CN113823790B - Cobalt iron selenide/graphene nanoribbon composite negative electrode material and preparation method thereof - Google Patents
Cobalt iron selenide/graphene nanoribbon composite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt-iron selenide/graphene nanoribbon composite negative electrode material which comprises a graphene nanoribbon matrix and spherical cobalt-iron selenide embedded in the graphene nanoribbon, wherein the mass percentage of the graphene nanoribbon in the cobalt-iron selenide/graphene nanoribbon composite negative electrode material is 20-80%, the width of the graphene nanoribbon is 10-100nm, and the particle size of the cobalt-iron selenide is 0.5-4 mu m. The invention also provides a preparation method of the cobalt iron selenide/graphene nanoribbon composite negative electrode material. The cobalt-iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multistage composite negative electrode material formed by embedding spherical cobalt-iron selenide into a graphene nanoribbon, can inhibit the volume expansion of the cobalt-iron selenide, can ensure the structural stability of the negative electrode material, and has excellent conductivity, electrochemical cyclicity and rate capability.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a negative electrode material and a preparation method thereof.
Background
In recent years, lithium ion batteries have shown great promise as a power source that can lead us to the revolution of Electric Vehicles (EVs) due to their excellent chargeability, suitable power density and excellent energy density. The commercial graphite negative electrode used in the current lithium battery has relatively low specific capacity (the theoretical capacity is 372 m.Ah.g) -1 ) It is difficult to meet the high requirements of next-generation energy storage devices, especially limiting the large-scale commercialization of vehicles and large-scale electrical storage devices. Metal selenides have higher capacities compared to conventional graphite anodes. Moreover, they exhibit relatively better rate and cycle performance.
AB of binary transition spinel structure 2 X 4 Recently, metal chalcogenides (where a and B are transition metals and X is a chalcogenide) have gained widespread interest in energy storage and conversion systems. The transition metals Fe, co have similar atomic radii, and their corresponding selenides generally have similar crystalline phases. In addition, the two combinations of iron and cobalt have "metalloid conductivity" as binary metal selenides. Therefore, iron and cobalt selenides are expected to be widely used.
Although the cobalt iron selenide has higher theoretical specific capacity compared with the traditional graphene negative electrode, the cobalt iron selenide can generate volume expansion during the alloying reaction involved in the charging and discharging process, so that the material pulverization is caused, and the structure stability and the long-term maintenance of the electrochemical performance of the cobalt iron selenide are not facilitated.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a cobalt iron selenide/graphene nanoribbon composite negative electrode material with good structural stability and excellent electrochemistry and a preparation method thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the cobalt iron selenide/graphene nanoribbon composite negative electrode material comprises a graphene nanoribbon matrix and spherical cobalt iron selenide embedded in the graphene nanoribbon, wherein the mass proportion of the graphene nanoribbon in the cobalt iron selenide/graphene nanoribbon composite negative electrode material is 20-80% (more preferably 40-60%), the width of the graphene nanoribbon is 10-100nm (more preferably 40-80 nm), and the particle size of the cobalt iron selenide is 0.5-4 μm (more preferably 1-2 μm).
Compared with the graphene nanoribbons, the cobalt-iron selenide material provided by the invention has a larger size, the two-dimensional ribbon structure of the graphene nanoribbons can be wound and coated with the cobalt-iron selenide, and the three-dimensional spherical cobalt-iron selenide can be embedded in a network structure interwoven by the graphene nanoribbons to form a conductive network.
Compared with the traditional graphite cathode, the cobalt iron selenide has high theoretical specific capacity. The cobalt iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multistage composite negative electrode material formed by limiting spherical cobalt iron selenide with high specific capacity in a graphene nanoribbon, the graphene nanoribbon can wrap the cobalt iron selenide to limit the volume expansion of the graphene nanoribbon, the graphene nanoribbon inherits the two-dimensional structure and excellent physical and chemical properties of graphene, and meanwhile, the special structure of the graphene nanoribbon enables the graphene nanoribbon to be a novel carbon material with unique properties. Due to the special structure, excellent electrical and mechanical properties, high specific surface area, rich edge active sites and controllability of a performance structure, the graphene nanoribbon improves the conductivity of the cobalt iron selenide and simultaneously can improve the transmission rate of lithium ions in the charging and discharging processes. Therefore, the spherical cobalt iron selenide is limited in the three-dimensional multi-stage composite negative electrode material formed in the graphene nanoribbon, the electronic conductivity of the material can be further improved, the volume expansion caused by the cobalt iron selenide in the charge-discharge cycle process is reduced, and the structural integrity and the stability are good.
The mass fraction of the graphene nanoribbons in the cobalt iron selenide/graphene nanoribbon composite negative electrode material is too low, so that the excellent conductivity of the graphene nanoribbons is difficult to exert; too high a mass fraction of the graphene nanoribbons may affect the specific capacity of the target material. The cobalt iron selenide has an excessively large particle size, and the ball body can be crushed in the mixing and grinding process of the smear assembled by the subsequent battery; the particle size is too small, so that the specific surface area of the material is too large, and more lithium ions are consumed in the formation process of an SEI film in the first charge-discharge process, so that the coulomb efficiency of the first circle of the material is low.
