CN109950480B - Preparation method of carbon-coated tin sulfide nanobelt of lithium ion battery cathode material - Google Patents
Preparation method of carbon-coated tin sulfide nanobelt of lithium ion battery cathode material Download PDFInfo
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- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002127 nanobelt Substances 0.000 title claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010406 cathode material Substances 0.000 title claims description 6
- 239000000243 solution Substances 0.000 claims abstract description 27
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007983 Tris buffer Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229920001690 polydopamine Polymers 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
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- 238000007605 air drying Methods 0.000 description 5
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- 239000006230 acetylene black Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- -1 transition metal sulfides Chemical class 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002074 nanoribbon Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a carbon-coated tin sulfide nanobelt of a negative electrode material of a lithium ion battery, which comprises the following preparation processes: preparing tin sulfide nanobelts; adding tin sulfide nano-belts into a tris buffer solution, and performing ultrasonic treatment to obtain a mixed solution; adding dopamine into the mixed solution, and stirring at room temperature for reaction; filtering, washing and drying the reaction product to obtain a polydopamine coated tin sulfide nanobelt; calcining the polydopamine coated tin sulfide nanobelt under the protection of inert atmosphere, and cooling to room temperature to obtain the carbon coated tin sulfide nanobelt. According to the method, the tin sulfide nanobelt is prepared by using a hydrothermal method, dopamine is used as a carbon source, a complex reaction process is not needed under proper temperature and pH, almost self-polymerization can be carried out on the surface of any object to generate a continuous high-strength polydopamine thin layer, the coating process is simple, and an ideal carbon layer can be formed after high-temperature carbonization.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a preparation method of a carbon-coated tin sulfide nanobelt of a lithium ion battery cathode material.
Background
The lithium ion battery has the characteristics of high energy density, long service life, high voltage, small self-discharge, small pollution and the like, and is widely used in mobile phones, digital cameras, notebooks and other portable equipment. Compared with materials such as traditional graphite (372 mAh/g) and the like, transition metal sulfides such as FeS, coS, niS, cuS and the like have higher theoretical capacity and are considered to be ideal negative electrode material substitutes for lithium ion batteries. The tin sulfide has the characteristics of low price, rich sources and high theoretical capacity (780 mAh/g), and has higher conductivity (120S cm), so that the tin sulfide has better rate capability, and meanwhile, the thermal effect in the charge and discharge process can be effectively reduced. However, snS, when used in a lithium ion battery, is liable to cause volume expansion to cause the battery to be destroyed or the capacity to be lowered. To overcome the above drawbacks, 3D nanoflower, 3D porous SnS, nanospheres, core-shell structures, nanoplatelets, nanorods, nanoribbons, and the like, of nanostructures are widely used to slow down their volume expansion. Among the above nanostructures, 1D SnS tends to exhibit better physical or chemical properties, but the 1D structure is still insufficient to eliminate the negative effects of volume expansion. And a porous carbon layer with good conductivity is wrapped on the surface of the tin sulfide, so that the volume expansion of the tin sulfide can be effectively restrained, and the electrochemical performance of the raw material is improved. Generally, graphene and carbon nanotubes are the most common carbon sources for carbon coating, but the material cost is high; while biomass carbon sources such as glucose, chitosan, sodium alginate, cellulose equivalents are relatively inexpensive, coating procedures are relatively complex.
Disclosure of Invention
Based on the defects of low specific capacity, low volume expansion, poor cycle performance, unsatisfactory multiplying power performance and the like existing in the prior graphite carbon material and transition metal sulfide material when the graphite carbon material and the transition metal sulfide material are used as the lithium ion battery anode material, the invention provides a preparation method of the carbon-coated tin sulfide nano-belt lithium ion battery anode material. The capacity of the battery anode material prepared by the method is far higher than that of a commercial carbon material, and the carbon layer can effectively inhibit volume expansion of tin sulfide in the charge and discharge process, and meanwhile, the conductivity of the material can be improved, so that the battery anode material has excellent cycle performance and rate capability.
