CN103855409A - Electrode structure of lithium-air or lithium-oxygen battery as well as preparation and application of electrode structure - Google Patents

Electrode structure of lithium-air or lithium-oxygen battery as well as preparation and application of electrode structure Download PDF

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CN103855409A
CN103855409A CN201210514445.2A CN201210514445A CN103855409A CN 103855409 A CN103855409 A CN 103855409A CN 201210514445 A CN201210514445 A CN 201210514445A CN 103855409 A CN103855409 A CN 103855409A
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electrode
binding agent
lithium
solvent
macropore
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张华民
张益宁
李婧
王美日
聂红娇
王倩
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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 Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention relates to an electrode of a lithium-air or lithium-oxygen battery and a preparation method of the electrode. Macropore channels are uniformly distributed in the electrode, the macropore diameter is 0.5-5 microns, the macropore interval is 0.5-5 microns, and the macropore capacity is 0.5-5 cm<3>/g and accounts for 20%-50% of the total macropore capacity of the electrode; the macropore channels are staggered and communicated with one another through other pore channels, and the other pore channels are 1-500 nanometers or 5-20 microns in diameter; in the whole discharging process of the battery, the macropore channels formed by macro pores are not easily blocked by solid discharge products and can always serve as dissolution diffusion channels of reactant oxygen, so that the space utilization rate of the whole electrode can be greatly increased and the battery discharge capacity can be increased.

Description

A kind of lithium-air or electrode structure and preparation and application for lithium-aeration cell
Technical field
The present invention relates to a kind of lithium-air battery or lithium-aeration cell electrode field, particularly its positive pole.
Background technology
Lithium-air battery is a kind of taking lithium metal as negative pole, and air electrode is anodal rechargeable type secondary cell, and negative pole lithium theoretical specific capacity is up to 3,862mAh/g, and can directly from air, obtain as the oxygen of positive active material, therefore, lithium-air battery has high specific capacity and specific energy.Taking lithium as standard, its theoretical specific energy density can reach 11,140Wh/Kg, and taking full battery as standard, its actual specific energy density is expected to reach 10 times of existing lithium ion battery, has application prospect in civilian and military domain.Following business-like pure electric vehicle requires the specific energy of electrokinetic cell more than 500Wh/kg, one of scientist's electrokinetic cell using lithium-air battery as following electric automobile.
Fig. 1 by anodal in lithium-air battery discharge process and the schematic diagram of generation electrochemical reaction.As shown in the figure, moved by negative side and the lithium ion that arrives in electrode material surface and diffusion and the oxygen composition generation product Li arriving 2o 2or Li 2o.Solid Li 2o 2or Li 2o is insoluble to electrolyte solution, can not depart from material surface, thus in this deposition until stop up electrode duct, guiding discharge reaction terminating.
At present, the electrode material of lithium-air battery positive pole is mainly made up of material with carbon element, as powder carbon black (business-like XC-72, BP2000, KB300, KB600 etc.), also can sneak into catalyst (as manganese oxide, platinum, gold etc.), become electrode by binding agent (as PTFE or PVDF) preparation.Unique discharge process of lithium-air battery and product existence, determine the physical parameter of electrode material (being mainly material with carbon element), especially pore structure has material impact to battery performance, and material pore volume is more conducive to improve more greatly the deposition of solid product conventionally, and then improves discharge capacity.But the pore size of material is also key factor, result of study generally believes aperture too little (as being less than 5nm), and very easily, because the generation accumulation of tapping solid product causes duct to stop up, inner duct is not used; On the other hand, aperture excessive (as being greater than 100nm), due to oxidate for lithium poorly conductive, is accompanied by the accumulation of discharging product on hole wall, and electric discharge is more and more difficult to carry out, until reaction terminating causes the core of macropore to be not used.Therefore, from the angle of duct space availability ratio, aperture is excessive or be too smallly all not suitable for, and suitable pore diameter range is 20-70nm conventionally, and this is also that current material with carbon element is prepared the target on aperture control.
Conventional electrodes material with carbon element, is mainly " class ball-type " carbon powder material, mainly formed by two parts by the electrode duct of its structure, and the one, the hole on carbon granule surface, is mainly micropore; The 2nd,, the hole that intergranular space forms, its aperture mainly determines by granular size, because lithium-air battery mainly concentrates on below 50nm with carbon powder material particle size, therefore this part space, duct is less than 100nm conventionally, is not suitable for for building oxygen transfer passage.But, if in order to build mass transfer channel, increase carbon granule particle diameter, certainly will reduce so the pore volume of the suitable solid product deposition below the 100nm of aperture, and then reduce discharge capacity of the cell.
