CN104282918B - Lithium-air battery negative electrode, lithium-air battery and the method for preparing lithium-air battery electrode - Google Patents
Lithium-air battery negative electrode, lithium-air battery and the method for preparing lithium-air battery electrode Download PDFInfo
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- CN104282918B CN104282918B CN201310275235.7A CN201310275235A CN104282918B CN 104282918 B CN104282918 B CN 104282918B CN 201310275235 A CN201310275235 A CN 201310275235A CN 104282918 B CN104282918 B CN 104282918B
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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Abstract
The present invention relates to lithium-air battery negative electrode, lithium-air battery and the method for preparing lithium-air battery electrode, provide a kind of lithium-air battery negative electrode, the negative electrode includes the carbon material of modification, characterized in that, the carbon material surface of the modification includes at least one hetero atom or heteroatom group.
Description
Technical field
This invention relates generally to the carbon material for the modification that can be used as lithium-air battery cathode.Exemplary embodiment bag
Including surface modification has hetero atom or the carbon material based on heteroatomic group.Also disclose the lithium made from the carbon material of the present invention
Battery, and prepare the carbon material method of modification.
Background technology
In all electrochemical power sources that can be practical, lithium air has highest specific capacity and energy density.It is empty in lithium
In pneumoelectric pond, lithium metal is oxidized in anode, and the oxygen directly extracted in environment is reduced in negative electrode, thus in discharge process
Middle generation electric current.Typically, the performance of lithium-air battery is limited by the efficiency reacted at negative electrode.And in four kinds of main Types
Lithium-air battery in, i.e. proton inertia system lithium-air battery, water system lithium-air battery, water-proton inertia mixed stocker lithium air
In battery and solid-state system lithium-air battery, the improvement reacted at negative electrode is influenceed by different parameters.
Compared with other types of lithium-air battery, proton inertia system lithium-air battery has some advantages, including can be with
Recharge, can spontaneously form barrier layer between anode and electrolyte, the barrier layer can prevent lithium metal and electrolyte
Further reaction.Although the theoretical capacity of proton inertia system lithium-air battery is very big, actual capacity is produced at negative electrode
Raw Li2O and/or Li2O2Limited.These compounds generally can not be dissolved in organic electrolyte, therefore can be along negative electrode-electrolysis
Liquid interface and assemble in the hole of negative electrode.This aggregation can finally prevent oxygen from being diffused into electrolyte and carry out further electricity
Tank discharge, and also result in the volumetric expansion of battery.Pass through the Li of releasing2O and/or Li2O2Barrier air cathode can even be led
Tank discharge termination is sent a telegraph, is finally obtained than relatively low battery actual capacity.Therefore, suitable for proton inertia system lithium-air battery
Efficient negative electrode should have the Li that can store releasing2O and/or Li2O2So as to prevent oxygen enters the passage of electrolyte from being hindered
The mode of plug.A kind of and Li that can effectively improve electrode pair releasing2O and/or Li2O2The technology of storage capacity is exactly to adjust
The number amount and type of negative electrode mesopore.
Because the Li-O at negative electrode2Reaction is occurred over just in three phase region（It is electrolysed by electron-conducting support, lithium ion conducting
Liquid and oxygen composition）, therefore, a kind of efficient negative electrode needs the surface area with very big electrochemical reaction.In the negative electrode
Abundant three phase boundary is beneficial to obtain high discharge capacity.And the effect of carrier-electrolyte-oxygen three phase boundary in negative electrode
Rate can be assessed by determining electrolyte in the contact angle of carrier surface.In some cases, big contact angle is just anticipated
Taste big three phase region.
In many lithium-air batteries, cathode carrier includes nonpolar carbon material.Carbon is due to very big ratio surface
Product, high electrical conductivity and loose structure, commonly used to as catalyst（Such as the electrochemical catalyst of nano-scale）Load
Body.However, nonpolar carbon material tends to the lipophile with height.In the carbon materials of proton inertia system lithium-air battery
Low surface tension between material and most of organic and/or nonaqueous electrolytic solution causes negative electrode to have low contact angle.This will
Carbon material surface is caused to be flooded by the endoporus of electrolyte wetting and/or electrode by electrolyte.This can be ultimately resulted in at negative electrode
Oxygen spreads the quantity and/or quality of the three phase region of the electrolyte membrane with suitable thickness on the carrier with discharge and recharge reaction
Decline.
