CN111180707B - Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof - Google Patents
Tin diselenide/tin oxide-rGO nano composite anode material and preparation method thereof Download PDFInfo
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Abstract
The tin diselenide/tin oxide-rGO nano composite anode material is formed by stacking flaky reduced graphene oxide, and a flaky cubic tin diselenide/tin oxide composite material is embedded between the flaky layers. The preparation method comprises the following steps: (1) dripping the tin source alcohol solution into the graphene oxide aqueous solution, uniformly mixing, centrifuging, washing the precipitate, and freeze-drying; (2) adding into anhydrous alcohol solution, stirring, ultrasonic dispersing, adding selenium source and reducing agent, stirring, placing into a sealed reaction kettle, performing solvent thermal reaction, cooling to room temperature with the furnace, centrifuging, washing precipitate, and drying; (3) and (4) performing heat treatment in an inert atmosphere to obtain the product. The battery assembled by the composite negative electrode material has high specific capacity, good cycle performance, excellent rate performance and stable structure. The method has the advantages of green and environment-friendly raw materials, low cost, simple process and short period, and is suitable for industrial production.
Description
Technical Field
The invention relates to a nano composite anode material and a preparation method thereof, in particular to a tin diselenide/tin oxide-rGO nano composite anode material and a preparation method thereof.
Background
Nowadays, with the rapid development of society, the environmental and energy problems facing human beings are increasingly prominent. The traditional fossil fuel is seriously polluted and faces exhaustion, and development of green sustainable energy sources is more and more remarkable. However, renewable clean energy such as solar energy, water energy, wind energy and the like is severely limited by climate and region, has the problems of poor supply continuity and instability, and is not beneficial to efficient utilization. The matching energy storage device becomes the key for high-efficiency utilization of clean energy, and the lithium ion battery is one of the most important green energy sources at present as a rechargeable secondary battery.
Although lithium ion batteries have been commercially used in portable devices on a large scale, the negative electrode materials still face some challenges as an important component that can directly determine battery performance. The theoretical lithium intercalation capacity of the traditional graphite cathode is low (372 mAh & g)-1) The rate discharge performance is poor. The tin-based negative electrode material which is concerned with high reversible capacity is low in intrinsic conductivity and large in volume change in the charging and discharging process, so that the further development of the tin-based negative electrode material is hindered.
Kai Chen et al synthesized SnSe/SnO by two-step hydrothermal method and high-temperature solid-phase selenization2The @ Gr composite material is SnSe/SnO2The nanospheres are uniformly dispersed on the graphene oxide nanosheets, and are used as the negative electrode material of the lithium ion battery at 200 mA.g-1At a current density of (D), the capacity was maintained at 810 mAh g after 200 cycles-1（CHEN K,WANG X, et al. A new generation of high performance anode materials with semiconductor heterojunction structure of SnSe/SnO2@Gr in lithium-ion batteries [J].Chemical Engineering Journal, 2018, 347,552-562.）。However, the method is complicated in production process and has a low electrochemical rate performance (3200 mA · g)-1The specific discharge capacity is only 225.3mAh/g under the current density).
CN106784678A discloses a solvothermal method for preparing flower-like SnSe2The method of-rGO is to disperse graphene oxide by using alcohol as a solvent, and hydrazine hydrate and oleylamine as auxiliary solvents to control the morphology. Although the method has simple process, the improvement on the conductivity of the material and the relief effect on the volume expansion in the charging and discharging process are limited, the electrochemical performance is poor, and hydrazine hydrate has severe toxicity and great harm to human bodies.
CN106058213A discloses a tin diselenide/polyethyleneimine composite material, a preparation method and application thereof, wherein sodium borohydride is used for preparation. Although the method is simple in process, a single material does not have the synergistic advantage of a complex phase material, the effects of improving the conductivity of the material and relieving volume expansion in the charging and discharging processes are limited, the electrochemical performance is poor, and the sodium borohydride is severe in toxicity and harmful to human bodies.
CN105304878A discloses a nano tin diselenide/graphene composite material, in which tin diselenide particles are grown between graphene sheets. However, the composite material has no obvious advantage of high-rate charge and discharge performance, and the specific discharge capacity under 5A/g is lower than 200 mAh/g.
CN106450207A discloses a selenium stannide/tin oxide composite material, which is a composite material of a simple transition metal chalcogenide, and has limited improvement in conductivity, which limits the improvement of large-rate performance.