As a general technical concept, the invention also provides a preparation method of the cobalt iron selenide/graphene nanoribbon composite negative electrode material, which comprises the following steps:
(1) Adding the graphene oxide nanoribbon into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide nanoribbon solution;
(2) Adding cobalt iron selenide and a reducing agent into deionized water, stirring, mixing with the graphene nanoribbon solution obtained in the step (1), placing in a closed reaction kettle for solvothermal reaction, cooling, centrifuging, washing, and freeze-drying after the reaction is finished to obtain initial powder of the cobalt iron selenide/graphene nanoribbon composite negative electrode material; the dosage of the cobalt iron selenide and the graphene nanoribbon is based on controlling the mass ratio of the graphene nanoribbon in the cobalt iron selenide/graphene nanoribbon composite negative electrode material to be 20-80%;
(3) And (3) carrying out heat treatment on the primary powder of the cobalt iron selenide/graphene nanoribbon composite negative electrode material obtained in the step (2) in an inert atmosphere to obtain the cobalt iron selenide/graphene nanoribbon composite negative electrode material.
In the above preparation method, preferably, the preparation method of the cobalt iron selenide comprises the following steps:
s1: adding a cobalt source into a solvent, uniformly stirring to obtain a solution A, adding an iron source 1,1' -ferrocenecarboxylic acid into the solvent, and uniformly stirring to obtain a solution B;
s2: mixing the solution A and the solution B, stirring for reaction, placing the mixture in a closed reaction kettle, carrying out solvothermal reaction, cooling, centrifuging, washing and drying after the reaction is finished to obtain a precursor;
s3: and mixing the precursor with selenium powder, placing the mixture in inert gas, and heating the mixture for selenylation treatment to obtain the cobalt iron selenide.
In the preparation method of the cobalt iron selenide, the cobalt iron selenide is of a hollow microsphere structure prepared by a template method, the prepared microsphere has uniform particle size and clear structural characteristics, and the hollow layered structure not only provides more active sites for redox reaction, but also shortens Li + The transmission distance of the electrochemical cycle can also effectively relieve serious volume change in the electrochemical cycle process. After the cobalt source and the iron source are added, no additional ligand is needed, 1' -ferrocenecarboxylic acid is used as the iron source, the ferrocene dicarbamate ligand can provide a spherical structure while providing iron ions, the three-dimensional hollow microspheres are obtained through solvothermal reaction, the spherical shape is good, the synthesis is simple, and the repetition rate is high. In addition, hydrazine hydrate with severe toxicity is not needed in the synthesis process, and the used reagent has little harm to human bodies.
In the above preparation method, preferably, in S1, the solvent is N, N-dimethylformamide; the cobalt source is one or more of cobalt nitrate, cobalt chloride or cobalt acetate (including hydrate thereof); the molar ratio of the cobalt source to the iron source is 1:1; the molar concentration of the cobalt source in the N, N-dimethylformamide solution is 0.05-0.2mol/L (more preferably 0.08-0.12 mol/L); the molar concentration of the iron source in the N, N-dimethylformamide solution is 0.05-0.2mol/L (more preferably 0.08-0.12 mol/L); the temperature when the mixture is uniformly stirred is room temperature, and the stirring time is 0.5-2.0h. The ratio of cobalt source to iron source is based on the stoichiometry of the cobalt iron selenide target product. Too high or too low a proportion will affect the final ratio of the target product. The concentration of the cobalt source and the iron source in the solvent is controlled within the range, so that the cobalt ions and the iron ions are uniformly dispersed in the solvent.
In the above preparation method, preferably, in S2, the temperature during the stirring reaction is room temperature, and the stirring time is 1.0 to 3.0 hours; the temperature of the solvothermal reaction is 100-150 ℃, and the time is 10-24h; the washing mode is that N, N-dimethylformamide solution and ethanol are sequentially and alternately washed for more than or equal to 3 times; the drying temperature is 50-80 ℃, and the drying time is 12-24h. The cobalt source and the iron source in the system can be uniformly distributed by stirring. The solvothermal reaction can enable the precursor to grow until the structure is complete and the reaction is complete. The solvent heat temperature is too low, the time is too short, the synthesis of a spherical precursor is not facilitated, and the particle size of the material is small and uneven; too high solvent temperature and too long time can result in larger particle size of the synthesized precursor and the subsequent material is broken, thereby affecting the electrochemical performance.
In the above preparation method, preferably, in S3, the mass ratio of the selenium powder to the precursor is (1.0-2.5): 1; the temperature of the selenizing treatment is 300-600 ℃ (more preferably 350-500 ℃), and the time is 2-4h; the inert gas is one or more of nitrogen, argon or helium. The mass ratio is controlled to be favorable for the full reaction of the precursor and the selenium powder. When the selenium powder is too much, elemental selenium remains in the finally obtained cobalt iron selenide, and the final electrochemical performance is affected. Meanwhile, selenium powder is wasted to a certain extent; when the selenium powder is too little, the selenization process is incomplete; the two influences can be avoided under the mass ratio, and meanwhile, the selenization process is ensured to be carried out. The roasting temperature is too high, and the material is easy to agglomerate; the roasting temperature is too low to be beneficial to forming cobalt iron selenide. If the selenizing roasting time is shorter, the completion of the selenizing process is not facilitated.
In the preparation method, preferably, in the step (1), the mass concentration of the graphene oxide nanoribbon in water is controlled to be 0.5-2.2g/mL (more preferably, 1.1-1.5 g/mL), the frequency of ultrasonic dispersion is controlled to be 20-40kHz, and the time is controlled to be 0.5-3.0h (more preferably, 2-2.5 h). The mass concentration is beneficial to uniform dispersion of the graphene oxide nanobelts.