A preparation method of a carbon-coated tin sulfide nanobelt of a lithium ion battery cathode material comprises the following steps:
1) Preparing tin sulfide nanobelts;
2) Adding tin sulfide nano-belts into Tris buffer solution, and performing ultrasonic treatment to obtain mixed solution;
3) Adding dopamine into the mixed solution, and stirring at room temperature for reaction;
4) Filtering, washing and drying the reaction product obtained in the step 3) to obtain a polydopamine coated tin sulfide nanobelt;
5) Calcining the polydopamine coated tin sulfide nanobelt under the protection of inert atmosphere, and cooling to room temperature to obtain the carbon coated tin sulfide nanobelt.
Further, the preparation method of the tin sulfide nanobelt in the step (1) comprises the following steps: firstly, adding 0.1-10g of urea, 0.1-10g of thioacetamide and 0.1-10g of stannous chloride dihydrate into 10-100mL of deionized water, and stirring to prepare a uniform solution; and transferring the solution into a hydrothermal kettle for hydrothermal reaction, cooling the reactant to room temperature, washing the reactant with deionized water and ethanol in sequence, and drying to obtain the tin sulfide nanobelt.
Here, the stirring is magnetic stirring or mechanical stirring for 30min.
Preferably, the hydrothermal temperature in the step 2) is 100-200 ℃, the hydrothermal time is 1-24h, and the cooling is natural cooling. The washing liquid is deionized water and absolute ethyl alcohol, and the washing times are 3 times respectively.
Further, the hydrothermal reaction is to heat the sealed hydrothermal kettle in a blast drying oven to 100-200 ℃ for 1-24h.
Further scheme, the width of the tin sulfide nano belt is 50-500nm, and the length is 1-10 mu m.
Further, the pH value of the tris buffer solution in the step (2) is 5-10.
Further, in the step (3), the adding mass of the dopamine accounts for 1-4mg/mL of the volume ratio of the mixed solution, and the stirring reaction time is 1-48h.
Further, in the step (5), the inert gas is one of nitrogen, helium, neon and argon; the calcination is carried out by heating to 100-800 ℃ at a heating rate of 1-10 ℃/min and a calcination time of 1-10h.
Further, the thickness of the carbon coating layer in the carbon-coated tin sulfide nano belt is 10-30nm.
The invention utilizes a hydrothermal method to prepare a tin sulfide nano-belt, which is characterized in that urea, thioacetamide and stannous sulfide dihydrate with a certain proportion are added into water, and the mixture is fully stirred and dissolved and then added into a hydrothermal kettle for hydrothermal reaction. Hydrothermal reactionHS generated during the reaction process - Sn ionized from ions and stannous chloride 2+ Direct formation of SnS and H by ions 2 S gas. H with pungent smell in hydrothermal kettle after hydrothermal reaction is finished 2 The S gas confirms the reaction, and the relevant reaction equation is as follows:
Sn 2+ +2HS - →SnS+H 2 S↑
in the reaction process, a large amount of SnS crystal nucleus grows into SnS nano particles, because of Sn 2+ And HS (high speed) - The dissolution and growth rates of ions in different directions are different, so that the growth rate of SnS nano particles in one direction is far greater than that in the other two directions, and finally a thin and long nano belt structure is formed.
Compared with the prior art, the invention has the advantages that:
according to the method, the tin sulfide nanobelt is prepared by using a hydrothermal method, dopamine is used as a carbon source, a complex reaction process is not needed under proper temperature and pH, almost self-polymerization can be carried out on the surface of any object to generate a continuous high-strength polydopamine thin layer, the coating process is simple, and an ideal carbon layer can be formed after high-temperature carbonization.
And coating a uniform polydopamine coating layer on the surface of the nano-belt by using the self-polymerization behavior of dopamine as a carbon source, and carbonizing at a high temperature to obtain the carbon-coated tin sulfide nano-belt. The rate performance and the cycle performance of the modified active material are greatly improved due to the conduction and the protection of the carbon layer. The material can still maintain the specific discharge capacity of 1260.29mAh/g after 220 charge and discharge cycles at the current density of 125mA/g, and the cycle life is far longer than that of uncoated tin sulfide.
The preparation method is simple, does not need expensive chemical reagents, and has low cost; high temperature is not needed, the method is clean and environment-friendly, the operation is safe, and the energy is saved.
