CN107026263B - Sea urchin-shaped bismuth sulfide/macroporous graphene composite material, preparation method and application thereof - Google Patents
Sea urchin-shaped bismuth sulfide/macroporous graphene composite material, preparation method and application thereof Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a sea urchin-shaped bismuth sulfide/macroporous graphene composite material, a preparation method and application thereof. The sea urchin-shaped bismuth sulfide/macroporous graphene compound is prepared by a simple hydrothermal method, wherein bismuth nitrate is used as a bismuth source, thiourea is used as a sulfur source, trimellitic acid is used as a binder, hexadecyl trimethyl ammonium bromide is used as a surfactant, and secondary distilled water is used as a solvent. The method is simple to operate, the reaction conditions are controllable, and the prepared bismuth sulfide is uniform in appearance and successfully loaded in the pores of the macroporous graphene; the macroporous graphene effectively buffers the volume expansion pressure of bismuth sulfide in the charging and discharging processes, the lithium ion and electron diffusion paths are better shortened in the circulating charging and discharging processes, and the circulating performance of the battery is greatly improved.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a sea urchin-shaped bismuth sulfide/macroporous graphene composite material, and a preparation method and application thereof.
Background
The lithium ion battery cathode material which has been commercialized at present is mainly a carbon-based material, but the problems of low specific capacity and safety of the carbon-based material become a technical bottleneck restricting further development of the carbon-based material.
Bismuth sulfide (Bi)2S3) Is an important semiconductor material, and Bi is an important semiconductor material in the aspect of lithium storage2S3The theoretical specific capacity of the nano material reaches 625 mAh/g, and the nano material has a completely reversible electrochemical reaction characteristic. On the other hand, Bi2S3The cathode material has the advantages of rich raw material resources, low cost, good safety performance, no pollution, easy preparation and the like, and has good application prospect. But Bi2S3The lithium ion battery cathode material has a large volume effect in the lithium intercalation and deintercalation process, so that the lithium ion battery cathode material has poor cycle stability in the charge and discharge processes, and the application of the lithium ion battery cathode material is restricted. Although in recent years, Bi with different morphologies is prepared2S3The cycle stability is improved, but it has not been solved fundamentally.
In the negative electrode material for a lithium battery, the larger the specific surface area of the material, the larger the contact area with the electrolyte, and the more favorable the insertion and extraction of lithium ions. Therefore, the preparation of the material with larger specific surface area becomes the research direction and difficulty, the conductivity of the material with higher conductivity is improved by doping the material with higher conductivity, and the rate capability of the composite material is further improved.
Disclosure of Invention
The invention aims to provide a bismuth sulfide/macroporous graphene composite material lithium ion battery cathode material which is low in cost and simple in process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a sea urchin-shaped bismuth sulfide/macroporous graphene composite material is formed by attaching sea urchin-shaped bismuth sulfide to holes of macroporous graphene, wherein the mass ratio of the sea urchin-shaped bismuth sulfide to the macroporous graphene is 1: 10.
Further, the macroporous graphene refers to graphene with irregular holes distributed on the surface.
The preparation method of the composite material comprises the following steps:
1) preparing macroporous graphene: preparing a graphene oxide solution with a certain mass concentration, carrying out ultrasonic treatment, carrying out hydrothermal reaction, and after the obtained sample is naturally cooled, carrying out freeze drying;
2) preparing a composite material: taking bismuth nitrate as a bismuth source, thiourea as a sulfur source, trimellitic acid as a binder, cetyl trimethyl ammonium bromide as a surfactant and secondary distilled water as a solvent, performing ultrasonic mixing on all the raw materials to make the raw materials uniform, performing hydrothermal reaction on the solution and the macroporous graphene prepared in the step 1), and cleaning and drying in vacuum after the reaction is finished to obtain the composite material.
Further, in the step 1), the mass concentration of the graphene oxide is 3 mg/mL, the ultrasonic treatment time is 2h, and the power is 55 kHz.
Further, in the step 1), the hydrothermal reaction temperature is 180 +/-10 ℃, and the hydrothermal reaction time is 12 h.
Further, in the step 2), the mass ratio of the bismuth nitrate to the thiourea is 1: 50.
Further, in the step 2), the hydrothermal reaction temperature is 120 +/-5 ℃, and the hydrothermal reaction time is 12 hours.
Further, in the step 2), the vacuum drying temperature is 60 ℃, and the vacuum drying time is 10-12 hours.
The composite material is applied as a negative electrode material of a lithium ion battery.
