CN103022436B - Electrode composite material preparation method - Google Patents
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- CN103022436B CN103022436B CN201110281925.4A CN201110281925A CN103022436B CN 103022436 B CN103022436 B CN 103022436B CN 201110281925 A CN201110281925 A CN 201110281925A CN 103022436 B CN103022436 B CN 103022436B
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Abstract
The invention relates to an electrode composite material preparation method, which comprises: 1, providing graphite oxide and graphene; 2, grinding silicon powder to obtain silicon micro-nano-particles; 3, adding the graphite oxide to water to carry out ultrasonic dispersion to form a graphene oxide solution having a uniformly dispersed single lamella layer, adding the silicon micro-nano-particles to the graphene oxide solution, and vigorously stirring at a room temperature to obtain silicon micro-nano-particles coated with the graphene oxide; 4, placing the silicon micro-nano-particles coated with the graphene oxide in a reduction atmosphere, heating, carrying out a complete reduction reaction, and cooling to a room temperature in the reduction atmosphere to obtain a silicon micro-nano-particle and graphene composite material; and 5, mixing the silicon micro-nano-particle and graphene composite material and the graphene, and carrying out ball milling to obtain the electrode composite material. The preparation method has an advantage of simpleness.
Description
[technical field]
The present invention relates to a kind of preparation method of electrode composite material, particularly relate to a kind of preparation method being applied to the electrode composite material of lithium ion battery, hybrid super capacitor etc.
[background technology]
Along with the development of various new forms of energy, the miniaturization of portable electric appts and electric automobile are to the widespread demand of large-capacity high-power chemical power source.Current commercial lithium ion battery adopts lithium graphite system mostly, although the electrochemical performance of this kind of system, but due to itself storage lithium ability lower (the theoretical 372mAh/g as graphite), so novel transition metal oxide/graphite system is subject to the attention widely of people.
In intercalation materials of li ions known at present, pure silicon is because having the highest theoretical lithium storage content (4200mAh/g), relatively low intercalation potential, charge and discharge process is not easily reunited, compared with other metal_based materials, there is higher physical stability and chemical stability, become the study hotspot in lithium ion battery negative material field at present.But there is a shortcoming in silica-base material: the effect of stress produced due to bulk effect in degree of depth removal lithium embedded process easily causes avalanche and the material efflorescence of silicon lattice structure, cause active material depart from electrode material system and lose activity, therefore there is very poor cyclical stability.At present, mainly improve one's methods and adopted metal and the Si compound such as Ni, Fe and Cu, formed with the activated centre of Si, take inert metal as the activity/inertia compound system of dispersible carrier, while improving the electric conductivity of material, improve the cycle performance of material, but this material easily forms the metallic silicon phase of inertia, and the molal weight of these metals itself is larger, belongs to non-intercalation materials of li ions, therefore weakens the specific volume of Si sill to a certain extent.Metal itself has electron conduction in addition, does not possess ionic conductivity, makes electrolyte be difficult to immerse, thus loses activity; Another method is exactly the coated method of material with carbon element, lower than the molal weight of metal, and electrolyte is easy to immerse, and relative efficacy comparatively metal will be got well, and material property has certain improvement, but or poor.
Graphene has good conductivity, space distribution and higher mechanical performance, utilizes grapheme material to substitute traditional material with carbon element, is combined silicon, the graphene combination electrode material prepared has good electrochemical stability with silicon.Traditional silicon, graphene combination electrode material mostly adopt wet-layer preparation, and the product obtained needs to carry out strict purification removal of impurities, and process is loaded down with trivial details, and efficiency is low, and product is usually mixed with impurity, affects the performance of electrode material.
[summary of the invention]
Based on this, be necessary to provide a kind of preparation method the preparation method of comparatively simple electrode composite material.