The carbon-coated tin sulfide nanobelt prepared by the method is used as an active material, is uniformly mixed with acetylene black and SBR/CMC, is added with a proper amount of water to prepare slurry, is uniformly coated on copper foil, and is dried to prepare the electrode slice. The half-cell is assembled in a glove box and tested for electrochemical performance, and the capacity of the half-cell is far higher than that of a common cell, and the half-cell has good rate capability and long cycle life.
Drawings
Fig. 1 is a cycle performance curve of a battery made of the negative electrode material prepared in comparative example 1.
Fig. 2 is a scanning electron microscope image and a transmission electron microscope image of the tin sulfide nanobelt prepared in comparative example 1.
Fig. 3 is a cycle performance curve of a battery made of the negative electrode material prepared in example 1.
FIG. 4 is a scanning electron microscope and a transmission electron microscope of the carbon-coated tin sulfide nanobelt prepared in example 1.
Fig. 5 is a graph showing the rate performance of batteries made of the negative electrode materials of comparative example 1 and example 2.
Detailed Description
Comparative example 1
1) 1.05g of urea, 1.32g of thioacetamide and 0.24g of stannous chloride dihydrate were accurately weighed and added to 70mL of deionized water, and stirred for 30min to prepare a uniform solution.
2) The solution was transferred to a 100mL hydrothermal kettle, sealed and placed in a forced air drying oven, and hydrothermal was performed at 170℃for 10 hours. And (3) cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and drying at 70 ℃ to obtain the tin sulfide nanobelt.
3) Mixing the obtained active material with acetylene black and SBR/CMC according to the mass ratio of 8:1:1, fully grinding, adding a certain amount of water to prepare slurry, uniformly coating the slurry on copper foil by an automatic film coating machine, and drying in vacuum at 120 ℃ for 12 hours. After drying, the copper foil was cut into 1.2cm diameter wafers.
4) 1M LiPF using copper foil as working electrode 6 EC: dec=1:1 (v: v) solution as electrolyte, lithium sheet as counter electrode, and assembled into button half cell in glove box. The electrochemical performance of the cells was tested using the new wiry cell test system, CHI660E electrochemical workstation.
As shown in FIG. 1, the cycle performance curve of the battery is that the initial discharge specific capacity of the battery is up to 1215mAh/g, which shows that the tin sulfide has high energy density. However, the specific discharge capacity of the battery is reduced to below 300mAh/g after 47 charge and discharge cycles. This is because the volume expansion generated by tin sulfide during the cycle causes the electrode material to fall off, thereby gradually decreasing the discharge capacity.
Fig. 2 is a scanning electron microscope (upper) and a projection electron microscope (lower) of the tin sulfide nanobelt, from which it can be seen that the shape of the tin sulfide nanobelt is a distinct stripe-shaped structure.
Example 1:
1) 1.05g of urea, 1.32g of thioacetamide and 0.24g of stannous chloride dihydrate were accurately weighed and added to 70mL of deionized water, and stirred for 30min to prepare a uniform solution.
2) The solution was transferred to a 100mL hydrothermal kettle, sealed and placed in a forced air drying oven, and hydrothermal was conducted at 170℃for 10 hours. And (3) cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and drying at 70 ℃ to obtain the tin sulfide nanobelt.
3) 264mg of tin sulfide nanobelt is taken and added into 50mL of Tris buffer solution (pH to 8.5), after 30min of ultrasound, 50mg of dopamine is added and stirred at 30 ℃ for reaction 24h. After the reaction is finished, deionized water is used for washing for 3 times, and the mixture is dried at 50 ℃ until the mixture is completely dried.
4) Under the nitrogen atmosphere, heating to 150 ℃ at the speed of 3 ℃/min, keeping the temperature for 1h, heating to 500 ℃ at the heating speed of 2 ℃/min, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the carbon-coated tin sulfide nanobelt.
