CN104183823A - SnO2, MnO or Mn3O4-based composite material based on three-dimensional carbon sphere framework structure and preparation method of material - Google Patents

SnO2, MnO or Mn3O4-based composite material based on three-dimensional carbon sphere framework structure and preparation method of material Download PDF

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CN104183823A
CN104183823A CN201410437168.9A CN201410437168A CN104183823A CN 104183823 A CN104183823 A CN 104183823A CN 201410437168 A CN201410437168 A CN 201410437168A CN 104183823 A CN104183823 A CN 104183823A
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余颖
胡浩
邱明强
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Huazhong Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a SnO2, MnO or Mn3O4-based composite material based on a three-dimensional carbon sphere framework structure and a preparation method of the material. The SnO2, MnO or Mn3O4-based composite material consists of microspheres formed by SnO2, MnO or Mn3O4 metal oxides packaged by crystallized carbon and amorphous carbon which are distributed in a crossing manner, wherein the diameter of the composite material is 100nm-800nm, and the particle diameters of metal oxides are 2nm-50nm. The composite material prepared by virtue of the preparation method has excellent electrochemical performance, particularly, the three-dimensional carbon sphere framework structure has a large space to allow volume expansion of stannic oxide or manganese oxide in lithium embedding and removing processes, besides, crystallized carbon which packages stannic oxide or manganese oxide particles and is distributed in the crossing manner can be bent during the volume expansion, and amorphous carbon around crystallized carbon is further compressed, so that the composite material has high toughness, the structural stability is guaranteed, and the cycling stability of the composite material is good.

Description

SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4based composites and preparation method thereof
Technical field
The invention belongs to technical field of lithium batteries, relate to a kind of SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4based composites and preparation method thereof.
Background technology
Tin ash, the metal oxides such as manganese monoxide because of its reserves abundant, low price, energy density is high, capacitance high (if the theoretical reversible capacity of tin ash is 993mAh/g, manganese monoxide be 755mAh/g.) etc. feature and receiving much concern, the star in lithium ion battery negative material of new generation, but these metal oxides are except conductivity is lower, also there is a fatal shortcoming: volumetric expansion is larger in lithium ion embeds and deviates from process, even cause lattice to cave in, material efflorescence, thus cause cycle life shorter, be difficult to actual production and application.Graphite-like material with carbon element is current conventional negative material, but its easy formation Li dendrite in discharging and recharging may puncture battery diaphragm and cause short circuit and cause potential safety hazard, and capacitance lower (theoretical reversible capacity is 372mAh/g) is high rate charge-discharge process especially.In recent years, the preparation of composite material and the research of the application in lithium ion battery negative material thereof about metal oxide and carbon are more and more, yet these are simply grown in metal oxide on material with carbon element, or material with carbon element is coated on metal oxide, and the method even the two being mixed not can solve the large volume expansion issues of metal oxide.The composite material of current more strikingly Graphene and metal oxide, it has excellent chemical property, but its synthesis technique is complicated, and cost is higher, only delay to a certain extent metal oxide volume expansion issues, but still be difficult to maintain 300 above long-life circulations.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, and a kind of SnO based on three-dimensional carbon ball frame structure is provided 2, MnO or Mn 3o 4based composites and preparation method thereof, it utilizes stable carbon ball framework by metal oxide particle SnO 2, MnO or Mn 3o 4be coated and fixed, make composite material not only there is good chemical property, and good cycling stability.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4based composites, described composite material diameter 100～800nm, is by SnO 2, MnO or Mn 3o 4metal oxide is wrapped up and the microballoon of formation by the crystallization carbon of cross-distribution and amorphous carbon, wherein: described metal oxide particle diameter is 2～50nm.
The present invention also provides the above-mentioned SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4the preparation method of based composites, comprises the following steps:
(1) prepare colloidal carbon sphere: the monose that compound concentration is 0.5～1.8mol/L or the aqueous solution of biglycan, the aqueous solution is placed in to hydrothermal reaction kettle, at 130～180 ℃ of hydro-thermal reaction 5～12h, product washing centrifugal treating obtains colloidal carbon sphere;
(2) preparation activation colloidal carbon sphere: step (1) gained colloidal carbon sphere is soaked in the water soluble acid of 0.1～4mol/L or the aqueous solution of alkali, under normal pressure, at the temperature of 50～120 ℃, activate 2～24h, the dry processing of products therefrom washing is obtained activating colloidal carbon sphere;
(3) SnO of preparation based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4based composites: step (2) gained activation colloidal carbon sphere is joined in the mixed solution of water that Sn or Mn ion concentration are 0.05～0.5mol/L and ethanol, mix after in 20～90 ℃ of water-bath 3～24h, again by the product that obtains of washing centrifugal treating under nitrogen or argon gas atmosphere, high-temperature process 2～10h under 400～800 ℃ of temperature conditions; In air, under 150～300 ℃ of temperature conditions, steadyization processed 0.5～3h subsequently, obtains the oxide of tin or manganese and the composite material of carbon.
