CN104183823B - 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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CN104183823B
CN104183823B CN201410437168.9A CN201410437168A CN104183823B CN 104183823 B CN104183823 B CN 104183823B CN 201410437168 A CN201410437168 A CN 201410437168A CN 104183823 B CN104183823 B CN 104183823B
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sno
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CN104183823A (en
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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
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    • 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
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    • 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
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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 structure2, MnO or Mn3O4Based composites and its system Preparation Method
Technical field
The invention belongs to technical field of lithium batteries, it is related to a kind of SnO based on three-dimensional carbon ball frame structure2, MnO or Mn3O4 Based composites and preparation method thereof.
Background technology
Tin ash, because of its rich reserves, low price, energy density is high, capacitance for the metal-oxide such as manganese monoxide High (the theoretical reversible capacity as tin ash is 993mAh/g, manganese monoxide for 755mAh/g.) the features such as and receive much concern, It is the star in lithium ion battery negative material of new generation, but these metal-oxides, in addition to electrical conductivity is relatively low, also have one Individual fatal shortcoming：During Lithium-ion embeding and abjection, volumetric expansion is larger, even results in lattice and caves in, material efflorescence, Thus leading to cycle life shorter it is difficult to actual production and application.Graphite-like material with carbon element is the negative material commonly used at present, but its Easily form Li dendrite and may puncture battery diaphragm in discharge and recharge and cause short circuit to cause potential safety hazard, capacitance is relatively low (theoretical Reversible capacity is 372mAh/g) especially high rate charge-discharge process.In recent years, with regard to the composite of metal-oxide and carbon Preparation and its research of application in lithium ion battery negative material get more and more, but metal is simply aoxidized by these Thing grows on the carbon material, or material with carbon element is coated on an metal oxide, or even the method that the two is mixed is not Can solve the large volume expansion issues of metal-oxide.Compare strikingly Graphene and metal-oxide at present Composite, it has excellent chemical property, but its synthesis technique is complicated, relatively costly, only to a certain extent Delay metal-oxide volume expansion issues, but still be difficult to maintain the long-life of more than 300 times to circulate.
Content of the invention
The technical problem to be solved is for deficiency above-mentioned present in prior art, provides one kind to be based on three The SnO of dimension carbon ball frame structure2, MnO or Mn3O4Based composites and preparation method thereof, it utilizes stable carbon ball framework by gold Belong to oxide particle SnO2, MnO or Mn3O4It is coated and fixed so that composite not only has excellent chemical property, and Good cycling stability.
The present invention by solving the problems, such as adopted technical scheme set forth above is：
SnO based on three-dimensional carbon ball frame structure2, MnO or Mn3O4Based composites, described composite diameter 100～ 800nm, is by SnO2, MnO or Mn3O4It is micro- that metal-oxide is formed by the crystallization carbon of cross-distribution and amorphous carbon parcel Ball, wherein：A diameter of 2～the 50nm of described metal oxide particle.
Present invention also offers the above-mentioned SnO based on three-dimensional carbon ball frame structure2, MnO or Mn3O4The system of based composites Preparation Method, comprises the following steps：
(1) prepare colloidal carbon sphere：Compound concentration is the monosaccharide of 0.5～1.8mol/L or the aqueous solution of biglycan, will be water-soluble Liquid is placed in hydrothermal reaction kettle, and in 130～180 DEG C 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 in the aqueous solution of alkali, activate 2～24h under normal pressure at a temperature of 50～120 DEG C, products therefrom washing dried is obtained final product To activation colloidal carbon sphere；
(3) SnO based on three-dimensional carbon ball frame structure for the preparation2, MnO or Mn3O4Based composites：Step (2) gained is lived Change colloidal carbon sphere and be added to mix homogeneously in the water that Sn or Mn ion concentration is 0.05～0.5mol/L and the mixed solution of ethanol After 20～90 DEG C of water-bath 3～24h, then the product that washing centrifugal treating is obtained is under nitrogen or argon gas atmosphere, in 400 High-temperature process 2～10h under～800 DEG C of temperature conditionss；Subsequently steadyization process 0.5 under 150～300 DEG C of temperature conditionss in atmosphere ～3h, that is, obtain stannum or the oxide of manganese and the composite of carbon.
By such scheme, the described Sn ion of step (3) is bivalence Sn ion or tetravalence Sn ion or both mixing；Institute Stating Mn ion is bivalence Mn ion.
By such scheme, the described monosaccharide of step (1) or biglycan are glucose, one or more are pressed and appoint in Fructose, sucrose The mixture of meaning ratio mixing.
By such scheme, the described water soluble acid of step (2) or alkali are hydrochloric acid, nitric acid, phosphoric acid, acetic acid, ammonia, hydroxide One of sodium, potassium hydroxide.
By such scheme, the pink salt needed for step (3) described configuration Sn or Mn solion is SnCl4、Sn(NO3)4、 SnCl2、Sn(NO3)2、SnC2O4One of or both mixture of mixing in any proportion；Manganese salt is MnCl2、Mn(NO3)2、 MnSO4One of or both mixture of mixing in any proportion.
