CN104183837A - Carbon network supported zinc oxide nanocrystalline composite material and preparation method and application thereof - Google Patents
Carbon network supported zinc oxide nanocrystalline composite material and preparation method and application thereof Download PDFInfo
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- CN104183837A CN104183837A CN201410324530.1A CN201410324530A CN104183837A CN 104183837 A CN104183837 A CN 104183837A CN 201410324530 A CN201410324530 A CN 201410324530A CN 104183837 A CN104183837 A CN 104183837A
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Abstract
The invention relates to a carbon network supported zinc oxide nanocrystalline composite material and a preparation method and application thereof. A zinc-containing precursor is synthesized by an internal reflux method and is subjected to carbonization treatment at different temperatures in an inert atmosphere. The preparation method comprises the following steps: dissolving zinc nitrate in a mixed solution of oleic acid and oleylamine, and introducing the mixed solution into an inert atmosphere; removing residual moisture in the reactants and air in a system, raising the temperature of the system, and washing and drying a product, thereby obtaining the zinc-containing precursor; performing carbonization treatment in the inert atmosphere, thereby obtaining the carbon skeleton coated zinc oxide nanocrystalline composite material. According to the invention, a surfactant serves as a carbon source, a high-stability carbon network structure is obtained through carbonization, and zinc oxide nanocrystalline particles are uniformly inlaid in the carbon network. The method is easy to operate, is easily controlled and implemented in process and has an environment-friendly effect. The prepared ZnO/C composite material successfully overcomes the defect that zinc oxide is poor in cycle performance in the aspect of lithium ion battery application and has good application prospects.
Description
Technical field
The invention belongs to the preparation field of metal oxide functional material, particularly a kind of preparation method of carbon offered load zinc-oxide nano crystal composite material.
Background technology
Lithium ion battery is widely used in every field because of its high voltage, long-life, the advantage such as capable of circulation.Due to the minimizing year by year of environmental factor and traditional energy, the application of lithium ion battery aspect power vehicle paid close attention to especially in recent years.Current business-like negative material is mainly graphite, but due to lower (372 mAhg of its specific capacity
-1), be difficult to meet the requirement to energy density as power lithium-ion battery.Transition metal oxide is because its higher theoretical capacity (is generally greater than 600 mAhg
-1), fail safe is higher, pollution-free etc., and advantage becomes a kind of brand-new material that may substitute graphite cathode.Zinc oxide is a kind of conventional wide bandgap semiconductor, because of advantages such as its rich content, pollution-free and excellent luminescent properties, obtains well application in fields such as solar cell, liquid crystal display, thin-film transistor, light-emitting diodes.Because its specific capacity is high, compare the features such as the better lithium ion transmission performance of other transition metal, also extensively concerned aspect lithium ion battery negative material recently.
Be different from " embedding " reaction of graphite cathode, there is " conversion-alloying " reaction in zinc oxide in charge and discharge process, and first ZnO is reduced into Metal Zn, then forms LiZn alloy with metal Li.This reaction mechanism is also to cause material that large volumetric expansion (~ 228%) occurs when making zinc oxide have compared with height ratio capacity, and specific capacity sharply declines, and another inevitable shortcoming of zinc oxide is poor electric conductivity in addition.Solution route mainly contains three kinds at present: the one, and material nano, reduce ZnO crystal to nanoscale, can bring as the transmission range that contacts, shortens lithium ion and electronics of intensifier electrode and electrolyte and alleviate the plurality of advantages such as volumetric expansion, but also can cause the problems such as irreversible capacity is high first, bulk density is low simultaneously; The 2nd, hollow/nucleocapsid structure, can alleviate the change in volume in cyclic process preferably, but complicated technology of preparing has limited its practical application; The 3rd, build a three-dimensional support and conductive network carrier, can solve the shortcoming of zinc oxide electrode efflorescence and poorly conductive simultaneously.A kind of common carrier of porous carbon load zincite crystal, because it has good conductivity, can alleviate change in volume greatly.Wang seminar adopts one-step method to obtain a kind of ZnO/ Nano Carbon structure, shows excellent electrochemical lithium storage performance (Nano Energy, 2013,2,579-585).Shen seminar adopts porous carbon loading ZnO quantum dot, has significantly improved circulation and the high rate performance (ACS Appl. Mater. Interfaces 2013,5,3118) of ZnO electrode.But the high-specific surface area of porous carbon and harsh preparation technology are still shortcomings of can not ignore.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carbon offered load zinc-oxide nano crystal composite material, preparation method and purposes.