Press such scheme, the described Sn ion of step (3) is divalence Sn ion or tetravalence Sn ion or both mixing; Described Mn ion is divalence Mn ion.
Press such scheme, the described monose of step (1) or biglycan are one or more mixtures that mix in any proportion in glucose, fructose, sucrose.
Press such scheme, the described water soluble acid of step (2) or alkali are a kind of in hydrochloric acid, nitric acid, phosphoric acid, acetic acid, ammoniacal liquor, NaOH, potassium hydroxide.
Press such scheme, step (3) described configuration Sn or the required pink salt of Mn solion are SnCl 4, Sn (NO 3) 4, SnCl 2, Sn (NO 3) 2, SnC 2o 4in a kind of or mixture that both mix in any proportion; Manganese salt is MnCl 2, Mn (NO 3) 2, MnSO 4in a kind of or mixture that both mix in any proportion.
Press such scheme, the volume ratio of the described water of step (3) and ethanol is 1:1～1:10.
Press such scheme, the ratio of the volume of the water that the quality of activation colloidal carbon sphere and Sn or Mn ion concentration are 0.05～0.5mol/L in described step (3) and the mixed solution of ethanol is 0.05～10g/100mL.
The present invention also provides the above-mentioned SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4the application of based composites in lithium ion battery negative material.
In preparation process of the present invention, under the high temperature and high pressure environment (in hydrothermal reaction kettle) of sealing anoxic, can there is polycondensation reaction and form spherical condensation polymer in monose or biglycan (glucose, fructose or sucrose) first, more further carbonization forms colloidal carbon sphere.Because formed colloidal carbon sphere has a large amount of spaces and duct, and a large amount of higher chemical bond of hydroxy kind activity, with acid (hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid) or alkali (NaOH, potassium hydroxide, ammoniacal liquor), after processing, easily, at inner acidity or the basic site of forming of colloidal carbon sphere, the adsorption capacity of colloidal carbon sphere to acidic oxide or basic anhydride can be strengthened in these sites.And then by choose (ethanol and the water mixed solution) of specific solvent, can make product exist with spherical structure form, reducing thus surface can settle out, this is because the difference of solution system can affect the stable chemical energy of product, when containing a certain amount of ethanol, the surface activity of product increases, and for reaching stable state, product can trend towards spherical structure form and exist.Then under protective atmosphere through high-temperature process, the predecessor that part activates colloidal-carbon absorption tin ion or manganese ion gained can be reduced to tin or manganese by carbon is corresponding, and metallic tin or manganese have excellent aromatization catalytic performance, can finally generate SnO thus 2, MnO or Mn 3o 4metal oxide is by the composite material of the crystallization carbon of cross-distribution and amorphous carbon parcel, and its preparation process as shown in Figure 1.
This composite material has the volumetric expansion in the de-lithium process of embedding lithium for metal oxide particle of larger space, in addition the crystallization carbon that is wrapped in metal oxide particle external chiasma distribution can be crooked when volumetric expansion, amorphous carbon is around compression further, thereby there is stronger toughness, guarantee the stability of structure.In addition, amorphous carbon and partially-crystallized carbon can effectively improve the conductivity of material, gained composite material has super large specific area and from micropore to mesoporous four sector hole footpath distribution characteristicss, be conducive to electrolyte mobile and lithium ion migration in material, can form different passages, be conducive to high rate charge-discharge.Its principle as shown in figure 11.
Beneficial effect of the present invention is:
1, the present invention is effectively by the high elastic coefficient of material with carbon element, high conductivity, the attributes such as the high power capacity of the characteristics such as stronger structural stability and preferably lithium ion diffusion coefficient and metal oxide, high-energy-density combine, overcome the low capacity of material with carbon element electrode and metal oxide and caused the poor problem of electrode stability because of volumetric expansion, prepared cell negative electrode material shows superior cycle performance and high rate performance, especially possesses high-power cyclical stability, there is good chemical property, for example SnO 2in the situation that current density is 300mA/g, through 350 its specific capacities that circulate, still remain on 653mAh/g with the composite material of carbon, be about the twice of graphite theoretical capacity, and corresponding SnO 2double-layer hollow ball (as shown in Figure 2 d) circulation just decays to 0 less than 100 times.The composite material that in addition prepared by the present invention is also showing excellent stability, for example SnO aspect high-power discharging and recharging 2under different multiplying, circulate after 93 times with the composite material of carbon, under the multiplying power of 20C, capacity is still up to 260mAh/g, and the conservation rate after 600 times that circulates reaches 84%, circulates 1000 times still up to 78%.The composite material of MnO and carbon in the situation that current density is 1C through 300 times circulation after specific capacity still remain on 498mAh/g, theoretical capacity far above graphite, and corresponding MnO specific capacity is only for conservation rate after 197mAh/g circulation 200 times reaches 89%, and the capacity of carbon ball under this multiplying power is almost close to zero.
