CN103855412B - Lithium-air battery positive pole porous carbon materials - Google Patents

Lithium-air battery positive pole porous carbon materials Download PDF

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CN103855412B
CN103855412B CN201210496351.7A CN201210496351A CN103855412B CN 103855412 B CN103855412 B CN 103855412B CN 201210496351 A CN201210496351 A CN 201210496351A CN 103855412 B CN103855412 B CN 103855412B
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template
hole
carbon element
lithium
carbon materials
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CN103855412A (en
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张华民
李婧
张益宁
王美日
聂红娇
周伟
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/861—Porous electrodes with a gradient in the porosity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

The present invention relates to the application in lithium-air battery of the hierarchical porous structure porous carbon materials, it is characterized in that material with carbon element has the hierarchical porous structure distribution being mutually communicated, i.e. there is mesopore and applicable oxygen, the macroporous structure of electrolyte transmission of applicable discharging product deposition.This material with carbon element is used as lithium-air battery electrode material, material with carbon element space availability ratio in charge and discharge process can be improved to greatest extent, it is effectively improved the specific discharge capacity of battery, voltage platform and multiplying power discharging ability, and then improves energy density and the power density of lithium-air battery.The invention have the advantage that preparation technology is simple, material source is extensive, and grading-hole material with carbon element pore structure controllable and control methods are various, can be easy to realize the doping of metal/metal oxide simultaneously.

Description

Lithium-air battery positive pole porous carbon materials
Technical field
The invention belongs to lithium-air battery field, be specifically related to a kind of anode material for lithium-air battery.
Background technology
Along with developing rapidly of electronics, communication equipment and electric motor car, battery performance is proposed more by people High request.Lithium-air battery is a kind of with lithium metal as negative pole, and air electrode is the secondary cell of positive pole. Lithium metal as negative material has minimum theoretical voltage, and its theoretical specific capacity is up to 3,862 MAh/g, and the oxygen as positive active material can directly obtain from air, therefore, lithium-air Battery has high specific capacity and specific energy.With lithium as standard, its theoretical specific energy density up to 11,140Wh/Kg, and actual specific energy is also far above lithium ion battery, civilian and military domain is great Application prospect.
At present, lithium-air battery mainly use various material with carbon element as positive electrode, by being mixed into PTFE, Air electrode prepared by the binding agents such as PVDF, Nafion.As it is shown in figure 1, be lithium-air battery positive pole Exoelectrical reaction process simulation figure.What exoelectrical reaction built between liquid electrolyte solution and material with carbon element consolidates Carrying out on liquid two-phase interface, carbon material surface generates solid insoluble product oxidate for lithium, along with reaction Carrying out, solid product accumulation makes internal gutter blocking then cause discharge off.
As electrochemical reaction occur place, material with carbon element pore structure physical parameter such as: specific surface area, Pore volume, pore-size distribution have important impact to battery performance, especially charge/discharge capacity.Therefore make Standby and selection has the material with carbon element of appropriate bore structure so that it is be beneficial to electrolyte and air in loose structure Transmission, thus accelerate electrode reaction speed and increase effective utilization in hole, for air electrode extremely Close important.
How to construct the material with carbon element of appropriate bore structure to improve the specific discharge capacity of lithium-air battery, electric discharge Platform is a difficult problem the most urgently to be resolved hurrily.Research at present is thought, the porous carbon with high pore volume can be The oxidate for lithium generated in discharge process provides more storage area, thus shows high specific capacity. Additionally, pore-size distribution is also the key factor affecting battery performance.Tran[1]Etc. have studied a series of high ratio Relation between pore-size distribution and the capacity of surface area porous carbon, the capacity of electrode is by not interfering with material In the large scale duct of transmission, the amount of oxidate for lithium is determined.Material with carbon element micropore canals and part mesopore hole Road can be discharged the oxidate for lithium blocking that initial period is formed, and the surface of this partial hole will be unable to again By air and electrolyte, therefore it is no longer participate in electrochemical reaction, causes discharge off.But, complete The full material with carbon element being made up of big hole dimension is in discharge process, due to oxidate for lithium poorly conductive, electric discharge Product ulking thickness on hole wall is limited, and the core of macropore is not used, can not be abundant Play hole utilizes space.