CN107706404A discloses a selenium-coated tin dioxide/graphene nanocomposite, but the composite is prepared by selenium coating with a high-temperature solid phase method, so that a uniform and dense coating layer cannot be obtained, and the electrochemical performance of the composite is poor when the composite is applied to a sodium-electricity negative electrode material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the tin diselenide/tin oxide-rGO nano composite cathode material which is high in specific capacity, good in cycle performance, excellent in rate capability and stable in structure.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the tin diselenide/tin oxide-rGO nano composite anode material, which has the advantages of green and environment-friendly raw materials, low cost, simple process and short period and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: the tin diselenide/tin oxide-rGO nano composite anode material is formed by stacking sheet-shaped reduced graphene oxide, and the sheet-shaped cubic tin diselenide/tin oxide composite material is embedded between the reduced graphene oxide sheet layers. The composite cathode material consists of SnSe2With SnO2The two tin compounds with different work functions are coupled to construct a semiconductor heterostructure, charge transfer can be accelerated through a huge built-in electric field on a phase interface, so that reaction kinetics are improved, and after the tin compounds are compounded with reduced graphene oxide, the electronic conductivity of the material can be further improved, the stability of the structure is ensured, and volume expansion is limited.
Preferably, the mass ratio of the tin diselenide to the tin oxide to the reduced graphene oxide is 3-10: 1-4: 1. If the content is too high compared with that of graphene oxide, it is difficult to fully exert the advantages of excellent conductivity and structural stability of graphene; if the content is too low, the specific capacity of the target material is lowered.
Preferably, the length and width of the flaky cubic tin diselenide/tin oxide composite material are 200-1200 nm, and the thickness of the flaky cubic tin diselenide/tin oxide composite material is 10-100 nm. The nanometer size design is beneficial to increasing the specific surface area and relieving the stress caused by volume expansion.
The technical scheme adopted for further solving the technical problems is as follows: the preparation method of the tin diselenide/tin oxide-rGO nano composite anode material comprises the following steps:
(1) dripping the tin source alcohol solution into the graphene oxide aqueous solution, uniformly mixing, centrifuging, washing a precipitate, and freeze-drying to obtain intermediate powder;
(2) adding the intermediate powder obtained in the step (1) into an anhydrous alcohol solution, uniformly stirring, performing ultrasonic dispersion, adding a selenium source and a reducing agent, uniformly stirring, placing in a closed reaction kettle, performing solvothermal reaction, cooling to room temperature along with a furnace, centrifuging, washing a precipitate, and drying to obtain a precursor;
(3) and (3) carrying out heat treatment on the precursor obtained in the step (2) in an inert atmosphere to obtain the tin diselenide/tin oxide-rGO nano composite anode material.
Preferably, in the step (1), the volume ratio of the tin source alcohol solution to the graphene oxide aqueous solution is 0.3-1.0: 1. The ratio helps tin ions to be uniformly dispersed in the graphene oxide aqueous solution.
Preferably, in the step (1), the mass concentration of the tin source alcohol solution is 1.5-3.1 mg/mL. The low-concentration alcohol solution is more beneficial to subsequent uniform dispersion in the graphene oxide aqueous solution.
Preferably, in the step (1), the mass concentration of the graphene oxide aqueous solution is 0.2-2.0 mg/mL (more preferably 0.3-1.3 mg/mL). The concentration helps the graphene oxide to disperse uniformly.
Preferably, in the step (1), the dropping speed is 5 to 20mL/min (more preferably 8 to 12 mL/min). The dropping speed contributes to uniform mixing of the two.
Preferably, in the step (1), the tin source is one or more of tin chloride, stannous chloride or stannous iodide.
Preferably, in the step (1), the alcohol solution is one or more of methanol, ethanol or ethylene glycol.
Preferably, in the step (1), the preparation method of the graphene oxide aqueous solution comprises: and adding the graphene oxide into water, stirring, and then performing ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass-to-volume ratio (mg/mL) of the graphene oxide to water is 0.2-2.0: 1 (more preferably 0.3-1.3: 1).
Preferably, the stirring time is 20-40 min.
Preferably, the frequency of ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h.
Preferably, in the step (1), the washing is carried out by alternately washing with water and ethanol for more than or equal to 3 times.
Preferably, in the step (1), the temperature of the freeze drying is-40 to-50 ℃, and the time is 24 to 72 hours (more preferably 36 to 60 hours). Freeze-drying avoids thermal agglomeration of the material, forming a loose structure, which contributes to complete drying of the material under the parameters described.