2, preparation method provided by the present invention is simple and convenient, by changing amount or the reaction temperature of reaction reagent, just can regulate and control like a cork the ratio of carbon and metal oxide, the solution system reacting by change and reaction time are the structure and morphology of adjustable compound, course of reaction is easy to control, productive rate is high, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the synthetic schematic diagram of the oxide of tin or manganese and the composite material of carbon;
Fig. 2 (a) is the SEM figure of prepared acidic activated colloidal carbon sphere in embodiment 1; (b) be SnO 2sEM figure with composite material (SPOCs) predecessor of carbon; (c) be SnO 2sEM figure with the composite material of carbon; (d) be SnO 2composite material carbon elimination gained SnO with carbon 2sEM figure;
I in Fig. 3 (a), ii, iii is respectively SnO 2with after the composite material predecessor of carbon, high-temperature process and steadyization process the XRD figure of afterproduct; (b), (c), (d) be respectively SnO 2composite material, carbonization colloidal-carbon (colloidal carbon sphere is placed in ar gas environment high-temperature calcination product) and carbon elimination gained SnO thereof with carbon 2bET (specific area test) and graph of pore diameter distribution;
Fig. 4 is SnO 2tEM and HRTEM figure with the composite material of carbon;
I in Fig. 5, ii, iii, iv is respectively SnO 2composite material carbon elimination gained SnO with carbon 2double-layer hollow ball, SnO 2raman collection of illustrative plates with composite material, carbonization colloidal-carbon and the commercialization Graphene of carbon;
Fig. 6 (a), (b) is respectively SnO 2cV figure after the battery initial cycle preparing with the composite material of carbon and circulation thereof 50 times;
Fig. 7 is SnO 2composite material carbon elimination gained SnO with carbon 2double-layer hollow ball, SnO 2cycle performance figure with composite material (SPOCs) electrode of carbon under 300mA/g;
Fig. 8 is SnO 2sEM figure after circulation with composite material (SPOCs) electrode of carbon under 300mA/g 350 times;
Fig. 9 (i), (ii), (iii) is respectively SnO 2composite material (SPOCs), SnO with carbon 2composite material carbon elimination gained SnO with carbon 2double-layer hollow ball, the high rate performance of carbonization colloidal-carbon (CCs) under 0.5-20C and coulomb efficiency (1C=690mA/g) figure;
Figure 10 is SnO 2first after different multiplying circulation, continue the cycle performance figure under 20C multiplying power with the composite material of carbon;
Figure 11 is SnO 2effectively overcome the mechanism figure of volumetric expansion problem with the composite material of carbon;
Figure 12 (a), (b) is the SEM figure of the composite material (nMCs) of MnO and carbon, (c), (d) is the SEM figure of its carbon elimination gained MnO particle;
The XRD figure of the MnO that Figure 13 is and the composite material of carbon and MnO particle;
Figure 14 is TEM (a), HRTEM (b), cross section TEM (c), spherical aberration TEM (d) and the C of the composite material of MnO and carbon, Mn, O distribution diagram of element (e, f, g);
Figure 15 is the composite material (nMCs) of MnO and carbon and the cycle performance figure under MnO mosaic electrode 1C (1C=660mAh/g) multiplying power;
Figure 16 is composite material (nMCs), MnO particle and the cycle performance figure of corresponding carbonization colloidal-carbon electrode under different multiplying (1C=660mAh/g) of MnO and carbon;
Figure 17 is that the composite material of MnO and carbon first continues the cycle performance figure under 20C multiplying power after different multiplying circulation;
Figure 18 (a), (b) is the SEM figure of embodiment 3 gained colloidal carbon spheres, (c), (d) is the SEM figure of embodiment 3 gained composite materials;
Figure 19 (a) is the XRD figure of embodiment 3 gained composite materials, (b) be the CV figure of embodiment 3 gained composite materials, (c), for it is the cycle performance figure under 1C (C=700mA/g) condition in current density, (d) be the AC impedance figure (frequency be 0.01～100000Hz) of embodiment 3 gained composite materials after the 1st circulation circulates with the 100th time;
Figure 20 (a), (b) is the SEM figure of embodiment 4 gained colloidal carbon spheres, (c), (d) is the SEM figure of embodiment 4 gained composite materials;
Figure 21 (a) is the XRD figure of embodiment 4 gained composite materials, (b) be the CV figure of embodiment 4 gained composite materials, (c) for it is the cycle performance figure under 500mA/g condition in current density, be (d) voltage-Capacity Plan of embodiment 4 gained composite materials;
Figure 22 (a), the SEM that (b) is respectively the prepared colloidal carbon sphere of 1.8M D/W and the prepared colloidal carbon sphere of 0.5M aqueous sucrose solution schemes;
Figure 23 (a) is the SEM figure of embodiment 5 gained composite materials, (b) be the XRD figure of embodiment 5 gained composite materials, (c) being the high rate performance of embodiment 5 gained composite materials under 1-20C and coulomb efficiency (1C=690mA/g) figure, is (d) the cycle performance figure under 600mA/g condition for it in current density.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
The present embodiment is prepared SnO 2with the composite material of carbon, its method step is as follows:
(1) prepare colloidal carbon sphere: by the D/W of 70mL 1.2M (1M=1mol/L) be placed in capacity be the hydrothermal reaction kettle of 100mL in 180 ℃ of reactions 5 hours, product is washed and centrifugally can obtain memnonious colloidal carbon sphere; Other conditions are constant, 1.2M D/W are changed to respectively to the D/W of 1.8M and the pattern of the prepared colloidal carbon sphere of 0.5M aqueous sucrose solution is shown in Figure 22.