Summary of the invention
It is an object of the invention to provide a kind of lithium-air battery electrode material with carbon element and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of lithium-air battery positive pole porous carbon materials, described material with carbon element has the classification being mutually communicated Pore structure, grading-hole includes mass transfer hole and deposition hole, and deposition hole accounts for the 40 ~ 95% of total hole pore volume, passes The 4 ~ 55% of Zhan Zong hole, matter hole pore volume, remaining is for aperture less than the hole of 5nm, and deposition hole aperture is 5 ~ 90nm, aperture, mass transfer hole is 0.1 ~ 6um, and between mass transfer hole, mutual spacing is 0.1 ~ 8um, total pore volume It is 0.5 ~ 5cm3/g。
Described material with carbon element uses sol-gal process to combine template or sol-gal process combines template and work Change method is prepared from.Preferred sols gel method combines template and activation method.
A sol-gal process combines template
Specifically it is prepared from according to the following procedure: resorcinol and template are scattered in solvent, then drip Adding formalin, being uniformly mixed at 30 ~ 80 DEG C until reacting formation gel；By gel 60～100 DEG C Lower vacuum drying processes for aging 3 ~ 10 days, and attrition grinding after taking-up obtains pressed powder；Through high temperature N2Or under Ar atmosphere after carbonization, remove template with acid or alkali, through filtering, being dried, obtain porous carbon Material；Wherein N2Or Ar charge flow rate controls at 2 ~ 100ml/min.
B uses sol-gal process to combine template and activation method
Specifically it is prepared from according to the following procedure: resorcinol and template are scattered in solvent, then add Add slaine or metal hydroxides continues to dissolve dispersion, then drip formalin, stir at 30 ~ 80 DEG C Mix mix homogeneously until reaction forms gel；Aging 3 ~ 10 days will be vacuum dried at gel 60～100 DEG C Process, attrition grinding after taking-up, obtain pressed powder；Through high temperature N2Or use after carbonization under Ar atmosphere Acid or alkali remove template and slaine or metal hydroxides, through filtering, being dried, obtain porous carbon Material,
It is characterized in that: described slaine or metal hydroxides for containing Fe, Co, Ni, Cu, Ag, Pt、Pd、Au、Ir、Ru、Nb、Y、Rh、Cr、Zr、Ce、Ti、Mo、Mn、Zn、W、 One or two or more kinds slaine of Sn, La and V or metal hydroxides；Slaine is the nitre of metal Hydrochlorate, carbonate, sulfate, acetate, halogenide, dinitroso diamine salts, acetylacetonate One or two or more kinds in thing or macro ring complex and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound.Wherein metal The mass percent scope of salt or metal hydroxides and resorcinol is 1 ~ 15%.Preferably Fe, Co, The nitrate of Ni, Cu, Mo, Mn, Mo, acetate.
Described template is SiO2Colloidal sol, zeolite, mesoporous Al2O3, mesoporous SiO2, magnesium oxide, vinegar Acid magnesium, magnesium gluconate, copper oxide, zinc oxide, ferrous oxide, iron sesquioxide, calcium carbonate, Magnesium carbonate, ferroso-ferric oxide, tin ash, silicon dioxide, aluminium oxide, zirconium oxide, molybdenum trioxide, Vanadium sesquioxide, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, metal In the hydroxide of magnesium, silicon dioxide microsphere, polystyrene microsphere, poly (methyl methacrylate) micro-sphere One or more, wherein template grain size scope is at 5 ~ 8000nm.Preferably SiO2Colloidal sol, carbon Acid calcium, magnesium carbonate, metallic nickel hydroxide, silicon dioxide microsphere, polystyrene microsphere.
Described resorcinol and solvent are in the ratio of 0.1～8ml solvent/1g resorcinol；Resorcinol Being 1:1～5:1 with the mol ratio of formaldehyde, the mass concentration of described formalin is 30～40%, carbonization temperature Degree scope is at 500 ~ 1700 DEG C, and carbonization time controls at 1 ~ 10h, wherein template and the matter of resorcinol Amount percentage range is 5 ~ 300%.
Described solvent is ethanol, isopropanol, acetone, N-N dimethylformamide, N-N dimethylacetamide One or two or more kinds in amine or N-Methyl pyrrolidone.
The acid solution going removing template to use is 0.5 ~ 3M hydrochloric acid, sulphuric acid, nitric acid or Fluohydric acid., aqueous slkali It it is 0.5 ~ 3M sodium hydroxide solution.The acid solution removing slaine or metal hydroxides use is 0.5 ~ 3M hydrochloric acid, sulphuric acid or nitric acid, aqueous slkali is 0.5 ~ 3M sodium hydroxide solution.
