CN103151501A - Preparation method of chromic oxide-grapheme nanometer sheet and prepared chromic oxide-graphene nanometer sheet materials - Google Patents

Preparation method of chromic oxide-grapheme nanometer sheet and prepared chromic oxide-graphene nanometer sheet materials Download PDF

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CN103151501A
CN103151501A CN2013100437610A CN201310043761A CN103151501A CN 103151501 A CN103151501 A CN 103151501A CN 2013100437610 A CN2013100437610 A CN 2013100437610A CN 201310043761 A CN201310043761 A CN 201310043761A CN 103151501 A CN103151501 A CN 103151501A
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graphene
chromium oxide
nanometer sheet
preparation
chromic oxide
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CN103151501B (en
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李家星
赵桂霞
王祥科
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Institute of Plasma Physics of CAS
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention aims to provide a preparation method of chromic oxide-graphene nanometer sheet materials. Graphene serves as a template, and chromate serves as a chromium source. Under a hydrothermal condition, the chromate oxidizes a carbon atom at a root position of the grapheme to obtain a hydration chromic oxide-grapheme nanometer sheet and a crystallized chromic oxide-grapheme nanometer sheet after a roasting process. The preparation method of the chromic oxide- graphene nanometer sheet materials is simple in production process, environment-friendly and suitable for industrialized mass production. The chromic oxide-graphene nanometer sheet prepared through the preparation method of the chromic oxide-graphene nanometer sheet materials is high in purity and large in specific surface area. The preparation method of the chromic oxide- graphene nanometer sheet materials can be used to the fields of catalyzed synthesis, functional materials and the like. Particularly, the preparation method has broad application prospects in the field of Li-ion battery materials.

