CN102306781A - Doped graphene electrode material, macro preparation method and application of doped graphene electrode material - Google Patents
Doped graphene electrode material, macro preparation method and application of doped graphene electrode material Download PDFInfo
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- CN102306781A CN102306781A CN201110260849A CN201110260849A CN102306781A CN 102306781 A CN102306781 A CN 102306781A CN 201110260849 A CN201110260849 A CN 201110260849A CN 201110260849 A CN201110260849 A CN 201110260849A CN 102306781 A CN102306781 A CN 102306781A
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Abstract
The invention relates to the field of graphene electrode materials, and in particular relates to a doped graphene electrode material, a macro preparation method as well as an application of the doped graphene electrode material in a high-capacity high-multiplying-power lithium ion battery. In the invention, graphene is taken as a raw material. The preparation method comprises the following steps: controlling the temperature rising speed rate through shielding gas; introducing gas containing nitrogen or boron elements in different concentrations at high temperature so as to realize the doping of heteroatoms of the graphene, and get the nitrogen or boron doped graphene; mixing the doped graphene, conductive carbon black and a bonding agent; adding a solvent; coating the mixture on a current collector after grinding; taking the mixture after drying, shearing and tabletting as a working electrode; adding electrolyte containing a lithium salt by taking a lithium plate as a counter electrode /reference electrode; assembling into a button-type lithium ion half-battery in a glove box; and carrying out constant current charge and discharge tests under the condition of high current density. According to the invention, the electrode stability of the material under the condition of high current density is improved, and the fact that the doped graphene has higher specific capacity and excellent cycle performance in a shorter time is realized.
Description
Technical field:
The present invention relates to the Graphene electrodes field of materials, be specially a kind of doped graphene electrode material and magnanimity preparation method thereof and the application in big capacity, high multiplying power lithium ion battery.
Background technology:
Environmental pollution and energy crisis two hang-ups impel modern society urgent to increasing demand high-power, the high-energy energy storage device, the especially exploitation of regenerative resource, various portable mobile apparatus and new forms of energy hybrid electric vehicle, plug-in electric motor car and pure electric vehicle.With traditional electrode materials such as graphite, cobalt acid lithiums is that the lithium ion battery of electrode can only provide lower-wattage, well below ultracapacitor, can not satisfy the demand of society.At present, lithium ion battery discharges and recharges in the time (a few minutes are to several seconds) and realizes that simultaneously high-specific-power and specific energy are still one of this research field huge challenge short.And the power-performance of lithium ion battery depends on lithium ion and the transmission speed of electronics in electrolyte and block electrode strongly.An important method that improves the electrode material power-performance is to adopt nano material to improve lithium ion and electronics in electrode surface and inner transmission speed, reduces lithium ion and electronics in path that electrode interior is transmitted etc.And different with traditional lithium ion battery, the carbon back ultracapacitor can react at electrode surface and electrode and electrolyte interface and realizes the high power characteristic through improving electric charge.Therefore; The power characteristic that improves lithium ion battery can be through the raw material of wood-charcoal material of the synthetic different nanostructures of design; The conductivity that improves material promotes the transmission rate of electronics; The three-dimensional structure of improving material makes its pore structure with big surface area and prosperity improve the rapid diffusion of ion, realizes the quick transmission of ion and electronics, improves the power characteristic of lithium ion battery.
Graphene has special two-dimensional nanostructure and excellent physicochemical properties, particularly high conductivity and flourishing flexible pore structure, is indicating that Graphene possibly be the electrode material of a kind of high-specific-power and high-energy-density.Theoretical Calculation shows that Graphene has high chemical diffusion speed, has reached 10
-7-10
-6Cm
2s
-1, be a kind of very desirable high-specific-power electrode material.At present, proposed several kinds of methods of producing Graphene, the method that wherein, the chemical stripping method is a kind of low cost, can produce Graphene in a large number is expected to satisfy the magnanimity materials demand of lithium ion battery applications.It is reported that the Graphene of chemical stripping method preparation has higher reversible specific capacity, for example, under low current density like 100mA g
-1, specific capacity can reach 1264mAh g
-1, but the Graphene of chemical stripping method preparation is at bigger initial current density 500mA g
-1Or more carry out the bigger capacity fluctuation of fast charging and discharging existence under the high current density.Mainly be because there is oxygen-containing functional group on the Graphene surface of chemical method preparation, greatly reduced its conductivity and thermal stability.The oxygen on electrolyte and Graphene surface can react when taking off lithium, possibly cause the electrochemical reaction process of electrode unstable.