A preparation method for electrode composite material, comprises the steps:
Step one, provide graphite oxide and Graphene;
Step 2, silicon powder grinding is obtained the micro-nano granules of silicon;
Step 3, be added to the water described graphite oxide ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer; Join in graphene oxide solution by the micro-nano granules of silicon, at room temperature vigorous stirring, obtain the micro-nano granules of the silicon being coated with graphene oxide, wherein, the micro-nano granules of described silicon and the mass ratio of described graphene oxide are 1: 2.5 ~ 100;
Step 4, the described micro-nano granules being coated with the silicon of graphene oxide is placed in reducing atmosphere under, 200 ~ 1200 DEG C are slowly heated to the speed of 10 ~ 100 DEG C/min, carry out abundant reduction reaction, be cooled to room temperature in the atmosphere of reproducibility again, obtain the micro-nano granules of silicon, graphene composite material; And
Step 5, with mass ratio be 1: 1 ~ 1: 3 the micro-nano granules of described silicon, graphene composite material are mixed with described Graphene after ball milling 1 ~ 4 hour, obtain described electrode composite material.
In a preferred embodiment, also comprise in step 2: the micro-nano granules hydrochloric acid of described silicon is carried out ultrasonic process, the mass concentration of described hydrochloric acid is 10 ~ 20%, and the consumption of described hydrochloric acid is the consumption of the micro-nano granules soaking described silicon completely.
In a preferred embodiment, the preparation method of graphite oxide described in step one comprises the steps:
Graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cool more than 6 hours, suction filtration, washing is to neutral, dry, obtains biased sample; And
Described biased sample is added in the concentrated sulfuric acid of 0 DEG C, add potassium permanganate again, the temperature of system remains on less than 20 DEG C, then keeps after 2 hours in the oil bath of 35 DEG C, slowly add deionized water, after 15 minutes, then add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that concentration is 10%, suction filtration, namely 60 DEG C of vacuumizes obtain graphite oxide again.
In a preferred embodiment, described graphite raw material is the natural flake graphite that purity is more than or equal to 99.5%.
In a preferred embodiment, described reducing atmosphere is the atmosphere of hydrogen or carbon monoxide.
In a preferred embodiment, in step 3, the time of stirring is 30 minutes ~ 24 hours.
In this preparation process, after being mixed with Graphene by the micro-nano granules of silicon, graphene composite material, ball milling obtains described electrode composite material, preparation process is relatively simple, and without the need to the dry purification step of complexity, directly can obtain product, thus preparation efficiency is higher, obtained composite material purity is high, and performance is guaranteed.
[accompanying drawing explanation]
By the more specifically explanation of the preferred embodiments of the present invention shown in accompanying drawing, above-mentioned and other object of the present invention, Characteristics and advantages will become more clear.Reference numeral identical in whole accompanying drawing indicates identical part, and does not deliberately draw accompanying drawing by actual size equal proportion convergent-divergent, focuses on purport of the present invention is shown.
Fig. 1 is the flow chart of the preparation method of the electrode composite material of an execution mode.
Fig. 2 is the SEM photo of the electrode composite material that embodiment 1 obtains.
[embodiment]
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Present embodiment provides a kind of preparation method of electrode composite material, and this electrode composite material is the composite material comprising silicon micro-nano particle and Graphene.This have a hierarchy, is first the silicon grain of nano level graphene coated, then is dispersed in the lamellar structure of Graphene by the silicon grain of graphene coated.This structure and silicon are directly dispersed in graphene sheet layer the difference having essence, and this structure can the stability of stable silicon bulk effect, holding structure in charge and discharge process more.
Preparation technology's flow process of above-mentioned electrode composite material is as follows:
Compound → silicon micro-nano the particle of graphite → graphite oxide → silicon micro-nano particle, graphite oxide, graphene complex → silicon micro-nano particle, Graphene negative material
Refer to Fig. 1, above-mentioned preparation method specifically comprises the steps:
Step S100, provides graphite oxide and Graphene.
Described graphite oxide can take graphite as raw material, prepares according to the Hummers method (selecting from JACS, 1958,80,1339) improved.Described Graphene can be obtained by mechanical stripping method and thermal expansion graphite method vegetation.