By such scheme, the volume ratio of the described water of step (3) and ethanol is 1：1～1：10.
By such scheme, in described step (3) quality of activation colloidal carbon sphere and Sn or Mn ion concentration be 0.05～ The ratio of the volume of the mixed solution of the water of 0.5mol/L and ethanol is 0.05～10g/100mL.
The present invention also provides the above-mentioned SnO based on three-dimensional carbon ball frame structure2, MnO or Mn3O4Based composites lithium from Application in sub- cell negative electrode material.
In preparation process of the present invention, monosaccharide or biglycan (glucose, Fructose or sucrose) are in the high temperature sealing anoxia first It may occur that polycondensation reaction forms spherical condensation polymer under environment under high pressure (in hydrothermal reaction kettle), further carbonization forms colloidal-carbon Ball.Colloidal carbon sphere by being formed has substantial amounts of space and duct, and the chemical bond that substantial amounts of hydroxy kind activity is higher, After being processed with sour (hydrochloric acid, sulphuric acid, phosphoric acid, acetic acid) or alkali (sodium hydroxide, potassium hydroxide, ammonia), easily in colloidal carbon sphere Portion forms acidity or basic site, and the energy of adsorption to acidic oxide or basic anhydride for the colloidal carbon sphere can be strengthened in these sites Power.And then by the selection (ethanol and water mixed solution) of specific solvent, product can be made to exist with spherical structure form, thus Reduce surface energy to settle out, this is because the difference of solution system can affect the stable chemical energy of product, when containing certain During the ethanol of amount, the surface activity of product increases, and for reaching steady statue, product can trend towards spherical structure form and deposit ?.Then through high-temperature process, the predecessor meeting of partial activation colloid carbon adsorption tin ion or manganese ion gained under protective atmosphere Stannum or manganese should be reduced to by carbon phase, and metallic tin or manganese have excellent aromatization catalytic performance, thus can ultimately generate SnO2、 MnO or Mn3O4Metal-oxide is by the composite of the crystallization carbon of cross-distribution and amorphous carbon parcel, its preparation process such as Fig. 1 Shown.
This composite has larger space and supplies volumetric expansion during embedding lithium takes off lithium for the metal oxide particle, this The crystallization carbon that outer wrapping is distributed in metal oxide particle external chiasma can bend in volumetric expansion, and the amorphous carbon of surrounding can enter One step compression, thus have stronger toughness it is ensured that the stability of structure.Additionally, amorphous carbon and partially-crystallized carbon can be effective Improve the electrical conductivity of material, gained composite has extra specific surface area and from micropore to mesoporous four sections of pore-size distribution spies Levy, be conducive to electrolyte to flow in the material and lithium ion mobility, different passages can be formed, be conducive to big multiplying power charge and discharge Electricity.Its principle is as shown in figure 11.
The beneficial effects of the present invention is：
1st, the present invention is effectively by the high elastic coefficient of material with carbon element, high conductivity, stronger structural stability and preferably The high power capacity of the characteristic such as lithium ion diffusion coefficient and metal-oxide, the attribute such as high-energy-density combine, overcome carbon The low capacity of material electrodes and metal-oxide cause the poor problem of electrode stability because of volumetric expansion, prepared battery Negative material shows superior cycle performance and high rate performance, especially possesses high-power cyclical stability, has excellent Chemical property, such as SnO2Circulate its ratio with the composite of carbon through 350 times in the case that electric current density is for 300mA/g Capacity stills remain in 653mAh/g, the about twice of graphite theoretical capacity, and corresponding SnO2Double-layer hollow ball is (as Fig. 2 d institute Show) circulation just decay to 0 less than 100 times.In addition the composite of present invention preparation also shows in terms of high-power discharge and recharge Excellent stability, such as SnO2Circulate under different multiplying after 93 times with the composite of carbon, under the multiplying power of 20C, capacity is still Up to 260mAh/g, after circulating 600 times, conservation rate reaches 84%, and circulation is still up to 78% 1000 times.MnO is existed with the composite of carbon Electric current density be 1C in the case of through 300 times circulation after specific capacity still remain in 498mAh/g, far above the theory of graphite Capacity, and corresponding MnO specific capacity is only conservation rate after 197mAh/g circulates 200 times and reaches 89%, and carbon ball is under this multiplying power Capacity is nearly close to zero.
2nd, preparation method provided by the present invention is simple and convenient, just can by the amount or reaction temperature changing reaction reagent The easily ratio of regulation and control carbon and metal-oxide, is scalable complex by changing the solution system reacting and response time Structure and morphology, course of reaction is easily controllable, yield high it is adaptable to large-scale production.
