CN103022436A - Electrode composite material preparation method - Google Patents
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- CN103022436A CN103022436A CN2011102819254A CN201110281925A CN103022436A CN 103022436 A CN103022436 A CN 103022436A CN 2011102819254 A CN2011102819254 A CN 2011102819254A CN 201110281925 A CN201110281925 A CN 201110281925A CN 103022436 A CN103022436 A CN 103022436A
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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, relate in particular to a kind of preparation method who is 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 development of portable electric appts and electric automobile are to the widespread demand of large-capacity high-power chemical power source.Present commercial lithium ion battery adopts lithium graphite system mostly, although the chemical property of this class system is excellent, but because itself stores up lithium ability lower (such as the theoretical 372mAh/g of graphite), so novel transition metal oxide/graphite system is subject to people's widely attention.
In the intercalation materials of li ions at present, pure silicon is because having the highest theoretical lithium storage content (4200mAh/g), relatively low embedding lithium current potential, charge and discharge process is difficult for reuniting, have higher physical stability and chemical stability than other metal_based materials, become at present the study hotspot in lithium ion battery negative material field.But there is a shortcoming in silica-base material: the effect of stress that produces owing 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 to break away from the electrode material system and lose activity, therefore have very poor cyclical stability.At present, mainly improved one's methods metals such as adopting Ni, Fe and Cu and Si is compound, formation is with the activated centre of Si, activity take inert metal as dispersible carrier/inertia compound system when improving the electric conductivity of material, has improved 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, has therefore weakened to a certain extent the specific volume of Si sill.Metal itself has electron conduction in addition, does not possess ionic conductivity, so that electrolyte is difficult to immersion, thereby loses activity; Another method is exactly the method that material with carbon element coats, and is lower than the molal weight of metal, and electrolyte is easy to immerse, and effect will be got well than metal relatively, and material property has certain improvement, but or relatively poor.
Graphene has good conductivity, the space distributes and higher mechanical performance, utilizes grapheme material to substitute traditional material with carbon element, and silicon, the graphene combination electrode material for preparing of being combined with silicon has good electrochemical stability.Traditional silicon, graphene combination electrode material mostly adopt wet method preparation, and the product that obtains need to carry out strict purification removal of impurities, and process is loaded down with trivial details, and efficient is low, and product usually is mixed with impurity, affect the performance of electrode material.
[summary of the invention]
Based on this, be necessary to provide a kind of preparation method preparation method of comparatively simple electrode composite material.
A kind of preparation method of electrode composite material comprises the steps:
Step 1, provide graphite oxide and Graphene;
Step 2, silicon powder ground the micro-nano granules obtain silicon;
Step 3, with the ultrasonic dispersion that is added to the water of described graphite oxide, form with the homodisperse graphene oxide solution of monolithic layer; The micro-nano granules of silicon is joined in the graphene oxide solution, and vigorous stirring at room temperature obtains being coated with the micro-nano granules of the silicon of graphene oxide, and 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 that is coated with the silicon of graphene oxide is placed under the reducing atmosphere, slowly be heated to 200～1200 ℃ with 10～100 ℃/minute speed, carry out abundant reduction reaction, atmosphere in reproducibility is cooled to room temperature again, obtains micro-nano granules, the graphene composite material of silicon; And
Step 5, mix with described Graphene take mass ratio as 1: 1～1: 3 micro-nano granules with described silicon, graphene composite material after ball milling 1～4 hour, obtain described electrode composite material.
In a preferred embodiment, also comprise in the step 2: the micro-nano granules of described silicon is carried out ultrasonic processing with hydrochloric acid, and the mass concentration of described hydrochloric acid is 10～20%, and the consumption of described hydrochloric acid is for soaking the consumption of the micro-nano granules of described silicon fully.
In a preferred embodiment, the preparation method of graphite oxide described in the step 1 comprises the steps:
Graphite raw material, potassium peroxydisulfate and phosphorus pentoxide be added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample; And
Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 2 hours in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
In a preferred embodiment, described graphite raw material is purity more than or equal to 99.5% natural flake graphite.
In a preferred embodiment, described reducing atmosphere is the atmosphere of hydrogen or carbon monoxide.
In a preferred embodiment, in the step 3, the time of stirring is 30 minutes～24 hours.
In this preparation process, ball milling obtained described electrode composite material after micro-nano granules, graphene composite material by silicon mixed with Graphene, preparation process is relatively simple, and need not complicated dry purification step, can directly obtain product, thereby preparation efficiency is higher, and the composite material purity that makes is high, and performance is guaranteed.
[description of drawings]
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose of the present invention, that Characteristics and advantages will become will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part, and deliberately draws accompanying drawing by actual size equal proportion convergent-divergent, focuses on illustrating purport of the present invention.