In the step (1), after the tin source and the graphene oxide are prepared into the intermediate powder, the positive valence bond of tin ions can be bonded with the negative bond on the surface of the graphene oxide, and the target material is formed on the graphene oxide in situ in the subsequent process and is combined with the graphene more stably.
Preferably, in the step (2), the mass-to-volume ratio (g/mL) of the intermediate powder to the anhydrous alcohol solution is 1: 200-600.
Preferably, in the step (2), the stirring time is 20-40 min.
Preferably, in the step (2), the frequency of the ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h.
Preferably, in the step (2), the anhydrous alcohol solution is one or more of anhydrous ethanol, ethylene glycol or methanol.
Preferably, in the step (2), the mass ratio of the selenium source and the reducing agent to the graphene oxide in the step (1) is 1-4: 100-200: 1.
Preferably, in the step (2), the selenium source is one or more of elemental selenium, selenium dioxide, sodium selenate and the like.
Preferably, in the step (2), the reducing agent is one or more of oleic acid, oleylamine, ethylenediamine, hydrazine hydrate, sodium borohydride and the like. The use of a reducing agent may facilitate the reduction of selenium to form tin selenide.
Preferably, in the step (2), the temperature of the solvothermal reaction is 120-200 ℃ and the time is 8-24 h. In the reducing atmosphere of the solvothermal process, metallic tin ions are oxidized, and non-metallic selenium is reduced to form tin selenide.
Preferably, in the step (2), the washing is carried out by alternately washing with water and ethanol for more than or equal to 3 times.
Preferably, in the step (2), the drying temperature is 50-80 ℃ and the drying time is 12-48 h. The drying is preferably air-blast drying.
Preferably, in the step (3), the temperature of the heat treatment is 300-500 ℃ (more preferably 350-450 ℃) and the time is 0.5-2.0 h. In the heat treatment process, the graphene oxide is further reduced to reduced graphene oxide, so that the electronic conductivity is improved, and the electron transmission is facilitated, and the crystallization degree of tin diselenide-tin oxide is improved, and the ion/electron transmission is facilitated.
Preferably, in the step (3), the inert gas is one or more of nitrogen, argon or helium. The inert gas used in the invention is high-purity gas with the purity of more than or equal to 99.9 percent.
The invention has the following beneficial effects:
(1) the battery assembled by taking the tin diselenide/tin oxide-rGO nano composite anode material as the anode has the voltage of 1 A.g within the range of 0.01-3V-1The discharge capacity of the first ring is 1673 mAh.g-1(the current density of the first 3 turns is 0.1 A.g-1) At 120 cycles (1A. g from the 4 th cycle)-1) After that, the specific discharge capacity is still kept at 808mAh g-1The specific capacity is high, and the cycle performance is good; at 5 A.g-1The specific discharge capacity of the lithium ion battery is still kept to 554mAh g-1The current density is recovered to 50mA g-1The specific discharge capacity is still kept at 1086mAh & g-1The composite negative electrode material shows excellent rate performance, which shows that the composite negative electrode material has stable structure;
(2) the method has the advantages of green and environment-friendly raw materials, low cost, simple process and short period, and is suitable for industrial production.
Drawings
Fig. 1 is an XRD pattern of tin diselenide/tin oxide-rGO nanocomposite cathode material of example 1 of the present invention;
fig. 2 is an SEM image of tin diselenide/tin oxide-rGO nanocomposite negative electrode material of example 1 of the present invention;
fig. 3 is a HRTEM of tin diselenide/tin oxide-rGO nanocomposite negative electrode material of example 1 of the present invention;
fig. 4 is a graph of the charge-discharge cycle performance of a battery assembled from tin diselenide/tin oxide-rGO nanocomposite cathode material according to example 1 of the present invention;
fig. 5 is a discharge rate performance graph of a tin diselenide/tin oxide-rGO nanocomposite cathode material assembled battery in accordance with example 1 of the present invention;
fig. 6 is an SEM image of tin diselenide/tin oxide-rGO nanocomposite negative electrode material of example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
The graphene oxide used in the reference example of the present invention is prepared according to the existing Hummers method; the density of the oleic acid used in the invention is 0.885g/mL, and the density of the hydrazine hydrate is 1.032 g/mL; the inert gases used in the embodiment of the invention are high-purity gases with the purity of more than or equal to 99.9 percent; the starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
Method for preparing graphene oxide aqueous solution reference example 1
Adding 100mg of graphene oxide into 200mL of water, stirring for 30min, and then performing ultrasonic dispersion for 2h at 40kHz to obtain a graphene oxide aqueous solution 1.
