CN114597369A - Carbon-tin nano composite material and preparation method and application thereof - Google Patents
Carbon-tin nano composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon-tin nano composite material and a preparation method and application thereof, the invention utilizes a three-dimensional network structure formed by spiral carbon nanofibers to improve the conductivity of the composite material, the network gap of the structure provides a buffer space for the expansion of tin nanoparticles grafted on the surface of the fiber to inhibit the volume expansion effect of tin, the sol-gel method and the reduction reaction are utilized to generate the tin nanoparticles with small particle size and uniform distribution, and the tin nanoparticles are uniformly grafted on the surface of the fiber, the tin nanocrystallization reduces the volume expansion effect of tin, the cycle stability of the composite material is improved, a carbon coating layer is formed by a vapor deposition method, so that the tin nanoparticles are used as an intermediate layer to cooperate with HCNFS and the carbon coating layer to form a sandwich structure, the volume expansion effect of tin is effectively inhibited, the cycle stability and the capacity rate are improved, and under the current density of 200mA/g, the cycle time is 200 times, and the specific capacity can reach 503.9 mAh/g.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a carbon-tin nano composite material and a preparation method and application thereof.
Background
Emerging electric vehicles, portable devices, newly introduced space exploration devices, and modern military equipment are all unable to leave efficient and safe energy storage devices. The traditional lead-acid storage battery and nickel-metal hydride battery are difficult to meet the higher energy storage requirement of modernization, and the lithium ion secondary battery is a research hotspot because of large specific capacity, high voltage and long cycle life. The negative electrode material is one of the key elements determining the performance of the lithium ion battery, and accounts for about 30% of the battery cost.
After the Yoshio Idato reports that the Sn-based oxide is used as the negative electrode material of the lithium ion battery for the first time in 1997, the Sn-based negative electrode material attracts extensive attention and is one of the hot spots for researching novel high-specific-capacity non-carbon negative electrode materials at present. The tin has a lithium intercalation potential (0.3V) higher than the precipitation potential of metallic lithium, and can avoid the metallic lithium accumulation under high multiplying power; the problem of solvent co-intercalation does not exist in the charging and discharging processes; the bulk density is high (75.46mol/L), is close to the bulk density of metallic lithium (73.36mol/L), and the metallic Sn has higher theoretical capacity of 994mAh g-1. However, pure tin as a negative electrode material of a lithium ion battery has a great volume change in the alloying/dealloying process, and tin itself is a ductile material, and its macroscopic mechanical properties make it unable to withstand the stress generated thereby, so that the electrode is prone to cracking and crushing, which limits its commercialization to a great extent. Therefore, how to reduce and limit the volume expansion effect of tin, thereby improving the capacity retention rate and the cycle stability thereof is one of the problems to be solved in the prior art.
Disclosure of Invention
The carbon-tin nano composite material prepared by the method provided by the invention can effectively inhibit the volume expansion effect of tin, and has the advantages of high capacity retention rate and excellent cycle stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a carbon-tin nano composite material, which comprises the following steps:
(1) mixing a tin tetrachloride pentahydrate solution and the spiral carbon nanofiber dispersion liquid for hydrolysis reaction to obtain a tin dioxide/spiral carbon nanofiber composite material;
(2) carrying out reduction reaction on the stannic oxide/spiral carbon nanofiber composite material obtained in the step (1) to obtain a stannic oxide/spiral carbon nanofiber composite material;
(3) and (3) carrying out carbon coating on the surface of the tin/spiral carbon nanofiber composite material obtained in the step (2) by using a vapor deposition method to obtain the carbon-tin nanocomposite material.
Preferably, the mixing in the step (1) is to dropwise add a tin tetrachloride pentahydrate solution to the spiral nano carbon fiber dispersion liquid.
Preferably, the dropping speed is 0.3-1.8 mL/min.
Preferably, the temperature of the hydrolysis reaction in the step (1) is 50-140 ℃, and the time of the hydrolysis reaction is 2-5 h.