Fig. 1 is preparation method's the flow chart of the electrode composite material of an execution mode.
Fig. 2 is the SEM photo of the electrode composite material that makes of embodiment 1.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subjected to the restriction of following public implementation.
Present embodiment provides a kind of preparation method of electrode composite material, and this electrode composite material is the composite material that comprises silicon micro-nano particle and Graphene.This have certain hierarchical structure, at first is the silicon grain of nano level graphene coated, and the silicon grain with graphene coated is dispersed in the lamellar structure of Graphene again.This structure and silicon directly are dispersed in the difference that essence is arranged in the graphene sheet layer, and this structure is the stability of stable silicon bulk effect, maintenance structure in charge and discharge process more.
Preparation technology's flow process of above-mentioned electrode composite material is as follows:
The compound of graphite → graphite oxide → silicon micro-nano particle, graphite oxide → silicon micro-nano particle, graphene complex → silicon micro-nano particle, Graphene negative material
See also 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, prepare according to improved Hummers method (selecting from JACS, 1958,80,1339).Described Graphene can obtain by mechanical stripping method and thermal expansion graphite method vegetation.
Preferably, described graphite oxide can adopt the preparation of following method: graphite raw material, potassium peroxydisulfate and phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample; Again biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 2 hours in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
Wherein, graphite raw material is preferably purity more than or equal to 99.5% natural flake graphite.
Step S200 grinds silicon powder the micro-nano granules that obtains silicon.
Preferably, silicon powder is ground the micro-nano granules that obtains silicon by high energy ball mill.In more preferred scheme, the micro-nano granules of the silicon that grinding is obtained carries out ultrasonic processing with hydrochloric acid, the impurity that is introduced into when the ball milling to remove silicon grain.The mass concentration of used hydrochloric acid is 10～20%, and the consumption of described hydrochloric acid is for soaking the consumption of the micro-nano granules of described silicon fully.The time of ultrasonic processing is preferably 1 hour.After handling, clean with deionization, until solution presents neutrality.
Step S300 with the graphite oxide ultrasonic dispersion that is added to the water, forms with the homodisperse graphene oxide solution of monolithic layer; The micro-nano granules of silicon is joined in the graphene oxide solution, at room temperature vigorous stirring is 30 minutes～24 hours, obtain being coated with the micro-nano granules of the silicon of graphene oxide, wherein, the micro-nano granules of silicon and the mass ratio of graphene oxide are 1: 2.5～100.
Step S400, the micro-nano granules that is coated with the silicon of graphene oxide is placed under the reducing atmosphere, slowly be heated to 200～1200 ℃ with 10～100 ℃/minute speed, carry out abundant reduction reaction, atmosphere in reproducibility is cooled to room temperature again, obtains micro-nano granules, the graphene composite material of silicon.
Preferably, the silicon micro-nano particle that the resulting graphene oxide of step S300 coats is put into the tube furnace that is connected with reducibility gas, be warming up to 200～1200 ℃ with the slow speed of 10～100 ℃/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, the micro-nano granules with silicon, graphene composite material mixed rear ball milling 1～4 hour with the Graphene of step S100 as 1: 1～1: 3 take mass ratio, obtained electrode composite material.
The electrode composite material for preparing by said method has following beneficial effect: in the composite material that prepare by the method (1), the nano level silicon grain of graphene coated can be good at being dispersed between the lamella of Graphene; (2) this composite material since the high conductivity of Graphene can be well with electrical conductivity to elemental silicon, improved conductivity, can give full play to the high capacity characteristics of silicon, be suitable as lithium ion battery, the negative material of hybrid super capacitor; (3) this composite material so composite material has good porosity, has good example transport properties because the Graphene of sheet has larger specific area, is suitable as lithium ion battery, the negative material of ultracapacitor.(4) in this preparation process, ball milling obtained described electrode composite material after micro-nano granules, graphene composite material by silicon mixed with Graphene, preparation process is relatively simple, and need not complicated dry purification step, can directly obtain product, thereby preparation efficiency is higher, and the composite material purity that makes is high, and performance is guaranteed.
It below is the specific embodiment part
Embodiment 1
The compound of graphite → graphite oxide → silicon micro-nano particle, graphite oxide → silicon micro-nano particle, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%;
(2) graphite oxide: make graphite oxide by improved Hummers method (selecting from JACS, 1958,80,1339).Its concrete steps are that 20g 50 purpose graphite powders, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, and more than the cooling 6h, washing is to neutral, drying.In the concentrated sulfuric acid with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate, the temperature of mixture remains on below 20 ℃ again, then behind the maintenance 2h, slowly adds the 920mL deionized water in 35 ℃ oil bath.Behind the 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, and suction filtration while hot is that 10% hydrochloric acid washs, suction filtration, namely obtains graphite oxide at 60 ℃ of vacuumize 48h with 5L concentration again.