Preferably, described graphite oxide can adopt following method to prepare: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, and cools more than 6 hours, suction filtration, and washing is to neutral, dry, obtains biased sample; Again biased sample is added in the concentrated sulfuric acid of 0 DEG C, add potassium permanganate again, the temperature of system remains on less than 20 DEG C, then keeps after 2 hours in the oil bath of 35 DEG C, slowly add deionized water, after 15 minutes, then add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that concentration is 10%, suction filtration, namely 60 DEG C of vacuumizes obtain graphite oxide again.
Wherein, graphite raw material is preferably the natural flake graphite that purity is more than or equal to 99.5%.
Step S200, obtains the micro-nano granules of silicon by silicon powder grinding.
Preferably, by high energy ball mill, silicon powder grinding is obtained the micro-nano granules of silicon.In more preferred scheme, carry out ultrasonic process by grinding the micro-nano granules hydrochloric acid of silicon obtained, to remove the impurity that silicon grain is introduced into when ball milling.The mass concentration of hydrochloric acid used is 10 ~ 20%, and the consumption of described hydrochloric acid is the consumption of the micro-nano granules soaking described silicon completely.The time of ultrasonic process has preferably 1 hour.After processing, clean, until solution presents neutrality with deionization.
Step S300, be added to the water graphite oxide ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer; The micro-nano granules of silicon is joined in graphene oxide solution, at room temperature vigorous stirring 30 minutes ~ 24 hours, obtain the micro-nano granules of the silicon being coated with graphene oxide, wherein, the micro-nano granules of silicon and the mass ratio of graphene oxide are 1: 2.5 ~ 100.
Step S400, under the micro-nano granules of the silicon being coated with graphene oxide is placed in reducing atmosphere, 200 ~ 1200 DEG C are slowly heated to the speed of 10 ~ 100 DEG C/min, carry out abundant reduction reaction, be cooled to room temperature in the atmosphere of reproducibility again, obtain the micro-nano granules of silicon, graphene composite material.
Preferably, the coated silicon micro-nano particle of the graphene oxide obtained by step S300 puts into the tube furnace being connected with reducibility gas, 200 ~ 1200 DEG C are warming up to the slow speed of 10 ~ 100 DEG C/min, insulation 1 ~ 10h, cool to powder with the furnace room temperature in the atmosphere of hydrogen again, obtain the composite material of silicon micro-nano particle, Graphene.
Step S500, with mass ratio be 1: 1 ~ 1: 3 the micro-nano granules of silicon, graphene composite material mixed with the Graphene of step S100 after ball milling 1 ~ 4 hour, obtain electrode composite material.
The electrode composite material prepared by said method has following beneficial effect: in the composite material that (1) is prepared by the method, and the nano level silicon grain of graphene coated can be good at being dispersed between the lamella of Graphene; (2) this composite material due to Graphene high conductivity can well by electrical conductivity on elemental silicon, improve conductivity, the high capacity characteristics of silicon can have been given full play to, be suitable as lithium ion battery, the negative material of hybrid super capacitor; (3) this composite material has larger specific area due to the Graphene of sheet, so composite material has good porosity, has good example transport properties, is suitable as lithium ion battery, the negative material of ultracapacitor.(4) in this preparation process, after being mixed with Graphene by the micro-nano granules of silicon, graphene composite material, ball milling obtains described electrode composite material, preparation process is relatively simple, and without the need to the dry purification step of complexity, directly can obtain product, thus preparation efficiency is higher, obtained composite material purity is high, and performance is guaranteed.
It is below specific embodiment part
Embodiment 1
Compound → silicon micro-nano the particle of graphite → graphite oxide → silicon micro-nano particle, graphite oxide, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%;
(2) graphite oxide: by the obtained graphite oxide of Hummers method (selecting from JACS, 1958,80,1339) improved.Its concrete steps are 20g 50 object graphite powder, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cooling more than 6h, and washing is to neutral, dry.Dried sample is added 0 DEG C, in the concentrated sulfuric acid of 230mL, then add 60g potassium permanganate, the temperature of mixture remains on less than 20 DEG C, after then keeping 2h in the oil bath of 35 DEG C, slowly adds 920mL deionized water.After 15min, add 2.8L deionized water (wherein containing 50mL concentration is the hydrogen peroxide of 30%) again, mixture color becomes glassy yellow afterwards, while hot suction filtration, then carries out washing with the hydrochloric acid that 5L concentration is 10%, suction filtration, namely obtain graphite oxide at 60 DEG C of vacuumize 48h.
