CN112357956B - Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof - Google Patents
Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 100
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 79
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 27
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 14
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 7
- 239000002159 nanocrystal Substances 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- SFXJSNATBHJIDS-UHFFFAOYSA-N disodium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[Na+].[Na+].[O-][Sn]([O-])=O SFXJSNATBHJIDS-UHFFFAOYSA-N 0.000 claims description 5
- 229960001031 glucose Drugs 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000002077 nanosphere Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention discloses a carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material, a preparation method thereof and application thereof in a lithium ion battery cathode material. Of said materials, SnO2The nano particles are assembled into mesoporous spheres through carbon, and are placed in SnO2The surface of the mesoporous sphere is coated with a layer of TiO2A nanocrystal and a layer of amorphous carbon. The preparation method comprises the following steps: first, SnO is synthesized by a hydrothermal method2Assembling nano particles/carbon into mesoporous spheres, and coating TiO by hydrolysis method2Finally, coating a layer of resorcinol-formaldehyde resin, and carbonizing to obtain the final product. The invention can improve SnO2Electrochemical activity, structural stability and cycling stability of the compound, so that SnO2Has high specific capacity and stable cycle performance. carbon/TiO 22Coated SnO2The nano-particle/carbon assembled mesoporous spheres have important application value as the negative electrode material of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof.
Background
Lithium ion batteries have become the main flow power source for electric vehicles and electric tools due to their advantages of high voltage, high specific energy, good safety, long cycle life, and the like. At present, the negative electrode material of the commercial lithium ion battery is mainly graphite, but the theoretical capacity of the graphite is only 372mAh g-1In addition, the safety performance of graphite is poor, and the rate capability is low, so that the development of a negative electrode material with higher energy density and better cycle stability is the key point of the research of lithium ion batteries.
SnO2High theoretical specific capacity (782mAh g)-1) The lithium has low insertion potential and low price, and is one of ideal negative electrode materials of the next generation lithium ion battery for replacing graphite. SnO2The method has the main problems that huge volume change is generated in the charging and discharging process, the volume change exceeds 300 percent, the specific capacity is rapidly attenuated, and the practical application of the method in the lithium ion battery is hindered.
Nano-sized and compounded with conductive material for improving SnO2An effective method of cycling stability. The patent specification with the publication number of CN110649258A discloses a three-dimensional porous tin oxide graphene composite electrode material, the patent specification with the publication number of CN108793233A discloses a multilayer hollow tin oxide material, and the report of how much is that SnO is reported2The composite negative electrode material of the/rGO lithium ion battery (He Tai, Koluol, Zhongsi Yi, Like, Wanglili, Tianjin university of Industrial science 39(3), (2020), 29-33). However, the conventional nano-design has difficulty in solving the problem of nano-material agglomeration, resulting in a significant reduction in nano-effect. SnO is not well suppressed by general composite structures2Volume change of (2), not to significantly improve SnO2The cycle stability of (c). Thus, there is provided a method for suppressing SnO effectively with a high specific capacity2Composite structure pair SnO with good volume expansion and cycle performance in charge and discharge process2The development of base materials is of great significance.
Disclosure of Invention
In view of the above-mentioned problems and deficiencies in the art, the present invention provides a carbon/titanium dioxide (TiO)2) Coated tin oxide (SnO)2) NanoparticlesA carbon assembled mesoporous sphere material.
The carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material is prepared from SnO2The nano particles are assembled by carbon adhesion, and the surfaces of the nano particles are sequentially coated with TiO2A layer and a carbon layer; the TiO is2The layer being made of TiO2Composition of nano-crystals; the carbon layer is amorphous carbon formed by carbonizing resorcinol-formaldehyde resin (RF resin).
The nanocrystals refer to crystalline nanoparticles. The TiO is2The nano-crystal is coated on the surface of the tin oxide nano-particle/carbon assembled mesoporous sphere.
Preferably, the tin oxide nanoparticle/carbon assembly mesoporous sphere contains micropores and mesopores inside;
the diameter of the tin oxide nano-particles/carbon assembled mesoporous spheres is 30-200nm, and the SnO2The particle size of the nano particles is 5-20 nm;
the content of carbon in the tin oxide nano-particles/carbon assembled mesoporous spheres is 1-20 wt%.
Further preferably, the TiO is2The grain diameter of the nano crystal is 5-15nm, and the TiO is2The thickness of the layer is 10-100 nm.
Even more preferably, the carbon layer is coated on the TiO2The thickness of the layer surface is 5-50 nm.
