of minus 40 ℃;
s2.3, annealing the dried material at the temperature of 700-900 ℃ to obtain Fe coated with carbon3O4A nanopowder;
s2.4, coating carbon-coated Fe by adopting ultrasound3O4Dispersing the nano powder, adding acid, stirring and etching to obtain the product containing gradient Fe3O4And washing the YCF nano cage with a polar organic solvent and water, and drying to obtain the final product.
The preparation method is different from the conventional template method commonly used for preparing hollow carbon materials and core-shell structure carbon materials, and simultaneously eliminates other methods for obtaining MOF derivatives by hydrothermal method3O4The nanosphere can generate hydrogel at normal temperature by only one step, and the method is simple and convenient and is beneficial to large-scale production.
In the above method, the polar organic solvent may be a polar organic solvent such as methanol, ethanol, ether, butanol, etc., and the polar organic solvent is mainly used to dissolve a solute, provide a homogeneous reaction system during the reaction to allow the reaction to proceed smoothly, and remove unreacted reactants in the product during washing, so long as the effect can be achieved, and it is common practice in the art, and preferably, the polar organic solvent is preferably ethanol. Further, the freeze dryer parameters used were: at-30 deg.C to-50 deg.C and 20-50 Pa, automatically cooling to below-40 deg.C and vacuum degree of less than 100Pa during freezing, and drying for 24-60 hr.
Further, in the present invention,the water-soluble iron salt is preferably Fe (NO)3)3·9H2O, of course, other water-soluble iron salts may be chosen, for example ferric chloride, which has the disadvantage that the gel formation is very small, but which is also possible if other reaction conditions are adjusted to improve. The pyromellitic acid is reacted with Fe (NO)3)3·9H2The mass ratio of O is 1: 1-3, and the specific mass ratio is selected according to actual needs.
Further, the acid for etching is preferably hydrochloric acid, the concentration of the hydrochloric acid is 20% -36%, the specific concentration is selected according to actual needs, and the acid can be dilute sulfuric acid or dilute nitric acid. Accordingly, the product is preferably washed with ethanol and water (distilled water) to a pH of 6-8 and then dried in a vacuum oven. In the process, the ultrasonic frequency adopted by ultrasonic dispersion is preferably in the range of 80-100 kW, and the vacuum degree is-0.08- (-0.1) MPa during vacuum drying.
In the present invention, since Fe3O4The core has magnetism, so the reactants are uniformly mixed in a stirring mode during etching, and the reactants can be uniformly stirred by using a stirring paddle.
The second invention of the present invention is directed to: aiming at the problems of the existing sulfur anode material, the core-shell structure sulfur anode material is provided, and the core-shell structure sulfur anode material takes the external carbon shell as a physical barrier and takes the internal nano Fe as a physical barrier3O4The polar balls are used as chemical adsorbents, and the two are cooperated to inhibit the shuttle effect of polysulfide, and simultaneously, the control of Fe3O4The content of the polar spheres balances the maximum sulfur carrying amount, inhibits the shuttle of polysulfide and accommodates the volume expansion, obtains the anode material with high coulombic efficiency and long service life, and overcomes the defects of the prior sulfur anode material.
The technical scheme adopted by the invention is as follows: the core-shell structure sulfur cathode material is characterized by comprising the YCF nanocage host material as a host material, wherein part of carbon shell wraps sulfur of an active substance and a final discharge product, and the core-shell structure sulfur cathode material consists of the following components in percentage by mass: the YCF nano cage host material accounts for 20 to 40 percent, and the elemental sulfur accounts for 60 to 80 percent.