Compared with the prior art, the invention has the following advantages: (1) the invention uses cetyl trimethyl ammonium bromide as a surfactant, which is convenient for the dispersion of bismuth nitrate, thiourea and trimellitic acid in the water solution and effectively prevents the agglomeration of bismuth sulfide; (2) controlling the hydrothermal temperature, and preparing the bismuth sulfide into a sea urchin-shaped appearance, so that the sea urchin-shaped appearance has a larger specific surface area, and the contact area with the electrolyte is increased, thereby improving the electrochemical performance of the sea urchin-shaped appearance; (3) the macroporous graphene has rich macroporous structures and multidimensional electron transfer ways, and inherent properties such as large specific surface area and stable structure promote the infiltration of electrolyte and accelerate the migration rate of lithium ions; (4) the pore structure of the macroporous graphene can effectively relieve the volume expansion pressure of bismuth sulfide in the process of lithium intercalation and deintercalation; (5) the preparation method has the advantages of low preparation cost, simple equipment requirement and short preparation period.
Drawings
Fig. 1 is an XRD pattern of the bismuth sulfide/macroporous graphene composite material prepared in example 1 of the present invention.
Fig. 2 is an SEM image of macroporous graphene prepared in example 1 of the present invention.
Fig. 3 is SEM images of bismuth sulfide (a, b) and bismuth sulfide/macroporous graphene (c, d) prepared using example 1 of the present invention.
Fig. 4 is a TEM and elemental surface scan of the bismuth sulfide/macroporous graphene composite material prepared in example 1 of the present invention.
Fig. 5 is a charge-discharge cycle performance diagram of the bismuth sulfide and bismuth sulfide/macroporous graphene composite material prepared in example 1 of the present invention.
Fig. 6 is a graph showing charge and discharge cycle performance of the bismuth sulfide/macroporous graphene (a) synthesized in example 1 of the present invention and the bismuth sulfide/macroporous graphene (b, c) synthesized in comparative examples 1 and 2.
Detailed Description
The following detailed description of the experimental procedures of the present invention is intended to make the design process, the design objective, the innovation point and the advantages of the present invention more apparent.
The conception of the invention is as follows: the echinoid bismuth sulfide is attached to the holes of the macroporous graphene to form the composite material, and the echinoid structure enables the echinoid bismuth sulfide to have a large specific surface area, so that the contact area between the echinoid bismuth sulfide and electrolyte is greatly increased, the insertion and extraction of lithium ions in the charging and discharging process are facilitated, and the charging and discharging performance of a battery is greatly improved. Graphene is an ideal two-dimensional conductive matrix, and due to good chemical stability, excellent electronic conductivity and large specific surface area, the macroporous graphene prepared from the graphene can more effectively buffer the volume expansion pressure of bismuth sulfide in the charge and discharge processes, the lithium ion and electron diffusion paths can be better shortened in the cyclic charge and discharge processes, and the cycle performance of the battery is greatly improved by the composite material.
Firstly, a preparation process:
example 1
1. Preparing 0.2 mol/L bismuth nitrate aqueous solution:
9.7020 g Bi (NO) were weighed out3)3·5H2And (3) placing the O into a small beaker, adding deionized water to dissolve the O, draining the O into a 100 mL volumetric flask by using a glass rod, and then fixing the volume by using the deionized water to obtain 0.2 mol/L bismuth nitrate aqueous solution.
2. Preparation of macroporous graphene
60 mg of graphene oxide is weighed and prepared into 3 mg mL-1After ultrasonic treatment (ultrasonic treatment time is 2h and power is 55 kHz), the suspension is transferred into a lining of a reaction kettle made of polytetrafluoroethylene, the lining is placed into the reaction kettle made of steel material, the upper cover of the reaction kettle is screwed down, and then the reaction kettle is placed in a constant-temperature air-blast drying oven to set the temperature at 180 DEG CoAnd C, reacting for 12 hours, wherein the macroporous graphene prepared under the conditions of the concentration, the temperature and the time has ideal appearance and rich pore structure. Wait forNaturally cooling the obtained sample, and freeze-drying;
3. preparing a bismuth sulfide/macroporous graphene composite material:
in a 50 mL beaker, 0.0210 g of trimellitic acid [ molar ratio C ] was added9H6O6/Bi(NO3)3R1=1:1]0.0365 g CTAB [ molar ratio CTAB/Bi (NO)3)3R2=1:1]0.3806 g of thiourea (5.0 × 10-3mol) [ molar ratio Thiourea/Bi (NO)3)3R3=50:1]0.50 mL (0.20M) of bismuth nitrate aqueous solution and 9.50 mL of secondary distilled water, and ultrasonically mixing the system to be uniform to obtain a light yellow solution, wherein the ultrasonic condition is 55 kHz, and the ultrasonic time is 2 hours. Under the ultrasonic condition, the macroporous graphene is uniformly dispersed in a removing system, and the prepared product has good dispersibility. Transferring the solution and macroporous graphene prepared in advance into a polytetrafluoroethylene reaction kettle lining, putting the lining into a steel reaction kettle, screwing an upper cover of the reaction kettle, putting the reaction kettle into a constant-temperature air-blast drying box, and setting the temperature to be 120 DEG CoAnd C, reacting for 12 hours, wherein the morphology of the synthesized bismuth sulfide is uniform sea urchin-shaped and is successfully loaded in the pores of the macroporous graphene at the temperature and in the time. Taking out the reaction kettle after the reaction is finished, naturally cooling, taking out black precipitated bismuth sulfide/macroporous graphene at the bottom of the lining of the reaction kettle, sequentially washing with distilled water and absolute ethyl alcohol for 3 times respectively, and finally washing at 60 DEG CoAnd (3) drying for 12h under the condition of C to obtain black powder, and drying at the temperature to effectively retain the structure of the macroporous graphene. The resulting sample is left for subsequent processing or characterization.