Preferably, the reduction reaction in the step (2) is carried out in an inert atmosphere, the temperature of the reduction reaction is 600-900 ℃, and the time of the reduction reaction is 3-7 h.
Preferably, the temperature rising mode of the reduction reaction in the step (2) is temperature programming, and the temperature programming rate is 3-7 ℃/min.
Preferably, the carbon source of the vapor deposition method in the step (3) is toluene, the carrier of the vapor deposition method is inert gas, and the flow rate of the inert gas is 40-300 mL/min.
Preferably, the temperature of carbon coating in the step (3) is 600-900 ℃, and the time of carbon coating is 0.5-3 h.
The invention also provides a carbon-tin nano composite material prepared by the preparation method in the technical scheme, which comprises the spiral carbon nanofibers, the tin nanoparticles grafted on the surfaces of the spiral carbon nanofibers, and a carbon coating layer coated on the surfaces of the spiral carbon nanofibers and the tin nanoparticles.
The invention also provides the application of the carbon-tin nano composite material in the technical scheme in battery materials.
The invention provides a preparation method of a carbon-tin nano composite material, which comprises the steps of firstly mixing tin tetrachloride pentahydrate and spiral nano carbon fiber HCNFS dispersion liquid for hydrolysis reaction, and hydrolyzing the tin tetrachloride pentahydrate to generate SnO2Nano particles are grafted on the surface of the spiral nano carbon fiber, namely, a sol-gel method is utilized to obtain the stannic oxide/spiral nano carbon fiber composite material (SnO)2/HCNFS composite material) and then carrying out reduction reaction to obtain SnO2Reducing the carbon-tin nano composite material into Sn, and then carrying out carbon coating by a vapor deposition method to finally obtain the carbon-tin nano composite material (C/Sn/HCNFS nano composite material). The invention adopts the spiral carbon nanofibers with special spiral structures as the matrix material, which can be intertwined into a stable three-dimensional network structure, the structure can improve the conductivity of the whole carbon-tin nano composite material, simultaneously, the network gap of the structure also provides a buffer space for the expansion of the tin nanoparticles grafted on the surface of the fiber, the volume expansion effect of tin can be effectively inhibited, spherical tin nanoparticles with small particle size and uniform distribution can be generated by synergistically utilizing a sol-gel method and a reduction reaction, and the generated tin nanoparticles are simultaneously promoted to be uniformly grafted and distributed on the surface of the spiral carbon nanofibers, the volume expansion effect of tin can be effectively reduced by the nanocrystallization of tin, so that the circulation stability of the composite material is obviously improved, and then, an outer carbon coating layer is formed by utilizing a vapor deposition method, so that the tin nanoparticles are used as an intermediate layer, cooperating with matrix materials HCNs and an outer carbon coating layer to form a sandwich structure, the volume expansion effect of tin can be further effectively inhibited, and the tin is prevented from being crushed due to excessive expansion, so that the circulation stability of the composite material is improvedAnd capacity rate of the composite material when used as a negative electrode material. Compared with the traditional method using stannic chloride, the method provided by the invention selects stannic chloride pentahydrate which has a stable crystallization state and is not easy to hydrolyze as a raw material, no pungent smell is generated, acid and alkali assistance is not required to be added, and meanwhile, the surface of the spiral carbon nanofiber is not required to be subjected to pre-oxidation treatment, so that the environmental pollution caused in the synthetic process is greatly reduced, the method is green and environment-friendly, for the spiral carbon nanofiber, the complex surface oxidation treatment in the traditional method is not required, the sol-gel method is adopted to uniformly load stannic nanoparticles on the surface of the spiral carbon fiber, the chemical vapor deposition method is used for carbon coating, the coating is more uniform, the thickness is controllable, and the process is simple. The results of the embodiment show that tin nanoparticles of the carbon-tin nano composite material prepared by the method are uniformly grafted and loaded on the surface of the spiral carbon nanofibers and used as a negative electrode material, the prepared button CR2032 type battery has the advantages that the cycle number is 200 times, the specific capacity can still reach 339.8-503.9 mAh/g under the atmospheric atmosphere of room temperature 25 ℃, the charging and discharging voltage range is 0.005-3V and the current density is 200mA/g, the capacity retention rate is high, the cycle stability is excellent, and the electrochemical performance is higher than that of comparative example 1 and comparative example 2.