(2) preparation activation colloidal carbon sphere: take colloidal carbon sphere prepared by 1g above-mentioned steps (1), add in 80mL 1M HCl, under normal pressure at 100 ℃ activation processing 12h, products therefrom washing is dry after, can obtain acidic activated colloidal carbon sphere.It is that uniform diameter is the microballoon of 150～500nm that SEM tests this carbon ball.
(3) prepare SnO 2composite material (SPOCs) with carbon: take the acidic activated colloidal carbon sphere of 0.3g (its pattern is shown in Fig. 2 (a)) of above-mentioned preparation, join 0.5M SnCl 280mL ethanol water system (volume ratio of water and ethanol is 1:3) in, in 50 ℃ of Water Unders, bathe reaction 8h, this process completes under constantly stirring, and obtains SnO 2composite material predecessor with carbon.Then by predecessor under argon atmosphere at 500 ℃ high-temperature process 3 hours, finally in air, in 250 ℃ of steadyization, process 1.5h, can obtain SnO 2composite material with carbon.
The synthetic schematic diagram of the present embodiment as shown in Figure 1, although that colloidal carbon sphere possesses a large amount of pore space structures is not strong to the adsorptivity of metal ion, can improve its adsorptivity to ion after activating by acid or alkali.In ethanol-water system, the microballoon that is conducive to adion utilizes your moral slaking mechanism of Oswald to form many shell structurres, and metal ion forms metal oxide simultaneously.Finally in protective atmosphere, anneal, in the process that the oxide of tin or manganese is reduced, catalysed promoted colloidal-carbon aromatization forms the compound of crystallization carbon and agraphitic carbon, and after in air, steadyization processed, the chemical property of metal oxide is more stable.
If Fig. 2 (a) is the SEM figure of the prepared acidic activated colloidal carbon sphere of 1.2M D/W; (b) be SnO 2sEM figure with composite material (SPOCs) predecessor of carbon; (c) be SnO 2sEM figure with the composite material of carbon; (d) be SnO 2composite material carbon elimination (500 ℃ of calcining 3h in air) gained SnO with carbon 2the SEM figure of double-layer hollow ball, known prepared SnO 2with the predecessor of the composite material of carbon be the spherical structure of diameter 200～500nm, the SnO obtaining after high-temperature process in argon atmosphere 2with the composite material diameter 300nm of carbon, continue in air after 500 ℃ of complete carbon eliminations of calcining 3h SnO 2become SnO with the composite material of carbon 2double-layer hollow spherical structure, illustrate that stannide can be affected by surface in the mixed solution of ethanol and water, finally in carbon framework and non-uniform Distribution, but concentrate in two-layer spherical shell.
As Fig. 3 (a) is depicted as the present embodiment SnO 2with after the composite material predecessor of carbon, high-temperature process and steadyization process the XRD figure of afterproduct, as seen from the figure SnO 2with the composite material predecessor of carbon be the composite material of tin ash and carbon, in nitrogen, after high-temperature process, tin ash partial reduction is metallic tin and tin monoxide, steadyization becomes again the composite material of tin ash and carbon after processing.Fig. 3 (b), (c), (d) is respectively SnO 2composite material, carbonization colloidal-carbon (colloidal carbon sphere is placed in the product of 500 ℃ of calcining 2h of ar gas environment) and carbon elimination gained SnO thereof with carbon 2bET (specific area test) and graph of pore diameter distribution, concentrated expression gained composite material there is 157.28m 2the super large specific area of/g, and possess by micropore to mesoporous, aperture is about the four sector hole footpath distribution characteristicss of 1.22nm, 10.6nm, 22.4nm and 40.0nm.Gained SnO is described in addition 2not only retained the bigger serface of colloidal-carbon with the composite material of carbon, and expanded aperture in the process of absorption tin ion formation tin ash, large aperture is more conducive to flowing of electrolyte.