Beneficial effect of the present invention
The material with carbon element of lithium-air battery novel hierarchical pore structure the most of the present invention, its structure has It is suitable for the deposition hole (aperture 5 ~ 100nm) of discharging product deposition, additionally runs through between deposition hole the most equal The even mass transfer hole (aperture 0.1um-6um) being dispersed with macropore, pitch of holes 0.1um-8um.The two In conjunction with, one is that the oxidate for lithium making generation uniformly sinks in the duct of the deposition hole suitable with its size Long-pending；Two is the storage chamber making mass transfer hole become electrolyte and dissolved oxygen, and running through deposition hole provides for it Reactant, is greatly shortened ion and oxygen diffusion length, and owing to hole dimension is much larger than oxidate for lithium Deposition size, even if therefore big multiplying power discharging in discharge process, mass transfer hole is the most blocked.Combine Close and consider, the material with carbon element of this novel hierarchical pore structure, it is greatly improved the space utilization of material with carbon element electrode Rate, Each performs its own functions to make the hole of each aperture size, sufficiently achieves high specific volume in cell operation Amount and power density.
2. hierarchical porous structure material with carbon element is used as lithium-air battery electrode, can be respectively used to the heavy of discharging product Amass and oxygen, the mass transfer of electrolyte, and shorten ion and oxygen diffusion length, improve to greatest extent The utilization rate in material with carbon element hole, is effectively improved the specific discharge capacity of battery, voltage platform and multiplying power discharging Ability, improves energy density and the power density of battery；
3. in the present invention, hierarchical porous structure material with carbon element preparation technology is simple, and material source is extensive, and material is honest and clean Valency is easy to get；
4. grading-hole material with carbon element pore structure controllable, from micron to nanometer range and modification scope is wide and side Formula is various；
5. the advantage using sol-gal process to combine template is: utilize the three-dimensional that sol-gal process is formed Network structure, can form electric conductivity excellence and have micropore and less mesoporous material with carbon element, and logical Cross the mode adding hard template, the hole of larger aperture can be formed by template occupy-place effect, finally Form the material with carbon element of the mesoporous hierarchical porous structure to macropore scope, meet battery discharge procedure needs. Wherein, stencil-chosen is in extensive range, and template particle size range is optional from several nanometers to tens micron.
6. the advantage using sol-gal process to combine template and activation method is: utilize sol-gal process shape The three-dimensional net structure become, can form electric conductivity excellence and have micropore and less mesoporous carbon material Material, and by the way of slaine or metal hydroxide catalysis activation, can be to the hole of network structure Reaming further, forms the hole of larger aperture, ultimately forms the mesoporous grading-hole to macropore scope and ties The material with carbon element of structure, meets battery discharge procedure needs.Wherein can in catalytic activation method preparation process Being prone to realize the doping of metal/metal oxide, being applied to lithium-air battery can be to discharge and recharge simultaneously Journey plays catalytic action, reduces discharge and recharge polarization, improves energy content of battery efficiency.
Accompanying drawing explanation
Fig. 1 electrode process simulation drawing；
Fig. 2 be embodiment 1 use with sol-gal process combine classifying porous material with carbon element prepared by template with The contrast of commercialization carbon powder material surface topography, A be classifying porous material with carbon element (HPC), B be business Change KB600 carbon dust.
Detailed description of the invention
Embodiment 1
Use sol-gal process to combine template and prepare hierarchical porous structure porous carbon materials.By 6.16g isophthalic Diphenol is dissolved in 10mL deionized water, forms clear solution；Take 2g commercialization SiO2Colloidal sol adds to In above-mentioned clear solution, mixed dissolution uniformly obtains solution；Solution in above-mentioned stirring drips 9.08g Formalin, is uniformly mixed further, continuously stirred in 20 DEG C of environment, until reaction is formed Gel；Gel is transferred to vacuum drying oven and at 70 DEG C, is vacuum dried burin-in process 7d, after taking-up Attrition grinding, obtains pressed powder；By pressed powder at N2In 900 DEG C process 3h, N2Purging is extremely Room temperature, 1M HF solution eccysis SiO2, obtain hierarchical porous structure porous carbon materials.
Cathode material structure prepared by embodiment 1 has substantial amounts of 10 ~ 40 nano aperture deposition hole, tool Having the grading-hole in 1 ~ 2 micron order mass transfer hole, between mass transfer hole, mutual spacing is 2 microns, mass transfer hole Run through deposition hole；Material with carbon element is cellular network structure (scanning electron microscope result Fig. 2 shows).Separately Outer BET result shows, prepared material with carbon element has the pore size distribution of concentration, material with carbon element at about 25nm Total pore volume be 1.32cm3/ g, deposition hole accounts for the 75% of total hole pore volume.