Description

A kind of preparation method of chromium oxide-graphene nanometer sheet and the chromium oxide that makes thereof-graphene nano sheet material
Technical field
The present invention relates to inorganic material synthetic field, particularly a kind of preparation method of chromium oxide-graphene nanometer sheet and the chromium oxide that makes thereof-graphene nano sheet material.
Background technology
Nano chromium oxide be a kind of developing and have broad prospect of application inorganic functional material, be widely used in the fields such as catalysis, functional paint, photoelectric material and organic synthesis.Its application potential at the lithium electrical domain is huge, Grugeon, and people's theoretical prediction chromium oxide lithium battery peak capacities such as S can reach 1058 mA h g -1(Chem. Mater. 2005, 17, 5041.).For many years, scientist studies the novel chromium oxide material for the lithium electricity always.The people such as Liu have prepared porous oxidation chromium nano particle by hard template method, and its reversible capacity under 0.1C is 500 mA h g approximately -1(Chem. Commun. 2012, 48, 865).The people such as Jiang have synthesized the chromium oxide-carbon complex of nucleocapsid structure, and its reversible capacity under 0.2C is 600 mA h g approximately -1（J.?Mater.?Chem . 2010,? 20,?7565）。Also do not prepare so far the more chromium oxide material of high reversible capacity.
Graphene is a kind of brand-new sequential 2 D material with carbon element in being, has unique physicochemical properties.Its distinctive bigger serface and good electric property thereof have determined its great potential in the lithium battery field.Graphene is to be made of monolayer carbon atom close-packed arrays, and lithium not only can be stored in the both sides of graphene sheet layer, can also store in the edge of graphene sheet layer and hole, and its theoretical capacity is more than several times of conventional graphite material.To greatly improve the battery lithium storage content with grapheme material as lithium cell cathode material, and then improve energy density.Therefore, there are some graphene nanocomposite materials to be used for the research of lithium electricity, a lot of reports as existing in composite materials such as cobalt/cobalt oxide, ferriferous oxide, Mn oxides, but seldom report about chromated oxide-graphene composite material.The report that one example is only arranged at present is chromium oxide synthesizes with the Graphene physical mixed (J. Mater. Chem., 2012, 22, 16318), because its fault of construction causes the lithium electrical property relatively poor.Its capacity is 77 mA h g under 0.1C -1, best sample capacity is 526 mA h g -1, and the capacity under higher electric current is low and unstable.
Prepare chromium oxide-graphene nanometer sheet composite material take Graphene as template and by chromate reduction, because chromium oxide is grown at Graphene in-situ oxidation carbon atom, and form the nanometer sheet structure of mesh structural porous two dimension, the structure of this uniqueness has not only effectively improved conductance and the energy density thereof of chromium oxide composite material, has more improved the stability of chromium oxide lithium ion battery.
Summary of the invention
The present invention aims to provide a kind of chromium oxide with good electric chemical property-graphene nanometer sheet material preparation method and the chromium oxide nanometer sheet that makes thereof, chromium oxide-graphene nano sheet material.Cardinal principle is: chromate grows into hydrated chromium oxide and forms the nanometer sheet of two-dimension netted porous at Graphene in-situ oxidation carbon atom, then obtains chromium oxide nanometer sheet material through Overheating Treatment.
Technical solution of the present invention is as follows:
A kind of preparation method of chromium oxide-graphene nanometer sheet, it is characterized in that: take Graphene as template, chromate is the chromium source, chromate obtains hydrated chromium oxide-graphene nanometer sheet in the Graphene original position by the carbonoxide atom under hydrothermal condition, then carry out thermal bake-out and process the chromium oxide-graphene nanometer sheet that obtains crystallization, specifically comprise the steps:
(1) portion (being mass ratio) Graphene and 0.2-10 part chromate are dispersed in 1000-5000 part pure water or water-alcohol solution, ultrasonic or stirred 0.5-24 hour, obtain uniform solution, regulating the pH value is 1.0-8.0, stirs;
(2) above-mentioned mixed liquor is transferred in hydrothermal reaction kettle, reaction is 1-100 hour under 110-300 ℃, with product filtration, washing, drying, obtains chromium oxide hydrate nanometer sheet;
(3) chromium oxide hydrate nanometer sheet was calcined 0.1-10 hour lower 200-1000 ℃ of argon gas (nitrogen or other inert gas) protection, can be obtained final chromium oxide or chromium oxide-graphene nano sheet material;
Described chromate is Na 2CrO 4, Na 2Cr 2O 7, K 2CrO 4, K 2Cr 2O 7, Li 2CrO 4, Li 2Cr 2O 7, MgCrO 4, MgCr 2O 7In a kind of, described alcohol is a kind of in ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol;
Described in step (1), the mass ratio of Graphene and chromate is 1:(1-10), in described water-alcohol solution, water and pure volume ratio are 100:(1-50);
Described in step (1), the mass ratio of Graphene and chromate is 1:(1-8);
The preparation method of described chromium oxide-graphene nanometer sheet prepared pure zirconia chromium nanometer sheet or chromium oxide-graphene nano sheet material;
Described chromium oxide-graphene nano sheet material is the porous nano-sheet composite construction, and the Graphene mass fraction is 0-95%;
The present invention has following advantage compared with prior art:
Being used at present the inorganic oxide-graphene composite material of lithium electric material, is all that coprecipitation is attached directly to the Graphene surface or graphene coated arrives oxide particle surface as cobalt oxide, iron oxide etc.Nano particle can not fully mix with the Graphene skeleton with strong conductivity, the present invention is that chromate is at the Graphene edge and vacancy in-situ oxidation carbon atom growth chromated oxide, form gradually the nanometer sheet structure of mesh structural porous two dimension in Graphene, the structure of this uniqueness has not only effectively improved conductance and the energy density thereof of chromium oxide composite material, has also improved the stability of chromium oxide lithium ion battery.
Raw material of the present invention only needs Graphene and chromate, and chromium oxide generates and obtain the mesh nano sheet composite material of structure uniqueness in the Graphene original position.Its preparation technology is simple to operation, and environmental protection is easy to suitability for industrialized production.The chromium oxide of preparation is the nano-sheet pattern, good dispersion, and specific area is large, and chromium oxide-Graphene is the G-Cr oxide and replaces network structure, has to show good especially electrochemical properties, has broad prospect of application at the high-performance lithium electrical domain.