The ratio of the amounts of bismuth nitrate and thiourea fed in this example was 1: 50, the morphology of the synthesized bismuth sulfide is uniform sea urchin-shaped and successfully loaded in the pores of the macroporous graphene at the ratio of the amount of the substances.
Comparative example 1
The procedure was as in example 1, but the ratio of the amounts of bismuth nitrate and thiourea fed in this example was 2: 50 hydrothermal temperature of 120 deg.CoAnd C, the hydrothermal time is 12 h.
Comparative example 2
The procedure was as in example 1, but the ratio of the amounts of bismuth nitrate and thiourea fed in this example was 1: 50 hydrothermal temperature of 100oAnd C, the hydrothermal time is 12 h.
Application example 1
1) Uniformly mixing bismuth sulfide/macroporous graphene, polyvinylidene fluoride (PVDF) and acetylene black according to the mass ratio of 8:1:1 by taking NMP as a solvent, then uniformly coating the slurry on an aluminum foil by using a coating machine, drying on the coating machine, tabletting, blanking to prepare a positive plate, and then drying in a vacuum drying oven.
2) Taking a prepared electrode plate as a negative electrode, a metal lithium plate as a positive electrode, a microporous polypropylene film as a diaphragm and 1M LiPF6Using the/EC + DMC + EMC (volume ratio 1:1: 1) as electrolyte of a button cell, assembling the cell and carrying out electrochemical performance test
Fig. 1 is an XRD pattern of the bismuth sulfide/macroporous graphene composite material prepared in example 1 of the present invention, and it can be seen from fig. 1 that: fig. 1 is an XRD spectrum of the prepared bismuth sulfide and bismuth sulfide/macroporous graphene. From the spectrum of bismuth sulfide, we can clearly see that strong diffraction peaks appear at 23.72 °, 24.93 °, 28.61 ° and 31.80 °, which correspond to the crystal faces (101), (130), (211) and (221), respectively, and compared with the standard card, all the diffraction peaks can be respectively indexed to orthorhombic bismuth sulfide (JCPDS No. 17-0320). In addition, no other impurity diffraction peaks were found, indicating that the product we prepared is a very pure sample of bismuth sulfide. As can be seen from the comparison of the spectra of bismuth sulfide and bismuth sulfide/macroporous graphene, the main peak of bismuth sulfide modified by macroporous graphene is not obviously changed, which indicates that the in-situ modification method has no influence on the formation of bismuth sulfide.
FIG. 2 is an SEM image of macroporous graphene prepared in example 1 of the present invention, and it can be seen from FIG. 2 that macroporous graphene has a rich pore structure
Fig. 3 is an SEM image of the bismuth sulfide/macroporous graphene composite material prepared in example 1 of the present invention, and it can be seen from fig. 3 that: it is clear from FIGS. 3a and 3b that the bismuth sulfide is sea urchin-like and consists ofBi of 1-2 μm length2S3Thin rods with a tip diameter of about 70 nm. Fig. 3c and 3d are scanned images of the composite material coated with macroporous graphene, and it is apparent that echinoid bismuth sulfide is successfully loaded in the pores of macroporous graphene.
To further characterize the distribution of bismuth sulfide and macroporous graphene in our obtained bismuth sulfide/macroporous graphene, we performed elemental plane scan tests, as shown in fig. 4. Through element surface scanning analysis, we can see that the composite material only contains Bi, S and C, and C is distributed in Bi2S3The outer periphery of (a).
