CN102881898A - Preparation method and application of carbon-coated grapheme-based metal oxide composite - Google Patents
Preparation method and application of carbon-coated grapheme-based metal oxide composite Download PDFInfo
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- CN102881898A CN102881898A CN2012103469731A CN201210346973A CN102881898A CN 102881898 A CN102881898 A CN 102881898A CN 2012103469731 A CN2012103469731 A CN 2012103469731A CN 201210346973 A CN201210346973 A CN 201210346973A CN 102881898 A CN102881898 A CN 102881898A
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Abstract
The invention discloses a preparation method and application of a carbon-coated grapheme-based metal oxide composite in a two-dimensional core-shell structure. The carbon-coated grapheme-based metal oxide composite in the two-dimensional core-shell structure is prepared by taking the two-dimensional grapheme in a single-layer carbon atom structure as a carrier and the phenolic resin or polysaccharide as the carbon source precursor. The metal oxide nanoparticles obtained by the method are uniformly loaded on a graphene sheet and well coated in the carbon-coated layer. The preparation method has the advantages of simple process, mild condition and low cost. The Electrochemical tests prove that the carbon-coated grapheme-based metal oxide composite in the two-dimensional core-shell structure has excellent cycle stability and rate properties. The experiments prove that: under the charge and discharge current of 200mAhg<-1>, the tin dioxide material has the discharge capacity of 200mAhg<-1>, and the ferroferric oxide material has the discharge capacity of 930mAhg<-1>. Therefore, better experimental data and theoretical support are provided for the research and the application of the metal oxide in the field of electrochemistry.
Description
Technical field
The present invention relates to a kind of method and application thereof of carbon coated graphite thiazolinyl metal oxide composite, relate in particular to a kind of method and application thereof of carbon coated graphite thiazolinyl metal oxide composite of two-dimentional core-shell structure.Belong to material science and technical field of electrochemistry.
Background technology
Along with day by day highlighting of energy and environment problem, New Energy Industry has obtained increasing attention.Hybrid vehicle and electric automobile industry development are rapid, and lithium ion battery is widely used as wherein important energy storage device.Lithium ion battery has energy density high, and some good performances such as good cycle also are considered at present one of the most effective energy storage mode, and therefore, further improving its energy density and cycle performance also is difficult point and the focus of instantly studying.
The negative pole of lithium ion battery is the important component part of battery, and its structure and performance directly affect capacity and the cycle performance of lithium ion battery.Commercial lithium ion battery negative material is take graphite as main at present, and the graphite cost is low, and wide material sources are suitable for commercialization; But its capacity is lower, and theoretical capacity only is 372mAhg
-1, be restricted when in the field that needs high-energy output, using.
Metal oxide such as Fe
3O
4, SnO
2Have very high specific capacity Deng as lithium ion battery negative material, its specific capacity is up to 700-1000mAh g
-1But most of metal oxide, especially SnO
2Change in volume is up to 200-300% in charge and discharge process as electrode material, and this change in volume can cause the efflorescence of electrode, causes opening circuit of active material and collector.Therefore, all there is rapidly problem of capacity attenuation in the most metals oxide during as lithium ion cell electrode, and this has also limited development and the practical application of metal oxide as lithium ion battery negative material.
At present, for expanding the application of metal oxide in lithium ion battery negative material, researchers conduct in-depth research for these problems that metal oxide exists, for example electrode material is carried out modification, comprise coating, doping, compound and preparations of nanomaterials, improve the performance of electrode material by these methods, particularly carry out the compound of nanoscale at metal oxide and material with carbon element, prepare the focus that novel nanostructure aspect has become present research.
Material with carbon element has its unique premium properties: stability, good conductivity, light weight; Make its carrier that can be used as good metal oxide, by the change in volume stress of absorption metal oxide in the lithium ion battery charge and discharge process, thus the cycle performance of enhancing metal oxide.Therefore, material with carbon element and metal oxide are carried out the composite material of the novel nano structure that combined structure goes out as the negative material of lithium ion battery, be expected to significantly improve the performance of lithium ion battery, and expand to use for it and also have far reaching significance.
Summary of the invention
Because the defects of prior art, technical problem to be solved by this invention provides the composite material that a kind of Two-dimensional Carbon that can strengthen the metal oxide cycle performance coats.