Summary of the invention:
The object of the present invention is to provide a kind of doped graphene electrode material and magnanimity preparation method thereof and, solve the instability problem that the chemical stripping legal system is equipped with Graphene electrodes in big capacity, high multiplying power lithium ion battery application.
Technical scheme of the present invention is:
Adopting the Graphene of the different carbon/oxygen ratio of chemical stripping method preparation is raw material; Through protective gas and control heating rate; Under hot conditions, feed the nitrogenous or boron element gas of variable concentrations, the regulation and control processing time; Realize the doping of the heteroatom of Graphene, obtain nitrogen or boron doped Graphene.
The assembling of lithium ion half-cell: doped graphene, conductive carbon black, binding agent are mixed, and by mass percentage, it is 50%～98% that doped graphene accounts for electrode material content, and the content that conductive carbon black and binding agent account for electrode material is respectively 25%～1%; Add the solvent that accounts for said mixture 50～1000wt%; Being coated in after the grinding on the collector, is work electrode behind drying, shearing, compressing tablet, with the lithium sheet as to electrode/reference electrode; Add the electrolyte that contains lithium salts, in glove box, be assembled into button-shaped lithium ion half-cell;
The test of lithium ion half-cell: under initial big current density condition, carry out the constant current charge-discharge test.
Among the present invention, the lateral dimension of the Graphene of the chemical stripping method of employing preparation is 50nm～200 μ m (being preferably 500nm～50 μ m), and the number of plies is 1～3 layer, and thickness is 0.8～2.3nm, and conductivity is 10
-4～10
4S/cm (is preferably 10～10
3S/cm).The C/O atomic ratio is 1: 1～50: 1 (preferred proportion is 5: 1～20: 1).Wherein, adopt the Hummer method that the graphite raw material oxidation is obtained graphite oxide, oxidization time is 20min-72h, is preferably 1h-24h.
" Hummer method " sees also document: Hummers W, Offman R.Journal of The American Chemical Society 1958,80:1339.
Among the present invention, described hot conditions is 200-1600 ℃, and preferred temperature is 500～1000 ℃.
Among the present invention, the described gas mixed volume ratio that contains corresponding nitrogen or boron doped chemical atmosphere and other protective gas is 1: 50～50: 1, and preferred gas mixed volume ratio is 1: 10-1: 1; Concrete nitrogenous gas is: N
2, NH
3, N
2O, NO, N
2O
5Or N
2O
3Deng; The gas of boracic is BCl
3, BF
3, BBr
3Or B
2H
6Deng; Protective gas is argon gas or helium etc.
Among the present invention, described protective gas is argon gas, helium or nitrogen etc.; Heating rate is 1 ℃/min～50 ℃/min, and preferred heating rate is 10 ℃/min～40 ℃/min; The high-temperature process time is 0.1～24h, and the preferred time is 1～10h.
Among the present invention, the doping of the heteroatom of described realization Graphene, wherein the doping content of nitrogen or boron atom is 0.1～30at%, preferred doping is 0.5～5at%.
Among the present invention; Described doped graphene, conductive carbon black, binding agent Kynoar are mixed by certain mass ratio; Wherein to account for electrode material content be 50%～98% (preferred content is 70%～90%) to doped graphene, and the content that conductive carbon black and binding agent account for electrode material is respectively 25%～1% (preferred content is 20%～5%).