On the other hand, because the discharge process of lithium-air battery mainly carries out (being the interface forming between solid-electrode material and liquid-electrolyte solution) at solid-liquid two phase reaction interface, therefore, in order to obtain larger reaction interface and more unobstructed Li +conduction pathway, requires electrolyte solution higher to electrode infiltration degree.But because the dissolving diffusivity of oxygen in electrolyte solution is poor, if electrode is infiltrated by electrolyte completely, the resistance to mass tranfer of oxygen in electrode is larger, especially for electrode inner side (away from oxygen side).When battery discharge enters the second half, or discharge current density is when larger, and the mass transfer diffusion admittance of oxygen to electrode interior, due to the accumulation of discharging product, further stopped up in electrode outside, causes the reduction of electrode interior space availability ratio.Therefore, how in electrode space, effectively building oxygen mass transfer passage is the problem that electrode structural designs institute must consideration.
Summary of the invention
In order effectively to promote the conduction of oxygen in electrode, especially infiltrated " class water logging " electrode causing by liquid electrolyte for lithium-air battery, the present invention adopts the scheme contrary with conventional thinking, in electrode space, build macropore (being greater than 500nm), utilize the macropore that space availability ratio is lower in electrode, to build oxygen mass transfer passage, and then improve the utilance of whole electrode space.The space availability ratio of macropore is low, in discharge process, its central space can not be used for holding solid discharging product, and exactly because this reason, in whole discharge process, be difficult for stopping up by the duct of its structure, oxygen can be realized the transmission in whole electrode by the dissolving diffusion at this segment space, thereby improves electrode, the especially utilance in medial electrode space.
For achieving the above object, the specific embodiments that the present invention adopts is as follows.
Lithium-air battery electrode structure of the present invention, in its electrode space, is uniformly distributed macropore duct, and the aperture in described macropore duct is 0.5um-5um, pitch of holes 0.5um-5um, pore volume 0.5 ~ 5cm 3/ g, accounts for the 20%-50% of the total pore volume of electrode.Macropore duct connects by all the other ducts are staggered, and electrolyte solution infiltrates wherein, and the dissolving diffusion that oxygen leans against in electrolyte realizes the transmission in whole electrode space, and all the other ducts are that aperture is the duct that 1nm-500nm and aperture are 5um-20um.
Electrode is mainly by material with carbon element, or material with carbon element and catalyst component formation, and wherein the shared mass fraction of catalyst component is 3%-50%.Described material with carbon element mainly comprises powder type material with carbon element, and its particle diameter is 10nm-100nm, comprises KB600, BP2000, XC-72, Acetylene black, KB300, Alkaline-activated carbon, carbon aerogels, carbon xerogel etc.; Described catalyst component is one or more in the oxide of nitrogen, boron, metal X or metal X, and wherein X comprises one or more in Pt, Au, Pd, Mn, Zr, Co, Cr, Fe, Ni, Cu, Ir, Ru, Rh, Os, Ti, Sn, V, Mo, Se.
The structure in macropore mass transfer duct in electrode, several schemes below main employing, but be not limited to this.
1) using the complex of material with carbon element or material with carbon element and catalyst component as basis material, by itself and binding agent blend, in solvent, wherein binder content is 2-8%, and solid matter and solvent ratios are 1-10mg solid/ml solvent; Under 40-80 degree Celsius dry, after at 300-360 degree Celsius of N 2or heat treatment 1-4 hour under Ar inert atmosphere protection, form material aggregation;
By material aggregation again with binding agent blend in solvent, obtain electrode slurry, solid matter and solvent ratios are 10 ~ 200mg solid/ml solvent; The mode that adopts blade coating, spraying or roll-in, prepares pellet electrode, makes electrode in 40-80 degree Celsius of oven dry.Wherein, in electrode slurry, to account for the mass fraction of solid matter in electrode slurry be 10-30% to binding agent gross mass, and binding agent gross mass comprises the binding agent in material aggregation and the quality of the binding agent that again adds.
Thus, in electrode, there is the large aperture mass transfer channel being built by space between aggregation, and deposit duct by the solid product that in aggregation, between carbon powder particle, space builds.