For achieving the above object, the invention provides a kind of preparation method and application thereof with carbon coated graphite thiazolinyl metal oxide composite of two-dimentional core-shell structure.Particularly, adopt the two-dimentional Graphene of monolayer carbon atomic structure as carrier, phenolic resins or polysaccharide are prepared the graphene-based metal oxide nano composite material of the carbon coating of two-dimentional core-shell structure as the carbon source presoma.
The present invention solves above-mentioned technical problem by the following technical programs:
On the one hand, the invention provides a kind of preparation method with carbon coated graphite thiazolinyl metal oxide composite of two-dimentional core-shell structure.
Preparation method of the present invention adopts two step synthesis to have the carbon coated graphite thiazolinyl metal oxide composite of two-dimentional core-shell structure.At first, with the graphene oxide table and then functionalization adopts metal chloride at the Graphene surface hydrolysis of functionalization, obtain graphene-based metal oxide nano-sheet by in situ synthesis; Secondly, by coating its surperficial metal oxide particle at this nanometer sheet surface aggregate one deck high molecular polymer; At last, by the calcining carbonization, obtain the composite material of the two-dimentional shell nuclear framework of carbon coating.
In the present invention, the concrete grammar of carbon coated graphite thiazolinyl metal oxide composite of preparation with two-dimentional core-shell structure comprises the steps:
Step 1, prepare graphene-based metal oxide nano-sheet:
At first, be the aqueous solution that adds polydiene alkyl dimethyl ammonium chloride (PDDA) in graphene oxide (GO) aqueous solution of 0.2-1mg/mL in concentration, ultrasonic mixing;
Secondly, add metal chloride in the above-mentioned dispersion liquid after, 60-90 ℃ of insulation 1-5 hour;
At last, with above-mentioned reacted solution centrifugal, with the deionized water washing, repeated centrifugation, washing operation repeatedly are scattered in the deionized water solid that obtains stand-by.
The graphene-based metal oxide nano-sheet that step 2, preparation carbon coat:
At first, add the aqueous solution of carbon source presoma in the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet, then carry out catalytic polymerization or Direct Hydrothermal carbonization treatment;
Secondly, above-mentioned reacted solution is carried out centrifugal, and carry out repeatedly centrifuge washing repeatedly with deionized water, the solid that obtains through super-dry, calcining, is finally obtained the composite material of the coated graphite thiazolinyl metal oxide of the two-dimentional core-shell structure of carbon.
Wherein, described metal chloride is preferably stannous chloride (SnCl
22H
2O) or frerrous chloride (FeCl
24H
2O).
In the specific embodiment of the present invention, when metal chloride is stannous chloride, preferably before in dispersion liquid, adding metal chloride, in dispersion liquid, add hydrochloric acid, regulator solution pH to 1-3 first; Then after under intense agitation, adding metal chloride, again 60～90 ℃ of insulations 1-5 hour.
In concrete preparation method of the present invention, the amount ratio of graphene oxide and PDDA (quality) is preferably 1 in the step 1: 4-16; More preferably, the amount ratio of graphene oxide and PDDA (quality) is 1: 8.
In the specific implementation, the metal chloride that adds in the step 1 and the mass ratio of graphene oxide are preferably 15-60: 1; More preferably, the metal chloride that adds and the mass ratio of graphene oxide are 30: 1.
In preferred implementation of the present invention, the concentration of the dispersion liquid of graphene-based metal oxide nano-sheet in deionized water is preferably 0.5-1mg/mL.
In preparation method of the present invention, when in the step 2 nanometer sheet being coated, adopt presoma to carry out polymerization or hydrothermal carbonization coats.When using presoma to carry out the polymerization coating, described presoma is preferably phenol compound and formaldehyde, such as phenol and formaldehyde or resorcinol and formaldehyde.When using presoma to carry out the hydrothermal carbonization coating, described presoma is preferably glucose.
When presoma is phenol compound and formaldehyde, after adding the aqueous solution of presoma in the dispersion liquid of graphene-based metal oxide nano-sheet, stir 15-30min 80-100 ℃ of oil bath, then add catalyst and carry out catalytic polymerization, add insulation 10-24 hour.Wherein, described catalyst is preferably NaOH or sodium carbonate.
Preferably, graphene-based metal oxide nano-sheet (take graphene oxide) is 1 with the mass ratio of phenol compound: 10-30, more preferably, graphene-based metal oxide nano-sheet (take graphene oxide) is 1: 20 with the mass ratio of phenol compound.