Among the present invention, described solvent comprises ethanol, acetone or N-methyl pyrrolidone etc.; Collector comprises Copper Foil, aluminium foil, titanium sheet, corrosion resistant plate or platinized platinum etc.
Among the present invention, the described electrolyte lithium salts that contains lithium salts comprises LiPF
6, LiClO
4Or LiAsF
6Deng, be electrolyte with the organic solvent that contains lithium salts, the molar concentration of electrolyte is 0.1-3mol/L, organic solvent is propene carbonate (PC), dimethyl carbonate (DMC) or ethylene carbonate (EC) etc.
Among the present invention, carrying out the constant current charge-discharge test condition under the described initial big current density condition is 10mAg
-1～50A g
-1, preferred high current density is 200mA g
-1～30A g
-1(scope is 10mA g at low current density
-1～100mA g
-1) under, the time of discharging and recharging is more than 10 hours, specific capacity is 600～2000mAh g
-1, preferred specific capacity scope is 800～1600mAh g
-1(scope is 100mA g at high current density
-1～50A g
-1) under, the time of discharging and recharging is in 1 hour to tens seconds, specific capacity is 100～600mAh g
-1
Characteristics of the present invention and beneficial effect are:
1. to adopt the Graphene of chemical stripping method preparation be raw material in the present invention, under the condition of high temperature, feeds and contain corresponding nitrogen or boron doped chemical atmosphere and other protective gas, regulates and control the different processing times, obtains the doped graphene of different nitrogen or boron content;
The present invention adopt high temperature gas phase doping preparation doped graphene as lithium ion battery electrode material; Significantly improve the electrical conductance and the thermostability of electrode material; Provide much more more storage lithiums reversible active sites, doped graphene is a kind of promising, big capacity, the high magnification electrode material that can under the fast charging and discharging condition, use;
3. technological process of the present invention is simple, processing ease, and cost is low, and doping efficiency is fast, chemical property is high and can be expected to advantage such as a large amount of productions.
In a word; Graphene through adopting the preparation of chemical stripping method is a raw material, adopts the high temperature gas phase doping to obtain nitrogen or boron doped graphene, has not only realized the doping at the Graphene lattice of nitrogen or boron heteroatom; And further remove oxygen-containing functional group; Improve the electrical conductance and the thermal stability of Graphene, increase the reversible active sites of storage lithium, obtain a kind of big capacity, powerful Graphene electrodes material.
Description of drawings:
Fig. 1. (a) transmission electron microscope of nitrogen-doped graphene and (b) electron scanning micrograph.
Fig. 2. (a) transmission electron microscope of boron doped graphene and (b) electron scanning micrograph.
Fig. 3. (a) scanning transmission electron microscope photo of nitrogen-doped graphene and at (b) carbon in figure (a) square frame district and (c) distribution map of nitrogen element; (d) scanning transmission electron microscope photo of boron doped graphene and at (e) carbon in figure (d) square frame district and (f) distribution map of boron element; (g) the N1s XPS spectrum of nitrogen-doped graphene, illustration is the sketch map of nitrogen doped forms in the Graphene lattice, N1 is a pyridine type nitrogen; N2 is pyrroles's type nitrogen; (h) the B1s XPS spectrum of boron doped graphene, illustration is the sketch map of boron doped forms in the Graphene lattice, B1 is BC
3Type boron, B2 are BC
2O type boron.