Drawings
FIG. 1 is an SEM image of a carbon-tin nanocomposite prepared according to example 1 of the present invention;
FIG. 2 is an SEM photograph of a C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) composite material prepared in comparative example 1 of the present invention;
FIG. 3 is a comparative XRD chart of carbon-tin nanocomposites prepared with example 1 of the present invention, C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) composites prepared with comparative example 1, and carbon spiraled fibers HCNFS;
FIG. 4 is a graph showing the trend of specific capacity change within 200 cycles of the carbon-tin nanocomposite prepared in example 1 according to the present invention, the C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) composite prepared in comparative example 1, and the nano Sn powder in comparative example 2.
Detailed Description
The invention provides a preparation method of a carbon-tin nano composite material, which comprises the following steps:
(1) mixing a tin tetrachloride pentahydrate solution and the spiral carbon nanofiber dispersion liquid for hydrolysis reaction to obtain a tin dioxide/spiral carbon nanofiber composite material;
(2) carrying out reduction reaction on the stannic oxide/spiral carbon nanofiber composite material obtained in the step (1) to obtain a stannic oxide/spiral carbon nanofiber composite material;
(3) and (3) carrying out carbon coating on the surface of the tin/spiral carbon nanofiber composite material obtained in the step (2) by using a vapor deposition method to obtain the carbon-tin nanocomposite material.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
According to the invention, a stannic chloride pentahydrate solution and a spiral carbon nanofiber dispersion are mixed for hydrolysis reaction, so as to obtain the stannic oxide/spiral carbon nanofiber composite material.
In the invention, the concentration of the tin tetrachloride pentahydrate in the tin tetrachloride pentahydrate solution is preferably 0.002-0.05 g/mL, and more preferably 0.003-0.01 g/mL. The method selects stannic chloride pentahydrate which has a stable crystallization state and is not easy to hydrolyze as a raw material, and compared with the traditional method using stannic chloride, the method does not generate pungent smell, does not need to add acid-base assistance, and is green and environment-friendly. In the present invention, the method for preparing the tin tetrachloride pentahydrate solution preferably includes: mixing tin tetrachloride pentahydrate and water under the ultrasonic condition.
The power of the ultrasound is not particularly limited in the present invention, and the power conventional in the art can be used. In the invention, the time of the ultrasonic treatment is preferably 5-15 min, and more preferably 8-12 min.
In the present invention, the method for preparing the spiral filamentous nanocarbon solution preferably includes: the spiral nano carbon fiber and water are mixed under the ultrasonic condition and then are subjected to preheating treatment.
The power of the ultrasound is not particularly limited in the present invention, and the power conventional in the art can be used. In the invention, the time of the ultrasonic treatment is preferably 25-35 min, and more preferably 28-32 min.
In the invention, the temperature of the preheating treatment is preferably 50-140 ℃, and more preferably 60-120 ℃. The temperature of the preheating treatment is controlled within the range, so that the subsequent hydrolysis reaction is promoted.
In the present invention, the mass ratio of the tin tetrachloride pentahydrate in the tin tetrachloride pentahydrate solution to the helical carbon nanofibers in the helical carbon nanofiber dispersion is preferably (1 to 8): 1, more preferably (2-5): according to the invention, the mass ratio of the tin tetrachloride pentahydrate in the tin tetrachloride pentahydrate solution to the spiral carbon nanofibers in the spiral carbon nanofiber dispersion is controlled within the above range, so that the phenomenon that tin dioxide generated by subsequent hydrolysis reaction is agglomerated in the grafting process is avoided, and the volume expansion effect of tin is relieved.