Brief description
Fig. 1 is the synthesis schematic diagram with the composite of carbon for the oxide of stannum or manganese；
Fig. 2 (a) is the SEM figure of prepared acidic activated colloidal carbon sphere in embodiment 1；B () is SnO2Composite wood with carbon The SEM figure of material (SPOCs) predecessor；C () is SnO2SEM figure with the composite of carbon；D () is SnO2Composite with carbon Remove carbonization gained SnO2SEM figure；
I in Fig. 3 (a), ii, iii are respectively SnO2With after the composite predecessor of carbon, high-temperature process and steadyization is processed The XRD figure of product afterwards；(b), (c), (d) is respectively SnO2With the composite of carbon, (colloidal carbon sphere is placed in argon to carbonization colloidal-carbon Environment high temperature calcined product) and its remove carbonization gained SnO2BET (specific surface area test) and graph of pore diameter distribution；
Fig. 4 is SnO2TEM and HRTEM figure with the composite of carbon；
I in Fig. 5, ii, iii, iv are respectively SnO2Remove carbonization gained SnO with the composite of carbon2Double-layer hollow ball, SnO2 Raman collection of illustrative plates with the composite, carbonization colloidal-carbon and commercialization Graphene of carbon；
Fig. 6 (a), (b) is respectively SnO2The battery initial cycle for preparing with the composite of carbon and its circulation 50 times CV figure afterwards；
Fig. 7 is SnO2Remove carbonization gained SnO with the composite of carbon2Double-layer hollow ball, SnO2Composite with carbon (SPOCs) cycle performance figure under 300mA/g for the electrode；
Fig. 8 is SnO2With the SEM figure after composite (SPOCs) electrode of the carbon circulation under 300mA/g 350 times；
Fig. 9 (i), (ii), (iii) is respectively SnO2Composite (SPOCs), SnO with carbon2Go with the composite of carbon Carbonization gained SnO2High rate performance under 0.5-20C of double-layer hollow ball, carbonization colloidal-carbon (CCs) and coulombic efficiency (1C= 690mA/g) figure；
Figure 10 is SnO2First after different multiplying circulation, continue the cycle performance under 20C multiplying power with the composite of carbon Figure；
Figure 11 is SnO2Effectively overcome the mechanism figure of volumetric expansion problem with the composite of carbon；
Figure 12 (a), (b) is the SEM figure of MnO and the composite (nMCs) of carbon, (c), and (d) removes carbonization gained MnO for it The SEM figure of granule；
The MnO that Figure 13 is and the composite of carbon and the XRD figure of MnO granule；
Figure 14 is MnO and the TEM (a) of composite, HRTEM (b), section TEM (c), spherical aberration TEM (d) and the C of carbon, Mn, O distribution diagram of element (e, f, g)；
Figure 15 is following under the composite (nMCs) of MnO and carbon and MnO mosaic electrode 1C (1C=660mAh/g) multiplying power Ring performance map；
Figure 16 is composite (nMCs), MnO granule and the corresponding carbonization colloid carbon electrode of MnO and carbon in different multiplying (1C=660mAh/g) cycle performance figure under；
Figure 17 is that MnO first continues the cycle performance figure under 20C multiplying power with the composite of carbon after different multiplying circulation；
Figure 18 (a), (b) is the SEM figure of embodiment 3 gained colloidal carbon sphere, (c), and (d) is embodiment 3 gained composite SEM figure；
Figure 19 (a) is the XRD figure of embodiment 3 gained composite, and (b) is that the CV of embodiment 3 gained composite schemes, C () is the cycle performance figure under the conditions of 1C (C=700mA/g) for it in electric current density, (d) is embodiment 3 gained composite AC impedance figure (frequency is 0.01～100000Hz) after the 1st circulation with the 100th circulation；
Figure 20 (a), (b) is the SEM figure of embodiment 4 gained colloidal carbon sphere, (c), and (d) is embodiment 4 gained composite SEM figure；
Figure 21 (a) is the XRD figure of embodiment 4 gained composite, and (b) is that the CV of embodiment 4 gained composite schemes, C () is it is the cycle performance figure under the conditions of 500mA/g in electric current density, (d) be embodiment 4 gained composite voltage- Capacity Plan；
Figure 22 (a), (b) is respectively prepared by colloidal carbon sphere prepared by 1.8M D/W and 0.5M aqueous sucrose solution The SEM figure of colloidal carbon sphere；
Figure 23 (a) is the SEM figure of embodiment 5 gained composite, and (b) is the XRD figure of embodiment 5 gained composite, C () is high rate performance under 1-20C for the embodiment 5 gained composite and coulombic efficiency (1C=690mA/g) figure, (d) is it It is the cycle performance figure under the conditions of 600mA/g in electric current density.
Specific embodiment
For making those skilled in the art more fully understand technical scheme, below in conjunction with the accompanying drawings the present invention is made into One step describes in detail.