In the core-shell structure sulfur cathode material, the carbon shell is coated with active elemental sulfur and final discharge products (namely polysulfide) layer by layer, so that the core-shell structure sulfur cathode material has large specific surface area and high conductivity, a rapid transmission electronic channel is formed, the conversion of the polysulfide and the reduction of self-discharge rate are promoted, active substances are physically blocked under the heavy coating of the carbon shell, and the loss of the active substances is greatly reduced. Further, the kernel is set to be of polarity Fe3O4Polar Fe3O4Has higher conductivity (5 × 10) than other polar oxides4S·m-1) S (active S) and Li for insulation2S2/Li2S conversion shows lower polarization and faster reaction kinetics in the charging and discharging processes, and meanwhile, due to the strong adsorption effect between metal atoms and polysulfide, the shuttle effect can be effectively inhibited, and the utilization rate of active substances is improved. In addition, the cavity part in the middle of the core-shell structure nano cage cathode material can be filled with more elemental sulfur and relieve volume expansion in the charging and discharging processes, and sufficient gaps are reserved, so that the preparation of the lithium-sulfur battery cathode is necessary, the material pulverization in the circulating process is prevented, and the circulating life is prolonged.
Preferably, the core-shell sulfur cathode material is Fe3O4The content being at an optimum value, i.e. Fe3O4The content of the YCF nano cage host material accounts for 26 to 31 percent. In the optimal range, the shuttle effect can be inhibited, the excellent charge and discharge performance of the battery can be ensured to the greatest extent, the conductivity of the anode can be ensured, and the rate performance improving effect is the best.
The invention also discloses a preparation method of the core-shell structure sulfur cathode material, which is characterized by comprising the following steps: the YCF nano cage host material and the sulfur are mixed according to the proportion, the temperature is raised to 160 ℃ in the protection of inert gas, then the temperature is kept for 8-12 h, the temperature is raised to 300 ℃ in 240 ℃ and the temperature is kept for 0.5-1 h, and then the anode material is obtained.
Further, the mass ratio of the YCF nano cage host material to the elemental sulfur is 1: 1.5-2.5.
further, the specific process of heating and heat preservation is as follows: heating to 150-160 ℃ under the protection of inert gas, then preserving heat for 8-12 h, heating to 240-300 ℃ and preserving heat for 0.5-1 h.
The third invention of the present invention is directed to: the core-shell structure nanocage sulfur anode is prepared by taking a core-shell structure nanocage anode material as a main body and blending the nanocage anode material with a conductive agent, a binder and the like, has the characteristics of high coulombic efficiency, long service life and the like, and overcomes the defects of the conventional lithium-sulfur battery anode.
The technical scheme adopted by the invention is as follows: a core-shell structure nanocage sulfur anode is prepared from a core-shell structure sulfur anode material, a conductive agent and a binder according to a mass ratio of (6-8): (1-3): 1, coating on an aluminum foil current collector, and drying to obtain the aluminum foil current collector.
Preferably, the core-shell structure sulfur cathode material, the conductive agent and the binder are mixed according to a mass ratio of 7: 2: 1. of course, the ratio can be adjusted within the above range, and the specific ratio is selected according to actual needs.
Preferably, the conductive agent is carbon black, and the binder is PVDF. Of course, other alternatives with the same or similar effect can be reasonably selected by those skilled in the art according to the relevant literature, which is easy to be realized by those skilled in the art.
The invention also discloses a preparation method of the core-shell structure nanocage sulfur anode, which is characterized by comprising the following steps of: adding the core-shell structure sulfur positive electrode material, the conductive agent and the binder in proportion, dissolving the mixture in methyl pyrrolidone, uniformly stirring the mixture, coating the mixture on an aluminum foil current collector, and drying the aluminum foil current collector at 40-60 ℃ to obtain the lithium ion battery.
The invention also discloses application of the core-shell structure nanocage sulfur anode, which is characterized in that the core-shell structure nanocage sulfur anode is used as the anode of a lithium sulfur battery.