Fig. 4. (a) constant current charge-discharge voltage curve of nitrogen-doped graphene and (b) cycle performance and coulombic efficiency under the low current density; (c) constant current charge-discharge voltage curve of boron doped graphene and (d) cycle performance and coulombic efficiency under the low current density.Current density is 50mAg
-1
Fig. 5. (a) nitrogen mixes and (b) the constant current charge-discharge voltage curve of boron doped graphene under the high current density, and current density is 50mAg
-1(c) nitrogen mixes and (d) high rate performance and the cycle performance curve of boron doped graphene under the different high current densities, and current density is 0.5Ag
-1To 25Ag
-1
Embodiment:
Embodiment 1
The lateral dimension that adopts the chemical peeling preparation is that 500nm～1 μ m, the number of plies are that 1～3 layer, conductivity are 1 * 10
3The Graphene of S/cm is a raw material, and C/O is 10 Graphene (50mg) than (carbon oxygen atom than), puts in the SiC pipe (long 1.5m, external diameter are 40mm), under argon shield, is warming up to 650 ℃ with 10 ℃/min heating rate, and feeding is at NH
3(bulk purity is～99.0%) keeps NH
3With the mixed volume ratio of argon gas be 1: 2, reaction 1h, obtaining nitrogen content is the nitrogen-doped graphene of 2.0at%.Nitrogen-doped graphene, conductive carbon black, Kynoar binding agent are mixed by certain mass ratio (80: 10: 10), add the N-methyl pyrrolidone that accounts for said mixture 200wt%, make through grinding to form even starchiness; Then slurry is coated on the Cu paper tinsel, 100 ℃ of dry 5h, make N-methyl pyrrolidone volatilization after; Shearing, compressing tablet; Dry 20h is a work electrode under 100 ℃ of vacuum, with the lithium sheet as to electrode/reference electrode, with 1M (mol/L) LiPF
6Ethylene carbonate EC/ dimethyl carbonate DMC (volume ratio 1: 1) solution as electrolyte, in glove box, be assembled into button-shaped lithium ion half-cell, under different current density conditions, carry out constant current charge-discharge test then.At low current density 50mA g
-1Down, reversible specific capacity is 950mAh g first
-1At high current density 25A g
-1Down, reversible specific capacity is 125mAhg
-1
Embodiment 2
Be with embodiment 1 difference:
The lateral dimension that adopts the chemical peeling preparation is that 500nm～5 μ m, the number of plies are that 1～3 layer, conductivity are 2 * 10
3The Graphene of S/cm is a raw material, and C/O puts in the SiC pipe (long 1.5m, external diameter are 40mm) than the Graphene (50mg) that is 9, through the helium protection down, is warming up to 700 ℃ with 20 ℃/min heating rate, feeds at NH
3(bulk purity is～99.0%) keeps NH
3With the mixed volume ratio of argon gas be 1: 3, reaction 2h, obtaining nitrogen content is the nitrogen-doped graphene of 3.1at%.Nitrogen-doped graphene, conductive carbon black, Kynoar binding agent are mixed by certain mass ratio (80: 10: 10), add the N-methyl pyrrolidone that accounts for said mixture 300wt%, make through grinding to form even starchiness; Then slurry is coated on the Cu paper tinsel, 100 ℃ of dry 5h, make N-methyl pyrrolidone volatilization after; Shearing, compressing tablet; Dry 20h is a work electrode under 100 ℃ of vacuum, with the lithium sheet as to electrode/reference electrode, with 1M LiPF
6Ethylene carbonate EC/ dimethyl carbonate DMC (volume ratio 1: 1) solution as electrolyte, in glove box, be assembled into button-shaped lithium ion half-cell, under different current density conditions, carry out constant current charge-discharge test then.At low current density 50mA g
-1Down, reversible specific capacity is 1040mAh g first
-1At high current density 25A g
-1Down, reversible specific capacity is 199mAh g
-1
Embodiment 3
Be with embodiment 1 difference:
The lateral dimension that adopts the chemical peeling preparation is that 500nm～5 μ m, the number of plies are that 1～3 layer, conductivity are 2 * 10
