CN105609771A - Nitrogen-doped multi-porous carbon negative electrode material and preparation method and application thereof - Google Patents
Nitrogen-doped multi-porous carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- CN105609771A CN105609771A CN201610041235.4A CN201610041235A CN105609771A CN 105609771 A CN105609771 A CN 105609771A CN 201610041235 A CN201610041235 A CN 201610041235A CN 105609771 A CN105609771 A CN 105609771A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
A nitrogen-doped multi-porous carbon negative electrode material comprises carbon, nitrogen and hydrogen, wherein based on mass percentage of each constituent, the nitrogen accounts for 10-25%, the hydrogen accounts for less than or equal to 10%, and the balance is the carbon; the material is internally provided with multi-porous passages which are different in sizes and are distributed on three sections of over 2-50 nanometers; the maximum specific area reaches 143 square meters per gram, and ion migration diffusion is facilitated; the nitrogen accounts for 10-25% so as to improve the conductivity; the hydrogen accounts for less than or equal to 10% so that ion insertion to the structure is facilitated; and the negative electrode material is prepared by pyrolysis of 1,2,4- triazole zinc salt/1,2,4-triazole univalent anion zinc complex and can be used as a negative plate or a negative electrode active filler of a button cell. The nitrogen-doped multi-porous carbon negative electrode material prepared according to the method has the advantages of high specific capacity, high rate performance, high long-period cycle performance, high material compatibility and wide application, is suitable for a lithium ion battery, and is also applicable for a sodium ion battery; and the preparation method is simple and is easy for industrial production.
Description
Technical field
The present invention relates to chargeable ion battery field, be specifically related to a kind of azepine multi-stage porous carbon negative material andPreparation method and application.
Background technology
Lithium ion battery with its high-energy-density, compare the high voltage of dry cell and become the daily of extensive useEnergy-storage travelling wave tube, and lithium ion battery also has the good characteristic of memory-less effect. But portability, high power capacityThe energy storage of changing requires to have made existing commercial li-ion battery day show embarrassed look, is badly in need of improving its energy density and powerDensity. Conventional commercial negative material uses the only graphite material of 372mAh/g of theoretical specific capacity, although cyclicityCan be well but poor performance under the low and high magnification of specific capacity, when high current charge-discharge, easily cause danger, greatly limitMake its application in extensive energy storage.
Compare rare loose precious metal element lithium, sodium is originate very extensive, the very considerable metallic element of reserves,As the most promising substitute of lithium ion battery---sodium-ion battery is very important in future source of energy storage.But the radius of sodium ion is larger than lithium ion far away, and diffusion is poor, embed potential barrier high, alloy tendency is little, normalWith the not enough 100mAh/g of graphite cathode sodium-ion battery theoretical capacity, greatly limited sodium-ion battery trendPractical.
Azepine porous carbon is that nitrogen-atoms part replaces the carbon atom in graphite-structure and the new material that obtains. Due to nitrogenAtom is triad and carbon is tetrad, has produced that structure is broken to be lacked and reducible so introduced nitrogen-atomsSaturated site, this diffusion mobility that is ion provides how possible passage and has more stored up lithium/storage sodium positionPoint. But volumetric expansion while the being limited to storage lithium/storage sodium destruction to material, at present most of such material followsRing performance and high rate performance are very poor, and traditional nitrating mode doping density is limited, process price is high and nitrogen is mixedAssorted irrational distribution, is difficult to drop into actual production life.
Summary of the invention
The object of the invention is for prior art existing problems, provide a kind of azepine multi-stage porous carbon negative material andIts preparation method and application, azepine multi-stage porous carbon negative material specific capacity prepared by the method is high, good rate capability,Long period good cycle, is not only applicable to lithium ion battery but also be applicable to sodium-ion battery, and material compatibility is good,Of many uses; Preparation method is simple, is easy to suitability for industrialized production; This material is for pole piece and contain this pole pieceButton cell, solves the current low problem of negative material finite capacity, high rate performance, solves high power capacity simultaneouslyNegative pole preparation complexity, the problem that is difficult to industrial-scale production.
