CN104477895A - Preparation method of nitrogen-doped graphene for cathode of lithium ion battery - Google Patents
Preparation method of nitrogen-doped graphene for cathode of lithium ion battery Download PDFInfo
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- CN104477895A CN104477895A CN201410766109.6A CN201410766109A CN104477895A CN 104477895 A CN104477895 A CN 104477895A CN 201410766109 A CN201410766109 A CN 201410766109A CN 104477895 A CN104477895 A CN 104477895A
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Abstract
The invention provides a preparation method of nitrogen-doped graphene for a cathode of a lithium ion battery. The method comprises three processes: preparing graphene oxide, restoring graphene oxide, and preparing the nitrogen-doped graphene. The nitrogen-doped graphene is prepared by the following steps: restoring the graphene oxide into prepared graphene; putting into a vacuum tube furnace; and carrying out high-temperature annealing in an ammonia gas at 500-700 DEG C. The prepared nitrogen-doped graphene is annealed in a high-temperature environment until the nitrogen doping amount reaches the maximal value, thus the electronic structure of the graphene is changed; the density of a free carrier of the graphene is improved; and the conductive property, the stability, the first charge-discharge efficiency and the reversible capacity of the graphene are further improved.
Description
Technical field
The present invention relates to the preparing technical field of Graphene, especially relate to a kind of preparation method of the nitrating Graphene for lithium ion battery negative.
Background technology
To the research of lithium ion battery negative material, mainly concentrate on the aspects such as carbonaceous material, alloy material and matrix material.Carbonaceous material is the earliest by people are studied and be applied to the commercial material of lithium ion battery, is still everybody so far and pays close attention to and one of the emphasis of research.Carbonaceous material can be divided into graphitizable charcoal soft charcoal according to its constructional feature), amorphous carbon (hard charcoal) and graphite-like.Mainly adopt various means to its modifying surface to the research of Carbon anode at present, but carry out surface treatment again to synthetic graphite and will increase manufacturing cost further, the emphasis therefore studied from now on will be natural graphite and the valuable amorphous carbon material of exploitation of how better utilised cheapness.Therefore, manufacturing the lithium ion battery negative material of low-cost and high-performance from graphite is present main direction of studying.
Graphene-based material, because the chemical property of its excellence, is expected to become lithium ion battery negative material of new generation, greatly improves the energy density of lithium ion battery, power density, service life cycle etc., thus realize the large-scale application of lithium-ion-power cell.But Graphene itself exists some problems, therefore need doping, improve various aspects of performance.
Nitrogen-doped graphene various aspects of performance is better than pure Graphene, because the two-dirnentional structure of the uniqueness of nitrogen-doped graphene, unordered surface topography, heteroatoms defect, better electrolytic solution electrode wetting property, the interlamellar spacing increased, the electric conductivity that improve and better thermostability make nitrogen-doped graphene conduct quickly and to adsorb lithium ion.
The preparation method of existing Graphene mainly contains micromechanics stripping method, chemical Vapor deposition process, graphite oxide reduction method, thermolysis SiC method.Micromechanics stripping method is simple, and the graphite that can obtain large size (maximum reach 100um) is rare, and the Graphene of preparation not easily exists textural defect, can keep more perfect crystalline network.But this method needs repeatedly to utilize microscope to find out by the Graphene of few quantity from a large amount of lamellas, length consuming time, productive rate is very low, and size not easily accurately controls, repeatable poor, therefore be only applicable to the fundamental research in laboratory, be difficult to realize large-scale industrial production.
Due to chemical Vapor deposition process method, to prepare Graphene simple, gained graphite is rare to be of high quality, large area deposition can be realized, and be easy to rare for the graphite of preparation transferring on various matrix to use, therefore the method is widely used in preparing the rare transistor of graphite and transparent conductive film, becomes gradually at present and prepares the rare main method of high quality graphite.
The rare reduction of graphite oxide is utilized to prepare Graphene technology comparatively ripe.This method is easy and cost is lower, by by rare for modified graphite oxide reduction, can prepare a large amount of graphite rare.But, reduction process can not recover the textural defect that rare, graphite causes because of oxidation completely, such as-0H unit structure defect or the topological defect such as five-ring, seven-membered ring, cause its performance loss such as part physical, chemistry, especially electrical properties, this can limit the application of the rare electronic applications in precision of graphite to a certain extent.
