CN105304887A - Mesoporous microspherical titanium niobate/carbon composite material and preparation method thereof - Google Patents
Mesoporous microspherical titanium niobate/carbon composite material and preparation method thereof Download PDFInfo
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Abstract
The application discloses a preparation method of a mesoporous microspherical titanium niobate/carbon composite material. The preparation method comprises the following steps of: ultrasonically dispersing or dissolving a carbon source in ethanol; adding a niobium source and a titanium source to the obtained solution; feeding the obtained mixed solution to an autoclave, and heating for reacting; and cooling, drying, and roasting under the protection of an inert gas to obtain the mesoporous microspherical titanium niobate/carbon composite material. The invention also discloses the mesoporous microspherical titanium niobate/carbon composite material prepared by the preparation method. According to the preparation method, the advantages of nanocrystallization, carbon material coating and mesopore structured materials are organically combined, a novel mesoporous microspherical titanium niobate/carbon composite material is creatively prepared, and the material, serving as a negative electrode material of a lithium ion battery, shows excellent high-rate charging/discharging performance. In addition, the preparation method of the titanium niobate/carbon composite material has the advantages of simple process, low cost, easiness for large-scale production and the like.
Description
Technical field
The application belongs to field of lithium ion battery material, specifically, relates to a kind of mesoporous microsphere shape titanium niobate/carbon composite and preparation method thereof.
Background technology
Along with the exhaustion of traditional fossil energy and highlighting of global environmental problems, novel green, regenerative resource are all actively being found in countries in the world.Wherein chemical energy source is one of very important research direction.Because of it, lithium ion battery, as a kind of new chemical energy, has that operating voltage is high, energy density is high and the advantage such as environmental pollution is little, is widely used in various portable type electronic product.Current by people's expansive approach to fields such as electric automobile, Aero-Space, energy storage, this just has higher requirement to lithium ion battery.Electrode material is core and the key of lithium ion battery, and it plays a decisive role to the performance of lithium ion battery, and the key therefore developing high performance lithium ion battery is the high performance electrode material of exploitation.
The lithium ion battery negative material of Current commercial is mainly various material with carbon element, due to the electrode potential of material with carbon element and the current potential of lithium metal close, easily cause the generation of Li dendrite, cause safety issue; In addition material with carbon element can not carry out fast charging and discharging, and this just can not meet the requirement that electric automobile fills soon.Recent years, titanium niobate (TiNb
2o
7) this novel negative material receives the concern of people.Titanium niobate electrode potential is high, not easily causes the generation of Li dendrite and solid electrolyte oxidation film (SEI), has excellent fail safe; This material change in volume in charge and discharge process is little, has excellent cycle performance; The theoretical specific capacity (387mAh/g) of this material is a little more than the theoretical specific capacity (372mAh/g) of material with carbon element.But due to the intrinsic conductivity of titanium niobate lower, make its chemical property under high current density undesirable, constrain the application of its large-scale commercial.
The current approach improving titanium niobate chemical property is mainly nanometer and carbon coated material.Nanometer can shorten the diffusion length of lithium ion and electronics; Carbon coated material can improve the conductivity of material.Lot of documents report is pointed out in recent years, and meso-hole structure material has specific area and the large advantage of pore volume, can increase the contact of electrode material and electrolyte, be conducive to the transmission of lithium ion.The advantages of nanometer and meso-hole structure is got up by the people such as Li, synthesize and assemble by nano particle the titanium niobate mesoporous microsphere formed, excellent chemical property is shown under little multiplying power, but its large high rate performance also undesirable (LiH, ShenL, PangG, FangS, LuoH, YangKandZhangX.TiNb
2o
7nanoparticlesassembledintohierarchicalmicrospheresashigh-ratecapabilityandlongcycle-lifeanodematerialsforlithiumi onbatteries.Nanoscale, 2015,7:619-624.).In addition, the compound of current titanium niobate and material with carbon element mostly utilize be Graphene, carbon nano-tube, graphene oxide etc. as additive, and these additives need separately preparation, and expensive, are difficult to large-scale industrial production.
Summary of the invention
In view of this, technical problems to be solved in this application there is provided a kind of mesoporous microsphere shape titanium niobate/carbon composite and preparation method thereof, solve the problem that titanium niobate/carbon composite complicated process of preparation and cost in the low and prior art of titanium niobate high rate performance are high.