Fig. 4 (a), (b), (c), (d) is SnO 2transmission electron microscope picture (TEM) and high resolution graphics (HRTEM) thereof with the composite material of carbon.Fig. 4 (a, b) can be clearly seen that SnO 2with the composite material of carbon be that stannic oxide particle is distributed in carbon ball double-layer spherical shell, Fig. 4 (c, d) lattice arrangement situation and spacing of lattice thereof show that two ball layers are the structure of crystallization carbon and agraphitic carbon parcel tin ash, between double-deck tin dioxide nucleic shell, be agraphitic carbon, its structural representation is as shown in wherein illustration.By Fig. 5 in conjunction with tin ash and commercialization Graphene further in figure the carbon-coating of D, G peak proof gained composite material contain agraphitic carbon, and determine and wherein contain crystallization carbon by 2D peak, and carbonization colloidal-carbon is only agraphitic carbon, this also just illustrates that the formation of crystallization carbon be unable to do without the catalysis of tin.In conjunction with Fig. 4 electronic scanning Electronic Speculum figure and transmission electron microscope picture, illustrate that resulting materials is SnO 2by the crystallization carbon of cross-distribution and amorphous carbon parcel, formed using carbon as support frame, there is double-deck microballoon, wherein: described metal oxide particle diameter is 5nm.
The SnO that said method prepares 2be applicable to lithium ion battery negative material with the composite material of carbon, can same S, LiMnO 4, LiFePO 4etc. common positive electrode assembling, help battery.The battery initial cycle preparing and the CV circulating after 50 times thereof scheme (cyclic voltammogram) as shown in Figure 6, in Fig. 6 (a) between 0.5～0.8V fainter broad peak corresponding to irreversible SEI film (solid electrolyte film, for electrolyte contact with electrode material after deposition generate) reaction of formation, the larger reduction peak of 0.05V left and right intensity, embedding lithium reaction corresponding to tin, 0.25, 0.50, 0.75 and the oxidation peak of 1.25V, correspond respectively to deviating from of the embedded lithium of carbon framework in composite material, the de-lithium reaction of double-deck ball ectonexine tin lithium and tin further with the reacting of lithia.Circulate after 50 times, can find out that its redox peak becomes very symmetrical, this is mainly because formed high speed lithium ion passage, thereby also makes this material have superior chemical property.
Fig. 7 is carbon elimination gained SnO 2double-layer hollow ball, SnO 2cycle performance figure with composite material (SPOCs) electrode of carbon under 300mA/g.Can see SnO 2in the situation that current density is 300mA/g, through 350 its specific capacities that circulate, still remain on 653mAh/g with the composite material of carbon, be about the twice of graphite theoretical capacity, and corresponding carbon elimination gained SnO 2(double-layer hollow ball) circulation just decays to 0 less than 100 times.
Fig. 8 is SnO 2the SEM figure circulating under 300mA/g after 350 times with composite material (SPOCs) electrode of carbon.Can know and find out, the structure stable existence that remains unchanged after this material circulation 350 times.
Fig. 9 (i), (ii), (iii) is respectively SnO 2composite material (SPOCs), SnO with carbon 2composite material carbon elimination gained SnO with carbon 2double-layer hollow ball, the high rate performance of carbonization colloidal-carbon (CCs) under 0.5-20C and a coulomb efficiency (1C=690mA/g, C refers to that battery emits the current value that its theoretical capacity is exported in official hour) figure.0.5,1,2,3,6,9,12 and the multiplying power of 20C under, SnO 2be respectively 680,590,510,450,400,360,300 and 260mAh/g with the capacity of the composite material of carbon, its cycle performance is obviously better than SnO 2double-layer hollow ball and carbonization colloidal-carbon (CCs), the especially multiplying power more than 3C, the superiority of this material is more obvious.Under the multiplying power of 20C, capacity still reaches 260mAh/g, the conservation rate after 600 times that circulates reaches 84%, circulate and still reached for 78% (as shown in figure 10) for 1000 times, and efficiency approaches this electrode material of 100% explanation and can effectively the electric weight being filled with all be discharged, and the capacity of carbonization colloidal-carbon under this multiplying power is practically negligible.In addition, by 20C, be switched to 0.5C when multiplying power as can be seen from Figure, or while being switched to 20C by 0.5C, the same rate capability of battery changes, and SnO is described very little 2there is good magnification transformable performance with the composite material of carbon.
SnO 2there is excellent chemical property with the composite material of carbon, mainly that its double-deck spherical structure has the volumetric expansion in the de-lithium process of embedding lithium for tin oxide of larger space, in addition the crystallization carbon that is wrapped in granules of stannic oxide external chiasma distribution can be crooked when volumetric expansion, amorphous carbon is around compression further, thereby there is stronger toughness, guarantee the stability of structure.In addition, the existence of amorphous carbon and partially-crystallized carbon can effectively improve the conductivity of material, and this compound mode has from micropore to mesoporous four sections of pore-size distributions, is conducive to electrolyte mobile and lithium ion migration in material, can form different passages, be conducive to high rate charge-discharge.Its principle as shown in figure 11.