Technical scheme of the present invention:
A kind of azepine porous carbon negative material, is made up of carbon, nitrogen and hydrogen, and the mass percentage content of each composition isNitrogen 10-25%, hydrogen≤10%, carbon are surplus, and that this material internal has is not of uniform size, be distributed in three intervalsMultistage pore canal, 2-10nm interval, 20-40nm interval and 50nm are above interval; Specific area is up to 143Meters squared per gram, is convenient to ion diffusion mobility; Nitrogen content is that 10-25% has increased electric conductivity, hydrogen content≤10%Making structure be convenient to ion inserts.
A preparation method for described azepine multi-stage porous carbon negative material, step is as follows:
1) by zinc salt/1 of 1,2,4-triazole monovalence anion, 2,4-triazole monovalence anion zinc complex,At inert atmosphere nitrogen or argon shield, 600-800 DEG C temperature, generate azepine through pyrolysis, coking manyHole carbon;
2) by above-mentioned azepine porous carbon with the salt acid soak that is 0.5mol/L by concentration with remove residual zinc salt andHydrochloric acid that Zn complex is 0.5mol/L by concentration, ethanol and/or water washing 2-3 time, then at temperature 60 CVacuum drying under above condition, obtains azepine multi-stage porous carbon negative material.
Described 1,2, zinc salt/1 of 4-triazole monovalence anion, the closing of 2,4-triazole monovalence anion zinc complexOne-tenth method, comprises the steps:
1,2,4-triazole and pure zinc oxide are joined in solvent, and described solvent is water, methyl alcohol or ethanol,The mol ratio of 1,2,4-triazole and zinc oxide and solvent is 3-2:1:20-100, in the atmospheric boiling point temperature of solventThe lower stirring of degree is boiled altogether until by solvent evaporate to dryness, after collection solid porphyrize, do in the temperature range of 100-150 DEG CDry more than 2 hours, obtain white product 1,2, zinc salt/1 of 4-triazole monovalence anion, 2,4-triazole monovalenceAnion zinc complex.
An application for described azepine multi-stage porous carbon negative material, fills out for button cell negative plate or negative electrode activeFill thing, method is as follows: button cell negative plate or negative electrode active filler by azepine multi-stage porous carbon negative material,Conductive agent and binding agent composition, described conductive agent is acetylene black, Ketjen black or SuperP, binding agent is poly-fourPVF, polyvinylidene fluoride, Lithium polyacrylate or polyvinylpyrrolidone, the mass percent of each component isConductive agent 0-40%, binding agent 10-20%, azepine multi-stage porous carbon negative material are surplus; Electrolyte uses1mol/L lithium hexafluoro phosphate solution or sodium perchlorate solution, solvent is the body of diethyl carbonate and ethylene carbonateLong-pending is metal lithium sheet or sodium sheet than for 1:1 mixed solvent or propene carbonate to electrode, group together with negative plateDress up as button cell.
Advantage of the present invention is:
Azepine multi-stage porous carbon negative material specific capacity prepared by the method is high, good rate capability, long period cyclicityCan be good, be not only applicable to lithium ion battery but also be applicable to sodium-ion battery, material compatibility is good, of many uses; SystemPreparation Method is simple, is easy to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is zinc salt/1 of 1,2,4-triazole monovalence anion, 2,4-triazole monovalence anion zinc complexX-ray powder diffraction spectrogram.
Fig. 2 is the field emission scanning electron microscope figure of nitrogen doping multi-stage porous carbon.
Fig. 3 is the X-ray powder diffraction figure of nitrogen doping multi-stage porous carbon, shows the amorphism of its height.
Fig. 4 is the 77K isothermal nitrogen adsorption desorption datagram of nitrogen doping multi-stage porous carbon, and wherein the little figure of interpolation isGraph of pore diameter distribution.
Fig. 5 is the lithium ion battery cyclic voltammetry scan curve that nitrogen doping multi-stage porous carbon is prepared negative pole, sweep limits0.05V-3.00V is (with respect to Li+/ Li electrode potential), sweep speed for 0.2mV/s.
Fig. 6 is that nitrogen doping multi-stage porous carbon is prepared the lithium ion battery of negative pole under 1A/g constant current charge-discharge condition and followedRing performance map.
Fig. 7 is the lithium ion battery high rate performance figure that nitrogen doping multi-stage porous carbon is prepared negative pole.
Fig. 8 is that nitrogen doping multi-stage porous carbon is prepared the lithium ion battery of negative pole under the normal charging or discharging current of 100mA/gLong period cycle performance figure.