The electronic property on the rare surface of graphite that thermolysis SiC method prepares is very large by the impact of SiC substrate.This method prepares big area, and to have the Graphene of single thickness more difficult, and need temperature higher than 1100 DEG C, and energy consumption is very large, is unsuitable for large-scale production.
The method preparing nitrogen-doped graphene has three classes: be chemical Vapor deposition process, direct current arc method and template respectively.As the people such as Guo Shouwu carry out nitration treatment the Graphene shone through enjoying too much ease and comfort; be prepared into N doping graphite rare; undertaken synthesizing N-shaped graphite respectively by the parameter of Control release rare rare with P type graphite, be expected to accomplish something in the rare battery electrode material large-scale production of graphite.Similar, there is people to carry out ammonia DC arc discharge evaporation process to Graphite Electrodes, obtain the nitrogen-doped graphene with 1-6 graphite linings.The concentration of nitrogen-doping changes along with the change of ammonia concentration, and in order to prepare in a large number, N doping graphite is rare provides feasible method.In addition, the people such as Dai Hongjie also prepare a large amount of nitrogen-doped graphenes with chemical vapour deposition technique, they are under the high temperature of 300-900 degree Celsius, nitration treatment is carried out to graphene oxide, make the doping while reduction of the rare oxide compound of graphite, when 500 degrees Celsius, nitrogen doped concentration is 5%, is the maximum in 300-900 degree Celsius of interval.Dai Liming etc. also introduce first ammonia and burn chemical vapour deposition system, prepare nitrogen-doped graphene.By testing alkaline fuel cell, result shows, and N doping graphite coal electrode is interval in high voltage range, many 2 times of its steady state catalytic current ratio conventional P t/C electrode, and the time of resistance to intercrossing and stability is longer.In addition, prepare N doping graphite rare also can with liquid phase nitrogenous compound replace ammonia do presoma.Fairly simple method is, take Copper Foil as substrate, second cyanogen makes presoma, 950 degrees Celsius of lower cracking, and direct synthesizing lithium ion battery negative pole.By the test to battery performance, find that its electrical capacity is than pure many one times of Tan Shi Mo Women, the preparation of current thin film flexible battery has become the focus of research, and the market outlook of its application are very bright.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of preparation method of the nitrating Graphene for lithium ion battery negative, change the electronic structure of Graphene, promote the free carrier density of Graphene, further increase the conductivity of Graphene, stability, charge and discharge efficiency first and reversible capacity.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of the nitrating Graphene for lithium ion battery negative, comprise the preparation of graphene oxide, the reduction of graphene oxide and nitrogen-doped graphene and prepare three processes, wherein nitrogen-doped graphene preparation process is graphene oxide is reduced the Graphene prepared, be placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 500 ~ 700 DEG C.
Preferably, graphene oxide is reduced the Graphene prepared, be placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 600 DEG C.
Preferably, the preparation process of graphene oxide, comprises the steps,
1), by Graphite Powder 99 0.4 ~ 0.6g and potassium permanganate 1.4 ~ 1.6g join in 10 ~ 30mL vitriol oil, and at 25 DEG C uniform stirring, then whole reaction system is stirred 2 ~ 3 hours at 55 ~ 65 DEG C;
2), by step 1) mixture that obtains is poured in deionized water after reaction, and continue stirring 12 ~ 17min, then add hydrogen peroxide;
3), carry out suction filtration, with dilute hydrochloric acid eccysis metal ion, then use deionized water eccysis disacidify;
4), by step 3) solid that obtains to join in the middle of deionized water ultrasonic 0.8 ~ 1.2 hour;
5), high speed centrifugation, obtain upper strata dark brown solution, solid below joins in the middle of deionized water again after ultrasonic 2.5 ~ 3.5 hours, and high speed centrifugation obtains upper strata dark brown solution, two-part dark brown solution is merged the aqueous dispersion liquid namely obtaining graphene oxide.
Preferably, step 1) in, it is in the vitriol oil of 98% that Graphite Powder 99 0.5g and potassium permanganate 1.5g is joined 20mL mass concentration, and at 25 DEG C uniform stirring, then whole reaction system is stirred 2.5 hours at 60 DEG C.