Embodiment 2
The present embodiment is prepared the composite material of MnO and carbon, and its method step is as follows:
(1) prepare colloidal carbon sphere: by the D/W of 70mL 1.8M be placed in capacity be the hydrothermal reaction kettle of 100mL in 180 ℃ of reactions 5 hours, product is washed and centrifugally can obtain memnonious colloidal carbon sphere;
(2) preparation activation colloidal carbon sphere: take the colloidal carbon sphere of the above-mentioned preparation of 1g, add 80mL 1MNH 3h 2in O, under normal pressure at 100 ℃ activation processing 12h, products therefrom washing is dry after, can obtain alkaline activation colloidal carbon sphere;
(3) prepare the composite material of MnO and carbon: take the 0.3g alkaline activation colloidal carbon sphere of above-mentioned preparation, join 0.5M MnCl 280mL ethanol water system (volume ratio of water and ethanol is 1:1) in, in 80 ℃ of Water Unders, bathe reaction 8h, this process completes under constantly stirring.Then by product under argon atmosphere, in 700 ℃ of high-temperature process 2 hours, finally in air, in 300 ℃ of steadyization, process 0.5h, can obtain the composite material of MnO and carbon.
The pattern of the composite material of MnO and carbon (nMCs) is as shown in Figure 12 (a), (b), and figure (c), (d) are the SEM figure of its carbon elimination gained MnO particle.The about 250nm of composite material particle diameter of MnO and carbon as seen from the figure, the about 5nm of the particle diameter of manganese monoxide and carbon elimination gained MnO particle reaches 200nm wherein, illustrates in heat treatment process that manganese monoxide has the trend of reunion and carbon ball framework can effectively stop manganese monoxide particle agglomeration.Figure 13 is the composite material of MnO and carbon and the XRD of MnO particle figure, and the oxide that can determine contained manganese in gained composite material is manganese monoxide.Figure 14 is TEM (a), HRTEM (b), cross section TEM (c), spherical aberration TEM (d) and the C of the composite material of MnO and carbon, Mn, O distribution diagram of element (e, f, g), the composite material that proves gained MnO and carbon is that manganese monoxide particle is by the crystallization carbon of cross-distribution and the coated non-hollow structure forming of amorphous carbon.
The composite material of MnO and carbon still remains on 498mAh/g through 300 its specific capacities that circulate in the situation that current density is 1C (C=660mA/g), and far above the theoretical capacity of graphite, and corresponding MnO particle is only 197mAh/g, as shown in figure 15.This material is also showing excellent stability aspect high-power discharging and recharging, after 0.5-30C circulation 100 times, under the multiplying power of 30C, capacity still reaches 132mAh/g, the conservation rate after 200 times that circulates reaches 89%, and the capacity of corresponding carbonization colloidal-carbon under this multiplying power is practically negligible, and efficiency approaches 100%, as shown in Figure 16,17, Figure 16 (i) wherein, (ii), (iii) be respectively composite material (nMCs), its carbon elimination gained MnO particle and the cycle performance figure of corresponding carbonization colloidal-carbon electrode under different multiplying (1C=660mAh/g) of MnO and carbon.
Embodiment 3
The present embodiment is prepared SnO 2with the composite material of carbon, its method step is as follows:
(1) prepare colloidal carbon sphere: the aqueous sucrose solution of 70mL 0.5M is placed in to hydrothermal reaction kettle in 130 ℃ of reactions 12 hours, product is washed and centrifugally can obtain memnonious colloidal carbon sphere;
(2) preparation activation colloidal carbon sphere: take the colloidal carbon sphere of the above-mentioned preparation of 1g, add 80mL 0.1M HNO 3in, under normal pressure at 50 ℃ activation processing 24h, products therefrom washing is dry after, can obtain acidic activated colloidal carbon sphere;
(3) prepare SnO 2composite material with carbon: take the acidic activated colloidal carbon sphere of 0.3g of above-mentioned preparation, join the SnCl containing 0.3M 2and 0.2M SnCl 480mL ethanol water system (volume ratio of water and ethanol is 1:5) in, in 90 ℃ of Water Unders, bathe reaction 3h, this process completes under constantly stirring.Then by product under argon atmosphere, at 400 ℃, high-temperature process is 10 hours, finally in air, in 150 ℃ of steadyization, processes 3h, can obtain SnO 2composite material with carbon.
The pattern of gained colloidal carbon sphere is as shown in Figure 18 (a), (b), and its particle diameter is about 300nm, and figure (c), (d) are SnO 2with the SEM figure of the composite material of carbon, its particle diameter is about 220nm.The compound that the known gained composite material of XRD data being shown by Figure 19 (a) is tin ash and carbon.