Embodiment 1
The present embodiment prepares SnO2With the composite of carbon, its method and step is as follows：
(1) prepare colloidal carbon sphere：It is 100mL that the D/W of 70mL 1.2M (1M=1mol/L) is placed in capacity Hydrothermal reaction kettle in 180 DEG C react 5 hours, by product washing centrifugation can obtain memnonious colloidal carbon sphere；Other Condition is constant, 1.2M D/W is changed to respectively D/W and the glue prepared by 0.5M aqueous sucrose solution of 1.8M The pattern of body carbon ball is shown in Figure 22.
(2) preparation activation colloidal carbon sphere：Weigh colloidal carbon sphere prepared by 1g above-mentioned steps (1), add 80mL 1M HCl In, under normal pressure at 100 DEG C activation processing 12h, by products therefrom washing be dried after, you can obtain acidic activated colloidal carbon sphere. SEM tests the microsphere that this carbon ball is uniformly a diameter of 150～500nm.
(3) prepare SnO2Composite (SPOCs) with carbon：Weigh the acidic activated colloidal carbon sphere of 0.3g of above-mentioned preparation (its pattern is shown in Fig. 2 (a)), is added to 0.5M SnCl280mL ethanol water system (volume ratio of water and ethanol is 1：3) In, water-bath 8h under the conditions of 50 DEG C, this process completes under being stirred continuously, and obtains SnO2Composite forerunner with carbon Thing.Then by predecessor under argon atmosphere high-temperature process 3 hours at 500 DEG C, finally process in 250 DEG C of steadyization in atmosphere 1.5h, you can obtain SnO2Composite with carbon.
The present embodiment synthesis schematic diagram is as shown in Figure 1 although but colloidal carbon sphere possesses substantial amounts of pore space structure to metal The adsorptivity of ion is not strong, can improve its adsorptivity to ion after acid or alkali activation.In ethanol-water system, The microsphere being conducive to adion forms many shell structurres using your moral ripening mechanism of Oswald, and metal ion forms metal simultaneously Oxide.Last anneal in protective atmosphere, the oxide of stannum or manganese be reduced during catalysed promoted colloidal-carbon aromatization Form the complex of crystallization carbon and agraphitic carbon, and after steadyization is processed in atmosphere, the chemical property of metal-oxide is more Stable.
The SEM figure being acidic activated colloidal carbon sphere prepared by 1.2M D/W as Fig. 2 (a)；B () is SnO2With carbon Composite (SPOCs) predecessor SEM figure；C () is SnO2SEM figure with the composite of carbon；D () is SnO2With carbon Composite removes carbonization (500 DEG C of calcining 3h in atmosphere) gained SnO2The SEM of double-layer hollow ball schemes the SnO it is known that prepared2 Predecessor with the composite of carbon is the spherical structure of diameter about 200～500nm, obtains after argon atmosphere high temperature is processed SnO2With the composite diameter about 300nm of carbon, continue in atmosphere 500 DEG C calcining 3h go carbonization completely after, SnO2With carbon Composite is changed into SnO2Double-layer hollow spherical structure, illustrate that stannide is subject to surface energy shadow in the mixed solution of ethanol and water Ring, finally in carbon framework and non-uniform Distribution, but concentrate in two-layer spherical shell.
As Fig. 3 (a) show the present embodiment SnO2With after the composite predecessor of carbon, high-temperature process and steadyization is processed The XRD figure of product afterwards, SnO as seen from the figure2Composite predecessor with carbon is the composite of tin ash and carbon, in nitrogen After high-temperature process, tin ash partial reduction is metallic tin and tin monoxide, and steadyization is changed into answering of tin ash and carbon again after processing Condensation material.Fig. 3 (b), (c), (d) is respectively SnO2With the composite of carbon, (colloidal carbon sphere is placed in ar gas environment to carbonization colloidal-carbon In 500 DEG C of calcining 2h product) and its remove carbonization gained SnO2BET (specific surface area test) and graph of pore diameter distribution, comprehensive anti- Reflect gained composite and there is 157.28m2The extra specific surface area of/g, and possess extremely mesoporous by micropore, aperture is about The four sector hole footpath distribution characteristicss of 1.22nm, 10.6nm, 22.4nm and 40.0nm.Gained SnO is additionally described2With being combined of carbon Material not only remains the bigger serface of colloidal-carbon, and adsorbs during tin ion forms tin ash and expand hole Footpath, big aperture is more conducive to the flowing of electrolyte.
Fig. 4 (a), (b), (c), (d) is SnO2Transmission electron microscope picture (TEM) and its high resolution graphics with the composite of carbon (HRTEM).Fig. 4 (a, b) can be clearly seen that SnO2It is distributed in carbon ball bilayer with the composite of carbon for stannic oxide particle In spherical shell, Fig. 4 (c, d) lattice arrangement situation and its spacing of lattice show that two layers of balls are crystallization carbon and agraphitic carbon wraps up dioxy Change the structure of stannum, be agraphitic carbon between double-deck tin dioxide nucleic shell, its structural representation is as shown in wherein illustration.Combined by Fig. 5 Tin ash and commercialization Graphene contain agraphitic carbon by the carbon-coating that in figure D, G peak proves gained composite further, and Determined by 2D peak and wherein contain crystallization carbon, and carbonization colloidal-carbon is only agraphitic carbon, this also just illustrates the formation of crystallization carbon from not Open the catalysis of stannum.In conjunction with Fig. 4 electron scanning electron microscope and transmission electron microscope picture, illustrate that resulting materials are SnO2By cross-distribution Crystallization carbon and amorphous carbon parcel and formed using carbon as support frame, there is double-deck microsphere, wherein：Described metal The a diameter of 5nm of oxide particle.