Description of drawings:
Fig. 1 a is the prepared crystallization chromium oxide of the embodiment of the present invention 1 nanometer sheet TEM figure, Fig. 1 b is the prepared crystallization chromium oxide of the embodiment of the present invention 1 nanometer sheet HRTEM figure, Fig. 1 c is that the present invention executes the prepared chromium oxide hydrate of example 4-graphene nanometer sheet SEM figure, Fig. 1 d is that the present invention executes the prepared chromium oxide hydrate of example 4-graphene nanometer sheet TEM figure, Fig. 1 e is that the present invention executes the prepared crystallization chromium oxide of example 4-graphene nanometer sheet TEM figure, and Fig. 1 f is that the present invention executes the prepared crystallization chromium oxide of example 4-graphene nanometer sheet HRTEM figure.
Fig. 2 a is the embodiment of the present invention 1, the XPS phenogram of 4 prepared chromium oxide (pitch black line) and chromium oxide-graphene nanometer sheet (light gray), Fig. 2 b is the TGA phenogram of the prepared chromium oxide of embodiment Isosorbide-5-Nitrae (pitch black line) and chromium oxide-graphene nanometer sheet (light gray line).Fig. 2 c is the XRD phenogram of the prepared chromium oxide of embodiment 1 (black line), and Fig. 2 d is the embodiment Isosorbide-5-Nitrae, the Ramman phenogram of 6 prepared chromium oxide (pitch black line) and chromium oxide-graphene nanometer sheet (light gray line GCN1,3).
Fig. 3 a is the embodiment of the present invention 1,4, the chemical property figure of 6 prepared chromium oxide (aterrimus) and chromium oxide-graphene nanometer sheet (light gray line), Fig. 3 b is the embodiment of the present invention 1,4,6 prepared chromium oxide (aterrimus) and chromium oxide-graphene nanometer sheet (light grey GCN1,3) constant current charge-discharge curve, Fig. 3 c is cycle performance and the coulombic efficiency figure of the embodiment of the present invention 6 made chromium oxide-graphene nanometer sheets, and Fig. 3 d is cycle performance and the coulombic efficiency figure of the embodiment of the present invention 1 made chromium oxide-graphene nanometer sheet.
Embodiment:
Embodiment 1
With 0.2g Graphene and 1.6gNa 2CrO 4(mass ratio 1:8) evenly spreads in deionized water, ultrasonic 2 hours.With acid for adjusting pH to 5.0, stirred 30 minutes, transfer in autoclave and seal, reaction is 12 hours under 150 ℃, and the filtration washing drying obtains hydrated chromium oxide nanometer sheet product, and then under argon shield, 700 ℃ of calcinings obtained final chromium oxide nanometer sheet in 3 hours.XRD shows that final chromium oxide has good crystalline form.The electron microscope picture shows that hydrated chromium oxide is a micron sheet porous structural, and chromium oxide is sheet-like particle and the even particle distribution of 20-30 nm.The test of lithium electrical property shows that its capacity is at 200mA g -1Under be 250 mA h g -1
Embodiment 2
Take step identical in embodiment 1, temperature is different, and reaction is 5 hours under 200 ℃, and the filtration washing drying obtains hydrated chromium oxide nanometer sheet product, and then under argon shield, 800 ℃ of calcinings obtained final chromium oxide nanometer sheet in 1 hour.XRD shows that final chromium oxide has good crystalline form.The electron microscope picture shows that hydrated chromium oxide is a micron sheet porous structural, and chromium oxide is the sheet-like particle of 20-30 nm.The test of lithium electrical property shows that its capacity is at 200mA g -1Under be about 230 mA h g -1
Embodiment 3
Take step identical in embodiment 1, with 0.2g Graphene and 1.6gNa 2Cr 2O 7(mass ratio 1:8) evenly spreads in deionized water.Resulting material structure pattern is identical with embodiment 1, and the test of lithium electrical property shows that its capacity is at 200mA g -1Under be about 255 mA h g -1
Embodiment 4
Take step identical in embodiment 1, different is with Na 2CrO 4Addition change 0.6g into, namely Graphene and chromate mass ratio are 1:3.XRD and TEM show that final product is chromium oxide-graphene composite material.The electron microscope picture shows that hydrated chromium oxide-Graphene is the micron sheet porous structural, and final chromium oxide-graphene composite material is tens sheet porous structurals to the hundreds of nanometer.Graphene content is about 38%, and its capacity of chromium oxide-graphene nano sheet material is at 200mA g -1Under up to being 700 mA h g -1
Embodiment 5
Take step identical in embodiment 4, different is with Na 2CrO 4Replace with Na 2Cr 2O 7Addition is constant.Resulting material structure pattern is similar to Example 4, and Graphene content is about 35%, and the test of lithium electrical property shows that its capacity is at 200mA g -1Under be about 685 mA h g -1
Embodiment 6
Take step identical in embodiment 1, that different is Na 2CrO 4Addition be 0.2g, namely Graphene and chromate mass ratio are 1:1.XRD and TEM show that final product is chromium oxide-graphene composite material.The electron microscope picture shows that hydrated chromium oxide-Graphene is the micron sheet porous structural, and final chromium oxide-graphene composite material is the sheet porous structural of hundred nanometers.Graphene content is about 52%, and its capacity of chromium oxide-graphene nano sheet material is at 200mA g -1Under up to being 990 mA h g -1
Embodiment 7
Take step identical in embodiment 6, different is with Na 2CrO 4Replace with K 2CrO 4Resulting material structure pattern is identical with embodiment 6, and the test of lithium electrical property shows that its capacity is at 200mA g -1Under be about 970 mA h g -1
Embodiment 8
Take step identical in embodiment 6, different is with Na 2CrO 4Replace with K 2Cr 2O 7Resulting material structure pattern is identical with embodiment 6, and the test of lithium electrical property shows that its reversible capacity is at 200mA g -1Under be 970 mA h g -1
Embodiment 9
Take step identical in embodiment 1, it is that in 5% ethanol water, the material structure that makes is identical with embodiment 1, is of a size of the sheet-like particle of 15-25 nm that different is Graphene and chromate is dispersed in concentration.The test of lithium electrical property shows that its reversible capacity is at 200mA g -1Under be about 255 mA h g -1
Embodiment 10
Take step identical in embodiment 6, it is in 20% ethanol water that different is Graphene and chromate is dispersed in concentration.Resulting material structure pattern is similar to Example 6, and the pattern of final products is the sheet porous structural of hundred nanometers.The test of lithium electrical property shows that its reversible capacity is at 200mA g -1Under be about 980 mA h g -1
Chromium oxide hydrate-the graphene nanometer sheet of the present invention's preparation and the Graphene content in chromium oxide-graphene nanometer sheet increase with the raising of Graphene and chromate ratio.