It is worth mentioning that the YCF nanocages of the present invention refer to carbon coated Fe3O4Nanospheres, i.e. C @ Fe having a nucleocapsid structure3O4Nanospheres, which are labeled YCF nanocages for ease of description.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the core-shell structure sulfur anode material provided by the invention has high coating degree, realizes the balance of sulfur carrying capacity, chemical adsorption and conductivity, ensures excellent battery charge and discharge performance while inhibiting shuttle effect, ensures the catalytic action to the maximum extent, and ensures the conductivity of the anode, thereby improving the rate capability;
2. the YCF nanocages are used as host materials of the positive electrode materials of the lithium-sulfur battery, the shell is a part of graphene carbon material, the carbon shell wraps active substance sulfur and polysulfide layer by layer, the carbon shell has large specific surface area and high conductivity, a rapid transmission electron channel can be formed, the conversion of the polysulfide and the reduction of the self-discharge rate are promoted, and meanwhile, the active substance is physically blocked under the heavy wrapping of the carbon shell, so that the loss of the active substance is greatly reduced;
3. the YCF nano cage kernel is polar Fe3O4Polar Fe3O4Has higher conductivity (5 × 10) than other polar oxides4S·m-1) S and Li favorable for insulation2S2/Li2S conversion shows lower polarization and faster reaction kinetics in the charging and discharging processes, and meanwhile, due to the strong adsorption effect between metal atoms and polysulfide, the shuttle effect can be effectively inhibited, and the utilization rate of active substances is improved;
4. the cavity part in the middle of the YCF nano cage can be filled with more sulfur simple substances and relieve the volume expansion in the charging and discharging processes, and enough clearance is reserved to be necessary for preparing the positive electrode of the lithium-sulfur battery so as to prevent the material pulverization in the circulating process and improve the circulating life;
5. the preparation method of the sulfur anode material provided by the invention adopts the direct carbonization of the gel powder after annealing and drying at high temperature to obtain the Fe coated with carbon3O4The nanosphere omits complex steps such as high-temperature aging, in-situ coating and the like, and the carbon host material with optimal performance is etched by controlling the core-shell ratio through regulating and controlling the volume of the acid.
Drawings
FIG. 1 is a TEM image of example 1 of the present invention;
FIG. 2 is C @ Fe in example 1 of the present invention3O4A partially enlarged TEM image of;
FIG. 3 is a TEM image of example 2 of the present invention;
FIG. 4 is a partially enlarged view of YCF-28 in example 1 of the present invention;
FIG. 5 is C @ Fe in example 1 of the present invention3O4X-ray diffraction (XRD) pattern of (A) and (B) Fe3O4And Fe PDF cards;
FIG. 6 is C @ Fe in example 1, example 2, comparative example 33O4TGA profiles of YCF-28, YCF-57, YCF-13;
FIG. 7 is the S/C @ Fe of example 13O4TGA, DTG profile of (a);
fig. 8 is a graph of cycle tests performed at a current density of 1C for the assembled cells of example 1 and comparative example 1;
fig. 9 is a graph of cycle tests performed at a current density of 1C for the assembled cells of example 2, comparative example 2, and comparative example 3;
FIG. 10 is a first cycle voltage profile at 0.1C current density for the assembled cells of example 1, example 2, comparative example 2, and comparative example 3;
fig. 11 is a graph of rate performance at 0.1C, 0.2C, 0.5C, 1C, 2C, 0.5C for the cells assembled in example 1, example 2, comparative example 3.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, all reagents and equipment used in the present invention that are not indicated by the manufacturer are commercially available, and any value in the ranges disclosed herein is not limited to the precise range or value, which ranges or values are to be understood to encompass values close to these ranges or values.
In the following examples 1 and 2, the material characterization analytical instrument used was as follows:
scanning Electron Microscope (SEM) testing: HITACHI S-4800 type field emission scanning electron microscope, Japan;
transmission Electron Microscope (TEM) testing: tecnai F30 model transmission electron microscopy, usa;
x-ray diffraction (XRD) test: rigaku UltimaIV-185X-ray diffractometer, Japan;
thermogravimetric analysis (TGA) test: STA449F3 model synchronous thermal analyzer, german Navy (NETZSCH);
all drugs/reagents used were purchased from the market without specific indication.
Assembly and testing of CR2025 button cells: the 2025 type button cell is assembled in an argon filled glove box (the oxygen content and the water content are both less than 1 ppm). The prepared S/YCF is cut into a small wafer with the diameter of 11mm to be used as a positive electrode, a metal lithium sheet is used as a negative electrode, and a Celgard2300 porous membrane is used as a diaphragm. The electrolyte uses 1, 3-dioxolane and ethylene glycol dimethyl ether (DOL: DME ═ 1: 1v/v) as solvents, 1.0M lithium bistrifluoromethylsulfonyl imide (LiTFSI) as a lithium salt, and 0.2M lithium nitrate (LiNO) is added3) As an additive.