The SnO that said method prepares2Be applied to lithium ion battery negative material with the composite of carbon, can same S, LiMnO4、LiFePO4Help battery etc. the assembling of common positive electrode.After the battery initial cycle for preparing and its circulation 50 times CV figure (cyclic voltammogram) as shown in fig. 6, broad peak fainter between 0.5～0.8V in Fig. 6 (a) correspond to irreversible SEI film (solid electrolyte film is electrolyte with electrode material contacts after deposition generate) reaction of formation, 0.05V about strong Spend larger reduction peak, corresponding to the embedding lithium reaction of stannum, 0.25,0.50,0.75 and 1.25V oxidation peak, correspond respectively to The abjection of lithium embedded by carbon framework in composite, the de- lithium reaction of double-layer ball ectonexine stannum lithium and stannum further with lithium oxide Reaction.Circulate 50 times afterwards it can be seen that its redox peaks becomes very symmetrical, this is primarily due to define high speed lithium Ion channel, thus also make this material have superior chemical property.
Fig. 7 is to remove carbonization gained SnO2Double-layer hollow ball, SnO2With composite (SPOCs) electrode of carbon under 300mA/g Cycle performance figure.SnO can be seen2Follow through 350 times in the case that electric current density is for 300mA/g with the composite of carbon Its specific capacity of ring stills remain in 653mAh/g, the about twice of graphite theoretical capacity, and corresponding removes carbonization gained SnO2(double Layer hollow ball) circulation just decay to 0 less than 100 times.
Fig. 8 is SnO2Circulate the figure of the SEM after 350 times with composite (SPOCs) electrode of carbon under 300mA/g.Permissible It is apparent from, after this material circulation 350 times, structure remains unchanged stable existence.
Fig. 9 (i), (ii), (iii) is respectively SnO2Composite (SPOCs), SnO with carbon2Go with the composite of carbon Carbonization gained SnO2High rate performance under 0.5-20C of double-layer hollow ball, carbonization colloidal-carbon (CCs) and coulombic efficiency (1C= 690mA/g, C refer to battery and release, within the time of regulation, the current value that its theoretical capacity is exported) figure.0.5,1,2,3,6,9, Under 12 and 20C multiplying power, SnO2With the capacity of the composite of carbon be respectively 680,590,510,450,400,360,300 and 260mAh/g, its cycle performance is substantially better than SnO2Double-layer hollow ball and carbonization colloidal-carbon (CCs), especially more than 3C times Rate, the superiority of this material becomes apparent from.Under the multiplying power of 20C, capacity still reaches 260mAh/g, and after circulating 600 times, conservation rate reaches 84%, circulation still reaches 78% (as shown in Figure 10) for 1000 times, and close to 100%, efficiency illustrates that this electrode material can be effective The electricity being filled with all is discharged, and capacity under this multiplying power for the carbonization colloidal-carbon is practically negligible.Additionally, as can be seen from Figure When multiplying power is switched to 0.5C by 20C, or when being switched to 20C by 0.5C, the same rate capability of battery varies less, and SnO is described2With The composite of carbon has preferable magnification transformable performance.
SnO2With the composite of carbon, there is excellent chemical property, being mainly its double-deck spherical structure has larger space For volumetric expansion during embedding lithium takes off lithium for the stannum oxide, the crystallization carbon being wrapped in granules of stannic oxide external chiasma distribution in addition can be Bend during volumetric expansion, the amorphous carbon of surrounding can compress further, thus there is stronger toughness it is ensured that the stablizing of structure Property.Additionally, the presence of amorphous carbon and partially-crystallized carbon can effectively improve the electrical conductivity of material, this compound mode has from micro- Hole, to mesoporous four sections of pore-size distributions, is conducive to electrolyte to flow in the material and lithium ion mobility, can form different leading to Road, is conducive to high rate charge-discharge.Its principle is as shown in figure 11.