When presoma is glucose, directly in the dispersion liquid of graphene-based metal oxide nano-sheet, add glucose, after mixing, with the mixed solution water heating kettle of packing into, and put into 120-180 ℃ of baking oven and carry out hydro-thermal reaction.
Preferably, graphene-based metal oxide nano-sheet (take graphene oxide) is 1 with the mass ratio of glucose: 75-200.
In a preferred embodiment of the invention, the product that step 2 obtains is at 60 ℃ of dry 10-16 hours, and through N
2Protection is lower to 500 ℃ of calcinings 1-3 hour.
In the present invention, when adopting presoma to carry out polymerization nanometer sheet is coated, polymerization reaction between the described phenolic aldehyde is this area polymerization reaction commonly used, wherein the amount ratio of formaldehyde and phenol compound is classified the synthetic ratio commonly used of phenolic resins as, and the consumption of its catalyst also is the synthetic usual amounts of this area phenolic resins.Those skilled in the art can regulate the consumption of phenolic aldehyde and catalyst according to actual needs, and this is not particularly limited.
In preparation method of the present invention, metal oxide particle is loaded on the Graphene surface, suppressed to a certain extent the reunion of its particle, increase specific area, thereby improve the capacity of material.Simultaneously the material surface in this two dimension coats one deck carbon, can absorb metal oxide such as the granules of stannic oxide change in volume in charge and discharge process, suppresses the pulverizing of its particle and comes off, thereby improved greatly the cyclical stability of material.Therefore, the adding of carbon coating layer can improve the conductivity of whole electrode material, realize the quick transmission of electronics, thereby so that material has high high rate performance.
On the other hand, the present invention also provides a kind of application with carbon coated graphite thiazolinyl metal oxide composite of two-dimentional core-shell structure.
Of the present invention have the carbon coated graphite thiazolinyl metal oxide composite advantageous applications of two-dimentional core-shell structure in lithium ion battery negative material.The composite material of Two-dimensional Carbon clad structure of the present invention can also strengthen its cycle performance during as lithium ion battery negative material when improving the negative material capacity.
In specific embodiments of the present invention, the button-shaped half-cell of lithium ion is take the carbon coated graphite thiazolinyl metal oxide composite that has as mentioned above two-dimentional core-shell structure as negative material, lithium metal just very, electrolyte is ethyl carbonate or the dimethyl carbonate solution of lithium hexafluoro phosphate solution.
The present invention adopts the two-dimentional Graphene of monolayer carbon atomic structure as carrier, and phenolic resins or carbohydrate are prepared the graphene-based metal oxide nano composite material of the carbon coating of two-dimentional core-shell structure as the carbon source presoma by simple two-step method.The method has technique simple, mild condition, the advantage such as with low cost.The metal oxide nanoparticles that obtains by the inventive method loads on the graphene film equably, and well is coated in the carbon coating layer.Prove that through electro-chemical test prepared composite material has excellent cyclical stability and high rate performance; Experiment showed, at 200mAg
-1Charging or discharging current under: the specific discharge capacity of the tin dioxide material that makes can reach 800mAh g
-1, the ferriferrous oxide material specific discharge capacity can reach 930mAhg
-1Therefore, the present invention provides good experimental data and theoretical the support for metal oxide in research and the application of electrochemical field.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand fully purpose of the present invention, feature and effect.
Description of drawings
Fig. 1 is the shape appearance figure of the graphene-based metal oxide nano-sheet of embodiments of the invention 1-2; Wherein, a, c are respectively embodiment 1,2 scanning electron microscopy (SEM) image, and b, d are respectively embodiment 1,2 transmission electron microscope (TEM) image.
Fig. 2 is the shape appearance figure of the carbon coated graphite thiazolinyl metal oxide nano-sheet of embodiments of the invention 1-3; Wherein, a, c are respectively embodiment 1,3 TEM image, and b is the SEM image of embodiment 2.
Fig. 3 is that the graphene-based tin ash composite material that coats of the graphene-based tin ash of embodiments of the invention 1 and carbon is as the cycle performance figure of lithium ion battery negative material.
Fig. 4 is that the graphene-based tin ash composite material that coats of the graphene-based tin ash of embodiments of the invention 1 and carbon is as the high rate performance figure of lithium ion battery negative material.