Fig. 9 is that nitrogen doping multi-stage porous carbon is prepared the sodium ion long period of negative pole under the charging or discharging current of 100mA/gCycle performance figure, demonstrates outstanding coulombic efficiency and after 300 weeks, exceedes the height ratio capacity of 300mAh/g.
Detailed description of the invention
In order more specifically to introduce meticulously this patent, now enumerate two specific embodiments for explanation, Dian XingshiReference when executing example and being intended to provide concrete enforcement, and be not suitable for restriction the present invention.
Embodiment 1:
A kind of azepine porous carbon negative material, is made up of carbon, nitrogen and hydrogen, and the mass percentage content of each composition isNitrogen 16.4%, hydrogen 8.5%, carbon are surplus, and that this material internal has is not of uniform size, be distributed in three intervalsMultistage pore canal, 2-10nm interval, 20-40nm interval and 50nm are above interval, and specific area reaches 143 squaresRice/gram, be convenient to ion diffusion mobility; Hydrogen content 8.5% has increased electric conductivity, nitrogen content be 16.4% make knotStructure is convenient to ion and is inserted; Preparation method's step of this negative material is as follows:
1) by zinc oxide at 600 DEG C after calcination 4h porphyrize for subsequent use, zinc oxide and 1,2,4-triazole are addedIn ethanol, boil altogether 40 minutes, zinc oxide, 1,2, the amount ratio of 4-triazole and ethanol is 0.1mol:0.25mol:100mL, under continuing to stir boils solvent to evaporate to dryness, collects after solid porphyrize, dry at the temperature of 110 DEG CDry 4 hours, obtain 1,2 of white, zinc salt/1 of 4-triazole monovalence anion, 2,4-triazole monovalence anionZn complex, pulverize is for subsequent use;
Fig. 1 is zinc salt/1 of 1,2,4-triazole monovalence anion, 2,4-triazole monovalence anion zinc complexX-ray powder diffraction spectrogram, can significantly indicate different from zinc oxide in figure.
2) by above-mentioned 1,2, zinc salt/1 of 4-triazole monovalence anion, 2,4-triazole monovalence anion zinc complex,Under nitrogen protection and under the condition of 800 DEG C, generate azepine porous carbon through isothermal pyrolysis, coking in 2 hours;The salt acid soak that is 0.5mol/L by concentration is to remove zinc salt residual in azepine porous carbon and Zn complex, warpCross 3 watery hydrochloric acid washings, 2 water washings and 3 ethanol washings, then true under the above condition of temperature 60 CEmpty dry, obtain azepine multi-stage porous carbon negative material.
Fig. 2 is the field emission scanning electron microscope figure of nitrogen doping multi-stage porous carbon, can clearly distinguish its multi-stage porousStructure.
Fig. 3 is the X-ray powder diffraction figure of nitrogen doping multi-stage porous carbon, shows the amorphism of its height.
Fig. 4 is the 77K isothermal nitrogen adsorption desorption datagram of nitrogen doping multi-stage porous carbon, and wherein the little figure of interpolation isGraph of pore diameter distribution, can see that main pore-size distribution is below 10nm, has simultaneously and is greater than the multistage of 10nmDuct, adsorption desorption data show that the BET specific area of this material is at 143 square metres/every gram.
By the azepine multi-stage porous carbon negative material of preparation, for button cell negative plate, method is as follows: button cellNegative plate is made up of azepine multi-stage porous carbon negative material, conductive agent and binding agent, and described conductive agent is acetylene black,Binding agent is polyvinylidene fluoride, and concrete steps are:
1), by negative material 80mg, acetylene black 10mg, be mixed in 500 microlitres and be dissolved with the poly-inclined to one side difluoro of 10mgIn the 1-METHYLPYRROLIDONE of ethene, after fully stirring, use film by wet method film, and 100 DEG C of vacuum drying6 hours, make negative plate;
2) above-mentioned negative plate is assembled into button cell, electrolyte uses 1mol/L lithium hexafluoro phosphate solution,Solvent is that the volume ratio of diethyl carbonate and ethylene carbonate is 1:1 mixed solvent, is metal lithium sheet to electrode.
Fig. 5 is the lithium ion battery cyclic voltammetry scan curve that nitrogen doping multi-stage porous carbon is prepared negative pole, sweep limits0.05V-3.00V is (with respect to Li+/ Li electrode potential), sweep speed for 0.2mV/s.