3The Graphene of S/cm is a raw material, and C/O puts in the SiC pipe (long 1.5m, external diameter are 40mm) than the Graphene (150mg) that is 9, through the helium protection down, is warming up to 600 ℃ with 30 ℃/min heating rate, feeds at NH
3(bulk purity is～99.0%) keeps NH
3With the mixed volume ratio of argon gas be 1: 4, reaction 4h, obtaining nitrogen content is the nitrogen-doped graphene of 3.2at%.Nitrogen-doped graphene, conductive carbon black, Kynoar binding agent are mixed by certain mass ratio (70: 15: 15), add the N-methyl pyrrolidone that accounts for said mixture 400wt%, make through grinding to form even starchiness; Then slurry is coated on the Cu paper tinsel, 110 ℃ of dry 2h, make N-methyl pyrrolidone volatilization after; Shearing, compressing tablet; Dry 24h is a work electrode under 100 ℃ of vacuum, with the lithium sheet as to electrode/reference electrode, with 1MLiClO
4Propene carbonate PC solution as electrolyte, in glove box, be assembled into button-shaped lithium ion half-cell, under different current density conditions, carry out constant current charge-discharge test then.At low current density 50mA g
-1Down, reversible specific capacity is 1020mAh g first
-1At high current density 20A g
-1Down, reversible specific capacity is 209mAh g
-1
Embodiment 4
Be with embodiment 1 difference:
The lateral dimension that adopts the chemical peeling preparation is that 500nm～10 μ m, the number of plies are that 1～3 layer, conductivity are 2 * 10
3The Graphene of S/cm is a raw material, and C/O puts in the SiC pipe (long 1.5m, external diameter are 40mm) than the Graphene (50mg) that is 10, under argon shield, is warming up to 800 ℃ with 30 ℃/min heating rate, feeds at BCl
3(bulk purity is～99.99%) keeps BCl
3With the mixed volume ratio of argon gas be 1: 5, reaction 2h, obtaining boron content is the boron doped graphene of 0.9at%.Boron doped graphene, conductive carbon black, Kynoar binding agent are mixed by certain mass ratio (80: 10: 10), add the N-methyl pyrrolidone that accounts for said mixture 300wt%, make through grinding to form even starchiness; Then slurry is coated on the Cu paper tinsel, 100 ℃ of dry 6h, make N-methyl pyrrolidone volatilization after; Shearing, compressing tablet; Dry 15h is a work electrode under 120 ℃ of vacuum, with the lithium sheet as to electrode/reference electrode, with 0.5MLiPF
6Propene carbonate PC solution as electrolyte, in glove box, be assembled into button-shaped lithium ion half-cell, under different current density conditions, carry out constant current charge-discharge test then.At low current density 50mA g
-1Down, reversible specific capacity is 1500mAh g first
-1At high current density 25A g
-1Down, reversible specific capacity is 210mAh g
-1
Be with embodiment 1 difference:
The lateral dimension that adopts the chemical peeling preparation is that 500nm～10 μ m, the number of plies are that 1～3 layer, conductivity are 1 * 10
3The Graphene of S/cm is a raw material, and C/O puts in the SiC pipe (long 1.5m, external diameter are 40mm) than the Graphene (100mg) that is 8, under argon shield, is warming up to 850 ℃ with 5 ℃/min heating rate, feeds at BCl
3(bulk purity is～99.99%) keeps BCl
3With the mixed volume ratio of argon gas be 1: 4, reaction 4h, obtaining boron content is the boron doped graphene of 1.5at%.Boron doped graphene, conductive carbon black, Kynoar binding agent are mixed by certain mass ratio (90: 5: 5), add the N-methyl pyrrolidone that accounts for said mixture 350wt%, make through grinding to form even starchiness; Then slurry is coated on the Cu paper tinsel, 100 ℃ of dry 5h, make N-methyl pyrrolidone volatilization after; Shearing, compressing tablet; Dry 20h is a work electrode under 100 ℃ of vacuum, with the lithium sheet as to electrode/reference electrode, with 1.5MLiClO
4Propene carbonate PC solution as electrolyte, in glove box, be assembled into button-shaped lithium ion half-cell, under different current density conditions, carry out constant current charge-discharge test then.At low current density 50mA g
-1Down, reversible specific capacity is 1300mAh g first
-1At high current density 20A g