In the above preparation method, preferably, the reducing agent is thiourea, and the mass ratio of the cobalt iron selenide to the thiourea is 1: (1.5-5.0) (more preferably 1 (2-4)), and the mass concentration of the cobalt iron selenide in water is controlled to be 1.0-5.0g/mL. The thiourea is used as a reducing agent for reducing the graphene oxide nanobelt, the mass ratio of the thiourea is too high (namely, the content of the thiourea is too high), and hetero atoms in the thiourea may influence the electrochemical performance of the material; if the mass ratio is too low, the reducing action of thiourea as a reducing agent is insufficient.
In the above preparation method, preferably, in the step (2), the stirring time is controlled to be 1.5 to 4.0 hours (more preferably, 2.0 to 3.5 hours); the temperature of the solvothermal reaction is 120-240 ℃ (more preferably 150-200 ℃) and the time is 8-15h; the washing mode is that water and ethanol are sequentially and alternately washed for more than or equal to 3 times; the temperature of the freeze drying is-40 to-50 ℃, and the time is 24 to 48 hours. Under the solvothermal condition, the graphene oxide nanoribbon can be hydrothermally reduced into a reduced graphene nanoribbon, and the conductivity is improved so as to improve the electrochemical performance of the composite material; in addition, the cobalt iron selenide microspheres are distributed more uniformly on the graphene nanoribbons, so that the method is suitable for large volume change in the charging and discharging process. The solvent heat temperature is too low or the time is too short, which is not beneficial to reducing the graphene oxide nanoribbon to the graphene nanoribbon.
In the above preparation method, preferably, the temperature of the heat treatment is 300-600 ℃ (more preferably 350-500 ℃) for 2-4h; the inert gas is one or more of nitrogen, argon or helium. In the heat treatment process, the graphene oxide nanoribbon is further reduced into a reduced graphene oxide nanoribbon, so that the electronic conductivity is improved, the crystallization degree of the cobalt iron selenide is improved, and the stability of the material structure is facilitated. According to the method, thiourea is used as a reducing agent to reduce the graphene nanoribbon, and the graphene nanoribbon is further reduced through high-temperature treatment subsequently. Therefore, when the heat treatment temperature is too low or the time is too short, the reduction degree is incomplete, and the electrochemical performance of the material is influenced; too high a temperature or too long a time for the heat treatment may cause unnecessary heat loss and may affect the electrochemical properties of the material.
Compared with the prior art, the invention has the advantages that:
1. the cobalt iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multistage composite negative electrode material formed by embedding spherical cobalt iron selenide into graphene nanoribbons, and the volume expansion of the cobalt iron selenide can be inhibited through the synergistic effect of the cobalt iron selenide and the graphene nanoribbons, so that the structural stability of the negative electrode material can be ensured, and the negative electrode material is excellent in conductivity, electrochemical cyclicity and rate capability.
2. The preparation method has the advantages of low raw material cost, no special requirements on the raw materials and good raw material universality; moreover, the preparation method has good repeatability, is environment-friendly, and is suitable for industrial and large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an XRD pattern of the cobalt iron selenide/graphene nanoribbon composite negative electrode material of example 1.
Fig. 2 is an SEM image of the cobalt iron selenide/graphene nanoribbon composite negative electrode material in example 1.
Fig. 3 is a charge-discharge cycle performance diagram of the battery assembled by the cobalt iron selenide/graphene nanobelt composite anode material in example 1 at a current density of 0.5A/g.
Fig. 4 is a rate performance diagram of a battery assembled by the cobalt iron selenide/graphene nanoribbon composite negative electrode material in example 1.
Fig. 5 is an SEM image of the cobalt iron selenide/graphene nanoribbon composite negative electrode material in example 2.
Fig. 6 is a graph of charge and discharge cycle performance at a current density of 0.5A/g for a battery assembled with cobalt iron selenide in comparative example 1.
Fig. 7 is a graph of rate performance of a battery assembled with cobalt iron selenide in comparative example 1.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the graphene oxide nanoribbon used in this embodiment is a product obtained by performing longitudinal oxidation cutting on a carbon tube with potassium permanganate (Nature, 2009, 458, 872-876), and the specific experimental steps are as follows: 150mg of multi-walled carbon nanotubes (purchased from Chengdu organic chemistry, inc., of Chinese academy of sciences) are added into 36mL of concentrated sulfuric acid, and the mixture is magnetically stirred for 2 hours; adding 750mg of potassium permanganate into the mixed solution, magnetically stirring for 1h, heating the mixed solution to 60 ℃, stirring for 2h, and then cooling to room temperature; then the mixed solution was poured into a container containing 5mLH 2 O 2 Removing supernatant in the ice water, and adding the precipitate into an ion dialysis bag for dialysis; adjusting pH to neutral to obtain GONRs dispersion, and freeze drying.
A cobalt iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multilevel composite negative electrode material formed by embedding spherical cobalt iron selenide in a graphene nanoribbon; the mass ratio of the graphene nanoribbons in the cobalt iron selenide/graphene nanoribbon composite negative electrode material is 43%; the mass ratio of the cobalt iron selenide to the graphene nanoribbons is 1:0.75; the grain size of the cobalt iron selenide is 1-2 mu m.
As shown in fig. 1, the characteristic peak shape and intensity of the cofe and the cofe of the cofe-selenide/graphene nanoribbon composite negative electrode material of the embodiment 2 、FeSe 2 The spectral lines of the standard cards are identical, the peak shapes are sharp, the crystallinity is good, and the results show that the cobalt iron selenide/graphene nanoribbon composite negative electrode material of the embodiment contains pure-phase CoSe 2 And FeSe 2 。
As shown in fig. 2, the cobalt-iron selenide/graphene nanoribbon composite negative electrode material of the present embodiment is a three-dimensional multilevel structure formed by embedding spherical cobalt-iron selenide in graphene nanoribbons, and the particle size of the cobalt-iron selenide is 1 to 2 μm.