Fig. 6 is that nitrogen doping multi-stage porous carbon is prepared the lithium ion battery of negative pole under 1A/g constant current charge-discharge condition and followedRing performance map, even if can see 100 weeks above specific capacities that still can reach 800mAh/g of large current cycle.
Fig. 7 is the lithium ion battery high rate performance figure that nitrogen doping multi-stage porous carbon is prepared negative pole, can find out this materialRemarkable stability, very high currents discharges and recharges the electric discharge of rear low current can also recover capacity.
Fig. 8 is that nitrogen doping multi-stage porous carbon is prepared the lithium ion battery of negative pole under the normal charging or discharging current of 100mA/gLong period cycle performance figure, demonstrates splendid coulombic efficiency and after 100 weeks, exceedes the height ratio of 1400mAh/gCapacity.
Embodiment 2:
A kind of azepine porous carbon negative material, is made up of carbon, nitrogen and hydrogen, and the mass percentage content of each composition isNitrogen 15.6%, hydrogen 8.7%, carbon are surplus, and that this material internal has is not of uniform size, be distributed in three intervalsMultistage pore canal, 2～10nm interval, 20～40nm interval and 50nm are above interval; Specific area is 143 squaresRice/gram, be convenient to ion diffusion mobility; Hydrogen content 8.7%% has increased electric conductivity, nitrogen content be 15.6% make knotStructure is convenient to ion and is inserted; Preparation method's step of this negative material is as follows:
1) by zinc oxide at 600 DEG C after calcination 4h porphyrize for subsequent use, zinc oxide and 1,2,4-triazole are addedIn methyl alcohol, boil altogether 30 minutes, zinc oxide, 1,2, the amount ratio of 4-triazole and ethanol is 0.1mol:0.25mol:100mL, under continuing to stir boils solvent to evaporate to dryness, collects after solid porphyrize, dry at the temperature of 100 DEG CDry 2 hours, obtain 1,2 of white, zinc salt/1 of 4-triazole monovalence anion, 2,4-triazole monovalence anionZn complex, pulverize is for subsequent use;
2) by above-mentioned 1,2, zinc salt/1 of 4-triazole monovalence anion, 2,4-triazole monovalence anion zinc complex,Under argon shield and under the condition of 750 DEG C, generate azepine porous carbon through isothermal pyrolysis, coking in 3 hours;The salt acid soak that is 0.5mol/L by concentration is to remove zinc salt residual in azepine porous carbon and Zn complex, warpCross 2 watery hydrochloric acid washings and 3 ethanol washings, then vacuum drying under the above condition of temperature 60 C,To azepine multi-stage porous carbon negative material.
By the azepine multi-stage porous carbon negative material of preparation, for button cell negative plate, method is as follows: button cellNegative plate is made up of azepine multi-stage porous carbon negative material, conductive agent and binding agent, and described conductive agent is acetylene black,Binding agent is polyvinylidene fluoride, and concrete steps are:
1), by negative material 80mg, acetylene black 10mg, be mixed in 500 microlitres and be dissolved with the poly-inclined to one side difluoro of 10mgIn the 1-METHYLPYRROLIDONE of ethene, after fully stirring, use film by wet method film, and 100 DEG C of vacuum drying6 hours, make negative plate;
2) above-mentioned negative plate is assembled into button cell, electrolyte uses 1mol/L sodium perchlorate solution, moltenAgent is propene carbonate, is sodium metal sheet to electrode.
Battery testing voltage is 3V-0.05V, and working method is constant current charge-discharge, and electric current arranges 100mA/ (1gNegative material) time, within 100 weeks, discharge and recharge the result that obtains Fig. 9. Fig. 9 is that nitrogen doping multi-stage porous carbon is prepared negative poleSodium ion long period cycle performance figure under the charging or discharging current of 100mA/g, demonstrates outstanding coulombic efficiencyWith 300 weeks after exceed the height ratio capacity of 300mAh/g.
More than, for attempting two preferred embodiments, do not form the restriction that patent content is realized, any substantial equivalenceSubstitute and the optimization of operation, change amendment and the merging of condition, all in scope of patent protection. Describing and sayingWhen bright, used a small amount of necessary term, it does not form the restriction to invention yet.