Constant current charge and discharge test: the LAND workstation adopted is a CT2001A LAND battery test system, Wuhan; charging and discharging voltage interval: 1.7-2.8V (vs. Li/Li)+) (ii) a The test temperature was 33 ℃.
And (3) testing alternating current impedance: using CHI660E electrochemical workstation, Shanghai Chenghua; the test voltage is 2.4V, and the test frequency range is as follows: 0.01 Hz-100 kHz, and 5mV of amplitude.
Example 1
This example provides a sulfur positive electrode material, which is Fe coated with carbon3O4The material carries sulfur, marked as S/C @ Fe3O4。
(1)C＠Fe3O4The preparation of (1):
s1, 1.21g Fe (NO)3)3·9H2Respectively adding O and 0.42g of trimesic acid (BTC) into 20ml of ethanol, stirring for 30mins, mixing the two solutions after the two solutions respectively present a yellow brown transparent solution and a colorless transparent solution, and instantly forming a brown yellow hydrogel;
s2, aging for 24 hours at normal temperature to enable the two to react more fully;
s3, washing out small molecules which are not completely reacted by using ethanol and distilled water, freezing the hydrogel at the temperature of-20 ℃ for 48 hours, and then transferring the hydrogel to a freeze dryer for drying, wherein the parameters are-40 ℃, the pressure is 35pa, and the hydrogel is brown yellow powder after 48 hours;
s4, slowly heating to 800 ℃ at a speed of 5 ℃/min in a tube furnace under the protection of argon atmosphere, and preserving heat for 5 hours;
s5, slowly cooling to normal temperature under argon atmosphere, transferring to a drying dish to obtain a black powder material with carbon coating, and recording as C @ Fe3O4。
(2)S/C＠Fe3O4Preparation of the positive electrode:
s1, preparing C @ Fe3O4Reacting with sulfur simple substance according to the weight ratio of 35: 65, uniformly mixing, preserving heat for 10 hours at 155 ℃, then heating to 220 ℃, and preserving heat for 0.5 hour;
s2, preparing C @ Fe3O4And a conductive agent-carbon black, a binder-PVDF according to the weight ratio of 7: 2: dissolving 1 in solvent methyl pyrrolidone (NMP), mixing for at least 20min, stirring, coating on clean aluminum foil current collector with scraper, drying at 55 deg.C in vacuum drying oven for 18h, cutting into 11mm round pieces with cutting machine to obtain sulfur anode, and marking the sulfur anode as S/C @ Fe3O4And (4) a positive electrode.
C＠Fe3O4The surface appearance is shown in figure 1, and is shown by TEM as C @ Fe3O4The medium-thin carbon shell is multi-layered and uniformly wrapped around the internal Fe3O4A polar nucleus.
C＠Fe3O4The XRD test result of (1) is shown in figure 5, and according to the comparison of PDF cards, the material components obtained after annealing are mainly amorphous carbon and Fe3O4However, the Fe peak is also present, probably due to the part of the outer Fe layer that is intimately surrounded by the carbon shell during annealing3O4Is reduced to Fe under the action of carbon.
C＠Fe3O4Middle Fe3O4The content was measured by TGA as shown in FIG. 6, and the temperature was raised to 800 ℃ under an air atmosphere, and the residual mass was 85.54%. Due to the reaction at elevated temperature: fe3O4+O2→Fe2O3(neglected because of the low Fe content), it is calculated to estimate Fe in the material3O4The occupancy is about 82.69%. S/C @ Fe3O4The sulfur content of the sulfur positive electrode was 58.40% as determined by TGA under an inert atmosphere, as shown in fig. 7.
The S/C @ Fe3O4 sulfur positive electrode was used in a lithium sulfur battery cycle with performance as shown in fig. 6. The initial capacity of the material is 702mAh g when the material is activated for three weeks at a current density of 0.1C－1. Initial capacity of 511.8mAh g at 1C current density－1The capacity after 200 weeks circulation was 424.6mAh g－1The weekly decay is about 0.0851%, and the slow decay curve is smooth, which shows that the material plays a certain role in inhibiting the shuttle effect.