The invention also provides a preparation method of the carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material, which comprises the following steps:
(1) adding 5mL of diethylenetriamine into 60mL of deionized water, and stirring for 10min to form a uniform oil-water mixed solution; sequentially adding 110mg of sodium stannate trihydrate, 400mg of thiourea and 50mg of D-anhydrous glucose into the oil-water mixed solution, stirring for 1h, transferring into a 100mL hydrothermal reaction kettle, sealing, heating to 180 ℃ and 220 ℃ for hydrothermal reaction for 1-48h, cooling to room temperature, centrifugally separating the product, washing with deionized water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SnO2Nanoparticle/carbon assembly mesoporous spheres;
(2) 25mg of SnO obtained in step (1)2Nanoparticle/carbon assembly mesoporous spheresDispersing in 50mL of absolute ethanol, performing ultrasonic treatment for 30min, adding 0.1-0.5mL of isopropyl titanate, stirring for 15min, heating to 50-80 deg.C, adding 1-5mL of deionized water, stirring for 90min, centrifuging, washing with absolute ethanol for 3 times, and oven drying at 60 deg.C to obtain TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres.
(3) 40mg of TiO obtained in the step (2)2Coated SnO2Dispersing the nano-particle/carbon assembled mesoporous spheres in a mixed solution of 30mL of deionized water and 12.5mL of absolute ethyl alcohol, adding 75mg of hexadecyl trimethyl ammonium bromide, stirring for 1h, heating to 30-40 ℃, adding 5-30mg of resorcinol, stirring for 10min, sequentially adding 0.05-0.4mL of ammonia water and 5-45 μ L of formaldehyde, stirring for reaction for 16h, centrifugally separating the product, washing for 3 times with absolute ethyl alcohol, drying at 60 ℃, placing in a quartz tube furnace, heating to 500 ℃ in an argon environment, preserving heat for 0.5-5h, and cooling to room temperature to obtain the carbon/TiO2Coated SnO2The nano-particle/carbon assembled mesoporous sphere material.
The preparation method comprises the following steps: first, SnO is synthesized by a hydrothermal method2Assembling nano particles/carbon into mesoporous spheres, and coating TiO by hydrolysis method2Finally, coating a layer of resorcinol-formaldehyde resin, and carbonizing to obtain the final product.
The invention also provides application of the carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material in a lithium ion battery cathode material.
In a preferred embodiment, the carbon/TiO of the present invention is used2Coated SnO2Preparing a lithium ion battery cathode by using the nanoparticle/carbon assembled mesoporous sphere material: respectively weighing the synthetic material, the acetylene black conductive agent and the polyvinylidene fluoride (PVDF) binder in a mass ratio of 8:1:1, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground synthetic material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
In the glove filled with high-purity argonAnd assembling the prepared electrode plate, a lithium plate and a diaphragm into the CR2025 button-type lithium ion battery in the box. The electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a new power battery test system to test the charge-discharge performance and the cycling stability of the lithium ion battery.
The invention can improve SnO2Electrochemical activity, structural stability and cycling stability of the compound, so that SnO2Has high specific capacity and stable cycle performance.
Compared with the prior art, the invention has the main advantages that:
(1)SnO2the nano particles have small size, large specific surface area and high electrochemical activity; SnO assembly by carbon2The nano particles form mesoporous spheres, so that the problem of agglomeration of nano materials is avoided, the full play of a nano effect is ensured, the mesoporous structure is favorable for the permeation and storage of electrolyte and the volume change of a containing material, and in addition, the carbon improves SnO2Electrical conductivity, these favorable factors being SnO2Has high specific capacity and high rate performance.
(2)TiO2The coating layer composed of the nanocrystalline has high structural strength and can effectively inhibit SnO2The volume expansion and contraction in the charging and discharging process is to improve SnO2The main factors of the structural stability and the cycling stability of the nanoparticle/carbon assembled mesoporous spheres. Furthermore, TiO2The nano-crystalline structure endows the composite material with higher electrochemical activity, can also provide charge and discharge capacity, and ensures higher specific capacity of the whole composite material.
(3) The coated carbon formed by carbonizing the RF resin enables the contact among the composite material particles to be high-conductivity carbon contact, improves the conductivity of the composite material, ensures the excellent high-rate performance of the material, and can inhibit SnO (SnO) by the coated carbon2The volume expansion and contraction in the charging and discharging process can further improve the structural stability and the cycling stability of the composite material. The amorphous carbon can also participate in lithium storage reaction, the amorphous structure endows the amorphous carbon with higher electrochemical activity, and the amorphous carbon can also provide charge and discharge capacity, so that the integral higher specific capacity of the composite material is ensured.