The SnO preparing 2with the chemical property of the composite electrode of carbon as shown in Figure 19 (b), in Figure 18 (b) between 0.5～0.8V fainter broad peak corresponding to the reaction of formation of irreversible SEI film, the larger reduction peak of 0.05V left and right intensity, embedding lithium reaction corresponding to tin, 0.25,0.50,0.75 and the oxidation peak of 1.25V, correspond respectively to deviating from of the embedded lithium of carbon framework in composite material, the de-lithium reaction of every layer of tin lithium of double-deck ball and tin further with the reacting of lithia.The composite material that Figure 19 (c) is MnO and carbon is the cycle performance figure under the condition of 1C (C=700mA/g) in current density, through 110 its specific capacities that circulate, still remain on 588mAh/g, far above the theoretical capacity of graphite, capacity attenuation is only 17.3%.The AC impedance figure (frequency be 0.01～100000Hz) of the composite material that Figure 19 (d) is MnO and carbon after the 1st circulation circulates with the 100th time, in figure, semicircle can be found out, circulate 100 AC impedance by greatly 309 ohm of 146 ohm of changes, there are not two half disk patterns, with regard to illustrative material, do not cave in yet.
Embodiment 4
The present embodiment is prepared Mn 3o 4with the composite material of carbon, its method step is as follows:
(1) prepare colloidal carbon sphere: the fructose water solution of 70mL 0.8M is placed in to hydrothermal reaction kettle in 160 ℃ of reactions 12 hours, product is washed and centrifugally can obtain memnonious colloidal carbon sphere;
(2) preparation activation colloidal carbon sphere: take the colloidal carbon sphere of the above-mentioned preparation of 1g, add in 80mL 4M NaOH, under normal pressure at 120 ℃ activation processing 2h, products therefrom washing is dry after, can obtain acidic activated colloidal carbon sphere;
(3) prepare Mn 3o 4composite material with carbon: take the 8g alkaline activation colloidal carbon sphere of above-mentioned preparation, join (the NO containing 3M Mn 3) 2and 2M MnSO 480mL ethanol water system (volume ratio of water and ethanol is 1:10) in, in 20 ℃ of Water Unders, bathe reaction 24h, this process completes under constantly stirring.Then by product under argon atmosphere, at 800 ℃, high-temperature process is 3 hours, finally in air, in 300 ℃ of steadyization, processes 0.5h, can obtain Mn 3o 4composite material with carbon.
The pattern of gained colloidal carbon sphere is as shown in Figure 20 (a), (b), and its particle diameter is about 800nm, and figure (c), (d) are Mn 3o 4with the SEM figure of the composite material of carbon, its particle diameter is about 700nm.The compound that is mangano-manganic oxide and carbon by the known gained composite material of Figure 21 (a) XRD data.
The Mn preparing 3o 4with the CV (multiple scanning 3 times) of the composite electrode of carbon as shown in Figure 21 (b), in figure 0.1 with the reduction peak of 0.5V corresponding to Mn 3o 4be reduced to Mn/Li 2o, and oxidation peak corresponding to 1.3V is Mn oxidation formation MnO.Figure 21 (c) is Mn 3o 4in the situation that current density is 500mA/g, through 200 its specific capacities that circulate, still remain on 497mAh/g with the composite material of carbon, far above the theoretical capacity of graphite, capability retention reaches 80%, and efficiency approaches 100%.Figure 21 (d) is Mn 3o 4with the voltage-Capacity Plan of the composite material of carbon, a wherein, b, c, d, e is followed successively by the 1st, 2,10,100,200 charging curves, i, ii, iii, iv, v is respectively the 1st, 2,10,100,200 discharge curves, as seen from the figure, after electric discharge, discharge platform tends towards stability first, along with the increase capacity attenuation of cycle-index has obtained good control.
Embodiment 5
The present embodiment is prepared SnO 2with the composite material of carbon, its method step is as follows:
(1) prepare colloidal carbon sphere: the aqueous sucrose solution of 70mL1M is placed in to hydrothermal reaction kettle in 160 ℃ of reactions 12 hours, product is washed and centrifugally can obtain memnonious colloidal carbon sphere;
(2) preparation activation colloidal carbon sphere: take the colloidal carbon sphere of the above-mentioned preparation of 1g, add 80mL 0.1M HNO 3in, under normal pressure at 50 ℃ activation processing 24h, products therefrom washing is dry after, can obtain acidic activated colloidal carbon sphere;
(3) prepare SnO 2composite material with carbon: take the acidic activated colloidal carbon sphere of 0.04g of above-mentioned preparation, join (the NO containing 0.3MSn 3) 4, 0.2MSnC 2o 4and 0.2MSn (NO 3) 280mL ethanol water system (volume ratio of water and ethanol is 1:5) in, in 90 ℃ of Water Unders, bathe reaction 3h, this process completes under constantly stirring.Then by product under argon atmosphere, at 400 ℃, high-temperature process is 10 hours, finally in air, in 150 ℃ of steadyization, processes 3h, can obtain SnO 2composite material with carbon.