Fig. 5 is that the graphene-based ferriferrous oxide composite material that coats of the graphene-based tri-iron tetroxide of embodiments of the invention 2 and carbon is as the cycle performance figure of lithium ion battery negative material.
Fig. 6 is that the graphene-based ferriferrous oxide composite material that coats of the graphene-based tri-iron tetroxide of embodiments of the invention 2 and carbon is as the high rate performance figure of lithium ion battery negative material.
Embodiment
The mass percent concentration of the polydiene alkyl dimethyl ammonium chloride aqueous solution is 20% among the embodiment.
Embodiment 1
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) to the middle aqueous solution (0.5mL) that adds 20% polydiene alkyl dimethyl ammonium chloride of the aqueous solution (60mL) of 0.2mg/mL graphene oxide, ultrasonic, form the dispersion liquid that mixes;
Wherein, the quality amount ratio of graphene oxide and polydiene alkyl dimethyl ammonium chloride is 1: 8 in the dispersion liquid.
(2) in above-mentioned dispersion liquid, add hydrochloric acid, regulator solution pH to 2; Under vigorous stirring, add stannous chloride (SnCl
22H
2O), add in 90 ℃ of insulations one hour, cooling;
Wherein, the SnCl of interpolation
22H
2The quality amount ratio of O and graphene oxide is 30: 1.
(3) carry out above-mentioned reacted solution centrifugal, with the deionized water washing, repeated centrifugation, washing operation three times obtain black solid, be graphene-based stannic oxide nanometer sheet, the SEM of this graphene-based stannic oxide nanometer sheet, TEM photo are respectively shown in Fig. 1 a, 1b.The solid that obtains is scattered in the deionized water stand-by, its concentration is 0.6mg/mL (press graphene oxide calculate).
The graphene-based stannic oxide nanometer sheet that second step, preparation carbon coat:
(1) dispersion liquid of getting the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of 50mL places conical flask, the aqueous solution that adds phenol and formaldehyde in this dispersion liquid, 30min are stirred in 90 ℃ of oil baths, then add NaOH and carry out catalytic polymerization, and be incubated 12 hours, cooling;
Wherein, the consumption mass ratio of graphene oxide and phenol is 1: 20, and it is greatly excessive that formaldehyde is equivalent to phenol; The consumption of NaOH is 100mg;
(2) with above-mentioned reacted solution centrifugal, carry out repeatedly centrifuge washing repeatedly with deionized water, with the solid that obtains through 60 ℃ of dry 12h, through N
2Protect lower 500 ℃ of calcining 2h, finally obtain the graphene-based tin ash composite material that carbon two dimension core-shell structure coats, the TEM photo of this carbon coated graphite thiazolinyl stannic oxide nanometer sheet is shown in Fig. 2 a.
Be assembled into the button-shaped half-cell of lithium ion (to electrode as lithium metal) take the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, and its cycle performance figure, high rate performance figure are respectively shown in Fig. 3,4.
Wherein, GN@SnO
2Charge, GN@SnO
2Dicharge is respectively graphene-based tin ash as charge and discharge figure, the GN@SnO of lithium ion battery negative material
2@C
PFCharge, GN@SnO
2@C
PFDischarge is respectively the graphene-based tin ash composite material of carbon coating as the charge and discharge figure of lithium ion battery negative material.As can be seen from Figure 3 the composite material of this Two-dimensional Carbon coating has demonstrated higher capacity (800mAh g
-1), and very superior cycle performance.It is still keeping 800mAh g after 100 circle circulations
-1Capacity, do not carry out the then in the past 800mAh g of ten circles of material capacity that carbon coats
-1Dropped to only 200mAhg
-1As shown in Figure 4, the material after carbon coats is at 5000mAg
-1Large electric current under still maintain 260mAh g
-1Capacity, this is very excellent high rate performance concerning tin dioxide material.
The first step, the graphene-based ferric oxide nano sheet of preparation
(1) in the aqueous solution (60mL) of 1mg/mL graphene oxide, add the 20% polydiene alkyl dimethyl ammonium chloride aqueous solution (5mL), ultrasonic, form the dispersion liquid that mixes;
Wherein, the quality amount ratio of the graphene oxide of interpolation and polydiene alkyl dimethyl ammonium chloride is 1: 16.