In order to solve the problems of the technologies described above, this application discloses a kind of preparation method of mesoporous microsphere shape titanium niobate/carbon composite, specifically comprising the following steps:
Step 1) by a certain amount of carbon source ultrasonic disperse or be dissolved in absolute ethyl alcohol;
Step 2) niobium source and titanium source are joined in above-mentioned solution respectively, wherein titanium/niobium atom ratio=0.4-0.9, stir 0.1-24 hour, wherein the concentration of niobium ion is 0.07-27mol/L;
Step 3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in thermostatic drying chamber, at 80-250 DEG C, add thermal response 1-72 hour;
Step 4) by step 3) reactant of gained is placed in drying box, dry at 50-130 DEG C, obtains yellowish powder;
Step 5) by step 4) the micro-yellow powder of gained is placed in tube furnace, under inert gas shielding, roasting 1-60 hour at 300-1150 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
Further, step 1) in carbon source be one or more in acetylene black, glucose, glycine, citric acid, sucrose, carbon black.
Further, step 2) in titanium source be one or more in titanium tetrachloride, titanium trichloride, butyl titanate, titanyl sulfate, titanium tetraisopropylate, titanium tetrafluoride.
Further, step 2) in niobium source be one or more in ethanol niobium, niobium oxalate, columbium pentachloride, ammonium niobium oxalate.
Further, step 3) in heating-up temperature be 100-235 DEG C.
Further, step 5) in inert gas be one or both in argon gas, nitrogen.
Further, step 5) in sintering temperature be 410-1100 DEG C.
Disclosed herein as well is a kind of mesoporous microsphere shape titanium niobate/carbon composite prepared by above-mentioned preparation method.
Further, mesoporous microsphere is assembled by a large amount of nano particle and is formed, and microballoon is of a size of 0.2-6 micron.
Compared with prior art, the application can obtain and comprise following technique effect:
1) nanometer, material with carbon element advantage that is coated and meso-hole structure material organically combine by the present invention, creationaryly prepare a kind of novel mesoporous microsphere shape titanium niobate/carbon composite.
2) mesoporous microsphere shape titanium niobate/carbon composite of preparing of the present invention, has good conductivity, lithium ion and the advantage that electron diffusion path is short and electrode material is large with electrolyte contacts area, thus makes it have the high rate charge-discharge performance of excellence.
3) titanium niobate provided by the invention/carbon composite preparation method has technique simply, and cost is low, is easy to the advantages such as large-scale production.
Certainly, the arbitrary product implementing the application must not necessarily need to reach above-described all technique effects simultaneously.
Accompanying drawing explanation
Accompanying drawing described herein is used to provide further understanding of the present application, and form a application's part, the schematic description and description of the application, for explaining the application, does not form the improper restriction to the application.In the accompanying drawings:
Fig. 1 is the x-ray diffraction pattern that the embodiment of the present application 1 prepares mesoporous microsphere shape titanium niobate/carbon composite;
Fig. 2 is ESEM (SEM) photo that the embodiment of the present application 1 prepares mesoporous microsphere shape titanium niobate/carbon composite;
Fig. 3 is transmission electron microscope (TEM) photo that the embodiment of the present invention 1 prepares mesoporous microsphere shape titanium niobate/carbon composite;
Fig. 4 is high resolution electron microscopy (HRTEM) photo that the embodiment of the present invention 1 prepares mesoporous microsphere shape titanium niobate/carbon composite;
Fig. 5 is that the embodiment of the present invention 1 prepares the first charge-discharge curve chart of mesoporous microsphere shape titanium niobate/carbon composite under different multiplying;
Fig. 6 is the circulation performance chart that the embodiment of the present invention 1 prepares mesoporous microsphere shape titanium niobate/carbon composite.
Embodiment
Drawings and Examples will be coordinated below to describe the execution mode of the application in detail, by this to the application how application technology means solve technical problem and the implementation procedure reaching technology effect can fully understand and implement according to this.
Embodiment 1
1) by a certain amount of glucose ultrasonic disperse or be dissolved in absolute ethyl alcohol;
2) join in above-mentioned solution respectively by niobium oxalate and titanium tetrachloride, wherein titanium/niobium atom is than=0.47, and stir 13 hours, wherein the concentration of niobium ion is 0.7mol/L;
3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, and be placed in thermostatic drying chamber, add thermal response at 87 DEG C 42 hours;
4) after reaction, gained reactant is placed in drying box, dry at 65 DEG C, obtain yellowish powder;
5) by step 4) the micro-yellow powder of gained is placed in tube furnace, and under argon shield, roasting 40 hours at 590 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
As shown in Figure 1, in the diffraction maximum of sample and standard P DF card, the diffraction maximum of titanium niobate matches, and do not find other impurity peaks, and diffraction maximum is wider, the particle size of interpret sample is less.As shown in Figure 2, sample presents microspheroidal, and the surface ratio of microballoon is more coarse.As shown in Figure 3, microballoon is assembled by a large amount of nano particles to be formed.As shown in Figure 4, the obvious carbon-coating of one deck is had at the edge of nano particle.As shown in Figure 5, along with the increase of charge-discharge magnification, the specific discharge capacity of sample reduces gradually, is about 380mAh/g in the first discharge specific capacity of 1C multiplying power, and the first discharge specific capacity under 10C multiplying power is about 310mAh/g.As shown in Figure 6, sample has good circulation performance, and under 1C multiplying power after 100 circulations, then through 100 circulations under 10C multiplying power, reversible specific capacity still can remain on about 250mAh/g.