The technical solution used in the present invention is:
A kind of carbon offered load zinc-oxide nano crystal composite material, this composite construction is as carrier by a stable amorphous carbon network configuration, zincite crystal is evengranular to be distributed in carrier, zincite crystal is positive tetrahedron shape, the length of side is 100-300 nm, and crystalline phase is hexagonal wurtzite-type.
In adopting successively, circumfluence method and in-situ carburization method prepare.
A preparation method for carbon offered load zinc-oxide nano crystal composite material, circumfluence method and in-situ carburization method in adopting successively.
Described interior circumfluence method adopts zinc nitrate to be dissolved in the mixed liquor that comprises oleic acid and oleyl amine and forms uniform solution, and reaction system is condensing reflux in inert atmosphere, reflux temperature 240-280
oc.
Described in-situ carburization method is that the powder that interior circumfluence method is obtained is calcined in inert atmosphere, and temperature is 500-700
oc, heating rate is 10
oc/min, obtains the ZnO crystal of different-grain diameter size.
Concrete steps are:
1) by 4 mmol Zn (NO
3)
26H
2o is dissolved in the mixed liquor that comprises 10-20 mL oleic acid and 2-4 mL oleyl amine, 120
othe 60min deacration that refluxes under C, rising system temperature is to 240-280
oc also keeps 120 min, and after system cool to room temperature, product is through centrifuge washing, and 80
oc is dried, and obtains the presoma containing zinc, and whole course of reaction is carried out under inert atmosphere;
2) presoma containing zinc step 1) being obtained is calcined, 500-700 in inert atmosphere
ocarbonization treatment 180 min under C, heating rate is 10
oc/min, obtaining macroscopical color is the carbon offered load zinc-oxide nano crystal composite material of black.
A purposes for described carbon offered load zinc-oxide nano crystal composite material, as lithium ion battery negative material.
Beneficial effect of the present invention:
1) the present invention adopts two-step method to obtain a kind of carbon offered load zinc-oxide nano crystal structure, method is reliable, environmental protection and be easy to realize, interior backflow in advance and later stage carbonisation are all to carry out under normal pressure, have avoided hydro-thermal reaction to require the shortcoming of high pressure sealing, can obtain industrial popularization;
2) the present invention adopts surfactant as carbon source, obtains a kind of carbon network configuration of high stability through in-situ carburization, and the zinc oxide nanocrystalline of positive tetrahedron shape is evengranular is embedded in carbon network configuration.
3) the carbon offered load nano structure of zinc oxide that the present invention prepares, can effectively alleviate the volumetric expansion of zincite crystal in the time reacting with lithium ion, and carbon network can further increase the conductivity of zinc oxide.This structure has successfully solved zinc oxide poor defect of cycle performance aspect lithium ion battery applications, has a good application prospect.
Brief description of the drawings
The XRD collection of illustrative plates of carbon offered load zinc-oxide nano crystal composite material under the different carburizing temperatures of Fig. 1.Collection of illustrative plates shows that the zinc oxide obtaining after presoma carbonization is hexagonal wurtzite-type, and carburizing temperature can not affect the crystal formation of product, and (ZnO/C-5, ZnO/C-7 represents that respectively carburizing temperature is 500 and 700
oc, lower same).In addition, do not see the peak crystallization of carbon, illustrate that carbon is to exist with amorphous state.