(3) by high energy ball mill, silicon powder grinding is obtained the micro-nano granules of silicon; By the micro-nano granules surface HCl treatment of silicon obtained; The mass concentration of hydrochloric acid is 10%, ultrasonic process 1 hour, then cleans, until solution presents neutrality with deionization.
(4) compound of silicon micro-nano particle, graphene oxide: be added to the water the graphite oxide prepared ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer, both mixing again, the ratio of silicon and graphene oxide is 1: 2.5, room temperature vigorous stirring 30min, obtain the mixture of homodisperse graphene oxide and silicon, vacuumize.
(5) containing the thermal reduction of reducibility gas atmosphere: silicon micro-nano particle coated for (4) gained graphene oxide is put into the tube furnace being connected with reducibility gas and be warming up to 1200 DEG C of heating 10h with the slow speed of 10 DEG C/min, cool to powder with the furnace room temperature in the atmosphere of hydrogen again, obtain the composite material of silicon micro-nano particle, Graphene.
(6) by quality ball millings such as the silicon micro-nano particle of gained, the composite material of Graphene and grapheme material 4 hours, the Graphene of uniform micro nano structure is obtained, the composite material of silicon.
The SEM picture of the silicon that embodiment 1 obtains, the negative material of Graphene as shown in Figure 1.
As seen from Figure 1, spherical or class is spherical is the silicon grain of graphene coated, and coated silicon grain is distributed on the Sheet Graphite alkene of bottom.
Embodiment 2
Compound → silicon micro-nano the particle of graphite → graphite oxide → silicon micro-nano particle, graphite oxide, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%;
(2) graphite oxide: by the obtained graphite oxide of Hummers method (selecting from JACS, 1958,80,1339) improved.Its concrete steps are 20g 50 order graphite powder, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cooling more than 6h, and washing is to neutral, dry.Dried sample is added 0 DEG C, in the concentrated sulfuric acid of 230mL, then add 60g potassium permanganate, the temperature of mixture remains on less than 20 DEG C, after then keeping 2h in the oil bath of 35 DEG C, slowly adds 920mL deionized water.After 15min, add 2.8L deionized water (wherein containing 50mL concentration is the hydrogen peroxide of 30%) again, mixture color becomes glassy yellow afterwards, while hot suction filtration, then carries out washing with the hydrochloric acid that 5L concentration is 10%, suction filtration, namely obtain graphite oxide at 60 DEG C of vacuumize 48h.
(3) by high energy ball mill, silicon powder grinding is obtained the micro-nano granules of silicon; By the micro-nano granules surface HCl treatment of silicon obtained; The mass concentration of hydrochloric acid is 20%, ultrasonic process 1 hour, then cleans, until solution presents neutrality with deionization.
(4) compound of silicon micro-nano particle, graphene oxide: be added to the water the graphite oxide prepared ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer, both business mix, the ratio of silicon and graphene oxide is 1: 5, room temperature vigorous stirring 24hour, obtain the mixture of homodisperse graphene oxide and silicon, vacuumize;
(5) containing the thermal reduction of reducibility gas atmosphere: silicon micro-nano particle coated for (4) gained graphene oxide is put into the tube furnace being connected with reducibility gas and be warming up to 200 DEG C of heating 1h with the slow speed of 100 DEG C/min, cool to powder with the furnace room temperature in the atmosphere of hydrogen again, obtain the composite material of silicon micro-nano particle, Graphene.
(6) by the silicon micro-nano particle of gained, the composite material of Graphene and grapheme material with 1: 2 quality less than mixing and ball milling 1 time, obtain the Graphene of uniform micro nano structure, the composite material of silicon.