Drawings
FIG. 1 is SnO prepared in example 12SEM photograph of nanoparticle/carbon assembled mesoporous spheres;
FIG. 2 is SnO prepared in example 12TEM photograph of nanoparticle/carbon assembled mesoporous spheres;
FIG. 3 shows the carbon/TiO prepared in example 12Coated SnO2SEM photograph of nanoparticle/carbon assembled mesoporous spheres;
FIG. 4 shows the carbon/TiO prepared in example 12Coated SnO2TEM photograph of nanoparticle/carbon assembled mesoporous spheres;
FIG. 5 shows the carbon/TiO prepared in example 12Coated SnO2Nanoparticle/carbon assembly mesoporous spheres at a current density of 1000mAg-1A cycle performance map of (a);
FIG. 6 shows the carbon/TiO prepared in example 12Coated SnO2A rate performance diagram of the nanoparticle/carbon assembled mesoporous spheres.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) Adding 5mL of diethylenetriamine into 60mL of deionized water, and stirring for 10min to form a uniform oil-water mixed solution; 110mg of sodium stannate trihydrate, 400mg of thiourea and 50mg of D-anhydrous glucose are added to the solution in sequence and stirred for 1 hour. Transferring the solution into a 100mL hydrothermal reaction kettle, sealing, heating to 200 ℃ for hydrothermal reaction for 24h, cooling to room temperature, centrifugally separating the product, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain SnO2Nanoparticle/carbon assembly mesoporous spheres;
(2) 25mg of SnO obtained in step (1)2Dispersing the nano-particle/carbon assembled mesoporous spheres in 50mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, adding 0.2mL of isopropyl titanate, stirring for 15min, heating to 60 ℃, and slowly adding 2mL of isopropyl titanate to remove ionsAdding water, stirring for 90min, centrifuging, washing with anhydrous ethanol for 3 times, and oven drying at 60 deg.C to obtain TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres.
(3) 40mg of TiO obtained in the step (2)2Coated SnO2Dispersing the nano-particle/carbon assembled mesoporous spheres in a mixed solution of 30mL of deionized water and 12.5mL of absolute ethyl alcohol, adding 75mg of hexadecyl trimethyl ammonium bromide, stirring for 1h, heating to 35 ℃, adding 16mg of resorcinol, stirring for 10min, sequentially adding 0.2mL of ammonia water and 22.6 mu L of formaldehyde, stirring for reacting for 16h, centrifugally separating a product, washing for 3 times by using absolute ethyl alcohol, and drying at 60 ℃. Placing the obtained product in a quartz tube furnace, heating to 600 ℃ in an argon environment, preserving heat for 2 hours, and cooling to room temperature to obtain carbon/TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres.
FIG. 1 shows SnO synthesized in step (1)2SEM photographs of the nanoparticle/carbon assembled mesoporous spheres revealed that the product was uniform nanospheres, approximately 70-90nm in diameter. The nanospheres are independent of each other and do not agglomerate. Fig. 2 is a TEM photograph thereof, and it can be seen that the nanospheres are formed by assembling some nanoparticles, which are about 15nm long and about 7nm wide. A large number of micropores/mesopores are formed among the nano particles and inside the nanospheres, so that the nanospheres have large specific surface areas. The nanospheres were found to contain 2 wt% carbon by energy spectroscopy. The carbon is distributed among the nano particles and is SnO2The main reason for the assembly of nanoparticles into mesoporous spheres. FIG. 3 shows the carbon/TiO synthesized in step (3)2Coated SnO2SEM photo of the nano-particle/carbon assembled mesoporous sphere shows that the surface of the nano-sphere becomes smooth and is obviously coated with a new material. Fig. 4 is a TEM photograph thereof, and it can be seen that two nanospheres of the same size are close to the center, with a diameter of about 90 nm. Outside the nanospheres are small particles of TiO2Nanocrystalline, TiO2The thickness of the cladding layer is about 50 nm. In TiO2The outer surface of the cladding is amorphous carbon and the thickness of the cladding is about 20 nm.
Using the carbon/TiO of this example2Coated SnO2Preparing a lithium ion battery cathode by using the nanoparticle/carbon assembled mesoporous sphere material: respectively weighing the synthetic materials with the mass ratio of 8:1:1The preparation method comprises the steps of dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground synthetic material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
And assembling the prepared electrode plate, a lithium plate and a diaphragm into the CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. The electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a novacar battery test system to test the charge-discharge performance and the cycle stability of the lithium ion battery, and the charge-discharge current density is 1000mA g-1The voltage range is 0.01-3.0V.