-1Down, reversible specific capacity is 230mAh g
-1
Embodiment 6
Be with embodiment 1 difference:
The lateral dimension that adopts the chemical peeling preparation is that 500nm～5 μ m, the number of plies are that 1～3 layer, conductivity are 1 * 10
3The Graphene of S/cm is a raw material, and C/O puts in the SiC pipe (long 1.5m, external diameter are 40mm) than the Graphene (50mg) that is 7, under argon shield, is warming up to 800 ℃ with 15 ℃/min heating rate, feeds at BCl
3(bulk purity is～99.99%) keeps BCl
3With the mixed volume ratio of argon gas be 1: 2, reaction 2h, obtaining boron content is the boron doped graphene of 2.1at%.Roc doped graphene, conductive carbon black, Kynoar binding agent are mixed by certain mass ratio (70: 15: 15), add the N-methyl pyrrolidone that accounts for said mixture 500wt%, make through grinding to form even starchiness; Then slurry is coated on the Cu paper tinsel, 120 ℃ of dry 2h, make N-methyl pyrrolidone volatilization after; Shearing, compressing tablet; Dry 20h is a work electrode under 100 ℃ of vacuum, with the lithium sheet as to electrode/reference electrode, with 1MLiPF
6Ethylene carbonate EC/ dimethyl carbonate DMC (volume ratio 1: 1) solution as electrolyte, in glove box, be assembled into button-shaped lithium ion half-cell, under different current density conditions, carry out constant current charge-discharge test then.At low current density 50mA g
-1Down, reversible specific capacity is 1200mAh g first
-1At high current density 20A g
-1Down, reversible specific capacity is 220mAh g
-1
As shown in Figure 1, show that doped graphene still has ultra-thin two-dimensional structure, good pliability, the transparency from the transmission electron microscope photo (a) of nitrogen-doped graphene; Electron scanning micrograph (b) shows that doped graphene is free distribution, and unordered being stacked formed the conductive network and abundant pore structure of phase lap knot.
As shown in Figure 2, show that doped graphene still has ultra-thin two-dimensional structure, good pliability, the transparency from the transmission electron microscope photo (a) of boron doped graphene; Electron scanning micrograph (b) shows that doped graphene is free distribution, and unordered being stacked formed the conductive network and abundant pore structure of phase lap knot.
As shown in Figure 3, (Fig. 3 a d) and to nitrogen mixes and the boron doped graphene has carried out distribution diagram of element (Fig. 3 b from the high angle of nitrogen or boron doped graphene annular details in a play not acted out on stage, but told through dialogues scanning transmission microphotograph; C and Fig. 3 e; F) analysis can know that except that carbon, nitrogen element (Fig. 3 c) or boron element (Fig. 3 f) are distributed in the Graphene surface equably; Explanation has realized that heteroatom nitrogen or the boron homogeneous on the Graphene plane mixes under the high-temperature heat treatment condition.Can know that from the xps energy spectrum analysis of nitrogen (Fig. 3 g) or boron (Fig. 3 h) element Graphene has not only been realized the doping of heteroatom, and realize the reduction of Graphene to a certain extent.
As shown in Figure 4, nitrogen mixes, and (Fig. 4 a b) mixes with boron that (Fig. 4 c, d) Graphene is at 50mA g
-1Constant current charge-discharge voltage curve and cycle performance, coulombic efficiency can be known under the lower current densities, and doped graphene has excellent chemical property under low current density.Doped graphene not only has high reversible capacity, and has improved the coulombic efficiency first and the capability retention of electrode material.
As shown in Figure 5, (Fig. 5 a is c) with boron doping (Fig. 3 b, d) Graphene (0.5A g under high current density from the nitrogen doping
-1To 25A g
-1) high rate performance and stable circulation linearity curve can know that doped graphene has excellent fast charging and discharging performance, high specific capacity, excellent high rate performance and cyclical stability under high current density.