Classifying porous material with carbon element prepared by embodiment 1 is used as lithium air battery positive electrode, its electrode load amount For 3mg/cm2 carbon, constitute at lithium trifluoromethanesulp,onylimide electrolytic salt and tetraethylene glycol dimethyl ether solvent Electrolyte under, room temperature is with 0.1mA/cm2Under electric current density, the O of 99.99% purity under 1atm2Bar Testing under part, first circle discharge capacity reaches 9000mAh/g.
Comparative example:
Using commercialization KB-600 carbon dust as lithium air battery positive electrode, under the same terms, its first circle is put Capacitance is only 3000mAh/g, the graded porous carbon material capacity relatively commercialization prepared by embodiment 1 Carbon dust KB-600 improves 200%, and discharge voltage plateau improves.
Embodiment 2
Use sol-gal process to combine template and prepare hierarchical porous structure porous carbon materials.By 6.16g isophthalic Diphenol is dissolved in 10mL deionized water, forms clear solution；Take 2g nickel hydroxide powder body and add to above-mentioned In clear solution, mixed dissolution uniformly obtains solution；Solution in above-mentioned stirring drips 9.08g first Aldehyde solution, is uniformly mixed further, continuously stirred in 20 DEG C of environment, until reaction is formed solidifying Glue；Gel is transferred to vacuum drying oven at 70 DEG C, is vacuum dried burin-in process 5d, powder after taking-up Breakdown mill, obtains pressed powder；By pressed powder 850 DEG C of process 3h, 1M HNO in Ar3Molten Liquid eccysis nickel oxide, after filtration drying, obtains described material with carbon element.
Embodiment 3
Use sol-gal process to combine template and prepare hierarchical porous structure porous carbon materials.By 6.16g isophthalic Diphenol is dissolved in 10mL deionized water, forms clear solution；Take on 4g aluminium sesquioxide powder body adds to Stating in clear solution, mixed dissolution uniformly obtains solution；Solution in above-mentioned stirring drips 9.08g Formalin, is uniformly mixed further, continuously stirred in 20 DEG C of environment, until reaction is formed Gel；Gel is transferred to vacuum drying oven and at 70 DEG C, is vacuum dried burin-in process 2d, after taking-up Attrition grinding, obtains pressed powder；By pressed powder at N2In 800 DEG C process 5h, 2M HCl molten Liquid eccysis aluminium sesquioxide, after filtration drying, obtains described material with carbon element.
Embodiment 4
Use sol-gal process to combine template and activation method prepares hierarchical porous structure porous carbon materials.Will 6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution；Take 0.29g six nitric hydrate Nickel adds in above-mentioned clear solution, and mixed dissolution uniformly obtains solution；Take 2g SiO2Colloidal sol adds to In above-mentioned clear solution；Solution in above-mentioned stirring drips 9.08g formalin, stirs further Mix homogeneously, continuously stirred in 20 DEG C of environment, until reaction forms gel；Gel is shifted the most pure virginity Empty drying baker is vacuum dried burin-in process 7d, attrition grinding after taking-up at 70 DEG C, obtains solid powder End；By pressed powder at N2In 900 DEG C of carbonization treatment 5h, wash with appropriate 1M HF and 2M nitric acid Except SiO2And nickel oxide, filtration drying, obtain described material with carbon element.
Embodiment 5
Use sol-gal process to combine template and activation method prepares hierarchical porous structure porous carbon materials.Will 6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution；Take the nitric acid of 0.358g 50% Manganese aqueous solution adds in above-mentioned clear solution, and mixed dissolution uniformly obtains solution；Take 1g calcium carbonate to add It is added in above-mentioned clear solution；Solution in above-mentioned stirring drips 9.08g formalin, further It is uniformly mixed, continuously stirred in 20 DEG C of environment, until reaction forms gel；Gel is shifted At 70 DEG C, burin-in process 4d it is vacuum dried to vacuum drying oven, attrition grinding after taking-up, consolidate Body powder；By pressed powder at N2In 800 DEG C of carbonization treatment 3h, wash oxidation off with appropriate 2M nitric acid Calcium and manganese oxide, filtration drying, obtain described material with carbon element.