In the present invention, the mixing is preferably performed by dropping a tin tetrachloride pentahydrate solution into the helical filamentous nanocarbon dispersion.
In the invention, the dripping speed is preferably 0.3-1.8 mL/min, and more preferably 0.5-1.5 mL/min. The method controls the dripping speed within the range, is favorable for controlling the hydrolysis reaction speed, promotes the hydrolysis reaction to be carried out more stably, avoids the phenomena of grafting and agglomeration caused by overhigh local reaction solution concentration due to overhigh dripping speed and overhigh integral hydrolysis reaction speed and energy consumption, and simultaneously avoids the tin nano-particles generated by the hydrolysis reaction to be uniformly grafted and distributed on the surface of the spiral nano carbon fiber.
In the invention, the temperature of the hydrolysis reaction is preferably 50-140 ℃, and more preferably 60-120 ℃. The temperature of the hydrolysis reaction is controlled within the range, so that the hydrolysis reaction is promoted to be carried out more stably, the phenomena that the reaction temperature is too low, the overall hydrolysis reaction rate is too low, energy is consumed, and the grafting agglomeration phenomenon can be caused by local violent reaction due to too high reaction temperature are avoided, so that the tin nano-particles generated by the hydrolysis reaction are uniformly grafted and distributed on the surface of the spiral nano carbon fiber.
In the invention, the time of the hydrolysis reaction is preferably 2-5 h, and more preferably 2.5-4 h. The method controls the time of the hydrolysis reaction within the range, is favorable for completely carrying out the hydrolysis reaction, avoids the condition that the grafting amount of the tin nanoparticles on the surface of the spiral carbon nanofibers cannot reach the expectation due to the over-short reaction time and incomplete reaction, reduces the performance of the prepared composite material, and saves the process time.
After the hydrolysis reaction is finished, the invention preferably carries out solid-liquid separation and drying on the products of the hydrolysis reaction in sequence to obtain the stannic oxide/spiral nano carbon fiber composite material.
In the present invention, the solid-liquid separation method is preferably vacuum filtration. In the invention, the drying temperature is preferably 60-90 ℃, and more preferably 70-85 ℃. In the invention, the drying time is preferably 8-14 h, and more preferably 10-12 h.
After the tin dioxide/spiral carbon nanofiber composite material is obtained, the tin dioxide/spiral carbon nanofiber composite material is subjected to reduction reaction to obtain the tin/spiral carbon nanofiber composite material.
In the present invention, the reduction reaction is preferably carried out in an inert atmosphere. In the present invention, the reduction reaction is preferably carried out in a corundum boat. In the invention, the temperature of the reduction reaction is preferably 600-900 ℃, and more preferably 700-850 ℃. In the invention, the time of the reduction reaction is preferably 3-7 h, and more preferably 4-6 h. The invention controls the temperature and time of the reduction reaction within the range, and is beneficial to completely remove SnO from carbon in the spiral carbon nanofibers2The nano particles are reduced into tin nano particles, so that the SnO with too low temperature of reduction reaction is avoided2Can not be completely reduced, and simultaneously avoids energy waste caused by overhigh temperature.
In the present invention, the temperature of the reduction reaction is preferably raised in a programmed manner. In the invention, the rate of the programmed temperature rise is preferably 3-7 ℃/min, and more preferably 4-6 ℃/min. The invention controls the rate of temperature programming within the range to control the rate of reduction reaction and promote the carbon in the spiral carbon nanofibers to more completely convert SnO2The nanoparticles are alsoThe tin nano-particles are originally used, and energy waste caused by too small temperature programming rate and too long temperature rising time is avoided.
After the tin/spiral carbon nanofiber composite material is obtained, the carbon coating is carried out on the surface of the tin/spiral carbon nanofiber composite material by utilizing a vapor deposition method, so as to obtain the carbon-tin nanocomposite material.