Embodiment 2
The present embodiment prepares the composite of MnO and carbon, and its method and step is as follows：
(1) prepare colloidal carbon sphere：The D/W of 70mL 1.8M is placed in the hydrothermal reaction kettle that capacity is 100mL In in 180 DEG C react 5 hours, by product washing centrifugation can obtain memnonious colloidal carbon sphere；
(2) preparation activation colloidal carbon sphere：Weigh the colloidal carbon sphere of the above-mentioned preparation of 1g, add 80mL 1MNH3·H2In O, often Depress activation processing 12h at 100 DEG C, after products therefrom washing is dried, you can obtain alkaline activation colloidal carbon sphere；
(3) prepare the composite of MnO and carbon：Weigh the 0.3g alkaline activation colloidal carbon sphere of above-mentioned preparation, be added to 0.5M MnCl280mL ethanol water system (volume ratio of water and ethanol is 1：1) in, water-bath under the conditions of 80 DEG C 8h, this process completes under being stirred continuously.Then, by product under argon atmosphere, in 700 DEG C of high-temperature process 2 hours, finally exist In the air processes 0.5h in 300 DEG C of steadyization, you can obtain the composite of MnO and carbon.
With shown in pattern such as Figure 12 (a), (b) of the composite (nMCs) of carbon, figure (c), (d) go to carbonization institute for it to MnO Obtain the SEM figure of MnO granule.The composite particle diameter about 250nm of MnO and carbon as seen from the figure, the wherein particle diameter of manganese monoxide About 5nm and go carbonization gained MnO granule to reach 200nm, illustrate that manganese monoxide in heat treatment process has the trend of reunion and carbon ball frame Frame can effectively stop manganese monoxide particle agglomeration.Figure 13 is MnO and the composite of carbon and the XRD figure of MnO granule, can be true The oxide determining contained manganese in gained composite is manganese monoxide.Figure 14 be MnO and carbon the TEM (a) of composite, HRTEM (b), section TEM (c), spherical aberration TEM (d) and C, Mn, O distribution diagram of element (e, f, g) is it was demonstrated that the answering of gained MnO and carbon The non-hollow structure that condensation material is coated and formed by the crystallization carbon of cross-distribution and amorphous carbon for manganese monoxide granule.
The composite of MnO and carbon circulates its ratio through 300 times in the case that electric current density is for 1C (C=660mA/g) Capacity stills remain in 498mAh/g, and far above the theoretical capacity of graphite, and corresponding MnO granule is only 197mAh/g, such as schemes Shown in 15.This material also shows excellent stability in terms of high-power discharge and recharge, after 0.5-30C circulates 100 times, Under the multiplying power of 30C, capacity still reaches 132mAh/g, and after circulating 200 times, conservation rate reaches 89%, and corresponding carbonization colloidal-carbon is in this times Capacity under rate is practically negligible, and efficiency is close to 100%, as shown in Figure 16,17, wherein Figure 16 (i), (ii), (iii) respectively For the composite (nMCs) of MnO and carbon, its remove carbonization gained MnO granule and corresponding carbonization colloid carbon electrode in different multiplying (1C=660mAh/g) cycle performance figure under.
Embodiment 3
The present embodiment prepares SnO2With the composite of carbon, its method and step is as follows：
(1) prepare colloidal carbon sphere：The aqueous sucrose solution of 70mL 0.5M is placed in hydrothermal reaction kettle and reacts 12 in 130 DEG C Hour, product washing centrifugation can be obtained memnonious colloidal carbon sphere；
(2) preparation activation colloidal carbon sphere：Weigh the colloidal carbon sphere of the above-mentioned preparation of 1g, add 80mL 0.1M HNO3In, often Depress activation processing 24h at 50 DEG C, after products therefrom washing is dried, you can obtain acidic activated colloidal carbon sphere；
(3) prepare SnO2Composite with carbon：Weigh the acidic activated colloidal carbon sphere of 0.3g of above-mentioned preparation, be added to and contain 0.3M SnCl2And 0.2M SnCl480mL ethanol water system (volume ratio of water and ethanol is 1：5) in, in 90 DEG C of conditions Lower water-bath 3h, this process completes under being stirred continuously.Then by product under argon atmosphere, high-temperature process at 400 DEG C 10 hours, finally process 3h in 150 DEG C of steadyization in atmosphere, you can obtain SnO2Composite with carbon.
Shown in the pattern of gained colloidal carbon sphere such as Figure 18 (a), (b), its particle diameter is about 300nm, and figure (c), (d) are SnO2With The SEM figure of the composite of carbon, its particle diameter is about 220nm.The XRD data being shown by Figure 19 (a) understands that gained composite is Tin ash and the complex of carbon.
The SnO preparing2Shown with chemical property such as Figure 19 (b) of the composite electrode of carbon, in Figure 18 (b) Between 0.5～0.8V, fainter broad peak corresponds to the reaction of formation of irreversible SEI film, 0.05V about intensity larger also Parent peak, corresponding to the embedding lithium reaction of stannum, 0.25,0.50,0.75 and 1.25V oxidation peak, corresponds respectively in composite The abjection of lithium embedded by carbon framework, the de- lithium reaction of every layer of stannum lithium of double-layer ball and the stannum reaction with lithium oxide further.Figure 19 C () is MnO is the cycle performance figure under conditions of 1C (C=700mA/g) with the composite of carbon in electric current density, through 110 Secondary its specific capacity of circulation stills remain in 588mAh/g, and far above the theoretical capacity of graphite, capacity attenuation is only 17.3%.Figure 19 (d) be MnO and carbon AC impedance figure after the 1st circulation with the 100th circulation for the composite (frequency is 0.01～ 100000Hz), 100 AC impedances of circulation be can be seen that by figure semicircle and become greatly 309 ohm by 146 ohm, do not occur Double half disk patterns, also do not cave in regard to illustrative material.