Claims (5)

1. the preparation method of a chromium oxide-graphene nanometer sheet, it is characterized in that: take Graphene as template, chromate is the chromium source, chromate obtains hydrated chromium oxide-graphene nanometer sheet in the Graphene original position by the carbonoxide atom under hydrothermal condition, then carry out thermal bake-out and process the chromium oxide-graphene nanometer sheet that obtains crystallization, specifically comprise the steps:
(1) portion (being mass ratio) Graphene and 0.2-10 part chromate are dispersed in 1000-5000 part pure water or water-alcohol solution, ultrasonic or stirred 0.5-24 hour, obtain uniform solution, regulating the pH value is 1.0-8.0, stirs;
(2) above-mentioned mixed liquor is transferred in hydrothermal reaction kettle, reaction is 1-100 hour under 110-300 ℃, with product filtration, washing, drying, obtains chromium oxide hydrate nanometer sheet;
(3) chromium oxide hydrate nanometer sheet was calcined 0.1-10 hour lower 200-1000 ℃ of argon gas (nitrogen or other inert gas) protection, can be obtained final chromium oxide or chromium oxide-graphene nano sheet material.
2. the preparation method of chromium oxide-graphene nanometer sheet according to claim 1, it is characterized in that: described chromate is Na 2CrO 4, Na 2Cr 2O 7, K 2CrO 4, K 2Cr 2O 7, Li 2CrO 4, Li 2Cr 2O 7, MgCrO 4, MgCr 2O 7In a kind of, described alcohol is a kind of in ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol.
3. the preparation method of chromium oxide-graphene nanometer sheet according to claim 1, it is characterized in that: described in step (1), the mass ratio of Graphene and chromate is 1:(1-10), in described water-alcohol solution, water and pure volume ratio are 100:(1-50).
4. the preparation method of chromium oxide-graphene nanometer sheet as claimed in claim 1 prepared pure zirconia chromium nanometer sheet or chromium oxide-graphene nano sheet material.
5. the preparation method of chromium oxide-graphene nanometer sheet as claimed in claim 5 prepared pure zirconia chromium nanometer sheet or chromium oxide-graphene nano sheet material, it is characterized in that: described chromium oxide-graphene nano sheet material, be the porous nano-sheet composite construction, the Graphene mass fraction is 0-95%.
CN201310043761.0A 2013-02-02 2013-02-02 A kind of preparation method of chromium oxide-graphene nanometer sheet and obtained chromium oxide-graphene nano sheet material thereof Expired - Fee Related CN103151501B (en)

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CN114774043A (en) * 2022-04-11 2022-07-22 中国航发北京航空材料研究院 Corrosion inhibiting primer for structural adhesive joint and preparation method thereof

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CN114774043B (en) * 2022-04-11 2023-08-04 中国航发北京航空材料研究院 Corrosion-inhibiting primer for structural adhesive bonding and preparation method thereof

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