Comparative example 1
This comparative example provides a sulfur positive electrode material that was Fe coated with carbon3O4The material carries sulfur, marked as S/C @ Fe3O4-150. The preparation method of the sulfur cathode material adopted by the comparative example comprises the following steps:
(1)C＠Fe3O4preparation of-150:
s1, 1.21g Fe (NO)3)3·9H2Respectively adding 20ml of ethanol into O and 0.42g of trimesic acid (BTC), stirring for 30min, mixing the two solutions until the two solutions respectively present a yellow brown transparent solution and a colorless transparent solution, and forming a brown yellow hydrogel instantly;
s2, transferring the gel into a hydrothermal kettle, and aging for 24 hours at 150 ℃ to ensure that the gel and the hydrothermal kettle react more fully;
s3, washing by using ethanol and distilled water to remove small molecules which are not completely reflected, freezing the hydrogel at the temperature of-20 ℃ for 2 days, and then transferring the hydrogel to a freeze dryer for drying, wherein the parameters are-40 ℃, the pressure is 35pa, and the hydrogel is brown yellow powder after 48 hours;
s4, heating to 800 deg.C at a rate of 5 deg.C/min in a tube furnace under the protection of argon, maintaining for 5h, slowly cooling to room temperature under argon, transferring to a drying dish to obtain black carbon-coated material C @ Fe3O4150 of powder.
(2)S/C＠Fe3O4-150 preparation of positive electrode: in the same manner as in example 1, the obtained positive electrode was designated as S/C @ Fe3O4-150 positive electrode.
S/C＠Fe3O4The-150 sulfur positive electrode was used for lithium sulfur battery cycling and the performance was as shown in fig. 8. At 0.1C activation for three weeks, the initial capacity was 582.1mAh g－11C initial capacity of 515.1mAh g－1The capacity after 200 weeks of circulation was 334mAh g－1The coulombic efficiency was 0.1758%. The high temperature in the hydrothermal process causes certain damage to a network structure formed by hydrogel at normal temperature, so that the material is further collapsed after annealing, and the electrochemical performance of the material is poor.
Example 2
This example provides a sulfur cathode material, and the sulfur host material is carbon-coated Fe etched by hydrochloric acid3O4YSC @ Fe core-shell structure obtained from material3O4It is collectively named as YCF. According to the residual Fe3O4The content is named as YCF-28, and the positive electrode of sulfur after sulfur loading is S/YCF-28.
The preparation method of the sulfur cathode material adopted in the embodiment comprises the following steps:
(1)C＠Fe3O4preparing nanospheres: the same as in example 1.
(2) Preparing a core-shell structure YCF nano cage:
s1, taking 1g of C @ Fe3O4Dispersing the powder in 50mL of deionized water, performing ultrasonic dispersion for 30min at the frequency of 100kW, adding 66mL of hydrochloric acid (the mass fraction is 36%), reacting for 2h, performing vacuum filtration to obtain a YCF-28 nanocage with a core-shell structure, washing the material with ethanol and distilled water until the pH value is approximately equal to 6-8, and drying in a vacuum drying oven at 60 ℃ for 24 h.
(3) Preparing a core-shell structure anode S/YCF-28: in the same manner as in example 1, the sulfur positive electrode thus obtained was designated as S/YCF-28.
YCF-28 has a surface morphology as shown in FIG. 3, which is determined by TEM as YCF-28 and C @ Fe3O4The difference is that a gap is formed between the carbon shell and the iron core, and the gap can well contain sulfur molecules, so that the active substances are uniformly distributed, the double effects of chemical adsorption of the iron core and physical obstruction of the carbon shell are fully exerted, and polysulfide shuttling is inhibited.
The YCF nanocages obtained by etching were characterized by TGA (see fig. 6), and were heated to 800 ℃ in air atmosphere, with a residual content of 28.45%. Fe is known from calculation3O4The content is about 27.50%. Therefore, it is designated as S/YCF-28.