Embodiment 3
Compound → silicon micro-nano the particle of graphite → graphite oxide → silicon micro-nano particle, graphite oxide, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%.
(2) graphite oxide: by the obtained graphite oxide of Hummers method (selecting from JACS, 1958,80,1339) improved.Its concrete steps are 20g 50 order graphite powder, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cooling more than 6h, and washing is to neutral, dry.Dried sample is added 0 DEG C, in the concentrated sulfuric acid of 230mL, then add 60g potassium permanganate, the temperature of mixture remains on less than 20 DEG C, after then keeping 2h in the oil bath of 35 DEG C, slowly adds 920mL deionized water.After 15min, add 2.8L deionized water (wherein containing 50mL concentration is the hydrogen peroxide of 30%) again, mixture color becomes glassy yellow afterwards, while hot suction filtration, then carries out washing with the hydrochloric acid that 5L concentration is 10%, suction filtration, namely obtain graphite oxide at 60 DEG C of vacuumize 48h.
(3) by high energy ball mill, silicon powder grinding is obtained the micro-nano granules of silicon; By the micro-nano granules surface HCl treatment of silicon obtained, the mass concentration of hydrochloric acid is 20%, ultrasonic process 4 hours, then cleans, until solution presents neutrality with deionization.
(4) compound of silicon micro-nano particle, graphene oxide: be added to the water the graphite oxide prepared ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer, both business mix, the ratio of silicon and graphene oxide is 1: 10, room temperature vigorous stirring 24hour, obtain the mixture of homodisperse graphene oxide and silicon, vacuumize;
(5) containing the thermal reduction of reducibility gas atmosphere: silicon micro-nano particle coated for (4) gained graphene oxide is put into the tube furnace being connected with reducibility gas and be warming up to 600 DEG C of heating 5h with the slow speed of 50 DEG C/min, cool to powder with the furnace room temperature in the atmosphere of hydrogen again, obtain the composite material of silicon micro-nano particle, Graphene.
(6) by the silicon micro-nano particle of gained, the composite material of Graphene and grapheme material with 1: 3 mass ratio mix after ball milling 2 hours, obtain the Graphene of uniform micro nano structure, the composite material of silicon.
Embodiment 4
Compound → silicon micro-nano the particle of graphite → graphite oxide → silicon micro-nano particle, graphite oxide, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%.
(2) graphite oxide: by the obtained graphite oxide of Hummers method (selecting from JACS, 1958,80,1339) improved.Its concrete steps are 20g 50 order graphite powder, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cooling more than 6h, and washing is to neutral, dry.Dried sample is added 0 DEG C, in the concentrated sulfuric acid of 230mL, then add 60g potassium permanganate, the temperature of mixture remains on less than 20 DEG C, after then keeping 2h in the oil bath of 35 DEG C, slowly adds 920mL deionized water.After 15min, add 2.8L deionized water (wherein containing 50mL concentration is the hydrogen peroxide of 30%) again, mixture color becomes glassy yellow afterwards, while hot suction filtration, then carries out washing with the hydrochloric acid that 5L concentration is 10%, suction filtration, namely obtain graphite oxide at 60 DEG C of vacuumize 48h.
(3) by high energy ball mill, silicon powder grinding is obtained the micro-nano granules of silicon; By the micro-nano granules surface HCl treatment of silicon obtained, the mass concentration of hydrochloric acid is 10%, ultrasonic process 2 hours, then cleans, until solution presents neutrality with deionization.
(4) compound of silicon micro-nano particle, graphene oxide: be added to the water the graphite oxide prepared ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer, both business mix, the ratio of silicon and graphene oxide is 1: 100, room temperature vigorous stirring 4hour, obtain the mixture of homodisperse graphene oxide and silicon, vacuumize;
(5) containing the thermal reduction of reducibility gas atmosphere: silicon micro-nano particle coated for (4) gained graphene oxide is put into the tube furnace being connected with reducibility gas and be warming up to 800 DEG C of heating 4h with the slow speed of 20 DEG C/min, cool to powder with the furnace room temperature in the atmosphere of hydrogen again, obtain the composite material of silicon micro-nano particle, Graphene.