Fig. 2 is the Raman collection of illustrative plates of composite material.In figure, be positioned at 426cm
-1left and right be the stretching vibration of Zn-O key.Be positioned at 1350 m
-1with 1600 cm
-1left and right be respectively D peak and the G peak of material with carbon element, what further prove network consisting structure is amorphous carbon.
Fig. 3 is scanning and the transmission electron microscope photo of the carbon offered load zinc-oxide nano crystal composite material that obtains under different carburizing temperatures: Fig. 3 is divided into several parts, (a), (b) be respectively that carburizing temperature is 500
othe scanning of the composite material obtaining when C and transmission electron microscope photo; (c), (d) respectively carburizing temperature be 700
othe scanning of the composite material obtaining when C and transmission electron microscope photo.Photo shows along with carburizing temperature is the key factor that affects ZnO crystal pattern and size and carbon network configuration integrality, as shown, and 500
oc forms the more positive tetrahedron shape ZnO nano crystalline substance of homogeneous, and its size is in about 150-250 nm, and is evenly distributed in a complete carbon network.
Fig. 4 is that carburizing temperature is 500
othe microstructure of the carbon offered load zinc-oxide nano crystal composite material that C obtains characterizes; (a) high resolution transmission electron microscopy photo; (b) selected area electron diffraction.In Fig. 4 a, measure to such an extent that interplanar distance is 0.81 nm, (100) crystal face of corresponding wurtzite-type ZnO, selected area electron diffraction is spot, shows that the ZnO obtaining is single crystal grain.
Fig. 5 is scanning and the transmission electron microscope photo of the composite material after hcl corrosion.Photo show ZnO dissolved fall after, carbon network still can keep its integrality.
Fig. 6 is that carburizing temperature is respectively 500
oc and 700
othe cycle performance of the composite construction obtaining when C during as lithium ion battery negative, pure ZnO crystal as a comparison.Be 110mAg in current density
-1time, ZnO/C-5 and Zn/C-7 all have excellent long-life cycle performance, and ZnO/C-5 shows higher specific capacity, and after 300 circulations, its specific capacity still can keep 500 mAhg
-1, and under same current density, pure zinc oxide specific capacity sharply declines with cycle-index.
Embodiment
Be elaborated further below in conjunction with embodiments of the invention, but the present embodiment is not limited to the present invention, every employing analog structure of the present invention and similar variation thereof, all should list in protection scope of the present invention.
By 1.24 g Zn (NO
3)
26H
2o is dissolved in the mixed liquor of 10 mL oleic acid and 2 mL oleyl amines, after stirring, is injected in three-neck flask, reaction system is passed into inert atmosphere, 120
ounder C, reflux 60 min to remove the air in moisture and system residual in reactant.Then be warmed up to 240
oc, and be incubated 120 min.After system temperature drops to room temperature, carry out centrifuge washing three times with alcohol, 80
oin the air dry oven of C, dry.Powder after 0.3 g is dried is put in tube furnace and carries out carbonization, and selecting temperature is 500
oc, temperature retention time 180 min, heating rate 10
oc/min.The composite construction carbon network obtaining under this condition is comparatively complete, and ZnO is positive tetrahedron shape, and size range is in 150-250 nm left and right, and comparatively homogeneous, has optimum cycle performance of lithium ion battery and the highest specific capacity.
embodiment 2
By 1.24 g Zn (NO
3)
26H
2o is dissolved in the mixed liquor of 10 mL oleic acid and 2 mL oleyl amines, after stirring, is injected in three-neck flask, reaction system is passed into inert atmosphere, 120
ounder C, reflux 60 min to remove the air in moisture and system residual in reactant.Then be warmed up to 240
oc, and be incubated 120 min.After system temperature drops to room temperature, carry out centrifuge washing three times with alcohol, 80
oin the air dry oven of C, dry.Powder after 0.3 g is dried is put in tube furnace and carries out carbonization, and selecting temperature is 700
oc, temperature retention time 180 min, heating rate 10
oc/min.The composite construction carbon network stabilization obtaining under this condition is general, and most ZnO are positive tetrahedron shape, a small amount of ZnO out-of-shape, and size range is in 100-350 nm left and right, and distribution of sizes is wider, and cycle performance of lithium ion battery is better, and specific capacity performance is common.