Preferably, step 2) in, by step 1) mixture that obtains after reaction pours in 200mL deionized water, and continue to stir 15min, then add the hydrogen peroxide that 15mL massfraction is 30%.
Preferably, step 3) in, be the dilute hydrochloric acid eccysis metal ion of 15% with massfraction.
Preferably, step 4) in, by step 3) solid that obtains to join in the middle of 200mL deionized water ultrasonic 1 hour.
Preferably, step 5) in, under 10000r/min centrifugal 0.5 hour, obtain upper strata dark brown solution, solid below to join in the middle of 75mL deionized water 10000r/min centrifugal acquisition upper strata dark brown solution after ultrasonic 3 hours again, two-part dark brown solution is merged the aqueous dispersion liquid namely obtaining graphene oxide.
Preferably, the reduction process of graphene oxide, comprise the steps, hydrazine hydrate and ammoniacal liquor are joined in the aqueous dispersion liquid of graphene oxide, reaction 0.8 ~ 1.0h in the middle of 85 ~ 95 DEG C of oil baths is put into after shaking up, obtain the redox graphene solution of homogeneous black, by the solution of above-mentioned redox graphene by membrane filter suction filtration then vacuum-drying obtain film and the Graphene with metalluster.
Preferably, it is in the aqueous dispersion liquid of the graphene oxide of 0.28mg/mL that 15 μ L 80wt% hydrazine hydrates and 80 μ L 30wt% ammoniacal liquor are joined 25mL mass concentration, reaction 0.9h in the middle of 90 DEG C of oil baths is put into after shaking up, obtain the redox graphene solution of homogeneous black, by the solution of above-mentioned redox graphene by membrane filter suction filtration then vacuum-drying obtain the film with metalluster.
The advantage that the present invention has and positively effect are:
1) itrogen content of getter with nitrogen doped of, being annealed in high temperature environments by the Graphene nitrating of preparation is maximum value, this object changes Graphene electronic structure, promotes the free carrier density of Graphene, improves the conductivity of Graphene further, stability, charge and discharge efficiency first and reversible capacity.
2), nitrating graphene from graphite alkene of the present invention in a nitrogen environment high temperature annealing be prepared from, Graphene prepares under being acted under reductive agent hydrazine hydrate by graphene oxide, graphene oxide is obtained by the Hummers method preparation improved, and this patent key is that raising graphene oxide prepares productive rate thus entirety improves nitrating Graphene productive rate.
3), present invention process is comparatively simple, and consuming time short, Preparation equipment is simple to operation, and feasibility is high, and preparation rate is high, environmental friendliness.
4), starting material are simple and easy to get, cheap, are applicable to laboratory and extension commercial production.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the nitrating Graphene of preparation in embodiment one;
Fig. 2 is the SEM figure of the nitrating Graphene of preparation in embodiment two;
Fig. 3 is the SEM figure of the nitrating Graphene of preparation in embodiment three;
Fig. 4 is the trend map of the nitrating per-cent in the nitrating Graphene prepared under differing temps;
Fig. 5 is nitrating Graphene reversible capacity comparison diagram prepared by pure Graphene reversible capacity and embodiment one;
Embodiment
The main raw material adopted in embodiment is natural graphite powder (98%, chemical pure, Tianjin great Mao chemical reagent factory); Hydrochloric acid (analytical pure), sulfuric acid (analytical pure), potassium permanganate (analytical pure), hydrogen peroxide (30wt%) ammoniacal liquor (28wt%) is all purchased from Guangzhou Chemical Reagent Factory.The vitriol oil (98%, Tianjin sky over the river Chemical Engineering Technology company limited); Potassium permanganate (99.5%, analytical pure, Tianjin sky over the river Chemical Engineering Technology company limited); Hydrogen peroxide (30%, analytical pure, Tianjin sky over the river Chemical Engineering Technology company limited), hydrochloric acid (30%, analytical pure, Tianjin sky over the river Chemical Engineering Technology company limited).