In the present invention, the carbon source for the vapor deposition method is preferably toluene. In the present invention, the carrier for the vapor deposition method is preferably an inert gas. In the present invention, the flow rate of the inert gas is preferably 40 to 300mL/min, and more preferably 50 to 200 mL/min. The method controls the flow of the inert gas within the range, avoids the phenomenon that the flow of the inert gas is too large, and the content of tin is reduced due to the fact that the carbon coating layer deposited on the surface of the tin nano-particles is too thick as the toluene volatile gas driven by the inert gas is too large, so that the capacity of the composite material is reduced, and simultaneously avoids the phenomenon that the flow of the inert gas is too small, the toluene volatile gas driven by the inert gas is too small, and the carbon coating layer deposited on the surface of the tin nano-particles is too thin, so that the volume expansion effect of tin cannot be effectively inhibited by the carbon coating layer structure.
In the invention, the temperature of the carbon coating is preferably 600-900 ℃, and more preferably 700-850 ℃. In the invention, the carbon coating time is preferably 0.5-3 h, and more preferably 1-2.5 h. The invention controls the temperature and time of carbon coating in the range, is beneficial to controlling the coating thickness of the carbon layer and saves energy sources.
The preparation method of the carbon-tin nano composite material provided by the invention has the advantages of wide raw material source, mild conditions, simple operation and suitability for large-scale production, compared with the traditional method using stannic chloride, the method provided by the invention selects stannic chloride pentahydrate which has more stable crystallization state and is not easy to hydrolyze as raw material, does not generate pungent smell, does not need to add acid-base assistance, meanwhile, the surface of the spiral carbon nanofiber does not need to be pre-oxidized, so that the environmental pollution caused in the synthesis process is greatly reduced, the method is green and environment-friendly, for the spiral carbon nanofibers, complex surface oxidation treatment in the traditional method is not needed, tin nanoparticles can be uniformly loaded on the surfaces of the spiral carbon fibers by adopting a sol-gel method, and carbon coating is carried out by utilizing a chemical vapor deposition method, so that the coating is more uniform, the thickness is controllable, and the process is simple.
The invention also provides a carbon-tin nano composite material prepared by the preparation method in the technical scheme, which comprises the spiral carbon nanofibers, the tin nanoparticles grafted on the surfaces of the spiral carbon nanofibers, and a carbon coating layer coated on the surfaces of the spiral carbon nanofibers and the tin nanoparticles.
The carbon-tin nano composite material prepared by the method provided by the invention can effectively inhibit the volume expansion effect of tin, and has high capacity retention rate and excellent cycle stability.
The invention also provides the application of the carbon-tin nano composite material in the technical scheme in battery materials.