embodiment 3
By 1.24 g Zn (NO
3)
26H
2o is dissolved in the mixed liquor of 20 mL oleic acid and 4 mL oleyl amines, after stirring, is injected in three-neck flask, reaction system is passed into inert atmosphere, 120
ounder C, reflux 60 min to remove the air in moisture and system residual in reactant.Then be warmed up to 240
oc, and be incubated 120 min.After system temperature drops to room temperature, carry out centrifuge washing three times with alcohol, 80
oin the air dry oven of C, dry.Powder after 0.3 g is dried is put in tube furnace and carries out carbonization, and selecting temperature is 700
oc, temperature retention time 180 min, heating rate 10
oc/min.The composite construction carbon network stabilization obtaining under this condition is better, ZnO crystal out-of-shape, and size range is in 100 about nm, the comparatively homogeneous that distributes, cycle performance of lithium ion battery is common, specific capacity better performances.
conclusion
The present invention adopts simple interior backflow and in-situ carburization method, obtains a kind of carbon offered load positive tetrahedron zinc-oxide nano crystal composite material.By XRD and Raman Characterization, the crystal formation that proves ZnO is that hexagonal wurtzite-type (Fig. 1) carbon network is to form (Fig. 2) by amorphous carbon.Experimental result shows that in-situ carburization temperature is the key factor that affects composite structure.Different heat treatment temperature can affect the integrality of carbon network configuration and the pattern of ZnO crystal and distribution of sizes (Fig. 3), and high resolution electron microscope and selected area electron diffraction prove that the ZnO of preparation is single crystal grain (Fig. 4).When falling after zinc oxide with hcl corrosion, still can keep complete three-dimensional carbon network configuration (Fig. 5).By performance test, the ZnO/C composite construction that the present invention obtains shows higher specific capacity and excellent cycle performance (Fig. 6).
Claims (7)
1. a carbon offered load zinc-oxide nano crystal composite material, it is characterized in that, this composite construction is as carrier by a stable amorphous carbon network configuration, zincite crystal is evengranular to be distributed in carrier, zincite crystal is positive tetrahedron shape, the length of side is 100-300 nm, and crystalline phase is hexagonal wurtzite-type.
2. carbon offered load zinc-oxide nano crystal composite material according to claim 1, is characterized in that, in adopting successively, circumfluence method and in-situ carburization method prepare.
3. a preparation method for carbon offered load zinc-oxide nano crystal composite material, is characterized in that, circumfluence method and in-situ carburization method in adopting successively.
4. preparation method according to claim 3, is characterized in that, described interior circumfluence method adopts zinc nitrate hexahydrate to be dissolved in the mixed liquor that comprises oleic acid and oleyl amine and forms uniform solution, and reaction system is condensing reflux in inert atmosphere, reflux temperature 200-280
oc.
5. preparation method according to claim 3, is characterized in that, described in-situ carburization method is that the powder that interior circumfluence method is obtained is calcined in inert atmosphere, and temperature is 500-700
oc, heating rate is 10
oc/min, obtains the ZnO crystal of different-grain diameter size.
6. preparation method according to claim 3, is characterized in that, concrete steps are:
1) by 4mmol Zn (NO
3)
26H
2o is dissolved in the mixed liquor that comprises 10-20 mL oleic acid and 2-4 mL oleyl amine, 120
othe 60min deacration that refluxes under C, rising system temperature is to 240-280
oc also keeps 120 min, and after system cool to room temperature, product is through centrifuge washing, and 80
oc is dried, and obtains the presoma containing zinc, and whole course of reaction is carried out under inert atmosphere;
2) presoma containing zinc step 1) being obtained is calcined, 500-700 in inert atmosphere
ocarbonization treatment 180 min under C, heating rate is 10
oc/min, obtaining macroscopical color is the carbon offered load zinc-oxide nano crystal composite material of black.