FIG. 5 shows the current density at 200 mA g after low current activation of bismuth sulfide/macroporous graphene and bismuth sulfide-1And respectively circulating for 60 circles, and performing circulating test when the voltage interval is 0.01-3V. For bismuth sulfide, the specific capacity is changed from 295 mAh g of the first turn due to the existence of irreversible capacity-1Then the solution is stabilized at 240 mAh g-1And after stabilization, the product accounts for 38.4 percent of theoretical specific capacity. Compared with bismuth sulfide, the bismuth sulfide/macroporous graphene is improved in cycle performance to the maximum extent, and the bismuth sulfide/macroporous graphene is 200 mAg-1The first discharge specific capacity of the lithium ion battery reaches 469 mAh g under the current density-1Then stabilize at 415 mAh g-1. Compared with bismuth sulfide, the capacity is improved by 72.9%, so that the electrochemical performance of the bismuth sulfide alloy is obviously improved by carbon coating treatment.
FIG. 6 shows the current density of 200 mA g after small current activation of bismuth sulfide/macroporous graphene (a) synthesized in example 1 of the present invention and bismuth sulfide/macroporous graphene (b, c) synthesized in comparative examples 1 and 2-1And respectively circulating for 60 circles, and performing circulating test when the voltage interval is 0.01-3V. It is obvious from the figure that the bismuth sulfide/macroporous graphene synthesized in comparative example 1 of the present invention has good cycling stability, but has low cycling specific capacity; in addition, the bismuth sulfide/macroporous graphene synthesized in comparative example 2 has poor stability, fast specific capacity reduction and low cyclic specific capacity. The result shows that the bismuth sulfide/macroporous graphene synthesized in the embodiment 1 of the invention has excellent electrochemical performance.
Claims (8)
1. A sea urchin-shaped bismuth sulfide/macroporous graphene composite material is characterized by being formed by attaching sea urchin-shaped bismuth sulfide to holes of macroporous graphene, wherein the mass ratio of the sea urchin-shaped bismuth sulfide to the macroporous graphene is 1: 10; the macroporous graphene refers to graphene with irregular holes distributed on the surface, and is prepared by the following steps:
1) preparing macroporous graphene: preparing a graphene oxide solution, carrying out ultrasonic treatment, carrying out hydrothermal reaction, and after the obtained sample is naturally cooled, carrying out freeze drying;
2) preparing a composite material: taking bismuth nitrate as a bismuth source, thiourea as a sulfur source, trimellitic acid as a binder, cetyl trimethyl ammonium bromide as a surfactant and secondary distilled water as a solvent, performing ultrasonic mixing on all the raw materials to make the raw materials uniform, performing hydrothermal reaction on the solution and the macroporous graphene prepared in the step 1), and cleaning and drying in vacuum after the reaction is finished to obtain the composite material.
2. A method of preparing a composite material according to claim 1, comprising the steps of:
1) preparing macroporous graphene: preparing a graphene oxide solution, carrying out ultrasonic treatment, carrying out hydrothermal reaction, and after the obtained sample is naturally cooled, carrying out freeze drying;
2) preparing a composite material: taking bismuth nitrate as a bismuth source, thiourea as a sulfur source, trimellitic acid as a binder, cetyl trimethyl ammonium bromide as a surfactant and secondary distilled water as a solvent, performing ultrasonic mixing on all the raw materials to make the raw materials uniform, performing hydrothermal reaction on the solution and the macroporous graphene prepared in the step 1), and cleaning and drying in vacuum after the reaction is finished to obtain the composite material.
3. The method of claim 2, wherein in the step 1), the mass concentration of the graphene oxide is 3 mg/mL, the ultrasonic treatment time is 2h, and the power is 55 kHz.
4. The method according to claim 2, wherein in the step 1), the hydrothermal reaction temperature is 180 ± 10 ℃ and the hydrothermal reaction time is 12 h.
5. The method of claim 2, wherein in step 2), the ratio of the amounts of bismuth nitrate to thiourea is 1: 50.
6. The method according to claim 2, wherein in the step 2), the hydrothermal reaction temperature is 120 +/-5 ℃ and the hydrothermal reaction time is 12 h.
7. The method according to claim 2, wherein in the step 2), the vacuum drying temperature is 60 ℃ and the vacuum drying time is 10-12 h.
8. Use of the composite material of claim 1 as a negative electrode material for lithium ion batteries.
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| CN102910617A (en) * | 2012-09-24 | 2013-02-06 | 同济大学 | Chemical preparation method of graphene-bismuth sulfide nanocomposite material |
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