Preparation method of graphene oxide aqueous solution reference example 2
160mg of graphene oxide is added into 200mL of water, stirred for 40min and then subjected to ultrasonic dispersion for 2.5h at 30kHz to obtain a graphene oxide aqueous solution 2.
Preparation method of graphene oxide aqueous solution reference example 3
Adding 60mg of graphene oxide into 200mL of water, stirring for 20min, and then performing ultrasonic dispersion for 1.5h at 50kHz to obtain a graphene oxide aqueous solution 3.
Tin diselenide/tin oxide-rGO nano composite anode material example 1
The composite cathode material is formed by stacking sheet-shaped reduced graphene oxide, and a sheet-shaped cubic tin diselenide/tin oxide composite material is embedded between the reduced graphene oxide sheet layers; the mass ratio of the tin diselenide to the tin oxide to the reduced graphene oxide is 9:2: 1; the length and width of the flaky cubic tin diselenide/tin oxide composite material are 200-800 nm, and the thickness of the flaky cubic tin diselenide/tin oxide composite material is 20-50 nm.
As shown in figure 1, the characteristic peak shape and strength of the tin diselenide/tin oxide-rGO nano composite anode material and SnSe2、SnO2The spectral lines of the standard cards are identical, the peak shape is sharp, and the crystallinity shows that the tin diselenide/tin oxide-rGO nano composite anode material contains pure-phase SnSe2And SnO2And no other impurities.
As shown in figure 2, the tin diselenide/tin oxide-rGO nano composite cathode material is of a flaky cubic structure, the length and width dimensions are 200-800 nm, and the thickness is 20-50 nm.
As shown in FIG. 3, SnO was observed by lattice spacing comparison2(110) Crystal face and SnSe2(102) Crystal face, which shows that the target material in the shape of flaky cubic is made of nano-scale SnO2With SnSe2The particles jointly consist of, and SnSe2And SnO2The nano particles are mutually contacted, and a heterostructure is formed on an interface, so that the formation of a built-in electric field is facilitated, the reaction kinetics can be improved, and the transmission of ionic electrons is promoted.
Preparation method of tin diselenide/tin oxide-rGO nano composite anode material in example 1
(1) Dripping 100mL of stannous chloride ethanol solution (2.256 mg/mL) into 160mL of graphene oxide aqueous solution 1 (0.5 mg/mL) at a speed of 10mL/min, uniformly mixing, centrifuging, alternately washing precipitates for 5 times by deionized water and absolute ethyl alcohol in sequence, and freeze-drying for 48 hours at-44 ℃ to obtain 0.3g of intermediate powder;
(2) adding 0.3g of the intermediate powder obtained in the step (1) into 100mL of absolute ethyl alcohol solution, stirring for 30min to be uniform, performing ultrasonic dispersion for 2h at 40kHz, adding 0.1579g (2 mmol) of elemental selenium powder and 10mL of oleic acid, stirring for 30min to be uniform, placing in a closed reaction kettle, performing solvothermal reaction for 12h at 180 ℃ in a forced air drying oven, cooling to room temperature along with the furnace, centrifuging, performing sequential cross washing on precipitates for 5 times by deionized water and absolute ethyl alcohol, and performing forced air drying for 24h at 60 ℃ to obtain a precursor;
(3) and (3) placing the precursor obtained in the step (2) into a tube furnace, and carrying out heat treatment for 1.5h at 400 ℃ in a high-purity argon atmosphere to obtain the tin diselenide/tin oxide-rGO nano composite anode material.
Assembling the battery: taking 42mg of tin diselenide/tin oxide-rGO nano composite negative electrode material obtained in the embodiment of the invention as an active substance, 12mg of conductive carbon black as a conductive agent, 6mg of polyvinylidene fluoride as a binder, adding the material into an agate mortar, crushing and grinding the material for 20min, then dropping 10mL of N-methyl pyrrolidone as a solvent, continuing grinding the material for 5min, then using a copper foil as a current collector, coating the uniformly ground slurry on the copper foil, and drying the slurry for 4h in vacuum 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 2h 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 polypropylene as a diaphragm and a metal lithium sheet and the manufactured electrode plate in a glove box filled with argon, and using 1mol/L LiPF6DMC (volume ratio 1: 1) as electrolyte, assembling CR2032 button cell, and testing electrochemical performance on LAND button cell tester.