The carbon-tin nano composite material prepared by the method provided by the invention is used as a negative electrode material, and the prepared battery has high capacity retention rate and excellent cycle stability.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation method of carbon-tin nano composite material
(1) Dropwise adding a stannic chloride pentahydrate solution into the spiral carbon nanofiber dispersion liquid at the rate of 0.5mL/min, carrying out hydrolysis reaction at 80 ℃ for 3 hours after dropwise adding is finished, carrying out vacuum filtration on a hydrolysis reaction product, and drying at 80 ℃ for 12 hours to obtain a stannic oxide/spiral carbon nanofiber composite material; the mass ratio of the tin tetrachloride pentahydrate in the tin tetrachloride pentahydrate solution to the spiral carbon nanofibers in the spiral carbon nanofiber dispersion is 3: 1;
the preparation method of the tin tetrachloride pentahydrate solution comprises the following steps: weighing 0.3g of stannic chloride pentahydrate in a 50mL beaker at room temperature, weighing 50mL of deionized water, and ultrasonically mixing the deionized water and the stannic chloride pentahydrate for 10 min;
the preparation method of the spiral carbon nanofiber dispersion liquid comprises the following steps: weighing 0.1g of spiral carbon nanofiber, putting the spiral carbon nanofiber into a 100mL beaker, adding 50mL of deionized water, performing ultrasonic mixing for 30min, pouring the mixture into a 250mL flask, and performing preheating treatment by stirring, wherein the temperature of the preheating treatment is 80 ℃;
(2) loading the tin dioxide/spiral carbon nanofiber composite material obtained in the step (1) into a corundum boat, placing the corundum boat in a tubular furnace, carrying out programmed temperature rise to 700 ℃ at the speed of 5 ℃/min under inert gas, and carrying out reduction reaction for 4 hours to obtain the tin/spiral carbon nanofiber composite material;
(3) and (2) placing 150mL of toluene in a gas washing bottle, taking inert gas as a carrier, controlling the flow of the inert gas to be 50mL/min, performing carbon coating on the surface of the tin/spiral carbon nanofiber composite material obtained in the step (2) at 700 ℃ for 1h by using a vapor deposition method, and naturally cooling to room temperature to obtain the carbon-tin nanocomposite material (C/Sn/HCNFS composite material) named as C/Sn/HCNFS-0.1 (tin tetrachloride pentahydrate).
Fig. 1 is an SEM image of the carbon-tin nanocomposite prepared in example 1, and as can be seen from fig. 1, in example 1, tin tetrachloride pentahydrate containing crystal water itself is used as a raw material, and a hydrolysis reaction is performed mildly, so that the generated tin dioxide nanoparticles can be uniformly grafted on the surface of the spiral carbon fiber, which is beneficial to uniform grafting of the tin nanoparticles on the surface of the spiral carbon fiber in the carbon-tin nanocomposite finally prepared in example 1.
Application example 1
Uniformly mixing the C/Sn/HCNFS composite material prepared in the example 1, CMC and conductive carbon black (SuperP) according to the ratio of 8:1:1, dissolving the mixture in deionized water to prepare slurry, uniformly coating the slurry on the surface of a copper foil current collector to prepare a working electrode, and then putting the working electrode into a vacuum drying oven at 80 ℃ to dry for 12 hours to obtain a negative electrode piece; using metal lithium sheet as reference electrode, 1M LiPF6The mixed solution of/EC + DEC + DMC (volume ratio 1:1:1) is used as electrolyte, Celgard 2400 polypropylene microporous membrane is used as diaphragm, and the oxygen content in water is smallAssembling a button type CR2032 battery in a glove box filled with argon gas at 0.1 PPm;
and (2) performing constant current charge and discharge test on the button CR2032 battery obtained by the assembly by adopting a CT-4000 battery tester of New Wille electronics Limited, Shenzhen, under the test conditions: the cycle times are 200 times under the atmospheric atmosphere at the room temperature of 25 ℃, the charging and discharging voltage range is 0.005-3V and the current density of 200 mA/g.
Example 2
Preparing a carbon-tin nano composite material named as C/Sn/HCNFS-0.13 according to the method of the embodiment 1;
in contrast to example 1, 0.4g of tin tetrachloride pentahydrate was weighed in preparing the tin tetrachloride pentahydrate solution in the step (1).
Application example 2
The carbon-tin nanocomposite prepared in example 2 was used as a raw material to prepare a button CR2032 type battery by the method of application example 1, and the button CR2032 type battery was subjected to constant current charge and discharge test using the same tester and test conditions, and the specific results are shown in table 1.
Example 3
Preparing a carbon-tin nano composite material named C/Sn/HCNFS-0.16 according to the method of the embodiment 1;
in contrast to example 1, 0.5g of tin tetrachloride pentahydrate was weighed in preparing the tin tetrachloride pentahydrate solution in the step (1).
Application example 3
The carbon-tin nanocomposite prepared in example 3 was used as a raw material to prepare a button CR2032 type battery by the method of application example 1, and the button CR2032 type battery was subjected to constant current charge and discharge test using the same tester and test conditions, and the specific results are shown in table 1.