Embodiment 4
The present embodiment prepares Mn3O4With the composite of carbon, its method and step is as follows：
(1) prepare colloidal carbon sphere：The Fructose aqueous solution of 70mL 0.8M is placed in hydrothermal reaction kettle and reacts 12 in 160 DEG C Hour, product washing centrifugation can be obtained memnonious colloidal carbon sphere；
(2) preparation activation colloidal carbon sphere：Weigh the colloidal carbon sphere of the above-mentioned preparation of 1g, add in 80mL 4M NaOH, normal pressure Under at 120 DEG C activation processing 2h, by products therefrom washing be dried after, you can obtain acidic activated colloidal carbon sphere；
(3) prepare Mn3O4Composite with carbon：Weigh the 8g alkaline activation colloidal carbon sphere of above-mentioned preparation, be added to containing 3M Mn(NO3)2And 2M MnSO480mL ethanol water system (volume ratio of water and ethanol is 1：10) in, under the conditions of 20 DEG C Water-bath 24h, this process completes under being stirred continuously.Then by product under argon atmosphere, high-temperature process 3 at 800 DEG C Hour, finally process 0.5h in 300 DEG C of steadyization in atmosphere, you can obtain Mn3O4Composite with carbon.
Shown in the pattern of gained colloidal carbon sphere such as Figure 20 (a), (b), its particle diameter is about 800nm, and figure (c), (d) are Mn3O4With The SEM figure of the composite of carbon, its particle diameter is about 700nm.Understand that gained composite is four oxidations by Figure 21 (a) XRD data Three manganese and the complex of carbon.
The Mn preparing3O4As shown in Figure 21 (b) with the CV (multiple scanning 3 times) of the composite electrode of carbon, in figure 0.1 and 0.5V reduction peak corresponds to Mn3O4It is reduced to Mn/Li2O, and the corresponding oxidation peak of 1.3V aoxidizes for Mn and forms MnO.Figure 21 (c) is Mn3O4Circulate its specific capacity with the composite of carbon through 200 times still in the case that electric current density is for 500mA/g It is maintained at 497mAh/g, far above the theoretical capacity of graphite, capability retention reaches 80%, efficiency is close to 100%.Figure 21 (d) is Mn3O4With the voltage-capacity figure of the composite of carbon, wherein a, b, c, d, e are followed successively by the song that charges the 1st, 2,10,100,200 time Line, i, ii, iii, iv, v are respectively the 1st, 2,10,100,200 discharge curve, as seen from the figure, discharge after discharging first Platform tends towards stability, and the increase capacity attenuation with cycle-index has obtained preferable control.
Embodiment 5
The present embodiment prepares SnO2With the composite of carbon, its method and step is as follows：
(1) prepare colloidal carbon sphere：The aqueous sucrose solution of 70mL1M is placed in little in 160 DEG C of reactions 12 in hydrothermal reaction kettle When, product washing centrifugation can be obtained memnonious colloidal carbon sphere；
(2) preparation activation colloidal carbon sphere：Weigh the colloidal carbon sphere of the above-mentioned preparation of 1g, add 80mL 0.1M HNO3In, often Depress activation processing 24h at 50 DEG C, after products therefrom washing is dried, you can obtain acidic activated colloidal carbon sphere；
(3) prepare SnO2Composite with carbon：Weigh the acidic activated colloidal carbon sphere of 0.04g of above-mentioned preparation, be added to Containing 0.3MSn (NO3)4、0.2MSnC2O4And 0.2MSn (NO3)280mL ethanol water system (water with the volume ratio of ethanol is 1：5) in, water-bath 3h under the conditions of 90 DEG C, this process completes under being stirred continuously.Then by product under argon atmosphere, High-temperature process 10 hours at 400 DEG C, finally process 3h in 150 DEG C of steadyization, you can obtain SnO in atmosphere2With being combined of carbon Material.
Gained SnO2With the composite of carbon pattern such as Figure 23 (a) shown in, size about 350nm.By Figure 23 (b) XRD data understands the complex that gained composite is tin ash and carbon.Battery prepared by this material is in high-power charge and discharge Electric aspect also shows excellent stability, such as shown in Figure 23 (c), after 1-20C circulates 100 times, battery under the multiplying power of 20C Capacity still reaches 198mAh/g.Additionally, as can be seen from Figure when multiplying power is switched to 2C by 20C, or when 20C is switched to by 2C, battery Vary less with rate capability, SnO is described2With the composite of carbon, there is preferable magnification transformable performance.Figure 23 (d) is SnO2 Circulate its specific capacity through 200 times with the composite of carbon in the case that electric current density is for 600mA/g to still remain in 631mAh/g, far above the theoretical capacity of graphite, capability retention reaches 90%, and coulombic efficiency is close to 100%.