7. a purposes for carbon offered load zinc-oxide nano crystal composite material as claimed in claim 1, is characterized in that, as lithium ion battery negative material.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470485A (en) * | 2015-12-16 | 2016-04-06 | 上海卫蓝海洋材料科技有限公司 | Low-temperature efficient preparation method for carbon-coated nano-titanium dioxide |
| CN107240694A (en) * | 2017-07-05 | 2017-10-10 | 中国矿业大学 | A kind of composite porous method for preparing sodium-ion battery for negative pole of zinc oxide/carbon |
| CN107317015A (en) * | 2017-07-05 | 2017-11-03 | 中国矿业大学 | A kind of zinc oxide/carbon composite is the method that negative pole prepares kalium ion battery |
| CN111554905A (en) * | 2020-05-14 | 2020-08-18 | 云南民族大学 | Preparation method, product and application of zinc oxide-based carbon composite nano material |
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| CN103606657A (en) * | 2013-12-10 | 2014-02-26 | 北京理工大学 | Lithium ion battery zinc oxide/porous carbon composite negative electrode material with high capacity and preparation method thereof |
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| CN103606657A (en) * | 2013-12-10 | 2014-02-26 | 北京理工大学 | Lithium ion battery zinc oxide/porous carbon composite negative electrode material with high capacity and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| C.W. YAO等: "Triangle-shape ZnO prepared by thermal decomposition", 《MATERIALS LETTERS》, vol. 61, no. 16, 8 December 2006 (2006-12-08), pages 2416 - 3420 * |
| ENHANCED ELECTROCHEMICAL PERFORMANCE OF ZNO-LOADED/POROUS CARBON: "Enhanced Electrochemical Performance of ZnO-Loaded/Porous Carbon Composite as Anode Materials for Lithium Ion Batteries", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 5, no. 8, 26 March 2013 (2013-03-26), pages 3118 - 3125 * |
| ZHIMIN REN 等: "TiO2/C composites nanorods synthesized by internal-reflux method for lithium-ionbattery anode materials", 《MATERIALS LETTERS》, vol. 117, 23 November 2013 (2013-11-23), pages 124 - 127, XP028810586, DOI: doi:10.1016/j.matlet.2013.11.058 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470485A (en) * | 2015-12-16 | 2016-04-06 | 上海卫蓝海洋材料科技有限公司 | Low-temperature efficient preparation method for carbon-coated nano-titanium dioxide |
| CN105470485B (en) * | 2015-12-16 | 2018-05-08 | 上海卫蓝海洋材料科技有限公司 | A kind of efficient cryogenic preparation method of carbon-coated nano titanium dioxide |
| CN107240694A (en) * | 2017-07-05 | 2017-10-10 | 中国矿业大学 | A kind of composite porous method for preparing sodium-ion battery for negative pole of zinc oxide/carbon |
| CN107317015A (en) * | 2017-07-05 | 2017-11-03 | 中国矿业大学 | A kind of zinc oxide/carbon composite is the method that negative pole prepares kalium ion battery |
| CN107240694B (en) * | 2017-07-05 | 2020-02-21 | 中国矿业大学 | Method for preparing sodium ion battery by taking zinc oxide/carbon porous composite material as negative electrode |
| CN111554905A (en) * | 2020-05-14 | 2020-08-18 | 云南民族大学 | Preparation method, product and application of zinc oxide-based carbon composite nano material |
| CN111554905B (en) * | 2020-05-14 | 2020-12-29 | 云南民族大学 | Preparation method, product and application of zinc oxide-based carbon composite nano material |
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Application publication date: 20141203 |