The S/YCF-28 was assembled in a lithium sulfur battery with cycling performance at 1C rate as shown in FIG. 9. Three weeks before activation by 0.1C, the material has higher first-cycle discharge specific capacity 1228mAh g－1Initial capacity at 1C 731.9mAh g－1Maintained at 684.9mAh g after 200 weeks of circulation－1The capacity fading is only 6.4%, the average weekly fading is 0.03%, and the capacity retention rate is good.
Comparative example 2
This example provides a sulfur cathode material, and the sulfur host material is carbon-coated Fe etched by hydrochloric acid3O4And obtaining the YCF with a core-shell structure by using the material. According to the residual Fe3O4The content is named as YCF-57, and the positive electrode of sulfur after sulfur loading is S/YCF-57.
(1)C＠Fe3O4Preparing the composite nanosphere: the same as in example 1.
(2) Preparing a core-shell structure YCF nano cage:
s1, taking 1g of C @ Fe3O4Dispersing the powder in 50mL of deionized water, performing ultrasonic dispersion for 30min at the frequency of 100kW, adding 50mL of hydrochloric acid, reacting for 2h, performing vacuum filtration to obtain a YCF nano cage with a core-shell structure, washing the material with ethanol and distilled water until the pH value is approximately equal to 6-8, and drying in a vacuum drying oven at 60 ℃ for 24 h.
(3) Preparing a core-shell structure anode S/YCF-57: in the same manner as in example 1, the sulfur positive electrode thus obtained was designated as S/YCF-57.
YSC @ Fe obtained by etching3O4The nanocages were characterized by TGA (as in figure 6), warming to 800 ℃ under air atmosphere, with a residual content of 57.40%. Fe is known from calculation3O4The content was about 55.49%, which was designated as S/YCF-57.
S/YCF-57 was assembled in a lithium sulfur battery with cycle performance at 1C as shown in FIG. 9. Three weeks before activation by 0.1C, first-week discharge specific capacity 1022.4mAh g－1Initial capacity at 1C 714.6mAh g－1Maintained at 551.7mAh g after 200 weeks of circulation－1The capacity fade was 22.8%.
Comparative example 3
The embodiment provides a sulfur cathode material, and the sulfur host material is YCF with a core-shell structure, which is obtained by etching carbon-coated Fe3O4 material with hydrochloric acid. The product is named YCF-13 according to the residual Fe3O4 content, and the sulfur anode after sulfur loading is S/YCF-13.
(1)C＠Fe3O4Preparing nanospheres: the same as in example 1.
(2) Preparing a core-shell structure YCF nano cage:
s1, taking 1g of C @ Fe3O4Dispersing the powder in 50mL of deionized water, performing ultrasonic dispersion for 30min at the frequency of 100kW, adding 82mL of hydrochloric acid, reacting for 2h, performing vacuum filtration to obtain a YCF nano cage with a core-shell structure, washing the material with ethanol and distilled water until the pH value is approximately equal to 6-8, and drying in a vacuum drying oven at 60 ℃ for 24 h.
(3) Preparing a core-shell structure S/YCF-13 positive electrode: the same as example 1, is labeled as S/YCF-13.
YSC @ Fe obtained by etching3O4The nanocages were characterized by TGA (as in figure 6), warming to 800 ℃ under air atmosphere, with a residual content of 13.69%. Fe is known from calculation3O4The content is about 13.23%, and is therefore designated as S/YCF-13.
S/YCF-13 was assembled in a lithium sulfur battery with cycle performance at 1C as shown in FIG. 9. Three weeks before activation by 0.1C, first-cycle discharge specific capacity 1024.3mAh g－1Initial capacity at 1C 683.4mAh g－1After 200 weeks of circulation, 461.3mAh g－1The capacity fade was 32.5%.
The first cycle voltage curve profiles of example 1, example 2, comparative example 2 and comparative example 3 at 0.1C show that the polarization is smaller in example 2 by comparison. Specific discharge capacities at different current densities are shown in fig. 11, and specific discharge rate results are shown in table 1.