(3) silicon powder is ground the micro-nano granules that obtains silicon by high energy ball mill; Micro-nano granules surface salt acid treatment with the silicon that obtains; The mass concentration of hydrochloric acid is 10%, and then ultrasonic processing 1 hour is cleaned with deionization, until solution presents neutrality.
(4) compound of silicon micro-nano particle, graphene oxide: with the graphite oxide that the prepares ultrasonic dispersion that is added to the water, formation is with the homodisperse graphene oxide solution of monolithic layer, both mix 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) contain the thermal reduction of reducibility gas atmosphere: the silicon micro-nano particle of (4) gained graphene oxide coating is put into the tube furnace that is connected with reducibility gas and be warming up to 1200 ℃ of heating 10h with the slow speed of 10 ℃/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) with quality ball millings such as the composite material of the silicon micro-nano particle of gained, Graphene and grapheme material 4 hours, obtain the Graphene of uniform micro nano structure, 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 to be the silicon grain of graphene coated, and the silicon grain of coating is distributed on the sheet layer graphene of bottom.
Embodiment 2
The compound of graphite → graphite oxide → silicon micro-nano particle, graphite oxide → silicon micro-nano particle, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%;
(2) graphite oxide: make graphite oxide by improved Hummers method (selecting from JACS, 1958,80,1339).Its concrete steps are that 20g 50 order graphite powders, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, and more than the cooling 6h, washing is to neutral, drying.In the concentrated sulfuric acid with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate, the temperature of mixture remains on below 20 ℃ again, then behind the maintenance 2h, slowly adds the 920mL deionized water in 35 ℃ oil bath.Behind the 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, and suction filtration while hot is that 10% hydrochloric acid washs, suction filtration, namely obtains graphite oxide at 60 ℃ of vacuumize 48h with 5L concentration again.
(3) silicon powder is ground the micro-nano granules that obtains silicon by high energy ball mill; Micro-nano granules surface salt acid treatment with the silicon that obtains; The mass concentration of hydrochloric acid is 20%, and then ultrasonic processing 1 hour is cleaned with deionization, until solution presents neutrality.
(4) compound of silicon micro-nano particle, graphene oxide: with the graphite oxide that the prepares ultrasonic dispersion that is added to the water, formation is with the homodisperse graphene oxide solution of monolithic layer, discussing both mixes, 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) contain the thermal reduction of reducibility gas atmosphere: the silicon micro-nano particle of (4) gained graphene oxide coating is put into the tube furnace that is connected with reducibility gas and be warming up to 200 ℃ of heating 1h with the slow speed of 100 ℃/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) with the composite material of the silicon micro-nano particle of gained, Graphene and grapheme material with 1: 2 quality than mixing and ball milling 1 hour, obtain the Graphene of uniform micro nano structure, the composite material of silicon.
Embodiment 3
The compound of graphite → graphite oxide → silicon micro-nano particle, graphite oxide → silicon micro-nano particle, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%.
(2) graphite oxide: make graphite oxide by improved Hummers method (selecting from JACS, 1958,80,1339).Its concrete steps are that 20g 50 order graphite powders, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, and more than the cooling 6h, washing is to neutral, drying.In the concentrated sulfuric acid with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate, the temperature of mixture remains on below 20 ℃ again, then behind the maintenance 2h, slowly adds the 920mL deionized water in 35 ℃ oil bath.Behind the 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, and suction filtration while hot is that 10% hydrochloric acid washs, suction filtration, namely obtains graphite oxide at 60 ℃ of vacuumize 48h with 5L concentration again.
(3) silicon powder is ground the micro-nano granules that obtains silicon by high energy ball mill; It is 20% that salt acid treatment, the mass concentration of hydrochloric acid use in the micro-nano granules surface of the silicon that obtains, and ultrasonic processing 4 hours is then clean with deionization, until solution presents neutrality.
(4) compound of silicon micro-nano particle, graphene oxide: with the graphite oxide that the prepares ultrasonic dispersion that is added to the water, formation is with the homodisperse graphene oxide solution of monolithic layer, discussing both mixes, 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) contain the thermal reduction of reducibility gas atmosphere: the silicon micro-nano particle of (4) gained graphene oxide coating is put into the tube furnace that is connected with reducibility gas and be warming up to 600 ℃ of heating 5h with the slow speed of 50 ℃/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) composite material of the silicon micro-nano particle of gained, Graphene and grapheme material are mixed with 1: 3 mass ratio after ball milling 2 hours, obtain the Graphene of uniform micro nano structure, the composite material of silicon.
Embodiment 4
The compound of graphite → graphite oxide → silicon micro-nano particle, graphite oxide → silicon micro-nano particle, graphene complex → silicon micro-nano particle, Graphene negative material
(1) graphite: purity 99.5%.