(6) by the silicon micro-nano particle of gained, the composite material of Graphene and the grapheme material of reduction with 1: 3 mass ratio mix after ball milling 4 hours, obtain the Graphene of uniform micro nano structure, the composite material of silicon.
The mensuration of conductivity: the sample powder of embodiment 1 ~ 4 is become disk at the pressure of 10MPa, with the two electrical measurement four-point probe testing conductivity of D41-11D/ZM type under room temperature.When measuring current is shown as probe coefficient, press the button of electricalresistivityρ, then screen directly shows electricalresistivityρ's value, directly calculates conductivity according to γ=1/ ρ.
Measured in embodiment 1 by four probe method, the conductivity of electrode composite material is 5.6 × 10
3s/m, illustrates silicon, the grapheme material conductivity (6.7 × 10 relative to silicon
-2s/m) improve a lot.
Table 1
| Embodiment | 1 | 2 | 3 | 4 |
| Conductivity S/m | 5.6×10 3 | 4.2×10 3 | 4.8×10 3 | 3.7×10 3 |
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (6)
1. a preparation method for electrode composite material, is characterized in that, comprises the steps:
Step one, provide graphite oxide and Graphene;
Step 2, silicon powder grinding is obtained the micro-nano granules of silicon;
Step 3, be added to the water described graphite oxide ultrasonic disperse, formed with the homodisperse graphene oxide solution of monolithic layer; Join in graphene oxide solution by the micro-nano granules of silicon, at room temperature vigorous stirring, obtain the micro-nano granules of the silicon being coated with graphene oxide, wherein, the micro-nano granules of described silicon and the mass ratio of described graphene oxide are 1:2.5 ~ 100;
Step 4, the described micro-nano granules being coated with the silicon of graphene oxide is placed in reducing atmosphere under, 200 ~ 1200 DEG C are slowly heated to the speed of 10 ~ 100 DEG C/min, carry out abundant reduction reaction, be cooled to room temperature in the atmosphere of reproducibility again, obtain the micro-nano granules of silicon, graphene composite material; And
Step 5, take mass ratio as ball milling 1 ~ 4 hour after the micro-nano granules of described silicon, graphene composite material mix with described Graphene by 1:1 ~ 1:3, obtain described electrode composite material, wherein, the nano level silicon grain of graphene coated is dispersed between the lamella of Graphene.
2. the preparation method of electrode composite material according to claim 1, it is characterized in that: also comprise in step 2: the micro-nano granules hydrochloric acid of described silicon is carried out ultrasonic process, the mass concentration of described hydrochloric acid is 10 ~ 20%, and the consumption of described hydrochloric acid is the consumption of the micro-nano granules soaking described silicon completely.
3. the preparation method of electrode composite material according to claim 1, is characterized in that: the preparation method of graphite oxide described in step one comprises the steps:
Graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in the concentrated sulfuric acid of 80 DEG C, stir, cool more than 6 hours, suction filtration, washing is to neutral, dry, obtains biased sample; And
Described biased sample is added in the concentrated sulfuric acid of 0 DEG C, add potassium permanganate again, the temperature of system remains on less than 20 DEG C, then keeps after 2 hours in the oil bath of 35 DEG C, slowly add deionized water, after 15 minutes, then add the deionized water containing hydrogen peroxide, until the color of solution becomes glassy yellow, suction filtration while hot, wash with the hydrochloric acid that concentration is 10%, suction filtration, namely 60 DEG C of vacuumizes obtain graphite oxide again.
4. the preparation method of electrode composite material according to claim 3, is characterized in that: described graphite raw material is the natural flake graphite that purity is more than or equal to 99.5%.
5. the preparation method of electrode composite material according to claim 1, is characterized in that: described reducing atmosphere is the atmosphere of hydrogen or carbon monoxide.
6. the preparation method of electrode composite material according to claim 1, is characterized in that: in step 3, and the time of stirring is 30 minutes ~ 24 hours.
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