Gained SnO 2with the composite material of carbon pattern as shown in Figure 23 (a), the about 350nm of particle size.The compound that is tin ash and carbon by the known gained composite material of Figure 23 (b) XRD data.The prepared battery of this material is also showing excellent stability aspect high-power discharging and recharging, and as shown in Figure 23 (c), after 1-20C circulation 100 times, under the multiplying power of 20C, battery capacity still reaches 198mAh/g.In addition, by 20C, be switched to 2C when multiplying power as can be seen from Figure, or while being switched to 20C by 2C, the same rate capability of battery changes, and SnO is described very little 2there is good magnification transformable performance with the composite material of carbon.Figure 23 (d) is SnO 2in the situation that current density is 600mA/g, through 200 its specific capacities that circulate, still remain on 631mAh/g with the composite material of carbon, far above the theoretical capacity of graphite, capability retention reaches 90%, and coulombic efficiency approaches 100%.

Claims (8)

1. the SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4based composites, is characterized in that described composite material diameter 100～800nm, is by SnO 2, MnO or Mn 3o 4metal oxide is wrapped up and the microballoon of formation by the crystallization carbon of cross-distribution and amorphous carbon, wherein: described metal oxide particle diameter is 2～50nm.
2. the SnO based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4the preparation method of based composites, is characterized in that comprising the following steps:
(1) prepare colloidal carbon sphere: the monose that compound concentration is 0.5～1.8mol/L or the aqueous solution of biglycan, the aqueous solution is placed in to hydrothermal reaction kettle, at 130～180 ℃ of hydro-thermal reaction 5～12h, product washing centrifugal treating obtains colloidal carbon sphere;
(2) preparation activation colloidal carbon sphere: step (1) gained colloidal carbon sphere is soaked in the water soluble acid of 0.1～4mol/L or the aqueous solution of alkali, under normal pressure, at the temperature of 50～120 ℃, activate 2～24h, the dry processing of products therefrom washing is obtained activating colloidal carbon sphere;
(3) SnO of preparation based on three-dimensional carbon ball frame structure 2, MnO or Mn 3o 4based composites: step (2) gained activation colloidal carbon sphere is joined in the mixed solution of water that Sn or Mn ion concentration are 0.05～5mol/L and ethanol, mix after in 20～90 ℃ of water-bath 3～24h, again by the product that obtains of washing centrifugal treating under nitrogen or argon gas atmosphere, high-temperature process 2～10h under 400～800 ℃ of temperature conditions; In air, under 150～300 ℃ of temperature conditions, steadyization processed 0.5～3h subsequently, obtains the oxide of tin or manganese and the composite material of carbon.
3. the SnO based on three-dimensional carbon ball frame structure according to claim 2 2, MnO or Mn 3o 4the preparation method of based composites, is characterized in that the described monose of step (1) or biglycan are one or more mixtures that mix in any proportion in glucose, fructose, sucrose.
4. the SnO based on three-dimensional carbon ball frame structure according to claim 2 2, MnO or Mn 3o 4the preparation method of based composites, is characterized in that the described water soluble acid of step (2) or alkali are a kind of in hydrochloric acid, nitric acid, phosphoric acid, acetic acid, ammoniacal liquor, NaOH, potassium hydroxide.
5. the SnO based on three-dimensional carbon ball frame structure according to claim 2 2, MnO or Mn 3o 4the preparation method of based composites, is characterized in that step (3) described configuration Sn or the required pink salt of Mn solion are SnCl 4, Sn (NO 3) 4, SnCl 2, Sn (NO 3) 2, SnC 2o 4in one or more mixtures that mix in any proportion; Manganese salt is MnCl 2, Mn (NO 3) 2, MnSO 4in one or more mixtures that mix in any proportion.
6. according to the SnO based on three-dimensional carbon ball frame structure described in claim 2 or 5 2, MnO or Mn 3o 4the preparation method of based composites, the volume ratio that it is characterized in that the described water of step (3) and ethanol is 1:1～1:10.
7. the SnO based on three-dimensional carbon ball frame structure according to claim 2 2, MnO or Mn 3o 4the preparation method of based composites, the ratio of the volume of the water that the quality that it is characterized in that activation colloidal carbon sphere in step (3) and Sn or Mn ion concentration are 0.05～5mol/L and the mixed solution of ethanol is 0.05～10g/100mL.
8. the SnO based on three-dimensional carbon ball frame structure preparing according to the method described in claim 2-7 2, MnO or Mn 3o 4the application of based composites in lithium ion battery negative material.
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