The preparation method of the cobalt iron selenide/graphene nanoribbon composite negative electrode material comprises the following steps:
(1) Adding 0.873g of cobalt nitrate hexahydrate into 30mLN, N-dimethylacetamide solvent, uniformly stirring to obtain 30mL of solution A, adding 0.822g of 1,1' -ferrocenecarboxylic acid into 30mLN, N-dimethylacetamide solvent, and uniformly stirring to obtain 30mL of solution B;
(2) Adding 30mL of the solution A obtained in the step (1) into 30mL of the solution B, stirring and reacting for 2h at room temperature, then placing the mixture into a stainless steel closed reaction kettle made of polytetrafluoroethylene, placing the reaction kettle in an electrothermal constant-temperature drying box, carrying out solvothermal reaction for 20h at 125 ℃, cooling to room temperature, centrifuging, sequentially and alternately washing and precipitating for 3 times by using an N, N-dimethylformamide solution and ethanol, and drying the precipitate for 15h at 60 ℃ to obtain a precursor;
(3) Mixing 0.2g of the precursor obtained in the step (2) with 0.4g of selenium powder, selenizing and roasting for 3 hours at 450 ℃ in a high-purity argon atmosphere, and cooling to room temperature along with a furnace to obtain cobalt iron selenide;
(4) Adding 45mg of graphene oxide nanoribbons into 37.5mL of deionized water, and performing ultrasonic dispersion for 2 hours at room temperature and 20kHz to obtain graphene oxide nanoribbon suspension;
(5) Adding 60mg of cobalt iron selenide and 0.21g of thiourea into deionized water, stirring for 3h, adding the graphene nanoribbon suspension obtained in the step (4), putting into a stainless steel closed reaction kettle made of polytetrafluoroethylene, placing in an electrothermal constant-temperature drying box, carrying out solvothermal reaction for 10h at 170 ℃, cooling to room temperature, centrifuging, carrying out cross washing and precipitation for 3 times by using the deionized water and ethanol, and carrying out freeze drying for 28h to obtain a composite material;
(6) And (4) placing the composite material obtained in the step (5) in a tube furnace, and carrying out heat treatment for 3 hours at 450 ℃ in a high-purity argon atmosphere to obtain the cobalt iron selenide/graphene nanoribbon composite cathode material.
Assembling the battery: taking 40mg of cobalt-iron selenide/graphene nanoribbon composite negative electrode material obtained in the embodiment as an active material, 5mg of conductive carbon black as a conductive agent, 5mg of polyvinylidene fluoride as a binder, adding the material into an agate mortar, grinding for 20min, then dropping 10 mLN-methyl pyrrolidone as a solvent, continuing grinding for 5min, then taking a copper foil as a current collector, coating the uniformly ground slurry on the copper foil, and drying in vacuum for 5h at 120 ℃; weighing the dried electrode plates, and obtaining the mass of slurry on each electrode plate according to the mass difference before and after the current collector is coated; after weighing, carrying out vacuum drying on the electrode plate for 3h at 60 ℃, and putting the dried electrode plate into a glove box to be assembled with a button cell; assembling the button cell by using a metal lithium sheet and the manufactured electrode sheet in a glove box filled with argon by using polypropylene as a diaphragm and using 1mol/L LiPF 6 EC: DMC (volume ratio 1.
As shown in FIG. 3, the battery assembled in this example has a voltage of 0.5 A.g in the range of 0.01 to 3V -1 The first-cycle discharge capacity is 1597.6mAh · g -1 (Current density 50mA · g for the first 3 turns) -1 ) At 50 cycles (0.5A. G from the 4 th cycle) -1 ) After that, the specific discharge capacity is still kept at 844.3mAh g -1 The specific capacity retention rate is higher, good cycle stability is shown, and the current density is 50 mA-g at 150 cycles (3 rd cycle) -1 ) After that, the specific discharge capacity is still maintained at 942.9mAh & g -1 The material has good cycle performance;
as shown in FIG. 4, the battery assembled in this example has a voltage of 0.5 A.g in the range of 0.01 to 3V -1 The first discharge specific capacity can reach 1556.8 mAh.g under the current density -1 (ii) a At 2 A.g -1 The specific discharge capacity of the alloy is kept to 671.3mAh g at the current density of (2) -1 The composite material has excellent rate performance; finally, the current density is recovered to 100mA g -1 The specific discharge capacity is still maintained at 765.2mAh g -1 And the capacity retention rate is higher, so that the cobalt iron selenide/graphene nanoribbon composite cathode material obtained in the embodiment is shownThe conductivity is greatly improved through the structural design and the compounding with GONRs, and the electrochemical performance of the material is improved.
Example 2:
the graphene oxide nanoribbons used in this example were the same as those used in example 1.
A cobalt iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multilevel composite negative electrode material formed by embedding spherical cobalt iron selenide in a graphene nanoribbon; the mass ratio of the graphene nanoribbons in the cobalt iron selenide/graphene nanoribbon composite negative electrode material is 50%; the mass ratio of the cobalt iron selenide to the graphene nanoribbons is 1:0.5; the grain size of the cobalt iron selenide is 1-2 mu m.