(2) graphite oxide: make graphite oxide by improved Hummers method (selecting from JACS, 1958,80,1339).Its concrete steps are that 20g 50 order graphite powders, 10g potassium peroxydisulfate and 10g phosphorus pentoxide are added in 80 ℃ the concentrated sulfuric acid, stir, and more than the cooling 6h, washing is to neutral, drying.In the concentrated sulfuric acid with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate, the temperature of mixture remains on below 20 ℃ again, then behind the maintenance 2h, slowly adds the 920mL deionized water in 35 ℃ oil bath.Behind the 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, and suction filtration while hot is that 10% hydrochloric acid washs, suction filtration, namely obtains graphite oxide at 60 ℃ of vacuumize 48h with 5L concentration again.
(3) silicon powder is ground the micro-nano granules that obtains silicon by high energy ball mill; It is 10% that salt acid treatment, the mass concentration of hydrochloric acid use in the micro-nano granules surface of the silicon that obtains, and ultrasonic processing 2 hours is then clean with deionization, until solution presents neutrality.
(4) compound of silicon micro-nano particle, graphene oxide: with the graphite oxide that the prepares ultrasonic dispersion that is added to the water, formation is with the homodisperse graphene oxide solution of monolithic layer, discussing both mixes, 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) contain the thermal reduction of reducibility gas atmosphere: the silicon micro-nano particle of (4) gained graphene oxide coating is put into the tube furnace that is connected with reducibility gas and be warming up to 800 ℃ of heating 4h with the slow speed of 20 ℃/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) grapheme material of the composite material of the silicon micro-nano particle of gained, Graphene and reduction is mixed with 1: 3 mass ratio 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 depressed to disk at the pressure of 10MPa, use the two electrical measurement four point probe tester testing conductivities of D41-11D/ZM type under the room temperature.When measuring current is shown as the probe coefficient, press electricalresistivityρ's button, then screen shows that directly the electricalresistivityρ is worth, and directly calculates conductivity according to γ=1/ ρ.
Measure among the embodiment 1 by four probe method, the conductivity of electrode composite material is 5.6 * 10
3S/m illustrates that silicon, grapheme material are with respect to the conductivity (6.7 * 10 of 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 has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.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. the preparation method of an electrode composite material is characterized in that, comprises the steps:
Step 1, provide graphite oxide and Graphene;
Step 2, silicon powder ground the micro-nano granules obtain silicon;
Step 3, with the ultrasonic dispersion that is added to the water of described graphite oxide, form with the homodisperse graphene oxide solution of monolithic layer; The micro-nano granules of silicon is joined in the graphene oxide solution, and vigorous stirring at room temperature obtains being coated with the micro-nano granules of the silicon of graphene oxide, and 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 that is coated with the silicon of graphene oxide is placed under the reducing atmosphere, slowly be heated to 200～1200 ℃ with 10～100 ℃/minute speed, carry out abundant reduction reaction, atmosphere in reproducibility is cooled to room temperature again, obtains micro-nano granules, the graphene composite material of silicon; And
Step 5, mix with described Graphene take mass ratio as 1: 1～1: 3 micro-nano granules with described silicon, graphene composite material after ball milling 1～4 hour, obtain described electrode composite material.
2. the preparation method of electrode composite material according to claim 1, it is characterized in that: also comprise in the step 2: the micro-nano granules of described silicon is carried out ultrasonic processing with hydrochloric acid, the mass concentration of described hydrochloric acid is 10～20%, and the consumption of described hydrochloric acid is for soaking the consumption of the micro-nano granules of described silicon fully.
3. the preparation method of electrode composite material according to claim 1, it is characterized in that: the preparation method of graphite oxide described in the step 1 comprises the steps:
Graphite raw material, potassium peroxydisulfate and phosphorus pentoxide be added in 80 ℃ the concentrated sulfuric acid, stir, cooling is more than 6 hours, suction filtration, and washing is to neutral, and drying obtains biased sample; And
Described biased sample is added in 0 ℃ the concentrated sulfuric acid, add potassium permanganate, the temperature of system remains on below 20 ℃ again, then keeps after 2 hours in 35 ℃ oil bath, slowly add deionized water, after 15 minutes, add again the deionized water that contains hydrogen peroxide, until the color of the solution becomes glassy yellow, suction filtration while hot, be that 10% hydrochloric acid washs with concentration again, suction filtration, 60 ℃ of vacuumizes namely obtain graphite oxide.
4. the preparation method of electrode composite material according to claim 3 is characterized in that: described graphite raw material is purity more than or equal to 99.5% natural flake graphite.
5. the preparation method of electrode composite material according to claim 1, it 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, it is characterized in that: in the step 3, the time of stirring is 30 minutes～24 hours.
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