As shown in FIG. 4, the battery assembled by the tin diselenide/tin oxide-rGO nano composite anode material obtained in the embodiment of the invention has a voltage of 1 A.g within a range of 0.01-3V-1The first discharge specific capacity can reach 1436 mAh.g under the current density-1(first 3 turns 0.1A. g-1) At 50 cycles (1A. g from the 4 th cycle)-1) Then, the specific discharge capacity is still kept to be 774mAh g-1The specific capacity retention rate is higher, good cycle stability is shown, the specific capacity is slightly improved along with the gradual activation of the material, and when the cycle reaches 120 circles, the capacity is stably increased to 808 mAh.g-1。
As shown in FIG. 5, the tin diselenide/tin oxide obtained in the embodiment of the inventionThe battery assembled by the-rGO nano composite anode material has the voltage of 50 mA.g within the range of 0.01 to 3V-1The first discharge specific capacity can reach 1685 mAh.g under the current density-1And the subsequent two circles decay slowly, showing higher reversibility; at 5 A.g-1The specific discharge capacity of the lithium ion battery is still kept to 554mAh g-1The composite material has excellent rate performance; finally, the current density is recovered to 50mA g-1The specific discharge capacity is still kept at 1086mAh & g-1The capacity retention rate is high, and therefore, the tin diselenide/tin oxide-rGO nano composite cathode material obtained in the embodiment of the invention greatly improves the conductivity and improves the electrochemical performance of the material through structural design and combination with rGO.
Tin diselenide/tin oxide-rGO nano composite anode material example 2
The composite cathode material is formed by stacking sheet-shaped reduced graphene oxide, and a sheet-shaped cubic tin diselenide/tin oxide composite material is embedded between the reduced graphene oxide sheet layers; the mass ratio of the tin diselenide to the tin oxide to the reduced graphene oxide is 10:3: 1; the length and width of the flaky cubic tin diselenide/tin oxide composite material are 300-1200 nm, and the thickness of the flaky cubic tin diselenide/tin oxide composite material is 40-100 nm.
Through detection, the characteristic peak shape and strength of the tin diselenide/tin oxide-rGO nano composite anode material and SnSe2、SnO2The spectral lines of the standard cards are identical, the peak shape is sharp, and the crystallinity shows that the tin diselenide/tin oxide-rGO nano composite anode material contains pure-phase SnSe2And SnO2And no other impurities.
As shown in FIG. 6, the tin diselenide/tin oxide-rGO nano composite anode material is of a flaky cubic structure, the length and width of the flaky cubic structure are 300-1200 nm, and the thickness of the flaky cubic structure is 40-100 nm.
The SnO can be observed through the detection and the lattice spacing comparison2(110) Crystal face and SnSe2(102) Crystal face, which shows that the target material in the shape of flaky cubic is made of nano-scale SnO2With SnSe2The particles jointly consist of, and SnSe2And SnO2The nanoparticles are in contact with each other at the boundaryThe surface forms a heterostructure, which is beneficial to the formation of a built-in electric field, can promote reaction kinetics and promote the transmission of ionic electrons.
Preparation method of tin diselenide/tin oxide-rGO nano composite anode material in example 2
(1) Dripping 100mL of stannous chloride glycol solution (2.962 mg/mL) into 120mL of graphene oxide aqueous solution 2 (0.8 mg/mL) at the speed of 8mL/min, uniformly mixing, centrifuging, alternately washing precipitates for 4 times by deionized water and absolute ethyl alcohol in sequence, and freeze-drying for 60 hours at the temperature of-40 ℃ to obtain 0.39g of intermediate powder;
(2) adding 0.39g of the intermediate powder obtained in the step (1) into 80mL of glycol solution, stirring for 40min to be uniform, performing ultrasonic dispersion for 2.5h at 30kHz, adding 0.2663g (2.4 mmol) of selenium dioxide and 20mL of oleic acid, stirring for 20min to be uniform, placing in a closed reaction kettle, performing solvothermal reaction for 8h at 200 ℃ in a forced air drying oven, cooling to room temperature along with the furnace, centrifuging, performing cross washing on precipitates for 4 times by deionized water and absolute ethyl alcohol sequentially, and performing forced air drying for 12h at 70 ℃ to obtain a precursor;
(3) and (3) placing the precursor obtained in the step (2) in a tubular furnace, and carrying out heat treatment for 2h at 450 ℃ in a high-purity nitrogen atmosphere to obtain the tin diselenide/tin oxide-rGO nano composite anode material.