The instrument of main use is thermostatic water-circulator bath groove (DC-2006, the new sesame in Ningbo), Large Copacity whizzer (TDL-50, Jintan, Zhejiang), vacuum pump using circulatory water (SHB-Ш, Zhengzhou section work), XRD (PANAlytical, Holland), scanning electron microscope (Nova NanoSEM 430, FEI), Hangzhou Hangke Precision Instrument Co., Ltd. (LIT0530)
Embodiment one
For a preparation method for the nitrating Graphene of lithium ion battery negative, comprise the preparation of graphene oxide, the reduction of graphene oxide and nitrogen-doped graphene and prepare three processes:
One, the preparation process of graphene oxide
1), by Graphite Powder 99 0.5g and potassium permanganate 1.5g joining 20mL mass concentration is in the vitriol oil of 98%, and at 25 DEG C uniform stirring, then whole reaction system is stirred 2.5 hours at 60 DEG C;
2), by step 1) mixture that obtains is poured in 200mL deionized water after reaction, and continue to stir 15min, then add the hydrogen peroxide that 15mL massfraction is 30%;
3), carry out suction filtration, be the dilute hydrochloric acid eccysis metal ion of 15% with massfraction, then use deionized water eccysis disacidify;
4), by step 3) solid that obtains to join in the middle of 200mL deionized water ultrasonic 1 hour;
5), under 10000r/min centrifugal 0.5 hour, obtain upper strata dark brown solution, solid below to join in the middle of 75mL deionized water 10000r/min centrifugal acquisition upper strata dark brown solution after ultrasonic 3 hours again, two-part dark brown solution is merged the aqueous dispersion liquid namely obtaining graphene oxide, productive rate is 80%.
Two, the reduction process of graphene oxide
It is in the aqueous dispersion liquid of the graphene oxide of 0.28mg/mL that 15 μ L 80wt% hydrazine hydrates and 80 μ L 30wt% ammoniacal liquor are joined 25mL mass concentration, reaction 0.9h in the middle of 90 DEG C of oil baths is put into after shaking up, obtain the redox graphene solution of homogeneous black, by the solution of above-mentioned redox graphene by membrane filter suction filtration then vacuum-drying obtain the film with metalluster.
Three, nitrogen-doped graphene preparation process
Graphene oxide is reduced the Graphene prepared, be placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 600 DEG C.In the nitrogen-doped graphene of preparation, itrogen content of getter with nitrogen doped is 6.02at%, and low current (45mA/g) reversible specific capacity is 902mAh/g.
Embodiment two
A kind of preparation method of the nitrating Graphene for lithium ion battery negative, comprise the preparation of graphene oxide, the reduction of graphene oxide and nitrogen-doped graphene and prepare three processes, wherein the first two process is with embodiment one, in nitrogen-doped graphene preparation process, graphene oxide is reduced the Graphene prepared, be placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 500 DEG C.In the nitrogen-doped graphene of preparation, itrogen content of getter with nitrogen doped is 4.98at%, and low current (45mA/g) reversible specific capacity is 827mAh/g.
Embodiment three
A kind of preparation method of the nitrating Graphene for lithium ion battery negative, comprise the preparation of graphene oxide, the reduction of graphene oxide and nitrogen-doped graphene and prepare three processes, wherein the first two process is with embodiment one, in nitrogen-doped graphene preparation process, graphene oxide is reduced the Graphene prepared, be placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 700 DEG C.In the nitrogen-doped graphene of preparation, itrogen content of getter with nitrogen doped is 4.77at%, and low current (45mA/g) reversible specific capacity is 790mAh/g.
Above three embodiments illustrate: the Nitrogen ion that 500 DEG C of temperature are not enough to allow ammonia decompose out and Graphene produce carbonnitrogen bond completely; And 700 DEG C of low reasons of itrogen content of getter with nitrogen doped are edges that N doping more may occur in defect or Graphene, in the nitrating Graphene at this method temperature, defect is not enough; Two is that pyroprocessing may destroy C-N key.Owing to introducing nitrogen atom structure in the carbon grid of Graphene, the active sites of graphenic surface adsorbing metal particles can be increased, thus strengthen the interaction of metallics and Graphene.Thus the nitrating Graphene reversible specific capacity that under 600 DEG C of ammonia atmospheres prepared by high temperature annealing is the highest.