Claims (8)

1. the SnO based on three-dimensional carbon ball frame structure2, MnO or Mn3O4Based composites are it is characterised in that described composite is straight Footpath 100～800nm, is by SnO2, MnO or Mn3O4Metal-oxide is wrapped up and shape by the crystallization carbon of cross-distribution and amorphous carbon The microsphere becoming, wherein：A diameter of 2～the 50nm of described metal oxide particle；
Its preparation method comprises the following steps：
(1) prepare colloidal carbon sphere：Compound concentration is the monosaccharide of 0.5～1.8mol/L or the aqueous solution of biglycan, and aqueous solution is put In hydrothermal reaction kettle, in 130～180 DEG C 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 water soluble acid or the alkali of 0.1～4mol/L Aqueous solution in, under normal pressure at a temperature of 50～120 DEG C activate 2～24h, by products therefrom washing dried lived Change colloidal carbon sphere；
(3) SnO based on three-dimensional carbon ball frame structure for the preparation2, MnO or Mn3O4Based composites：Step (2) gained is activated glue Body carbon ball is added in the water that Sn or Mn ion concentration is 0.05～5mol/L and the mixed solution of ethanol mix homogeneously after 20 ～90 DEG C of water-bath 3～24h, then by the washing product that obtains of centrifugal treating under nitrogen or argon gas atmosphere, in 400～800 High-temperature process 2～10h under DEG C temperature conditionss；Subsequent steadyization process 0.5～3h under 150～300 DEG C of temperature conditionss in atmosphere, Obtain stannum or the oxide of manganese and the composite of carbon.
2. the SnO based on three-dimensional carbon ball frame structure2, MnO or Mn3O4The preparation method of based composites is it is characterised in that include Following steps：
(1) prepare colloidal carbon sphere：Compound concentration is the monosaccharide of 0.5～1.8mol/L or the aqueous solution of biglycan, and aqueous solution is put In hydrothermal reaction kettle, in 130～180 DEG C 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 water soluble acid or the alkali of 0.1～4mol/L Aqueous solution in, under normal pressure at a temperature of 50～120 DEG C activate 2～24h, by products therefrom washing dried lived Change colloidal carbon sphere；
(3) SnO based on three-dimensional carbon ball frame structure for the preparation2, MnO or Mn3O4Based composites：Step (2) gained is activated glue Body carbon ball is added in the water that Sn or Mn ion concentration is 0.05～5mol/L and the mixed solution of ethanol mix homogeneously after 20 ～90 DEG C of water-bath 3～24h, then by the washing product that obtains of centrifugal treating under nitrogen or argon gas atmosphere, in 400～800 High-temperature process 2～10h under DEG C temperature conditionss；Subsequent steadyization process 0.5～3h under 150～300 DEG C of temperature conditionss in atmosphere, Obtain stannum or the oxide of manganese and the composite of carbon.
3. the SnO based on three-dimensional carbon ball frame structure according to claim 22, MnO or Mn3O4The preparation of based composites Method it is characterised in that the described monosaccharide of step (1) or biglycan be glucose, in Fructose, sucrose one or more press arbitrarily than The mixture of example mixing.
4. the SnO based on three-dimensional carbon ball frame structure according to claim 22, MnO or Mn3O4The preparation of based composites Method is it is characterised in that the described water soluble acid of step (2) or alkali are hydrochloric acid, nitric acid, phosphoric acid, acetic acid, ammonia, sodium hydroxide, hydrogen One of potassium oxide.
5. the SnO based on three-dimensional carbon ball frame structure according to claim 22, MnO or Mn3O4The preparation of based composites Method it is characterised in that the described Sn or Mn ion concentration of step (3) be the water of 0.05～5mol/L and the mixed solution of ethanol by Pink salt or manganese salt are prepared and are obtained, and described pink salt is SnCl4、Sn(NO3)4、SnCl2、Sn(NO3)2、SnC2O4One or more of The mixture mixing in any proportion；Manganese salt is MnCl2、Mn(NO3)2、MnSO4One or more of mix in any proportion Mixture.
6. the SnO based on three-dimensional carbon ball frame structure according to claim 2 or 52, MnO or Mn3O4Based composites Preparation method is it is characterised in that the volume ratio of 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 22, MnO or Mn3O4The preparation of based composites Method it is characterised in that in step (3) quality and Sn the or Mn ion concentration of activation colloidal carbon sphere be the water of 0.05～5mol/L Ratio with the volume of the mixed solution of ethanol is 0.05～10g/100mL.
8. the SnO based on three-dimensional carbon ball frame structure according to the arbitrary described method preparation of claim 2-72, MnO or Mn3O4 Application in lithium ion battery negative material for the based composites.
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