(2) in above-mentioned dispersion liquid, add frerrous chloride (FeCl
24H
2O), add in 90 ℃ of insulations 5 hours, cooling;
Wherein, the FeCl of interpolation
24H
2The quality amount ratio of O and graphene oxide is 15: 1.
(3) carry out above-mentioned reacted solution centrifugal, with the deionized water washing, repeated centrifugation, washing operation three times obtain black solid, be graphene-based alkali formula ferric oxide nano sheet, the SEM of this graphene-based alkali formula ferric oxide nano sheet, TEM photo are respectively shown in Fig. 1 c, 1d.The solid that obtains is scattered in stand-by in the deionized water (dispersion liquid concentration is calculated as 0.6mg/mL by graphene oxide concentration).
The graphene-based ferroferric oxide nano-piece that second step, preparation carbon coat
(1) dispersion liquid of getting the graphene-based alkali formula ferric oxide nano sheet of the above-mentioned preparation of 50mL places conical flask, the aqueous solution that adds phenol and formaldehyde in this dispersion liquid, 30min are stirred in 90 ℃ of oil baths, then add NaOH and carry out catalytic polymerization, and be incubated 12 hours, cooling;
Wherein, the consumption mass ratio of graphene oxide and phenol is 1: 30, and it is greatly excessive that formaldehyde is equivalent to phenol; The consumption of NaOH is 100mg;
(2) with above-mentioned reacted solution centrifugal, carry out repeatedly centrifuge washing repeatedly with deionized water, with the solid that obtains through 60 ℃ of dry 12h, through N
2Protect lower 500 ℃ of calcining 2h, finally obtain the graphene-based ferriferrous oxide composite material that carbon two dimension core-shell structure coats, the SEM photo of this carbon coated graphite thiazolinyl ferroferric oxide nano-piece is shown in Fig. 2 b.
Be assembled into the button-shaped half-cell of lithium ion (to electrode as lithium metal) take the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, and its cycle performance figure, high rate performance figure are respectively shown in Fig. 5,6.Wherein, G@Fe
3O
4@C Charge/Dicharge, G@Fe
3O
4Charge/Dicharge is respectively graphene-based ferriferrous oxide composite material that carbon coats, do not carry out graphene-based tri-iron tetroxide that carbon coats as the charge/discharge figure of lithium ion battery negative material.As can be seen from Figure 5, the composite material that the Two-dimensional Carbon that makes coats demonstrates high capacity (930mAh g
-1) and very superior cycle performance.It is still keeping 930mAh g after 100 circle circulations
-1Capacity, and the capacity that does not carry out the material that carbon coats is 600mAh g
-1As shown in Figure 6, the composite material after carbon coats is at 5000mAg
-1Large electric current under still maintain 600mAh g
-1Capacity.
Embodiment 3
The first step, the graphene-based stannic oxide nanometer sheet of preparation:
(1) in the aqueous solution (60mL) of 0.5mg/mL graphene oxide, add the 20% polydiene alkyl dimethyl ammonium chloride aqueous solution (1.25mL), ultrasonic, form the dispersion liquid that mixes;
Wherein, the quality amount ratio of the graphene oxide of interpolation and polydiene alkyl dimethyl ammonium chloride is: 1: 8.
(2) in above-mentioned dispersion liquid, add hydrochloric acid, regulator solution pH to 2; Under vigorous stirring, add stannous chloride (SnCl
22H
2O), add in 90 ℃ of insulations one hour, cooling;
Wherein, the SnCl of interpolation
22H
2The quality amount ratio of O and graphene oxide is 30: 1.
(3) above-mentioned reacted solution is carried out centrifugal, with deionized water washing, repeated centrifugation, washing operation three times obtain black solid, are graphene-based stannic oxide nanometer sheet.The solid that obtains is scattered in the deionized water stand-by, its concentration is 0.6mg/mL (press graphene oxide calculate).