Embodiment result shows; The present invention carries out the doping of heteroatom through the Graphene to the preparation of chemical stripping method; Through mixing conductivity and the thermal stability that has further improved Graphene; Provide more storage lithiums reversible active sites, significantly improved the electrochemical lithium storage performance of Graphene, obtained big capacity, powerful Graphene electrodes material.The sharpest edges of doped graphene have been to improve the electrode stability of material under the high current density condition, have realized that doped graphene has very high specific capacity within a short period of time, and have had excellent cycle performance.Its chemical property obviously is superior to the Graphene and other raw material of wood-charcoal material of chemical stripping method preparation, and disclosing doped graphene is a kind of very promising electrode material.
Claims (10)
1. a doped graphene electrode material is characterized in that, in the said doped graphene electrode material, the doping content of nitrogen or boron atom is 0.1～30at%.
2. according to the described doped graphene electrode material of claim 1, it is characterized in that, the chemical stripping method preparation that said Graphene adopts, the lateral dimension of Graphene is 50nm～200 μ m, and the number of plies is 1～3 layer, and thickness is 0.8～2.3nm, and conductivity is 10
-4～10
4S/cm, carbon/oxygen atom ratio is 1: 1～50: 1.
3. according to the magnanimity preparation method of the described doped graphene electrode material of claim 1, it is characterized in that adopting the Graphene of the different carbon/oxygen ratio of chemical stripping method preparation is raw material; Through protective gas and control heating rate; Under hot conditions, feed the nitrogenous or boron element gas of variable concentrations, the regulation and control processing time; Realize the doping of the heteroatom of Graphene, obtain nitrogen or boron doped Graphene.
4. according to the magnanimity preparation method of the described doped graphene electrode material of claim 3, it is characterized in that: said protective gas is argon gas, helium or nitrogen; Heating rate is 1 ℃/min～50 ℃/min, and hot conditions is 200-1600 ℃.
5. according to the magnanimity preparation method of the described doped graphene electrode material of claim 3, it is characterized in that: in the said step (1), the gas of nitrogenous element is: N
2, NH
3, N
2O, NO, N
2O
5Or N
2O
3The gas that contains boron element is BCl
3, BF
3, BBr
3Or B
2H
6Wherein, containing the gas of corresponding nitrogen or boron element and the volume ratio of protective gas is 1: 50～50: 1.
6. according to the magnanimity preparation method of the described doped graphene electrode material of claim 3, it is characterized in that: in the said step (1), the doping treatment time is 0.1～48h under the hot conditions.
7. according to the application of the described doped graphene electrode material of claim 1; It is characterized in that; (1) assembling of lithium ion half-cell: doped graphene, conductive carbon black, binding agent are mixed; By mass percentage, it is 50%～98% that doped graphene accounts for electrode material content, and the content that conductive carbon black and binding agent account for electrode material is respectively 25%～1%; Add the solvent that accounts for said mixture 50～1000wt%; Being coated in after the grinding on the collector, is work electrode behind drying, shearing, compressing tablet, with the lithium sheet as to electrode/reference electrode; Add the electrolyte that contains lithium salts, in glove box, be assembled into button-shaped lithium ion half-cell; (2) test of lithium ion half-cell: under initial big current density condition, carry out the constant current charge-discharge test.
8. according to the application of the described doped graphene electrode material of claim 7, it is characterized in that: said solvent is ethanol, acetone or N-methyl pyrrolidone; Said collector is Copper Foil, aluminium foil, titanium sheet, corrosion resistant plate or platinized platinum.
9. according to the application of the described doped graphene electrode material of claim 7, it is characterized in that: in the said electrolyte that contains lithium salts, lithium salts is LiPF
6, LiClO
4Or LiAsF
6, the molar concentration that contains the electrolyte of lithium salts is 0.1-3mol/L.
10. according to the application of the described doped graphene electrode material of claim 7, it is characterized in that: carrying out the constant current charge-discharge test condition under the said initial big current density condition is 10mA g
-1～50A g
-1
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| CN102543469A (en) * | 2012-01-11 | 2012-07-04 | 山东理工大学 | Dye-sensitized solar cell nitrogen-doping graphene counter electrode and preparation method thereof |
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