Through detection, the characteristic peak shape and strength of the cobalt iron selenide/graphene nanoribbon composite negative electrode material and CoSe 2 、FeSe 2 The spectral lines of the standard cards are identical, the peak shapes are sharp, and the crystallinity is good, which indicates that the CoSe of pure phase is contained in the CoFeSe/graphene nanoribbon composite cathode material of the embodiment 2 And FeSe 2 。
As shown in fig. 5, the cobalt iron selenide/graphene nanoribbon composite negative electrode material of the present embodiment is a three-dimensional multi-level composite negative electrode material formed by embedding spherical cobalt iron selenide in graphene nanoribbons, and the particle size of the spherical cobalt iron selenide is about 1-2 μm.
The preparation method of the cobalt iron selenide/graphene nanoribbon composite negative electrode material comprises the following steps:
(1) Adding 0.611g of cobalt nitrate hexahydrate into a 20mLN, N-dimethylacetamide solvent, uniformly stirring to obtain 20mL of solution A, adding 0.576g of 1,1' -ferrocenecarboxylic acid into the 20mLN, N-dimethylacetamide solvent, and uniformly stirring to obtain 20mL of solution B;
(2) Adding 20mL of the solution A obtained in the step (1) into 20mL of the solution B, stirring and reacting for 1.5h at room temperature, then placing into a polytetrafluoroethylene stainless steel closed reaction kettle, placing into an electrothermal constant-temperature drying oven, carrying out solvothermal reaction for 18h at 120 ℃, cooling to room temperature, centrifuging, sequentially and alternately washing and precipitating for 3 times by using an N, N-dimethylformamide solution and ethanol, drying the precipitate for 20h at 60 ℃ to obtain a precursor;
(3) Mixing 0.18g of the precursor obtained in the step (2) with 0.27g of selenium powder, selenizing and roasting for 2 hours at 500 ℃ in a high-purity argon atmosphere, and cooling to room temperature along with a furnace to obtain cobalt iron selenide;
(4) Adding 30mg of graphene oxide nanoribbon into 25mL of deionized water, and performing ultrasonic dispersion for 2h at 20kHz and room temperature to obtain a graphene oxide nanoribbon suspension;
(5) Adding 60mg of cobalt iron selenide and 0.25g of thiourea into deionized water, stirring for 3 hours, adding the graphene nanoribbon solution obtained in the step (4), putting the mixture into a polytetrafluoroethylene stainless steel closed reaction kettle, placing the reaction kettle in an electrothermal constant-temperature drying box, carrying out solvothermal reaction for 12 hours at 180 ℃, cooling to room temperature, centrifuging, sequentially and alternately washing and precipitating for 3 times by using the deionized water and ethanol, and carrying out freeze drying for 28 hours to obtain a composite material;
(6) And (4) placing the composite material obtained in the step (5) in a tube furnace, and carrying out heat treatment for 2 hours at 500 ℃ in a high-purity argon atmosphere to obtain the cobalt iron selenide/graphene nanoribbon composite negative electrode material.
Assembling the battery: the same as in example 1.
The battery assembled in this example was tested to have a voltage of 0.5 A.g in the range of 0.01-3V -1 The first discharge capacity is 1430.4mAh g -1 (Current density 50mA · g for the first 3 turns) -1 ) At 50 cycles (0.5A · g from the 4 th cycle) -1 ) Then, the specific discharge capacity is still maintained at 815.0mAh g -1 The specific capacity retention rate is high, good cycle stability is shown, and the current density is 50 mA-g at the cycle of 100 circles (the current density at the cycle of 4 th circle) -1 ) After that, the specific discharge capacity is still kept at 950.7mAh g -1 The specific capacity retention rate is higher, and good cycle stability is shown.
The battery assembled in this example was tested to have a voltage of 0.5 A.g.in the range of 0.01-3V -1 The first discharge specific capacity can reach 1453.8 mAh.g under the current density of -1 (ii) a At 2 A.g -1 The specific discharge capacity is still kept at 620.8mAh g under the current density of (2) -1 The composite material has excellent rate performance; final current density recoveryTo 100 mA.g -1 The specific discharge capacity is still maintained at 898.4mAh g -1 The capacity retention rate is high, and thus, the cobalt iron selenide/graphene nanoribbon composite negative electrode material obtained in the embodiment greatly improves the conductivity and improves the electrochemical performance of the material through structural design and compounding with GONRs.
Example 3:
the graphene oxide nanoribbons used in this example were the same as those used in example 1.
A cobalt iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multilevel composite negative electrode material formed by embedding spherical cobalt iron selenide in a graphene nanoribbon; the mass ratio of the graphene nanoribbons in the cobalt iron selenide/graphene nanoribbon composite negative electrode material is 33%; the mass ratio of the cobalt iron selenide to the graphene nanoribbons is 1:1; the grain size of the cobalt iron selenide is 1-2 mu m.
Through detection, the characteristic peak shape and strength of the cobalt iron selenide/graphene nanoribbon composite negative electrode material and CoSe 2 、FeSe 2 The spectral lines of the standard cards are identical, the peak shapes are sharp, the crystallinity is good, and the results show that the cobalt iron selenide/graphene nanoribbon composite negative electrode material of the embodiment contains pure-phase CoSe 2 And FeSe 2 。
The cobalt iron selenide/graphene nanoribbon composite negative electrode material is a three-dimensional multistage composite negative electrode material formed by embedding spherical cobalt iron selenide into a graphene nanoribbon, and the particle size of the spherical cobalt iron selenide is about 1-2 μm.