Adopt PTFE as binding agent, solvent is alcohol, water or alcohol-water mixture, and in alcohol-water mixture, alcohol is 1:4-4:1 with water quality ratio; Wherein, alcohol comprises ethanol, isopropyl alcohol, ethylene glycol, one or more in glycerol etc.
While adopting PVDF as binding agent, solvent is 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethyl formamide, carbonic acid triethyl, dimethyl sulfoxide (DMSO), one or more in acetone.
2) by the complex of material with carbon element or material with carbon element and catalyst component and conductive carbon material mechanical mixture, obtain mixture; Wherein conductive carbon material is conductive black and/or the graphite of particle diameter 0.5-10um, and its mass fraction is 5-30%.Using this mixture as electrode material, binding agent, the selection of solvent and electrode production process are with method 1).
By above-mentioned preparation process, than conventional method (utilize binding agent, directly adopt material with carbon element to prepare electrode), in electrode macropore pore volume and in the total pore volume of electrode proportion all get a promotion.As:
KB600, adopts conventional method, and 0.5 ~ 5um aperture pore volume is about 0.3 ~ 0.5cm 3/ g, in total pore volume, proportion is about 10 ~ 20%, adopts method of the present invention, and 0.5 ~ 5um aperture pore volume is about 0.6 ~ 1.5cm 3/ g, in total pore volume, proportion is about 20 ~ 50%.
KB300, adopts conventional method, and 0.5 ~ 5um aperture pore volume is about 0.25 ~ 0.5cm 3/ g, in total pore volume, proportion is about 10 ~ 20%, adopts method of the present invention, and 0.5 ~ 5um aperture pore volume is about 0.5 ~ 1.2cm 3/ g, in total pore volume, proportion is about 20 ~ 40%.
XC-72, adopts conventional method, and 0.5 ~ 5um aperture pore volume is about 0.1 ~ 0.4cm 3/ g, in total pore volume, proportion is about 10 ~ 20%, adopts method of the present invention, and 0.5 ~ 5um aperture pore volume is about 0.5 ~ 1.0cm 3/ g, in total pore volume, proportion is about 20 ~ 30%.
Electrode prepared by said process strikes out definite shape, cold pressing and be integrated with nickel screen, itself and other battery component is assembled into lithium-air or lithium-oxygen monocell by known method, as adopt 2016 button cell shells as battery pack, successively by lithium sheet, electrolyte membrance material (as celgard2340), electrode is placed on battery cathode shell, on electrode, drip electrolyte solution (as 1M LiPF6 carbonic allyl ester solution) some, to electrode and film complete wetting, then electrodes anode cover (anode cover surface through hole, to transmit oxygen).On button cell sealing machine, said modules combined pressure is integrated, completes battery assembling.
Above-mentioned battery is placed in to dry pure oxygen environment (water content is lower than 1ppm), adopts known method, carry out the battery performance evaluation of material.Taking electrode carbon material as benchmark, under certain quality current density, as 30mA/g material with carbon element, 60mA/g material with carbon element, carries out constant-current discharge, and cut-ff voltage is 2V, obtains the specific discharge capacity of material.
Tool of the present invention has the following advantages:
1. adopt the treatment process of secondary granulation, utilize binding agent and through heat treatment, form the large particle diameter material aggregation being formed by carbon powder material, bonding state in aggregation between powder granule is constant, therefore, can between ensureing by particle, the discharging product of space structure pile up on the basis that duct pore volume is constant, build large mass transfer by the space between material aggregation.
2. adopt and add large particle diameter conductive carbon material, also can maintain bonding state between original powder granule constant, build mass transfer channel by the space between large particle diameter material with carbon element.
3. by adopting the present invention to prepare lithium-air battery or lithium-aeration cell positive pole, utilize the low and not susceptible to plugging feature of macropore space availability ratio, in electrode, build oxygen transmission network, can significantly improve electrode space utilance than traditional electrode structure, especially electrode interior space, thus discharge capacity of the cell significantly improved.
Brief description of the drawings
The anodal interfacial electrochemistry course of reaction of Fig. 1 simulation drawing;
Fig. 2 adopts the KB600 of structure optimization to prepare electrode front and back performance comparison.
Embodiment
Below by specific embodiment in detail the present invention is described in detail.