Comparative example 1
(1) Weighing 2g of HCl and 0.22g of stannic chloride in a 50mL beaker at room temperature, adding 50mL of deionized water, and carrying out ultrasonic treatment for 10min to uniformly mix to obtain a mixed solution;
(2) weighing 0.1g of spiral carbon nanofiber and 0.6g of NaOH, putting the spiral carbon nanofiber and the NaOH into a 100mL beaker, adding 50mL of deionized water, carrying out ultrasonic treatment for 30min, pouring the mixture into a 250mL flask, and preheating for 5min under the conditions of stirring and 80 ℃ to obtain the spiral carbon nanofiber dispersion liquid.
(3) Dropwise adding the mixed solution obtained in the step (1) into the spiral carbon nanofiber dispersion liquid obtained in the step (2), wherein the titration speed is 0.5mL/min, reacting for 4 hours at 80 ℃ after titration is finished, filtering the obtained product, washing and drying to obtain the Sn/HCNs composite material;
(4) and (3) carrying out carbon coating on the composite material obtained in the step (3) by adopting the same method as the embodiment 1 to obtain the C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) composite material.
Comparative example 2
Nano Sn powder with particle size of 30nm
The C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) composite material prepared in the comparative example 1 and the nano Sn powder in the comparative example 2 are used as raw materials to prepare the button CR2032 type battery by the method of the application example 1, the button CR2032 type battery is subjected to constant-current charge and discharge tests by the same tester and test conditions, and specific results are shown in Table 1.
FIG. 2 is a SEM image of a C/Sn/HCNFS-0.1 (anhydrous stannic chloride) composite material prepared in comparative example 1, and it can be seen from FIG. 2 that in the comparative example, stannic chloride is used as a raw material, and due to the influence of alkaline environment (the anhydrous stannic chloride is grafted under alkaline condition in comparative example 1, because the spiral carbon nanofibers are mixed with sodium hydroxide in advance, and the solution prepared by mixing anhydrous stannic chloride with hydrochloric acid is dripped into the spiral carbon system to be neutralized by acid, so that the alkali environment is adopted), hydrolysis is more severe, so that the agglomeration phenomenon of stannic nanoparticles is serious, and the stannic nanoparticles cannot be uniformly loaded on the surface of the spiral carbon nanofibers.
FIG. 3 is a comparative XRD diagram of the carbon-tin nanocomposite prepared in example 1, C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) prepared in comparative example 1 and spiral carbon fibers HCNFS, and it can be seen from FIG. 3 that the carbon-tin nanocomposite prepared in example 1 contains the main characteristic peaks of tin in XRD, which shows that the carbon-tin nanocomposite prepared in example 1 has been successfully prepared.
FIG. 4 is a graph showing the trend of specific capacity change within 200 cycles of the carbon-tin nanocomposite prepared in example 1, the C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) prepared in comparative example 1, and the nano Sn powder in comparative example 2.
TABLE 1 carbon-tin nanocomposite prepared in example 1, C/Sn/HCNFS-0.1 (anhydrous tin tetrachloride) prepared in comparative example 1, and specific capacity of nano Sn powder in comparative example 2 within 200 cycles
As can be seen from table 1 and fig. 4, the button CR2032 type battery prepared by using the carbon-tin nanocomposite prepared in example 1 as the negative electrode material has a specific capacity of 503.9mAh/g, a high capacity retention rate, excellent cycle stability, and electrochemical performance much higher than those of comparative example 1 and comparative example 2, under the atmospheric atmosphere at 25 ℃ and at a charging/discharging voltage range of 0.005-3V and a current density of 200mA/g, and a cycle number of 200 cycles.