TABLE 1 specific discharge capacity (mA h/g) results at different current densities
According to the test results, when the core-shell structure YCF is used for the positive electrode of the lithium sulfur battery, the content and the utilization rate of active substances of the positive electrode material of the lithium sulfur battery can be obviously improved, the volume expansion is relieved, the electronic transmission channel is rapid, the polysulfide shuttling effect is relieved, the capacity attenuation speed is obviously relieved, and the cycle life is prolonged. The raw materials used in the method disclosed by the invention are low in cost, environment-friendly, simple in whole process steps, high in efficiency and strong in operability, so that a promising preparation process is provided for developing high-performance lithium-sulfur batteries.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A YCF nanocage host material, wherein said YCF nanocage host material is composed of a carbon shell and Fe3O4The YCF nano cage host material is made of Fe coated with carbon obtained after drying and annealing iron-based hydrogel3O4Nanospheres, then partially etched with an acid, said carbon shell having a three-dimensional skeletal structure.
2. The method of making a YCF nanocage host material of claim 1, comprising the steps of:
s2.1, dissolving water-soluble iron salt and trimesic acid in a polar organic solvent, reacting to prepare iron-based hydrogel, and aging at normal temperature for 20-48 h;
s2.2, washing the hydrogel by using a polar organic solvent and water, freezing the hydrogel for 2-3 days at the temperature of minus 10- (-40) DEG C after washing, then transferring the hydrogel to a freeze drier, and freeze-drying the hydrogel at the temperature of minus 40 ℃;
s2.3, annealing the dried material at the temperature of 700-900 ℃ to obtain Fe coated with carbon3O4A nanopowder;
s2.4, coating carbon-coated Fe by adopting ultrasound3O4Dispersing the nano powder, adding acid, stirring and etching to obtain the product containing gradient Fe3O4And washing the YCF nano cage with a polar organic solvent and water, and drying to obtain the final product.
3. The method of claim 2, wherein the water-soluble iron salt is Fe (NO)3)3·9H2O, the pyromellitic acid and Fe (NO)3)3·9H2The mass ratio of O is 1: 1-3.
4. the method of claim 3 wherein the etching acid is hydrochloric acid, said hydrochloric acid having a concentration of 20% to 36%.
5. A core-shell structure sulfur positive electrode material, characterized by comprising, as a host material, a YCF nanocage host material prepared by the preparation method according to any one of claims 2 to 4, in which a part of a carbon shell surrounds sulfur of an active material and a final discharge product, and the core-shell structure sulfur positive electrode material is composed of, in mass percent: the YCF nano cage host material accounts for 20 to 40 percent, and the elemental sulfur accounts for 60 to 80 percent.
6. The preparation method of the core-shell structure sulfur cathode material according to claim 5, comprising the following steps: mixing the YCF nano cage host material and sulfur elementary substance according to the proportion of 1: blending at a ratio of 1.5-2.5, heating to 160 ℃ under the protection of inert gas, then preserving heat for 8-12 h, heating to 300 ℃ under 240 ℃ and preserving heat for 0.5-1 h.
7. The preparation method of the core-shell structure sulfur cathode material according to claim 6, wherein the core-shell structure sulfur cathode material contains Fe3O4The content of the YCF nano cage host material accounts for 26 to 31 percent.
8. The core-shell structure nanocage sulfur positive electrode is characterized by being prepared from the core-shell structure sulfur positive electrode material of claim 5.
9. The preparation method of the nanocage sulfur positive electrode with the core-shell structure according to claim 8, characterized by comprising the following steps: the preparation method comprises the following steps of (6-8) preparing a core-shell structure sulfur positive electrode material, a conductive agent and a binder according to a mass ratio: (1-3): dissolving the mixture 1 in methyl pyrrolidone, mixing, coating on aluminum foil current collector, and drying at 40-60 deg.C.
10. The application of the core-shell structure nanocage sulfur positive electrode is characterized by comprising the core-shell structure nanocage sulfur positive electrode in claim 8, wherein the core-shell structure nanocage sulfur positive electrode is used as a positive electrode of a lithium sulfur battery.
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