Embodiment 1
1) carbon powder particle KB600 and binding agent PTFE are uniformly mixed in water with mass ratio 95:5,5mg carbon dust/ml water, filtering drying, after in nitrogen atmosphere 340 degrees Celsius of heat treatments within 2 hours, obtain the carbon granule aggregation that particle diameter is larger, itself and PTFE are stirred in isopropyl alcohol with mass ratio 4:1,100mg solid/ml alcohol, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
Adopt 2016 button cell shells as battery pack, successively by lithium sheet, electrolyte membrance material celgard 2340, electrode is placed on battery cathode shell, drips electrolyte solution 1M LiPF on electrode 6carbonic allyl ester solution, to electrode and film complete wetting, electrodes anode cover (anode cover surface through hole, to transmit oxygen).On button cell sealing machine, said modules combined pressure is integrated, completes battery assembling.
2) prepare electrode with the KB600 without structure optimization:
Itself and PTFE are stirred in isopropyl alcohol with mass ratio 4:1,100mg solid/ml alcohol, sonic oscillation mixes, and obtains pasty mixture, adopts roll-in method to obtain electrode pancake, strikes out definite shape, colds pressing and is integrated with nickel screen, the dry electrode for preparing.
Adopt identical battery packaging technology, assembling monocell is to carry out performance evaluation.
3) above-mentioned battery is placed in to dry pure oxygen environment (water content is lower than 1ppm), adopts known method, carry out the battery performance evaluation of material.Taking electrode carbon material as benchmark, under the quality current density of 60mA/g material with carbon element, carry out constant-current discharge, cut-ff voltage is 2V, obtains the specific discharge capacity of material
Adopt nitrogen to carry out the test of physics adsorption desorption to electrode, or carry out mercury injection method test to characterize electrode aperture distribution, adopt scan electrode to characterize electrode pattern.
Than the prepared electrode of the KB600 without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 0.8um, and pitch of holes is 3 ~ 4um, and pore volume is by about 0.45cm 3/ g, is promoted to 0.7cm 3/ g, accounts for approximately 32% of the total pore volume of electrode, and discharge capacity of the cell improves 50%(60mA/g C), as shown in Figure 2.
Embodiment 2
1) carbon powder particle KB300 and binding agent PVDF are uniformly mixed in NMP with mass ratio 96:4,6mg carbon dust/mlNMP, naturally dry, in Ar gas atmosphere, 340 degrees Celsius of heat treatments obtain the carbon granule aggregation that particle diameter is larger for 3 hours, itself and PTFE are stirred in isopropyl alcohol with mass ratio 5:1,150mg solid/ml alcohol, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
2) prepare electrode with the KB300 without structure optimization:
Carbon powder particle KB300 and PTFE are stirred in isopropyl alcohol with mass ratio 5:1,150mg solid/ml alcohol, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
Adopt battery assembling and evaluation method that embodiment 1 is identical, evaluate battery performance, identical method characterizes electrode hole structure.
Than the prepared electrode of the KB300 without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 1.2um, pitch of holes 3 ~ 4um, and pore volume is by about 0.35cm 3/ g, is promoted to 0.65cm 3/ g, accounts for approximately 40% of the total pore volume of electrode, and discharge capacity of the cell improves 35%(60mA/g C).
Embodiment 3
1) carbon powder particle XC-72 and binding agent PTFE are uniformly mixed in ethanol with mass ratio 94:6,7mg carbon dust/ml ethanol, naturally dry, after in nitrogen atmosphere 340 degrees Celsius of heat treatments within 2 hours, obtain the carbon granule aggregation that particle diameter is larger, itself and PTFE are stirred in ethanol with mass ratio 4:1,180mg solid/ml alcohol, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
2) prepare electrode with the XC-72 without structure optimization:
Carbon powder particle XC-72 and PTFE are stirred in ethanol with mass ratio 4:1,180mg solid/ml alcohol, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
Adopt battery assembling and evaluation method that embodiment 1 is identical, evaluate battery performance, identical method characterizes electrode hole structure.
Than the prepared electrode of the XC-72 without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 1.5um, pitch of holes 2 ~ 3um, and pore volume is by about 0.24cm 3/ g, is promoted to 0.55cm 3/ g, accounts for approximately 37% of the total pore volume of electrode, and discharge capacity of the cell improves 25%.