FIG. 5 is a carbon/TiO drawing2Coated SnO2The nano-particle/carbon assembled mesoporous sphere material has the current density of 1000mA g-1Cycle performance map of (c). The specific discharge capacity at 1 st cycle was 1409mAh g-1Then the discharge capacity decreased and stabilized to 1000mAh g-1The specific discharge capacity is reduced to 995mAh g by the 100 th cycle-1. The average specific discharge capacity of 100 cycles was 1002mAh g-1. carbon/TiO 22Coated SnO2The specific discharge capacity and cycling stability of the nanoparticle/carbon assembled mesoporous spheres are superior to those of the patent technologies published under the numbers CN111640925A and CN111549321A, and the work of zhijing Hu et al (z.q.hu, x.f.xu, x.f.wang, k.f.yu, c.liang, Journal of Alloys and Compounds835(2020) 155446).
FIG. 6 is a carbon/TiO plot2Coated SnO2And (3) a rate performance graph of the nanoparticle/carbon assembled mesoporous sphere material. At 200, 500, 1000, 1500 and 2000mA g-1The average specific discharge capacity of the composite material is 1138, 1070, 984, 925 and 805mAh g at the current density of (A)-1And exhibits excellent rate capability. When the current density returns to 200mA g-1The discharge specific capacity is recovered to 1108mAh g-1The recovery rate reaches 97.4 percent, which shows that the carbon/TiO2Coated SnO2The nano-particle/carbon assembled mesoporous sphere material has good performanceStructural stability and circulation stability, can carry out the heavy current reaction.
Example 2
(1) Adding 5mL of diethylenetriamine into 60mL of deionized water, and stirring for 10min to form a uniform oil-water mixed solution; 110mg of sodium stannate trihydrate, 400mg of thiourea and 50mg of D-anhydrous glucose are added to the solution in sequence and stirred for 1 hour. Transferring the solution into a 100ml hydrothermal reaction kettle, sealing, heating to 200 ℃ for hydrothermal reaction for 24h, cooling to room temperature, centrifugally separating the product, washing 3 times with deionized water and absolute ethyl alcohol respectively, and drying at 60 ℃ to obtain SnO2Nanoparticle/carbon assembly mesoporous spheres;
(2) 25mg of SnO obtained in step (1)2Dispersing the nano-particle/carbon assembled mesoporous spheres in 50mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, adding 0.3mL of isopropyl titanate, stirring for 15min, heating to 60 ℃, slowly adding 3mL of deionized water, continuously stirring for 90min, performing centrifugal separation on the product, washing for 3 times by using absolute ethyl alcohol, and drying at 60 ℃ to obtain TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres.
The subsequent process was the same as in example 1.
Product carbon/TiO2Coated SnO2The microstructure of the nanoparticle/carbon assembly mesoporous spheres is the same as that of example 1, with the main difference being that TiO2Becomes 72 nm.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 1000mA g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The specific discharge capacity of the 1 st cycle was 1242mAh g-1Then the specific discharge capacity is reduced and stabilized to 830mAh g-1The specific discharge capacity is reduced to 825mAh g by the 100 th cycle-1. The average specific discharge capacity over 100 cycles was 836mAh g-1。
Example 3
(1) Adding 5mL of diethylenetriamine into 60mL of deionized water, and stirring for 10min to form a uniform oil-water mixed solution; 110mg of sodium stannate trihydrate, 400mg of thiourea and 50mg of D-anhydrous glucose are added to the solution in sequence and stirred for 1 hour. Will be at the topTransferring the solution into a 100ml hydrothermal reaction kettle, sealing, heating to 200 ℃ for hydrothermal reaction for 24h, cooling to room temperature, centrifugally separating the product, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ to obtain SnO2Nanoparticle/carbon assembly mesoporous spheres;
(2) 25mg of SnO obtained in step (1)2Dispersing the nano-particle/carbon assembled mesoporous spheres in 50mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, adding 0.2mL of isopropyl titanate, stirring for 15min, heating to 60 ℃, slowly adding 2mL of deionized water, continuously stirring for 90min, performing centrifugal separation on the product, washing for 3 times by using absolute ethyl alcohol, and drying at 60 ℃ to obtain TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres.