Embodiment 2
1) by a certain amount of acetylene black ultrasonic disperse or be dissolved in absolute ethyl alcohol;
2) join in above-mentioned solution respectively by ethanol niobium and butyl titanate, wherein titanium/niobium atom is than=0.6, and stir 6 hours, wherein the concentration of niobium ion is 11mol/L;
3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, and be placed in thermostatic drying chamber, add thermal response at 240 DEG C 67 hours;
4) after reaction, gained reactant is placed in drying box, dry at 120 DEG C, obtain yellowish powder;
5) by step 4) the micro-yellow powder of gained is placed in tube furnace, and under nitrogen protection, roasting 24 hours at 1100 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
Embodiment 3
1) by a certain amount of glycine ultrasonic disperse or be dissolved in absolute ethyl alcohol;
2) join in above-mentioned solution respectively by columbium pentachloride and titanium tetraisopropylate, wherein titanium/niobium atom is than=0.53, and stir 23 hours, wherein the concentration of niobium ion is 15mol/L;
3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, and be placed in thermostatic drying chamber, add thermal response at 140 DEG C 37 hours;
4) after reaction, gained reactant is placed in drying box, dry at 79 DEG C, obtain yellowish powder;
5) by step 4) the micro-yellow powder of gained is placed in tube furnace, and under argon shield, roasting 37 hours at 820 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
Embodiment 4
Step 1) by a certain amount of citric acid ultrasonic disperse or be dissolved in absolute ethyl alcohol;
Step 2) ethanol niobium and butyl titanate are joined in above-mentioned solution respectively, wherein titanium/niobium atom is than=0.4, and stir 0.1 hour, wherein the concentration of niobium ion is 0.07mol/L;
Step 3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in thermostatic drying chamber, add thermal response at 80 DEG C 72 hours;
Step 4) by step 3) reactant of gained is placed in drying box, dry at 50 DEG C, obtains yellowish powder;
Step 5) by step 4) the micro-yellow powder of gained is placed in tube furnace, under argon gas protection, roasting 60 hours at 300 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
Embodiment 5
Step 1) by a certain amount of sucrose ultrasonic disperse or be dissolved in absolute ethyl alcohol;
Step 2) niobium oxalate and titanyl sulfate are joined in above-mentioned solution respectively, wherein titanium/niobium atom is than=0.9, and stir 24 hours, wherein the concentration of niobium ion is 27mol/L;
Step 3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in thermostatic drying chamber, add thermal response at 100 DEG C 1 hour;
Step 4) by step 3) reactant of gained is placed in drying box, dry at 130 DEG C, obtains yellowish powder;
Step 5) by step 4) the micro-yellow powder of gained is placed in tube furnace, under argon gas protection, roasting 1 hour at 410 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
Embodiment 6
Step 1) by a certain amount of carbon black ultrasonic disperse or be dissolved in absolute ethyl alcohol;
Step 2) titanium tetrafluoride and columbium pentachloride are joined in above-mentioned solution respectively, wherein titanium/niobium atom is than=0.5, and stir 12 hours, wherein the concentration of niobium ion is 8mol/L;
Step 3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in thermostatic drying chamber, add thermal response at 120 DEG C 24 hours;
Step 4) by step 3) reactant of gained is placed in drying box, dry at 65 DEG C, obtains yellowish powder;
Step 5) by step 4) the micro-yellow powder of gained is placed in tube furnace, under nitrogen protection, roasting 15 hours at 600 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
Embodiment 7
Step 1) by a certain amount of acetylene black ultrasonic disperse or be dissolved in absolute ethyl alcohol;
Step 2) niobium source and titanium source are joined in above-mentioned solution respectively, wherein titanium/niobium atom is than=0.8, and stir 20 hours, wherein the concentration of niobium ion is 24mol/L;
Step 3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in thermostatic drying chamber, add thermal response at 235 DEG C 60 hours;
Step 4) by step 3) reactant of gained is placed in drying box, dry at 100 DEG C, obtains yellowish powder;
Step 5) by step 4) the micro-yellow powder of gained is placed in tube furnace, under nitrogen protection, roasting 50 hours at 750 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
In this preparation method, the selection of carbon source is particularly important, only has when selecting above-mentioned carbon source and can obtain spherical morphology, if the improper of carbon source selection can not get spherical morphology; Reaction temperature of the present invention and calcining heat are also particularly important, if select improper, then can not prepare mesoporous microsphere shape titanium niobate/carbon composite of the present invention.In the selection of reaction temperature: the heat resisting temperature of general polytetrafluoroethylene reactor is less than 260 DEG C, and temperature crosses higher position needs special substance, expensive, and dangerous large; The words that temperature is too low may can not react, and can not get product.Sintering temperature can affect degree of crystallinity and the size of product, and temperature is too high to waste energy, and the particle size of material can be made to grow up; The too low meeting of temperature makes the crystallization of material bad or can not get titanium niobate/carbon composite.