Embodiment 6
Use sol-gal process to combine template and activation method prepares hierarchical porous structure porous carbon materials.Will 6.16g resorcinol is dissolved in 10mL deionized water, forms clear solution；Take 0.808g ferric nitrate to add In above-mentioned clear solution, mixed dissolution uniformly obtains solution；Take 1g calcium carbonate and add to above-mentioned transparent In solution；Solution in above-mentioned stirring drips 9.08g formalin, is uniformly mixed further, In 20 DEG C of environment continuously stirred, until reaction formed gel；Gel is transferred to vacuum drying oven exist It is vacuum dried burin-in process 3d, attrition grinding after taking-up at 70 DEG C, obtains pressed powder；By solid Powder is at N2In 800 DEG C of carbonization treatment 3h, wash ferrum oxide and calcium oxide, mistake off with appropriate 2M hydrochloric acid It is filtered dry dry, obtains described material with carbon element.

Claims (6)

1. lithium-air battery positive pole porous carbon materials, it is characterised in that: described material with carbon element has phase The most through hierarchical porous structure, grading-hole includes mass transfer hole and deposition hole, and deposition hole accounts for total hole pore volume 40～95%, the 4～55% of Zhan Zong hole, mass transfer hole pore volume, remaining for aperture less than the hole of 5nm, Deposition hole aperture is 5～90nm, and aperture, mass transfer hole is 0.1～6 μm, and between mass transfer hole, mutual spacing is 0.1～8 μm, mass transfer hole is interconnected by deposition hole, and total pore volume of material with carbon element is 1.32～5cm3/g；
Described material with carbon element uses sol-gal process to combine template or sol-gal process combine template and Activation method is prepared from；
Described material with carbon element uses sol-gal process to combine template and is prepared from according to the following procedure, between inciting somebody to action Benzodiazepines and template are scattered in solvent, then drip formalin, and at 30～80 DEG C, stirring mixing is all It is even until reaction forms gel；To be vacuum dried at aging 3～10 days at gel 60～100 DEG C Reason, attrition grinding after taking-up, obtain pressed powder；After carbonization under high temperature inert atmosphere with acid or Alkali removes template, through filtering, being dried, obtains porous carbon materials；
Described material with carbon element uses sol-gal process to combine template and activation method is prepared according to the following procedure and Become: resorcinol and template are scattered in solvent, then add slaine or metal hydroxides Continue to dissolve dispersion, then dripping formalin, being uniformly mixed until reacting at 30～80 DEG C Form gel；Process in aging 3～10 days, powder after taking-up will be vacuum dried at gel 60～100 DEG C Breakdown mill, obtains pressed powder；After carbonization under high temperature inert atmosphere with acid or alkali remove template and Slaine or metal hydroxides, through filtering, being dried, obtain porous carbon materials.
Porous carbon materials the most according to claim 1, it is characterised in that: described slaine or Metal hydroxides be containing Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V One or two or more kinds slaine or metal hydroxides；Slaine is the nitrate of metal, carbon Hydrochlorate, sulfate, acetate, halogenide, dinitroso diamine salts, acetylacetonate or One or two or more kinds in macro ring complex, wherein slaine or metal hydroxides and isophthalic two The mass percent scope of phenol is 1:100～3:20.
Porous carbon materials the most according to claim 1, it is characterised in that: described isophthalic two Phenol and solvent are in the ratio of 0.1～8ml solvent/1g resorcinol；Resorcinol with The mol ratio of formaldehyde is 1:1～5:1, and wherein the mass percent scope of template and resorcinol is 1:20～3:1, the mass concentration of described formalin is 30～40%, and the gas that carbonization is used is N2Or Ar, carburizing temperature scope is at 500～1700 DEG C, and carbonization time controls 1～10h.
Porous carbon materials the most according to claim 1, it is characterised in that: described template be zeolite, Magnesium oxide, magnesium acetate, magnesium gluconate, copper oxide, zinc oxide, ferrous oxide, three oxidations two Ferrum, calcium carbonate, magnesium carbonate, ferroso-ferric oxide, tin ash, silicon dioxide, aluminium oxide, oxidation Zirconium, molybdenum trioxide, Vanadium sesquioxide, nano titanium oxide powder, metallic nickel hydroxide, metal Iron hydroxide, the hydroxide of magnesium metal, polystyrene microsphere, polymethyl methacrylate are micro- One or more in ball, wherein template grain size scope is 5～8000nm.
Porous carbon materials the most according to claim 1, it is characterised in that: described solvent is second Alcohol, isopropanol, acetone, N-N dimethylformamide, N-N dimethyl second One or two or more kinds in amide or N-Methyl pyrrolidone.
Porous carbon materials the most according to claim 1, it is characterised in that:
The acid solution that described removing template and slaine or metal hydroxides use is 0.5～3M hydrochloric acid, sulphuric acid or nitric acid, aqueous slkali is 0.5～3M sodium hydroxide Solution.
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