(3) 40mg of TiO obtained in the step (2)2Coated SnO2Dispersing the nano-particle/carbon assembled mesoporous spheres in a mixed solution of 30mL of deionized water and 12.5mL of absolute ethyl alcohol, adding 75mg of hexadecyl trimethyl ammonium bromide, stirring for 1h, heating to 35 ℃, adding 24mg of resorcinol, stirring for 10min, sequentially adding 0.3mL of ammonia water and 33.9 muL of formaldehyde, stirring for reacting for 16h, centrifugally separating a product, washing for 3 times by using absolute ethyl alcohol, and drying at 60 ℃. Placing the obtained product in a quartz tube furnace, heating to 600 ℃ in an argon environment, preserving heat for 2h, and cooling to room temperature to obtain carbon/TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres.
Product carbon/TiO2Coated SnO2The microstructure of the nanoparticle/carbon assembly mesoporous spheres was the same as in example 1, with the main difference that the carbon coating thickness was changed to 27 nm.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 1000mA g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The 1 st specific cyclic discharge capacity is 1322mAh g-1Then the specific discharge capacity is reduced and stabilized to 940mAh g-1And the specific discharge capacity is reduced to 934mAh g by the 100 th cycle-1. The average specific discharge capacity of 100 cycles was 944mAh g-1。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. The carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material is characterized in that the tin oxide nanoparticle/carbon assembled mesoporous sphere is made of SnO2The nano particles are assembled by carbon adhesion, and the surfaces of the nano particles are sequentially coated with TiO2A layer and a carbon layer; the TiO is2The layer being made of TiO2Composition of nano-crystals; the carbon layer is amorphous carbon formed by carbonizing resorcinol-formaldehyde resin.
2. The carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material according to claim 1, wherein the tin oxide nanoparticle/carbon assembled mesoporous sphere contains micropores and mesopores inside;
the diameter of the tin oxide nano-particles/carbon assembled mesoporous spheres is 30-200nm, and the SnO2The particle size of the nano particles is 5-20 nm;
the content of carbon in the tin oxide nano-particles/carbon assembled mesoporous spheres is 1-20 wt%.
3. The carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material of claim 2, wherein the TiO is selected from the group consisting of2The grain diameter of the nano crystal is 5-15nm, and the TiO is2The thickness of the layer is 10-100 nm.
4. The carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material of claim 3, wherein the carbon layer is coated on TiO2The thickness of the layer surface is 5-50 nm.
5. The method for preparing carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembly mesoporous sphere material according to any one of claims 1 to 4, comprising the steps of:
(1) 5mL of diethylenetriamine was addedStirring the mixture for 10min in 60mL of deionized water to form a uniform oil-water mixed solution; sequentially adding 110mg of sodium stannate trihydrate, 400mg of thiourea and 50mg of D-anhydrous glucose into the oil-water mixed solution, stirring for 1h, transferring into a 100mL hydrothermal reaction kettle, sealing, heating to 180 ℃ and 220 ℃ for hydrothermal reaction for 1-48h, cooling to room temperature, centrifugally separating the product, washing with deionized water and absolute ethyl alcohol for 3 times, and drying at 60 ℃ to obtain SnO2Nanoparticle/carbon assembly mesoporous spheres;
(2) 25mg of SnO obtained in step (1)2Dispersing the nano-particle/carbon assembled mesoporous spheres in 50mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, adding 0.1-0.5mL of isopropyl titanate, stirring for 15min, heating to 50-80 ℃, adding 1-5mL of deionized water, continuing stirring for 90min, performing centrifugal separation on a product, washing for 3 times by using absolute ethyl alcohol, and drying at 60 ℃ to obtain TiO2Coated SnO2Nanoparticle/carbon assembly mesoporous spheres;
(3) 40mg of TiO obtained in the step (2)2Coated SnO2Dispersing the nano-particle/carbon assembled mesoporous spheres in a mixed solution of 30mL of deionized water and 12.5mL of absolute ethyl alcohol, adding 75mg of hexadecyl trimethyl ammonium bromide, stirring for 1h, heating to 30-40 ℃, adding 5-30mg of resorcinol, stirring for 10min, sequentially adding 0.05-0.4mL of ammonia water and 5-45 μ L of formaldehyde, stirring for reaction for 16h, centrifugally separating the product, washing for 3 times with absolute ethyl alcohol, drying at 60 ℃, placing in a quartz tube furnace, heating to 500 ℃ in an argon environment, preserving heat for 0.5-5h, and cooling to room temperature to obtain the carbon/TiO2Coated SnO2The nano-particle/carbon assembled mesoporous sphere material.
6. The use of the carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembly mesoporous sphere material according to any one of claims 1 to 4 in a negative electrode material of a lithium ion battery.
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