Above-mentioned explanation illustrate and describes some preferred embodiments of the present invention, but as previously mentioned, be to be understood that the present invention is not limited to the form disclosed by this paper, should not regard the eliminating to other embodiments as, and can be used for other combinations various, amendment and environment, and can in invention contemplated scope described herein, changed by the technology of above-mentioned instruction or association area or knowledge.And the change that those skilled in the art carry out and change do not depart from the spirit and scope of the present invention, then all should in the protection range of claims of the present invention.
Claims (9)
1. a preparation method for mesoporous microsphere shape titanium niobate/carbon composite, is characterized in that, specifically comprise the following steps:
Step 1) by a certain amount of carbon source ultrasonic disperse or be dissolved in absolute ethyl alcohol;
Step 2) niobium source and titanium source are joined in above-mentioned solution respectively, wherein titanium/niobium atom ratio=0.4-0.9, stir 0.1-24 hour, wherein the concentration of niobium ion is 0.07-27mol/L;
Step 3) by step 2) gained mixed liquor is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in thermostatic drying chamber, at 80-250 DEG C, add thermal response 1-72 hour;
Step 4) by step 3) reactant of gained is placed in drying box, dry at 50-130 DEG C, obtains yellowish powder;
Step 5) by step 4) the micro-yellow powder of gained is placed in tube furnace, under inert gas shielding, roasting 1-60 hour at 300-1150 DEG C, obtains mesoporous microsphere shape titanium niobate/carbon composite.
2. the preparation method of mesoporous microsphere shape titanium niobate/carbon composite according to claim 1, is characterized in that, described step 1) in carbon source be one or more in acetylene black, glucose, glycine, citric acid, sucrose, carbon black.
3. the preparation method of mesoporous microsphere shape titanium niobate/carbon composite according to claim 1, it is characterized in that, described step 2) in titanium source be one or more in titanium tetrachloride, titanium trichloride, butyl titanate, titanyl sulfate, titanium tetraisopropylate, titanium tetrafluoride.
4. the preparation method of mesoporous microsphere shape titanium niobate/carbon composite according to claim 1, is characterized in that, described step 2) in niobium source be one or more in ethanol niobium, niobium oxalate, columbium pentachloride, ammonium niobium oxalate.
5. the preparation method of mesoporous microsphere shape titanium niobate/carbon composite according to claim 1, is characterized in that, described step 3) in heating-up temperature be 100-235 DEG C.
6. the preparation method of mesoporous microsphere shape titanium niobate/carbon composite according to claim 1, is characterized in that, described step 5) in inert gas be one or both in argon gas, nitrogen.
7. the preparation method of mesoporous microsphere shape titanium niobate/carbon composite according to claim 1, is characterized in that, described step 5) in sintering temperature be 410-1100 DEG C.
8. the mesoporous microsphere shape titanium niobate/carbon composite prepared by the preparation method described in claim arbitrary in claim 1-7.
9. mesoporous microsphere shape titanium niobate/carbon composite according to claim 8, is characterized in that, mesoporous microsphere is assembled by a large amount of nano particle and formed, and microballoon is of a size of 0.2-6 micron.
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| CN105552346A (en) * | 2016-02-26 | 2016-05-04 | 南阳师范学院 | Titanium niobate/carbon composite electrode material and preparation method thereof |
| CN105776334A (en) * | 2016-04-07 | 2016-07-20 | 南阳师范学院 | Spherical Ti2Nb10O29 material and preparation method thereof |
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