The preparation method of the cobalt iron selenide/graphene nanoribbon composite negative electrode material comprises the following steps:
(1) Adding 0.524g of cobalt nitrate hexahydrate into 18mLN, N-dimethylacetamide solvent, uniformly stirring to obtain 18mL of solution A, adding 0.493g of 1,1' -ferrocenecarboxylic acid into 18mLN, N-dimethylacetamide solvent, and uniformly stirring to obtain 18mL of solution B;
(2) Adding 18mL of the solution A obtained in the step (1) into 18mL of the solution B, stirring and reacting for 1.8h at room temperature, then placing into a polytetrafluoroethylene stainless steel closed reaction kettle, placing into an electrothermal constant-temperature drying oven, carrying out solvothermal reaction for 12h at 130 ℃, cooling to room temperature, centrifuging, sequentially and alternately washing and precipitating for 3 times by using N, N-dimethylformamide solution and ethanol, precipitating at 60 ℃, and drying for 20h to obtain a precursor;
(3) Mixing 0.18g of the precursor obtained in the step (2) with 0.27g of selenium powder, selenizing and roasting the mixture for 2 hours at 450 ℃ in a high-purity argon atmosphere, and cooling the mixture to room temperature along with a furnace to obtain cobalt iron selenide;
(4) Adding 60mg of graphene oxide nanoribbon into 60mL of deionized water, and performing ultrasonic dispersion for 2h at 20kHz and room temperature to obtain a graphene oxide nanoribbon suspension;
(5) Adding 60mg of cobalt iron selenide and 0.21g of thiourea into deionized water, stirring for 3 hours, adding the graphene nanoribbon solution obtained in the step (4), putting the mixture into a polytetrafluoroethylene stainless steel closed reaction kettle, placing the reaction kettle in an electrothermal constant-temperature drying box, carrying out solvothermal reaction for 12 hours at 180 ℃, cooling to room temperature, centrifuging, sequentially and alternately washing and precipitating for 3 times by using the deionized water and ethanol, and carrying out freeze drying for 28 hours to obtain a composite material;
(6) And (4) placing the composite material obtained in the step (5) in a tube furnace, and carrying out heat treatment for 2 hours at 450 ℃ in a high-purity argon atmosphere to obtain the cobalt iron selenide/graphene nanoribbon composite negative electrode material.
Assembling the battery: the same as in example 1.
The battery assembled in this example was tested to have a voltage of 0.5 A.g.in the range of 0.01-3V -1 The first discharge capacity is 1269.8mAh g -1 (Current density 50mA · g for the first 3 turns) -1 ) At 50 cycles (0.5A · g from the 4 th cycle) -1 ) After that, the specific discharge capacity is still kept to be 657.1mAh g -1 The specific capacity retention rate is high, good cycle stability is shown, and the current density is 50 mA-g at the cycle of 100 circles (the current density at the cycle of 4 th circle) -1 ) Then, the specific discharge capacity is still kept to be 879.3mAh g -1 The specific capacity retention rate is higher, and good cycle stability is shown.
The battery assembled in this example was tested to have a voltage of 0.5 A.g in the range of 0.01-3V -1 The first discharge specific capacity can reach 1233.4mAh under the current density·g -1 (ii) a At 2 A.g -1 The specific discharge capacity of the lithium ion battery is still maintained at 594.7mAh g -1 The composite material has excellent rate performance; finally, the current density is recovered to 100 mA.g -1 The specific discharge capacity is still kept to 659.9mAh g -1 The capacity retention rate is high, and therefore, the cobalt iron selenide/graphene nanoribbon composite negative electrode material obtained in the embodiment greatly improves the conductivity and improves the electrochemical performance of the material through structural design and compounding with GONRs.
Comparative example 1:
in the comparative example, the cobalt iron selenide prepared in example 1 is used to replace the cobalt iron selenide/graphene nanoribbon composite negative electrode material in example 1 to assemble a battery, and electrochemical characterization is performed on the battery, and the results are shown in fig. 6 and 7.
As can be seen from fig. 6, after the cobalt iron selenide and the graphene nanoribbon are compounded, the cycling stability of the cobalt iron selenide is obviously improved. Unmodified CoSe 2 /FeSe 2 The specific discharge capacity of the cathode material at 20 circles is 696.5 mAh.g -1 And then its specific discharge capacity also decreases from cycle to cycle. The possible reasons are: after a certain cycle, the volume change generated in the charge and discharge process causes pulverization of the active material, cracking of the SEI film, and capacity fading. After the graphene nano belt is compounded, the composite material shows good circulation stability. At 0.5A · g -1 The 919.3 mAh.g can be maintained even after 100 cycles of circulation under the current density -1 The specific discharge capacity of the material is in an ascending trend.
As can be seen from fig. 7, after the cobalt iron selenide and the graphene nanoribbon are compounded, the rate capability of the cobalt iron selenide is remarkably improved. Unmodified CoSe 2 /FeSe 2 The specific discharge capacity of the negative electrode material is inclined downwards under the increasing current density. After the graphene nano-belt is compounded with the graphene nano-belt, the capacity retention rate of the composite material is good under different current densities. When the current density is recovered to 100mAh g after 50 times of circulation -1 The specific discharge capacity of the material is 765.2mAh g -1 (about 10 times more unmodified).