Above the embodiment of the invention has been described in detail, but described content being only the preferred embodiment of the invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the invention scope change and improve, and all should still belong within this patent covering scope.
Claims (10)
1. the preparation method for the nitrating Graphene of lithium ion battery negative, it is characterized in that: comprise the preparation of graphene oxide, the reduction of graphene oxide and nitrogen-doped graphene and prepare three processes, wherein nitrogen-doped graphene preparation process is graphene oxide is reduced the Graphene prepared, be placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 500 ~ 700 DEG C.
2. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 1, is characterized in that: graphene oxide is reduced the Graphene prepared, and is placed in vacuum tube furnace, high temperature annealing under the ammonia atmosphere of 600 DEG C.
3. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 1 and 2, is characterized in that: the preparation process of graphene oxide, comprises the steps,
1), by Graphite Powder 99 0.4 ~ 0.6g and potassium permanganate 1.4 ~ 1.6g join in 10 ~ 30mL vitriol oil, and at 25 DEG C uniform stirring, then whole reaction system is stirred 2 ~ 3 hours at 55 ~ 65 DEG C;
2), by step 1) mixture that obtains is poured in deionized water after reaction, and continue stirring 12 ~ 17min, then add hydrogen peroxide;
3), carry out suction filtration, with dilute hydrochloric acid eccysis metal ion, then use deionized water eccysis disacidify;
4), by step 3) solid that obtains to join in the middle of deionized water ultrasonic 0.8 ~ 1.2 hour;
5), high speed centrifugation, obtain upper strata dark brown solution, solid below joins in the middle of deionized water again after ultrasonic 2.5 ~ 3.5 hours, and high speed centrifugation obtains upper strata dark brown solution, two-part dark brown solution is merged the aqueous dispersion liquid namely obtaining graphene oxide.
4. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 3, it is characterized in that: step 1) in, it is in the vitriol oil of 98% that Graphite Powder 99 0.5g and potassium permanganate 1.5g is joined 20mL mass concentration, and at 25 DEG C uniform stirring, then whole reaction system is stirred 2.5 hours at 60 DEG C.
5. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 3, it is characterized in that: step 2) in, by step 1) mixture that obtains is poured in 200mL deionized water after reaction, continue to stir 15min, then add the hydrogen peroxide that 15mL massfraction is 30%.
6. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 3, is characterized in that: step 3) in, be the dilute hydrochloric acid eccysis metal ion of 15% with massfraction.
7. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 3, is characterized in that: step 4) in, by step 3) solid that obtains to join in the middle of 200mL deionized water ultrasonic 1 hour.
8. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 3, it is characterized in that: step 5) in, under 10000r/min centrifugal 0.5 hour, obtain upper strata dark brown solution, solid below to join in the middle of 75mL deionized water 10000r/min centrifugal acquisition upper strata dark brown solution after ultrasonic 3 hours again, two-part dark brown solution is merged the aqueous dispersion liquid namely obtaining graphene oxide.
9. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 1 and 2, it is characterized in that: the reduction process of graphene oxide, comprise the steps, hydrazine hydrate and ammoniacal liquor are joined in the aqueous dispersion liquid of graphene oxide, reaction 0.8 ~ 1.0h in the middle of 85 ~ 95 DEG C of oil baths is put into after shaking up, obtain the redox graphene solution of homogeneous black, by the solution of above-mentioned redox graphene by membrane filter suction filtration then vacuum-drying obtain film and the Graphene with metalluster.
10. the preparation method of the nitrating Graphene for lithium ion battery negative according to claim 9, it is characterized in that: it is in the aqueous dispersion liquid of the graphene oxide of 0.28mg/mL that 15 μ L 80wt% hydrazine hydrates and 80 μ L 30wt% ammoniacal liquor are joined 25mL mass concentration, reaction 0.9h in the middle of 90 DEG C of oil baths is put into after shaking up, obtain the redox graphene solution of homogeneous black, by the solution of above-mentioned redox graphene by membrane filter suction filtration then vacuum-drying obtain the film with metalluster.
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| CN106252617A (en) * | 2016-08-03 | 2016-12-21 | 深圳市微纳集成电路与***应用研究院 | A kind of composite and preparation method thereof |
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