In conclusion, in the carbon-tin nano composite material prepared by the method, tin nano particles are uniformly grafted and loaded on the surface of the spiral carbon nano-fibers and used as a negative electrode material, and the prepared button-type CR2032 battery has the advantages that the specific capacity can still reach 503.9mAh/g, the capacity retention rate is high, the cycling frequency is 200 times under the atmospheric atmosphere at the room temperature of 25 ℃, the charging and discharging voltage range is 0.005-3V and the current density of 200mA/g, and the electrochemical performance is higher than that of the comparative examples 1 and 2. The invention adopts the spiral carbon nanofibers with special spiral structures as the matrix material, the spiral carbon nanofibers can be interlaced into a stable three-dimensional network structure, the structure can improve the conductivity of the whole carbon-tin nano composite material, simultaneously, the network gap of the structure also provides a buffer space for the expansion of the tin nanoparticles grafted on the surface of the fiber, the volume expansion effect of tin can be effectively inhibited, spherical tin nanoparticles with small particle size and uniform distribution can be generated by synergistically utilizing a sol-gel method and a carbothermic reduction reaction, and the generated tin nanoparticles are uniformly grafted and distributed on the surface of the spiral carbon nanofibers, the volume expansion effect of tin can be effectively reduced by the nanocrystallization of tin, so the circulation stability of the composite material is obviously improved, and then, a carbon coating layer on the outer layer is formed by utilizing a vapor deposition method, so that the tin nanoparticles are used as the middle layer, the composite material can be used for forming a sandwich structure by cooperating with matrix materials HCNFs and an outer carbon coating layer, so that the volume expansion effect of tin can be further effectively inhibited, and the tin can be prevented from being broken due to excessive expansion, thereby improving the cycle stability of the composite material and the capacity rate of the composite material when the composite material is used as a negative electrode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon-tin nano composite material comprises the following steps:
(1) mixing a tin tetrachloride pentahydrate solution and the spiral carbon nanofiber dispersion liquid for hydrolysis reaction to obtain a tin dioxide/spiral carbon nanofiber composite material;
(2) carrying out reduction reaction on the stannic oxide/spiral carbon nanofiber composite material obtained in the step (1) to obtain a stannic oxide/spiral carbon nanofiber composite material;
(3) and (3) carrying out carbon coating on the surface of the tin/spiral carbon nanofiber composite material obtained in the step (2) by using a vapor deposition method to obtain the carbon-tin nanocomposite material.
2. The production method according to claim 1, wherein the mixing in the step (1) is dropwise addition of a tin tetrachloride pentahydrate solution to the spiral filamentous nanocarbon dispersion.
3. The method according to claim 2, wherein the dropping is performed at a rate of 0.3 to 1.8 mL/min.
4. The preparation method according to claim 1, wherein the temperature of the hydrolysis reaction in the step (1) is 50-140 ℃, and the time of the hydrolysis reaction is 2-5 h.
5. The preparation method according to claim 1, wherein the reduction reaction in the step (2) is carried out in an inert atmosphere, the temperature of the reduction reaction is 600-900 ℃, and the time of the reduction reaction is 3-7 h.
6. The preparation method according to claim 1 or 5, wherein the temperature rise manner of the reduction reaction in the step (2) is temperature programming, and the temperature programming rate is 3-7 ℃/min.
7. The method according to claim 1, wherein the carbon source for the vapor deposition in step (3) is toluene, the carrier for the vapor deposition is an inert gas, and the flow rate of the inert gas is 40 to 300 mL/min.
8. The preparation method according to claim 1, wherein the temperature of the carbon coating in the step (3) is 600 to 900 ℃ and the time of the carbon coating is 0.5 to 3 hours.
9. The carbon-tin nanocomposite material prepared by the preparation method of any one of claims 1 to 8, which comprises spiral carbon nanofibers, tin nanoparticles grafted on the surfaces of the spiral carbon nanofibers, and a carbon coating layer coated on the surfaces of the spiral carbon nanofibers and the tin nanoparticles.
10. Use of the carbon tin nanocomposite material according to claim 9 in a battery material.
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