Assembling the battery: the same as in example 1.
Through detection, the battery assembled by the tin diselenide/tin oxide-rGO nano composite anode material obtained in the embodiment of the invention has the voltage of 1 A.g within the range of 0.01-3V-1The first discharge specific capacity can reach 1541 mAh.g under the current density-1(first 3 turns 0.1A. g-1) At 100 cycles (1A. g from the 4 th cycle)-1) After that, the specific discharge capacity is still maintained at 738mAh g-1The specific capacity retention rate is higher, and good cycle stability is shown.
Through detection, the battery assembled by the tin diselenide/tin oxide-rGO nano composite cathode material obtained in the embodiment of the invention has the voltage of 100 mA.g within the range of 0.01-3V-1The first discharge specific capacity can reach 1450mAh g under the current density-1And the subsequent two circles decay slowly, showing higher reversibility; at 5 A.g-1The specific discharge capacity of the lithium ion battery is still maintained at 424mAh g-1The composite material has excellent rate performance; finally, the current density is recovered to 100mA g-1The specific discharge capacity is maintained at 850mAh g-1The capacity retention rate is high, and therefore, the tin diselenide/tin oxide-rGO nano composite cathode material obtained in the embodiment of the invention greatly improves the conductivity and improves the electrochemical performance of the material through structural design and combination with rGO.
Tin diselenide/tin oxide-rGO nanocomposite negative electrode material example 3
The composite cathode material is formed by stacking sheet-shaped reduced graphene oxide, and a sheet-shaped cubic tin diselenide/tin oxide composite material is embedded between the reduced graphene oxide sheet layers; the mass ratio of the tin diselenide to the tin oxide to the reduced graphene oxide is 6:1: 1; the length and width of the flaky cubic tin diselenide/tin oxide composite material are 400-1000 nm, and the thickness of the flaky cubic tin diselenide/tin oxide composite material is 30-80 nm.
Through detection, the characteristic peak shape and strength of the tin diselenide/tin oxide-rGO nano composite anode material and SnSe2、SnO2The spectral lines of the standard cards are identical, the peak shape is sharp, and the crystallinity shows that the tin diselenide/tin oxide-rGO nano composite anode material contains pure-phase SnSe2And SnO2And no other impurities.
Through detection, the tin diselenide/tin oxide-rGO nano composite anode material disclosed by the invention is of a flaky cubic structure, the length and width dimensions are 400-1000 nm, and the thickness is 30-80 nm.
The SnO can be observed through the detection and the lattice spacing comparison2(110) Crystal face and SnSe2(102) Crystal face, which shows that the target material in the shape of flaky cubic is made of nano-scale SnO2With SnSe2The particles jointly consist of, and SnSe2And SnO2The nano particles are mutually contacted, and a heterostructure is formed on an interface, so that the formation of a built-in electric field is facilitated, the reaction kinetics can be improved, and the transmission of ionic electrons is promoted.
Preparation method of tin diselenide/tin oxide-rGO nano composite anode material in example 3
(1) Dripping 100mL of tin chloride ethanol solution (1.606 mg/mL) into 200mL of graphene oxide aqueous solution 3 (0.3 mg/mL) at the speed of 12mL/min, uniformly mixing, centrifuging, alternately washing precipitates for 6 times by deionized water and absolute ethyl alcohol in sequence, and freeze-drying for 36h at-50 ℃ to obtain 0.22g of intermediate powder;
(2) adding 0.22g of intermediate powder obtained in the step (1) into 120mL of absolute ethyl alcohol solution, stirring for 20min to be uniform, performing ultrasonic dispersion for 1.5h at 50kHz, adding 0.0868g (1.1 mmol) of elemental selenium powder and 10mL of hydrazine hydrate, stirring for 40min to be uniform, placing in a closed reaction kettle, performing solvothermal reaction for 16h at 160 ℃ in a forced air drying oven, cooling to room temperature along with the furnace, centrifuging, performing cross washing on precipitates for 6 times by deionized water and absolute ethyl alcohol sequentially, and performing forced air drying for 36h at 50 ℃ to obtain a precursor;
(3) and (3) placing the precursor obtained in the step (2) into a tube furnace, and carrying out heat treatment for 1h at 350 ℃ in a high-purity argon atmosphere to obtain the tin diselenide/tin oxide-rGO nano composite anode material.