5) Mixing the obtained carbon-coated tin sulfide nanobelt serving as a negative electrode active material with acetylene black and SBR/CMC according to the mass ratio of 8:1:1, fully grinding, adding a certain amount of water to prepare slurry, uniformly coating the slurry on a copper foil by using an automatic film coater, and drying in vacuum for 12 hours at 120 ℃. After drying, the copper foil was cut into 1.2cm diameter wafers. 1M LiPF using copper foil as working electrode 6 EC: dec=1:1 (v: v) solution as electrolyte, lithium sheet as counter electrode, and assembled into button half cell in glove box. The electrochemical performance of the cells was tested using the new wiry cell test system, CHI660E electrochemical workstation.
The cycle performance curve of the assembled battery of this example 1 is shown in fig. 3. As can be seen from fig. 3, the initial specific discharge capacity of the battery is 920.7mAh/g, and the specific discharge capacity of the composite material is slightly lower than that of pure tin sulfide due to the presence of carbon element. In the battery cycle process, the discharge capacity is gradually increased due to the activation of the electrode material, and finally the battery still has a discharge specific capacity of 1260.29mAh/g after 220 cycles. This is because the carbon shell protects the internal tin sulfide from damage, greatly enhancing the cycle life of the battery.
Fig. 4 is a scanning electron microscope (upper) and a transmission electron microscope (lower) of the carbon-coated tin sulfide nanoribbon prepared in example 1. Comparing it with fig. 2, it can be clearly seen that the smooth tin sulfide nanobelt is coated with a relatively rough carbon layer having a thickness of about 21nm.
Example 2:
1) 1.05g of urea, 1.32g of thioacetamide and 0.24g of stannous chloride dihydrate were accurately weighed and added to 70mL of deionized water, and stirred for 30min to prepare a uniform solution.
2) The solution was transferred to a 100mL hydrothermal kettle, sealed and placed in a forced air drying oven, and hydrothermal was conducted at 170℃for 10 hours. And (3) cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and drying at 70 ℃ to obtain the tin sulfide nanobelt.
3) 264mg of tin sulfide nanobelt is taken and added into 50mL of Tris buffer solution (pH to 8.5), after 30min of ultrasound, 100mg of dopamine is added and stirred at 30 ℃ for reaction for 24h. After the reaction is finished, deionized water is used for washing for 3 times, and the mixture is dried at 50 ℃ until the mixture is completely dried.
4) Under the nitrogen atmosphere, heating to 150 ℃ at the speed of 3 ℃/min, keeping the temperature for 1h, heating to 500 ℃ at the heating speed of 2 ℃/min, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the carbon-coated tin sulfide nanobelt.
5) Mixing the obtained carbon-coated tin sulfide nanobelt serving as a negative electrode active material with acetylene black and SBR/CMC according to the mass ratio of 8:1:1, fully grinding, adding a certain amount of water to prepare slurry, uniformly coating the slurry on a copper foil by an automatic film coater, and vacuum drying at 120 DEG CAnd 12h. After drying, the copper foil was cut into 1.2cm diameter wafers. 1M LiPF using copper foil as working electrode 6 EC: dec=1:1 (v: v) solution as electrolyte, lithium sheet as counter electrode, and assembled into button half cell in glove box. The electrochemical performance of the cells was tested using the new wiry cell test system, CHI660E electrochemical workstation.
Fig. 5 is a graph showing the rate performance of the assembled batteries of comparative example 1 and example 2. As can be seen from the graph, the uncoated tin sulfide nanobelt has poor rate capability, and when the current density is increased to 5A/g, the specific capacity is reduced to below 100 mAh/g. The carbon-coated tin sulfide nanobelt has excellent multiplying power performance, and when the current density is increased to 5A/g, the material can still exert the capacity of 500mAh/g, and when the current density is fallen to 0.2A/g, the specific discharge capacity can be immediately increased.
Example 3:
1) 1.05g of urea, 1.32g of thioacetamide and 0.24g of stannous chloride dihydrate are accurately weighed, added into 70mL deionized water and stirred for 30min to prepare a uniform solution.
2) The solution was transferred to a 100mL hydrothermal kettle, sealed and placed in a forced air drying oven, and hydrothermal was conducted at 170℃for 10 hours. And (3) cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and drying at 70 ℃ to obtain the tin sulfide nanobelt.