Embodiment 4
1) carbon powder particle KB600 is mixed with mass ratio 5:1 with expanded graphite (caliber 3um), in isopropyl alcohol, stir with mass ratio 4:1 with binding agent PTFE again, 180mg solid/ml alcohol, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
2) prepare electrode with the KB600 without structure optimization:
Itself and PTFE are stirred in isopropyl alcohol with mass ratio 4:1,180mg solid/ml alcohol, sonic oscillation mixes, and obtains pasty mixture, adopts roll-in method to obtain electrode pancake, strikes out definite shape, colds pressing and is integrated with nickel screen, the dry electrode for preparing.
Adopt battery assembling and evaluation method that embodiment 1 is identical, evaluate battery performance, identical method characterizes electrode hole structure.
Than the prepared electrode of the KB600 without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 2um, pitch of holes 3 ~ 4um, and pore volume is by about 0.45cm 3/ g, is promoted to 0.65cm 3/ g, accounts for approximately 39% of the total pore volume of electrode, and discharge capacity of the cell improves 25%.
Embodiment 5
1) carbon powder particle KB300 is mixed with mass ratio 8:1 with conductive black (particle diameter 9um), in dimethylacetylamide, stir with mass ratio 3:1 with binding agent PVDF again, 150mg solid/ml solvent, sonic oscillation mixes, and obtains pasty mixture, adopts knife coating to obtain electrode pancake, 60 degrees Celsius of oven dry, strike out definite shape, cold pressing and be integrated with nickel screen, prepare electrode.
2) prepare electrode with the KB300 without structure optimization:
Carbon powder particle KB300 and binding agent PVDF are stirred in dimethylacetylamide with mass ratio 3:1,150mg solid/ml solvent, sonic oscillation mixes, obtain pasty mixture, adopt knife coating to obtain electrode pancake, 60 degrees Celsius of oven dry, strike out definite shape, cold pressing and be integrated with nickel screen, prepare electrode.
Adopt battery assembling and evaluation method that embodiment 1 is identical, evaluate battery performance, identical method characterizes electrode hole structure.
Than the prepared electrode of the KB300 without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 4um, pitch of holes 4-4.7um, and pore volume is by about 0.35cm 3/ g, is promoted to 0.76cm 3/ g, accounts for approximately 45% of the total pore volume of electrode, and discharge capacity of the cell improves 45%.
Embodiment 6
1) carbon powder particle XC-72 is mixed with mass ratio 3:1 with graphite powder (particle diameter 4um), in isopropyl alcohol, stir with mass ratio 4:1 with binding agent PTFE again, 180mg solid/ml solvent, sonic oscillation mixes, and obtains pasty mixture, adopts roll-in method to obtain electrode pancake, 60 degrees Celsius of oven dry, strike out definite shape, cold pressing and be integrated with nickel screen, prepare electrode.
2) prepare electrode with the XC-72 without structure optimization:
Carbon powder particle XC-72 and PTFE are stirred in isopropyl alcohol with mass ratio 4:1,180mg solid/ml solvent, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, 60 degrees Celsius of oven dry, strike out definite shape, cold pressing and be integrated with nickel screen, prepare electrode.
Adopt battery assembling and evaluation method that embodiment 1 is identical, evaluate battery performance, identical method characterizes electrode hole structure.
Than the prepared electrode of the XC-72 without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 3um, pitch of holes 2-3um, and pore volume is by about 0.24cm 3/ g, is promoted to 0.66cm 3/ g, accounts for approximately 35% of the total pore volume of electrode, and discharge capacity of the cell improves 28%.
Embodiment 7
1) carbon powder granulated alkali activated carbon (particle diameter 20nm) is uniformly mixed with mass ratio 97:3 with binding agent PTFE in water, 4mg carbon dust/ml water, naturally dry, after in nitrogen atmosphere 340 degrees Celsius of heat treatments within 2 hours, obtain the carbon granule aggregation that particle diameter is larger, itself and PTFE are stirred in water with mass ratio 4:1,180mg carbon dust/ml water, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
2) prepare electrode with the carbon powder granulated alkali activated carbon without structure optimization:
Carbon powder granulated alkali activated carbon and binding agent PTFE are uniformly mixed in water with mass ratio 4:1,180mg carbon dust/ml water, sonic oscillation mixes, obtain pasty mixture, adopt roll-in method to obtain electrode pancake, strike out definite shape, cold pressing and be integrated with nickel screen, the dry electrode for preparing.
Adopt battery assembling and evaluation method that embodiment 1 is identical, evaluate battery performance, identical method characterizes electrode hole structure.