Assembling the battery: the same as in example 1.
Through detection, the battery assembled by the tin diselenide/tin oxide-rGO nano composite anode material obtained in the embodiment of the invention has the voltage of 1 A.g within the range of 0.01-3V-1The first discharge specific capacity can reach 1673 mAh.g under the current density-1(first 3 turns 0.1A. g-1) At 180 cycles (1A. g from the 4 th cycle)-1) After that, the specific discharge capacity is still kept to 657mAh g-1The specific capacity retention rate is higher, and good cycle stability is shown.
Through detection, the battery assembled by the tin diselenide/tin oxide-rGO nano composite cathode material obtained in the embodiment of the invention has the voltage of 100 mA.g within the range of 0.01-3V-1The first discharge specific capacity can reach 1570mAh g under the current density-1And the subsequent two circles decay slowly, showing higher reversibility; at 5 A.g-1The specific discharge capacity is still kept at 426mAh g under the current density of (A)-1Is provided withExcellent rate performance; finally, the current density is recovered to 100mA g-1The specific discharge capacity is still maintained at 900mAh g-1The capacity retention rate is high, and therefore, the tin diselenide/tin oxide-rGO nano composite cathode material obtained in the embodiment of the invention greatly improves the conductivity and improves the electrochemical performance of the material through structural design and combination with rGO.
Claims (12)
1. A tin diselenide/tin oxide-rGO nano composite anode material is characterized in that: the composite cathode material is formed by stacking sheet-shaped reduced graphene oxide, and a sheet-shaped cubic tin diselenide/tin oxide composite material is embedded between the reduced graphene oxide sheet layers;
the preparation method of the tin diselenide/tin oxide-rGO nano composite anode material comprises the following steps:
(1) dripping the tin source alcohol solution into the graphene oxide aqueous solution, uniformly mixing, centrifuging, washing a precipitate, and freeze-drying to obtain intermediate powder;
(2) adding the intermediate powder obtained in the step (1) into an anhydrous alcohol solution, uniformly stirring, performing ultrasonic dispersion, adding a selenium source and a reducing agent, uniformly stirring, placing in a closed reaction kettle, performing solvothermal reaction, cooling to room temperature along with a furnace, centrifuging, washing a precipitate, and drying to obtain a precursor;
(3) and (3) carrying out heat treatment on the precursor obtained in the step (2) in an inert atmosphere to obtain the tin diselenide/tin oxide-rGO nano composite anode material.
2. The tin diselenide/tin oxide-rGO nanocomposite negative electrode material of claim 1, wherein: the mass ratio of the tin diselenide to the tin oxide to the reduced graphene oxide is 3-10: 1-4: 1; the length and width of the flaky cubic tin diselenide/tin oxide composite material are 200-1200 nm, and the thickness of the flaky cubic tin diselenide/tin oxide composite material is 10-100 nm.
3. The tin diselenide/tin oxide-rGO nanocomposite anode material according to claim 1 or 2, characterized in that: in the step (1), the volume ratio of the tin source alcohol solution to the graphene oxide aqueous solution is 0.3-1.0: 1; the mass concentration of the tin source alcohol solution is 1.5-3.1 mg/mL; the mass concentration of the graphene oxide aqueous solution is 0.2-2.0 mg/mL; the dropping speed is 5-20 mL/min; the tin source is one or more of tin chloride, stannous chloride or stannous iodide; the alcoholic solution is one or more of methanol, ethanol or ethylene glycol.
4. The tin diselenide/tin oxide-rGO nanocomposite anode material according to claim 1 or 2, characterized in that: in the step (1), the preparation method of the graphene oxide aqueous solution comprises the following steps: adding graphene oxide into water, stirring, and then performing ultrasonic dispersion to obtain the graphene oxide; the mass volume ratio of the graphene oxide to the water is 0.2-2.0: 1; the stirring time is 20-40 min; the frequency of ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h; the washing is carried out by sequentially and alternately washing with water and ethanol for more than or equal to 3 times; the temperature of the freeze drying is-40 to-50 ℃, and the time is 24 to 72 hours.
5. The tin diselenide/tin oxide-rGO nanocomposite negative electrode material of claim 3, wherein: in the step (1), the preparation method of the graphene oxide aqueous solution comprises the following steps: adding graphene oxide into water, stirring, and then performing ultrasonic dispersion to obtain the graphene oxide; the mass volume ratio of the graphene oxide to the water is 0.2-2.0: 1; the stirring time is 20-40 min; the frequency of ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h; the washing is carried out by sequentially and alternately washing with water and ethanol for more than or equal to 3 times; the temperature of the freeze drying is-40 to-50 ℃, and the time is 24 to 72 hours.