The graphene-based stannic oxide nanometer sheet that second step, preparation carbon coat
(1) dispersion liquid of getting the graphene-based stannic oxide nanometer sheet of the above-mentioned preparation of 50mL places conical flask, stir after adding 3g glucose in this dispersion liquid, then be transferred in the 100mL water heating kettle, and with solution dilution to 80mL, in 180 ℃ of hydro-thermals and be incubated 12 hours, cooling;
Wherein, the quality amount ratio of graphene oxide and glucose is 1: 100;
(2) with above-mentioned reacted solution centrifugal, carry out repeatedly centrifuge washing repeatedly with deionized water, with the solid that obtains through 60 ℃ of dry 12h, through N
2Protect lower 500 ℃ of calcining 2h, finally obtain the graphene-based tin ash composite material that carbon two dimension core-shell structure coats, the TEM photo of this carbon coated graphite thiazolinyl stannic oxide nanometer sheet is shown in Fig. 2 c.
Be assembled into the button-shaped half-cell of lithium ion (to electrode as lithium metal) take the gained composite material as lithium ion battery negative material, the button-shaped half-cell of this lithium ion is carried out electro-chemical test, can learn that from its cycle performance figure, high rate performance figure the composite material of the Two-dimensional Carbon coating that makes demonstrates high capacity (790mAh g
-1) and very superior cycle performance.It is still keeping 780mAh g after 100 circle circulations
-1Capacity, and the capacity that does not carry out the material that carbon coats is 200mAh g
-1
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variations.Therefore, all in the art technical staff all should be in the determined protection range by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. the preparation method of the carbon coated graphite thiazolinyl metal oxide composite of a two-dimentional core-shell structure is characterized in that, may further comprise the steps;
Step 1, prepare graphene-based metal oxide nano-sheet:
At first, be to add the polydiene alkyl dimethyl ammonium chloride aqueous solution, ultrasonic mixing in the graphite oxide aqueous solution of 0.2-1mg/mL to concentration;
Secondly, add metal chloride in the above-mentioned dispersion liquid after, 60-90 ℃ of insulation 1-5 hour;
At last, above-mentioned reacted solution is carried out centrifugal, deionized water washing is scattered in the deionized water solid that obtains stand-by;
The graphene-based metal oxide nano-sheet that step 2, preparation carbon coat:
At first, add the aqueous solution of carbon source presoma in the dispersion liquid of above-mentioned graphene-based metal oxide nano-sheet, then carry out catalytic polymerization or Direct Hydrothermal carbonization treatment;
Secondly, above-mentioned reacted solution is carried out centrifugal, with the deionized water washing, the solid that obtains finally obtains the composite material of the coated graphite thiazolinyl metal oxide of the two-dimentional core-shell structure of carbon through super-dry, calcining;
Wherein, described metal chloride is two hydrated stannous chlorides or Iron dichloride tetrahydrate; Described carbon source presoma is phenol and formaldehyde, resorcinol and formaldehyde or glucose.
2. preparation method as claimed in claim 1 is characterized in that, the consumption mass ratio of graphene oxide and polydiene alkyl dimethyl ammonium chloride is 1 in the described step 1: 4-16; The mass ratio of graphene oxide and metal chloride is 1: 15-60.
3. preparation method as claimed in claim 2 is characterized in that, the consumption mass ratio of graphene oxide and polydiene alkyl dimethyl ammonium chloride is 1: 8 in the described step 1.
4. preparation method as claimed in claim 2 is characterized in that, the metal chloride that adds in the described step 1 and the mass ratio of graphene oxide are 30: 1.
5. preparation method as claimed in claim 1 is characterized in that, in the described step 2, when described carbon source presoma was phenol and formaldehyde, resorcinol and formaldehyde, the mass ratio of graphene-based metal oxide nano-sheet and described carbon source presoma was 1: 10-30.
6. preparation method as claimed in claim 5 is characterized in that, the mass ratio of graphene-based metal oxide nano-sheet and described carbon source presoma is 1: 20 in the described step 2.
7. preparation method as claimed in claim 1 is characterized in that, in the described step 2, when described carbon source presoma was glucose, the mass ratio of graphene-based metal oxide nano-sheet and described carbon source presoma was 1: 75-200.
8. such as each described preparation method of claim 1-7, it is characterized in that the solid that obtains in the described step 2 is at 60 ℃ of dry 10-16 hours, and through N
2Protection is lower to 500 ℃ of calcinings 1-3 hour.
9. according to the carbon coated graphite thiazolinyl metal oxide composite of the two-dimentional core-shell structure for preparing such as each described preparation method of claim 1-8.
10. the application of carbon coated graphite thiazolinyl metal oxide composite in lithium ion battery of two-dimentional core-shell structure as claimed in claim 9.
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