Claims (4)
1. an azepine porous carbon negative material, is characterized in that: be made up of the matter of each composition carbon, nitrogen and hydrogenAmount degree is that nitrogen 10-25%, hydrogen≤10%, carbon are surplus, that this material internal has is not of uniform size,Be distributed in three interval multistage pore canals, 2-10nm interval, 20-40nm interval and 50nm are above interval; Than tableArea is up to 143 meters squared per gram, is convenient to ion diffusion mobility; Nitrogen content is that 10-25% has increased electric conductivity,Hydrogen content≤10% makes structure be convenient to ion insertion.
2. a preparation method for azepine multi-stage porous carbon negative material described in claim 1, is characterized in that stepAs follows:
1) by zinc salt/1 of 1,2,4-triazole monovalence anion, 2,4-triazole monovalence anion zinc complex,At inert atmosphere nitrogen or argon shield, 600-800 DEG C temperature, generate azepine through pyrolysis, coking manyHole carbon;
2) by above-mentioned azepine porous carbon with the salt acid soak that is 0.5mol/L by concentration with remove residual zinc salt andHydrochloric acid that Zn complex is 0.5mol/L by concentration, ethanol and/or water washing 2-3 time, then at temperature 60 CVacuum drying under above condition, obtains azepine multi-stage porous carbon negative material.
3. the preparation method of azepine multi-stage porous carbon negative material according to claim 2, is characterized in that: instituteState zinc salt/1 of 1,2,4-triazole monovalence anion, the synthetic method of 2,4-triazole monovalence anion zinc complex,Comprise the steps:
1,2,4-triazole and pure zinc oxide are joined in solvent, and described solvent is water, methyl alcohol or ethanol,The mol ratio of 1,2,4-triazole and zinc oxide and solvent is 3-2:1:20-100, in the atmospheric boiling point temperature of solventThe lower stirring of degree is boiled altogether until by solvent evaporate to dryness, after collection solid porphyrize, do in the temperature range of 100-150 DEG CDry more than 2 hours, obtain white product 1,2, zinc salt/1 of 4-triazole monovalence anion, 2,4-triazole monovalenceAnion zinc complex.
4. an application for azepine multi-stage porous carbon negative material as claimed in claim 1, is characterized in that: forButton cell negative plate or negative electrode active filler, method is as follows: button cell negative plate or negative electrode active are filledThing is made up of azepine multi-stage porous carbon negative material, conductive agent and binding agent, and described conductive agent is acetylene black, section's qinBlack or SuperP, binding agent is polytetrafluoroethylene (PTFE), polyvinylidene fluoride, Lithium polyacrylate or polyethylene pyrrolesAlkane ketone, the mass percent of each component is that conductive agent 0-40%, binding agent 10-20%, azepine multi-stage porous carbon are negativeUtmost point material is surplus; Electrolyte uses 1mol/L lithium hexafluoro phosphate solution or sodium perchlorate solution, and solvent is carbonThe volume ratio of diethyl phthalate and ethylene carbonate is 1:1 mixed solvent or propene carbonate, is lithium metal to electrodeSheet or sodium sheet are assembled into button cell together with negative plate.
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| CN109553081A (en) * | 2018-11-20 | 2019-04-02 | 桑顿新能源科技有限公司 | A kind of preparation method of novel sodium cell negative pole material |
| CN113659137A (en) * | 2021-08-17 | 2021-11-16 | 广东工业大学 | Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof |
| CN115928463A (en) * | 2022-11-30 | 2023-04-07 | 江苏润禾纺织实业有限公司 | Low-salt low-alkali energy-saving environment-friendly dyeing process |
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| JP2014035915A (en) * | 2012-08-09 | 2014-02-24 | Sony Corp | Electrode material and method for manufacturing the same and secondary battery |
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| JP2014035915A (en) * | 2012-08-09 | 2014-02-24 | Sony Corp | Electrode material and method for manufacturing the same and secondary battery |
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| CN109553081A (en) * | 2018-11-20 | 2019-04-02 | 桑顿新能源科技有限公司 | A kind of preparation method of novel sodium cell negative pole material |
| CN113659137A (en) * | 2021-08-17 | 2021-11-16 | 广东工业大学 | Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof |
| CN115928463A (en) * | 2022-11-30 | 2023-04-07 | 江苏润禾纺织实业有限公司 | Low-salt low-alkali energy-saving environment-friendly dyeing process |
| CN115928463B (en) * | 2022-11-30 | 2023-09-26 | 江苏润禾纺织实业有限公司 | Low-salt low-alkali energy-saving environment-friendly dyeing process |
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