6. The tin diselenide/tin oxide-rGO nanocomposite anode material according to claim 1 or 2, characterized in that: in the step (2), the mass-to-volume ratio of the intermediate powder to the absolute alcohol solution is 1: 200-600; the stirring time is 20-40 min; the frequency of ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h; the absolute alcohol solution is one or more of absolute alcohol, glycol or methanol; the mass ratio of the selenium source to the reducing agent to the graphene oxide in the step (1) is 1-4: 100-200: 1; the selenium source is one or more of elemental selenium, selenium dioxide or sodium selenate; the reducing agent is one or more of oleic acid, oleylamine, ethylenediamine, hydrazine hydrate or sodium borohydride; the temperature of the solvothermal reaction is 120-200 ℃, and the time is 8-24 h; the washing is carried out by sequentially and alternately washing with water and ethanol for more than or equal to 3 times; the drying temperature is 50-80 ℃, and the drying time is 12-48 h.
7. The tin diselenide/tin oxide-rGO nanocomposite negative electrode material of claim 3, wherein: in the step (2), the mass-to-volume ratio of the intermediate powder to the absolute alcohol solution is 1: 200-600; the stirring time is 20-40 min; the frequency of ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h; the absolute alcohol solution is one or more of absolute alcohol, glycol or methanol; the mass ratio of the selenium source to the reducing agent to the graphene oxide in the step (1) is 1-4: 100-200: 1; the selenium source is one or more of elemental selenium, selenium dioxide or sodium selenate; the reducing agent is one or more of oleic acid, oleylamine, ethylenediamine, hydrazine hydrate or sodium borohydride; the temperature of the solvothermal reaction is 120-200 ℃, and the time is 8-24 h; the washing is carried out by sequentially and alternately washing with water and ethanol for more than or equal to 3 times; the drying temperature is 50-80 ℃, and the drying time is 12-48 h.
8. The tin diselenide/tin oxide-rGO nanocomposite anode material of claim 4, wherein: in the step (2), the mass-to-volume ratio of the intermediate powder to the absolute alcohol solution is 1: 200-600; the stirring time is 20-40 min; the frequency of ultrasonic dispersion is 30-50 kHz, and the time is 1.5-2.5 h; the absolute alcohol solution is one or more of absolute alcohol, glycol or methanol; the mass ratio of the selenium source to the reducing agent to the graphene oxide in the step (1) is 1-4: 100-200: 1; the selenium source is one or more of elemental selenium, selenium dioxide or sodium selenate; the reducing agent is one or more of oleic acid, oleylamine, ethylenediamine, hydrazine hydrate or sodium borohydride; the temperature of the solvothermal reaction is 120-200 ℃, and the time is 8-24 h; the washing is carried out by sequentially and alternately washing with water and ethanol for more than or equal to 3 times; the drying temperature is 50-80 ℃, and the drying time is 12-48 h.
9. The tin diselenide/tin oxide-rGO nanocomposite anode material according to claim 1 or 2, characterized in that: in the step (3), the temperature of the heat treatment is 300-500 ℃, and the time is 0.5-2.0 h; the inert atmosphere is one or more of nitrogen, argon or helium.
10. The tin diselenide/tin oxide-rGO nanocomposite negative electrode material of claim 3, wherein: in the step (3), the temperature of the heat treatment is 300-500 ℃, and the time is 0.5-2.0 h; the inert atmosphere is one or more of nitrogen, argon or helium.
11. The tin diselenide/tin oxide-rGO nanocomposite anode material of claim 4, wherein: in the step (3), the temperature of the heat treatment is 300-500 ℃, and the time is 0.5-2.0 h; the inert atmosphere is one or more of nitrogen, argon or helium.
12. The tin diselenide/tin oxide-rGO nanocomposite negative electrode material of claim 6, wherein: in the step (3), the temperature of the heat treatment is 300-500 ℃, and the time is 0.5-2.0 h; the inert atmosphere is one or more of nitrogen, argon or helium.
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| CN113097484B (en) * | 2021-04-01 | 2023-04-28 | 陕西科技大学 | Carbon-coated sandwich-like structure SnSe/r-GO@C compound and preparation method and application thereof |
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