Than the prepared electrode of the activated carbon without structure optimization, after optimizing, there is the macropore of 0.5 ~ 5um in material in electrode, its major bore is 0.9um, pitch of holes 2-3um, and pore volume is by about 0.24cm 3/ g, is promoted to 0.55cm 3/ g, accounts for approximately 29% of the total pore volume of electrode, and discharge capacity of the cell improves 25%.

Claims (9)

1. lithium-air or lithium-aeration cell electrode structure, is characterized in that: described electrode be the complex that forms using material with carbon element or material with carbon element and catalyst component as basis material, wherein catalyst component accounts for the 3-50% of basis material gross mass; In electrode, be evenly distributed with macropore pore passage structure, the aperture in described macropore duct is 0.5-5um, pitch of holes 0.5-5um, pore volume 0.5-5cm 3/ g, accounts for the 20-50% of the total pore volume of electrode; Macropore duct connects by all the other ducts are staggered, and all the other ducts are that aperture is the duct that 1nm-500nm and aperture are 5um-20um.
2. electrode structure according to claim 1, is characterized in that: described material with carbon element is one or more in KB600, KB300, BP2000, XC-72, Acetylene black, Alkaline-activated carbon, carbon aerogels or the carbon xerogel of 10-100nm of particle diameter.
3. electrode structure according to claim 1, it is characterized in that: described catalyst component is one or more in the oxide of nitrogen, boron, metal X or metal X, and wherein X comprises one or more in Pt, Au, Pd, Mn, Zr, Co, Cr, Fe, Ni, Cu, Ir, Ru, Rh, Os, Ti, Sn, V, Mo, Se.
4. electrode structure according to claim 1, is characterized in that: described electrode is made up of basis material and binding agent, and the shared mass fraction of binding agent is 10-30%.
5. a preparation method for electrode structure as claimed in claim 1, is characterized in that, described electrode is prepared from according to the following procedure,
1) by basis material and binding agent blend in solvent, that wherein binding agent accounts for basis material and binding agent gross mass mark is 2-8%, basis material is 1-10mg solid/ml solvent with solid matter and solvent ratios that binding agent forms; Under 40-80 degree Celsius dry, after at 300-360 degree Celsius of N 2or heat treatment 1-4 hour under Ar inert atmosphere protection, form material aggregation;
2) by material aggregation again with binding agent blend in solvent, obtain electrode slurry, solid matter and solvent ratios are 10 ~ 200mg solid/ml solvent; The mode that adopts blade coating, spraying or roll-in, prepares pellet electrode, makes electrode in 40-80 degree Celsius of oven dry;
In electrode slurry, to account for the mass fraction of solid matter in electrode slurry be 10-30% to binding agent gross mass, and binding agent gross mass comprises the binding agent in material aggregation and the quality of the binding agent that again adds.
6. a preparation method for electrode structure as claimed in claim 1, is characterized in that, described electrode also can be prepared from according to the following procedure,
1) by basis material and conductive carbon material mechanical mixture, obtain mixture; Wherein conductive carbon material is conductive black and/or the graphite of particle diameter 0.5-10um, and its mass fraction is 5-30%;
2) mixture and binding agent blend are obtained to electrode slurry in solvent, wherein to account for the mass fraction of solid matter in electrode slurry be 10-30% to binding agent quality, and solid matter and solvent ratios are 10-200mg solid/ml solvent; The mode that electrode slurry is adopted to blade coating, spraying or roll-in, makes pellet electrode, under 40-80 degree Celsius, dries and makes electrode.
7. according to electrode structure preparation method described in claim 5 or 6, it is characterized in that, described binding agent is PTFE or PVDF,
Adopt PTFE as binding agent, solvent is alcohol, water or alcohol-water mixture, and in alcohol-water mixture, alcohol is 1:4 ~ 4:1 with water quality ratio;
Or, adopt PVDF as binding agent, solvent is one or more in 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethyl formamide, carbonic acid triethyl, dimethyl sulfoxide (DMSO) or acetone.
8. the preparation method of electrode structure according to claim 7, is characterized in that: described alcohol comprises one or more in ethanol, isopropyl alcohol, ethylene glycol or glycerol.
9. an application for electrode structure described in claim 1,2,3 or 4, is characterized in that: described electrode is as lithium-sky or the anodal use of lithium-aeration cell.
CN201210514445.2A 2012-12-04 2012-12-04 Electrode structure of lithium-air or lithium-oxygen battery as well as preparation and application of electrode structure Pending CN103855409A (en)

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Application publication date: 20140611