Comparative example 2:
a preparation method of a cobalt iron selenide/graphene nanoribbon composite negative electrode material comprises the following steps:
(1) Adding 0.498g of terephthalic acid into 40mLN, N-dimethylacetamide solvent, uniformly stirring to obtain 40mL of solution A, adding 0.291g of cobalt nitrate hexahydrate and 0.404g of ferric nitrate nonahydrate into the solution A, and stirring to react for 2 hours at room temperature to obtain solution B;
(2) Putting the solution B obtained in the step (1) into a polytetrafluoroethylene stainless steel closed reaction kettle, placing the stainless steel closed reaction kettle in an electric heating constant-temperature drying box, carrying out solvothermal reaction for 20 hours at 125 ℃, cooling to room temperature, centrifuging, carrying out cross washing and precipitation for 3 times by using an N, N-dimethylformamide solution and ethanol, carrying out precipitation at 60 ℃, and drying for 15 hours to obtain a precursor;
(3) Mixing 0.2g of the precursor obtained in the step (2) with 0.4g of selenium powder, selenizing and roasting the mixture for 3 hours at 450 ℃ in a high-purity argon atmosphere, and cooling the mixture to room temperature along with a furnace to obtain cobalt iron selenide;
(4) - (6) same as in steps (4) - (6) of example 1.
Assembling the battery: the same as in example 1.
The battery assembled in this example was tested to have a voltage of 0.5 A.g.in the range of 0.01-3V -1 The discharge capacity of the first ring is 858.3 mAh.g -1 (Current density 50mA · g for the first 3 turns) -1 ) At 50 cycles (0.5A · g from the 4 th cycle) -1 ) Then, the specific discharge capacity was 487.2mAh · g -1 At 100 cycles (current density at 4 th cycle 50mA · g) -1 ) Then, the specific discharge capacity was 323.9mAh · g -1 。
The battery assembled in this example was tested to have a voltage of 0.5 A.g in the range of 0.01-3V -1 The first discharge specific capacity is 849.0 mAh.g at the current density of (A) -1 (ii) a At 2 A.g -1 The specific discharge capacity of the electrode material is 365.3mAh & g -1 (ii) a Finally, the current density is recovered to 100mA g -1 The specific discharge capacity is 279.3mAh g -1 。
Claims (9)
1. The cobalt iron selenide/graphene nanoribbon composite negative electrode material is characterized by comprising a graphene nanoribbon matrix and spherical cobalt iron selenide embedded in the graphene nanoribbon, wherein the mass ratio of the graphene nanoribbon in the cobalt iron selenide/graphene nanoribbon composite negative electrode material is 20-80%, the width of the graphene nanoribbon is 10-100nm, and the particle size of the cobalt iron selenide is 0.5-4 mu m;
the preparation method of the cobalt iron selenide comprises the following steps:
s1: adding a cobalt source into a solvent, uniformly stirring to obtain a solution A, adding an iron source 1,1' -ferrocenecarboxylic acid into the solvent, and uniformly stirring to obtain a solution B;
s2: mixing the solution A and the solution B, stirring for reaction, placing the mixture in a closed reaction kettle, carrying out solvothermal reaction, cooling, centrifuging, washing and drying after the reaction is finished to obtain a precursor;
s3: and mixing the precursor with selenium powder, placing the mixture in inert gas, heating the mixture and carrying out selenylation treatment to obtain the cobalt iron selenide.
2. The cobalt iron selenide/graphene nanoribbon composite anode material as claimed in claim 1, wherein in the S1, the solvent is N, N-dimethylformamide; the cobalt source is one or more of cobalt nitrate, cobalt chloride or cobalt acetate; the molar ratio of the cobalt source to the iron source is 1:1; the molar concentration of the cobalt source in the N, N-dimethylformamide solution is 0.05-0.2mol/L; the molar concentration of the iron source in the N, N-dimethylformamide solution is 0.05-0.2mol/L.
3. The cobalt iron selenide/graphene nanoribbon composite negative electrode material as claimed in claim 1, wherein in the step S2, the temperature during the stirring reaction is room temperature, and the stirring time is 1.0-3.0h; the temperature of the solvothermal reaction is 100-150 ℃, and the time is 10-24h; the washing mode is that N, N-dimethylformamide solution and ethanol are sequentially and alternately washed for more than or equal to 3 times; the drying temperature is 50-80 ℃ and the drying time is 12-24h.
4. The cobalt iron selenide/graphene nanoribbon composite anode material of claim 1, wherein in the S3, the mass ratio of the selenium powder to the precursor is (1.0-2.5): 1; the temperature of the selenizing treatment is 300-600 ℃, and the time is 2-4h.
5. The preparation method of the cobalt iron selenide/graphene nanoribbon composite anode material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Adding the graphene oxide nanoribbon into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide nanoribbon solution;
(2) Adding cobalt iron selenide and a reducing agent into deionized water, stirring, mixing with the graphene nanoribbon solution obtained in the step (1), placing in a closed reaction kettle for solvothermal reaction, cooling, centrifuging, washing, and freeze-drying after the reaction is finished to obtain initial powder of the cobalt iron selenide/graphene nanoribbon composite negative electrode material;
(3) And (3) carrying out heat treatment on the primary powder of the cobalt iron selenide/graphene nano-belt composite negative electrode material obtained in the step (2) in an inert atmosphere to obtain the cobalt iron selenide/graphene nano-belt composite negative electrode material.
6. The preparation method according to claim 5, wherein in the step (1), the mass concentration of the graphene oxide nanoribbon in water is controlled to be 0.5-2.2g/mL, the frequency of ultrasonic dispersion is controlled to be 20-40kHz, and the time is controlled to be 0.5-3.0h.