3) 264mg of tin sulfide nanobelt is taken and added into 50mL of Tris buffer solution (pH to 8.5), after 30min of ultrasound, 50mg of dopamine is added, and stirring reaction is carried out for 48h at 30 ℃. After the reaction is finished, deionized water is used for washing for 3 times, and the mixture is dried at 50 ℃ until the mixture is completely dried.
4) Under the nitrogen atmosphere, heating to 150 ℃ at the speed of 3 ℃/min, keeping the temperature for 1h, heating to 500 ℃ at the heating speed of 2 ℃/min, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the carbon-coated tin sulfide nanobelt.
Example 4:
1) 1.05g of urea, 1.32g of thioacetamide and 0.24g of stannous chloride dihydrate were accurately weighed and added to 70mL of deionized water, and stirred for 30min to prepare a uniform solution.
2) The solution was transferred to a 100mL hydrothermal kettle, sealed and placed in a forced air drying oven, and hydrothermal was conducted at 170℃for 10 hours. And (3) cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and drying at 70 ℃ to obtain the tin sulfide nanobelt.
3) 264mg of tin sulfide nanobelt is taken and added into 50mL of Tris buffer solution (pH to 8.5), after 30min of ultrasound, 50mg of dopamine is added and stirred at 30 ℃ for reaction for 24h. After the reaction is finished, deionized water is used for washing for 3 times, and the mixture is dried at 50 ℃ until the mixture is completely dried.
4) And in a nitrogen atmosphere, heating to 500 ℃ at a speed of 5 ℃/min, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain the carbon-coated tin sulfide nanobelt.
The foregoing description of the preferred embodiments of the present invention should not be construed as limiting the invention to the above embodiments, but it should be understood that all technical solutions and modifications according to the present invention are included in the scope of the present invention.
Claims (6)
1. A preparation method of a carbon-coated tin sulfide nanobelt of a lithium ion battery cathode material is characterized by comprising the following steps: the preparation process comprises the following steps:
1) Preparing a tin sulfide nano belt, wherein the width of the tin sulfide nano belt is 50-500nm, and the length of the tin sulfide nano belt is 1-10 mu m;
2) Adding tin sulfide nano-belts into a tris buffer solution, and performing ultrasonic treatment to obtain a mixed solution;
3) Adding dopamine into the mixed solution, and stirring at room temperature for reaction;
4) Filtering, washing and drying the reaction product obtained in the step 3) to obtain a polydopamine coated tin sulfide nanobelt;
5) Calcining the polydopamine coated tin sulfide nanobelt under the protection of inert atmosphere, and cooling to room temperature to obtain a carbon coated tin sulfide nanobelt; the thickness of the carbon coating layer in the carbon-coated tin sulfide nano belt is 10-30nm;
the carbon-coated tin sulfide nano-belt is used as a negative electrode active material of a lithium ion battery, the discharge capacity of the lithium ion battery is gradually increased in the battery cycle process, and the battery still has a discharge specific capacity of 1260.29mAh/g after 220 cycles.
2. The method of manufacturing according to claim 1, characterized in that: the preparation method of the tin sulfide nanobelt in the step (1) comprises the following steps: firstly, adding 0.1-10g of urea, 0.1-10g of thioacetamide and 0.1-10g of stannous chloride dihydrate into 10-100mL of deionized water, and stirring to prepare a uniform solution; and transferring the solution into a hydrothermal kettle for hydrothermal reaction, cooling the reactant to room temperature, washing the reactant with deionized water and ethanol in sequence, and drying to obtain the tin sulfide nanobelt.
3. The preparation method according to claim 2, characterized in that: the hydrothermal reaction is to heat the sealed hydrothermal kettle in a blast drying oven to 100-200 ℃ for 1-24h.
4. The method of manufacturing according to claim 1, characterized in that: the pH value of the tris buffer solution in the step (2) is 5-10.
5. The method of manufacturing according to claim 1, characterized in that: in the step (3), the adding mass of the dopamine accounts for 1-4mg/mL of the volume ratio of the mixed solution, and the stirring reaction time is 1-48h.
6. The method of manufacturing according to claim 1, characterized in that: the inert atmosphere in the step (5) is one of helium, neon and argon; the calcination is carried out by heating to 100-800 ℃ at a heating rate of 1-10 ℃/min and a calcination time of 1-10h.
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