7. The preparation method according to claim 5, wherein the reducing agent is thiourea, and the mass ratio of the cobalt iron selenide to the thiourea is 1: (1.5-5.0), and controlling the mass concentration of the cobalt iron selenide in water to be 1.0-5.0g/mL.
8. The preparation method according to claim 5, wherein in the step (2), the temperature of the solvothermal reaction is 120-240 ℃ and the time is 8-15h; the washing mode is that water and ethanol are sequentially and alternately washed for more than or equal to 3 times; the temperature of the freeze drying is-40 to-50 ℃, and the time is 24 to 48 hours.
9. The method of claim 5, wherein the heat treatment is carried out at a temperature of 300 to 600 ℃ for 2 to 4 hours.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460921A (en) * | 2015-11-20 | 2016-04-06 | 复旦大学 | Molybdenum selenide nanosheets/graphene nanoribbons composite material and preparation method thereof |
| CN105609745A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Nickel selenide/graphene sodium ion battery composite negative material as well as preparation method and application thereof |
| CN105789584A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material |
| CN106129344A (en) * | 2016-06-06 | 2016-11-16 | 重庆大学 | A kind of tin ash/Titanium dioxide spherical granule and the preparation method of graphene nano belt composite |
| CN107482207A (en) * | 2017-09-27 | 2017-12-15 | 中南大学 | A kind of titanium dioxide/graphene nanobelt composite negative pole material and preparation method thereof |
| CN108615864A (en) * | 2018-04-25 | 2018-10-02 | 中南大学 | Sodium-ion battery anode material ferrous selenide/graphene and preparation method thereof |
| CN110867571A (en) * | 2019-08-27 | 2020-03-06 | 肇庆市华师大光电产业研究院 | Preparation method of hexagonal-prism-shaped iron-cobalt bimetallic selenide |
| CN110867570A (en) * | 2019-11-27 | 2020-03-06 | 中原工学院 | Preparation method of iron-doped cobalt diselenide nanosheet/reduced graphene composite electrode material |
| CN110943216A (en) * | 2019-12-20 | 2020-03-31 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt-iron bimetallic selenide sodium-ion battery cathode material |
| CN111924810A (en) * | 2020-07-28 | 2020-11-13 | 中国科学技术大学 | Iron-cobalt bimetallic selenide nano material, preparation method thereof and lithium ion battery |
| CN113130865A (en) * | 2021-03-31 | 2021-07-16 | 中南大学 | Bimetallic selenide carbon microsphere composite material and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101466310B1 (en) * | 2013-09-09 | 2014-11-27 | 아주대학교산학협력단 | Manufacturing method of metal oxide/graphene nanocomposites and electrode manufacturing method of metal oxide/graphene nanocomposites |
| US11374216B2 (en) * | 2019-11-07 | 2022-06-28 | Global Graphene Group, Inc. | Graphene foam-protected phosphorus material for lithium-ion or sodium-ion batteries |
| CN112007667A (en) * | 2020-07-31 | 2020-12-01 | 金陵科技学院 | Selenium-modified reduced graphene oxide-loaded CoSe2Preparation method and application thereof |
-
2021
- 2021-08-23 CN CN202110970223.0A patent/CN113823790B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460921A (en) * | 2015-11-20 | 2016-04-06 | 复旦大学 | Molybdenum selenide nanosheets/graphene nanoribbons composite material and preparation method thereof |
| CN105609745A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Nickel selenide/graphene sodium ion battery composite negative material as well as preparation method and application thereof |
| CN105789584A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material |
| CN106129344A (en) * | 2016-06-06 | 2016-11-16 | 重庆大学 | A kind of tin ash/Titanium dioxide spherical granule and the preparation method of graphene nano belt composite |
| CN107482207A (en) * | 2017-09-27 | 2017-12-15 | 中南大学 | A kind of titanium dioxide/graphene nanobelt composite negative pole material and preparation method thereof |
| CN108615864A (en) * | 2018-04-25 | 2018-10-02 | 中南大学 | Sodium-ion battery anode material ferrous selenide/graphene and preparation method thereof |
| CN110867571A (en) * | 2019-08-27 | 2020-03-06 | 肇庆市华师大光电产业研究院 | Preparation method of hexagonal-prism-shaped iron-cobalt bimetallic selenide |
| CN110867570A (en) * | 2019-11-27 | 2020-03-06 | 中原工学院 | Preparation method of iron-doped cobalt diselenide nanosheet/reduced graphene composite electrode material |
| CN110943216A (en) * | 2019-12-20 | 2020-03-31 | 肇庆市华师大光电产业研究院 | Preparation method of cobalt-iron bimetallic selenide sodium-ion battery cathode material |
| CN111924810A (en) * | 2020-07-28 | 2020-11-13 | 中国科学技术大学 | Iron-cobalt bimetallic selenide nano material, preparation method thereof and lithium ion battery |
| CN113130865A (en) * | 2021-03-31 | 2021-07-16 | 中南大学 | Bimetallic selenide carbon microsphere composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Graphene nanoribbons wrapping double nanoshells of SnO2@TiO2 for high lithium storage;Xinlu Li etal;《Journal of Power Sources》;20161029;全文 * |
| Iron-Doping-Induced Phase Transformation in Dual-Carbon-Confi ned Cobalt Diselenide Enabling Superior Lithium Storage;Yang Liu etal;《ACS NANO》;20190509;全文 * |
| 石墨烯负载纳米二硫化钴的制备及其在锂离子电池方面的应用研究;董丽坤等;《无机盐工业》;20200708(第07期);全文 * |
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