The carbon material surface that oleophobic and/or hydrophobic property are provided with by some chemical modifications has been used for improving often
The fuel cell and lithium-air battery carbon carrier of rule.
Think in traditional sense, as a kind of inert material, itself simply makees carbon material without electrochemical catalysis activity
Used for mechanical carrier, therefore, the catalytic action of negative electrode mostly come from be carried on metal in carbon material or on carbon material or
Metal oxide catalyst, it is generally only to be mixed by simple mechanical mixture mode.
The electrode of traditional carbon supported catalyst mainly includes the carbon surface covered by active catalyst sites（The carbon of catalysis
Surface）, and the carbon surface without active site（Non-catalytic carbon surface）.In discharge process, it is known that oxygen reduction
It can also occur in non-catalytic carbon surface, without the auxiliary by metal or metal oxide catalyst.Occur empty in lithium
Non-catalytic exoelectrical reaction in the non-catalytic carbon pores in pneumoelectric pond can cause than relatively low discharge voltage.In charging process,
Because the intimate contact being deposited between the discharging product and catalytic site in non-catalytic carbon pores lacks, meeting limits reactivity,
And it result in higher charging voltage or high overpotential.And thus caused overpotential be in lithium-air battery another is tight
The defects of weight.
In addition, the size of current of effective and acceptable lithium-air battery and the ratio catalytic surface of avtive spot accumulate
There is certain proportional relation to a certain extent with the decentralization of supported catalyst.Therefore, it is sought after preparing a kind of tool
There is the negative electrode of the catalytic site of high dispersive, the cell reaction of homogeneous catalysis can be provided.
The content of the invention
The present invention is related to the negative electrode of the carbon material for including modification for lithium-air battery, example in each embodiment
Such as include the carbon material of at least one hetero atom or heteroatom group.This carbon material can be by side chemically or physically
Method is modified, for example, chemical treatment, atmosphere processing or Plasma-Modified.
In one embodiment, the surface oxygen content of the carbon material after modification is at least about 2.5mol%, surface sulfur content
Less than about 0.2mol%, 15 °, and/or BET specific surface area are at least about with the angle of wetting containing salt and the electrolyte of organic solvent
It is at least about 40m2/g。
The carbon material is selected from carbon black, activated carbon, activated carbon, acetylene carbon black, CNT, carbon nanocoils, carbon fiber, carbon
Nanometer foam, carbon nano-fiber, charcoal, coke, mesoporous carbon, fibrous carbon, carbon gel, carbon foam, mesoporous carbon particulate, various forms
Graphite, including graphite particle, graphene, graphite alkene, pre-oxidize carbon, wooden activated carbon, and the combination of above-mentioned various materials.
Hetero atom or heteroatom group account for the about 0.5-30 weight % for the carbon material being modified, these hetero atoms or hetero atom
Group may be selected from H, B, P, O, N, S, F, Cl, Br, I, oxy radical, carbonyl, carboxyl, carboxylic acid anhydrides, phenolic hydroxyl group, lactone group, phenolic group,
Quinonyl, xanthyl, ether, acyl chloride, methyl ester, diazomethane group, hydroxy-acid group is peroxide-based, superoxides
Base, nitrogenous base, C=N, N-H, cyano group, halogeno-group, C-F, thionyl chloride, and combinations thereof.
The hetero atom or heteroatom group with physical absorption or can be chemically bound in the surface of carbon material.The hetero atom
Or heteroatom group can be included but is not limited to by any of chemical bonding in carbon material surface, the chemical bond,
Ionic bond, covalent bond, metallic bond, dipole-dipole interaction and hydrogen bond.It is various there is disclosed herein being modified for carbon material
Chemically and physically method, but these methods are exemplary, are not limited to that.
The lithium-air battery of the negative electrode material comprising the carbon material containing the modification is also disclosed, this kind of lithium-air battery is at least
Specific capacity with about 800mAh/g, and/or at least about 55% cycle efficieny.
More objects and advantages, which will be described in more detail below in part, to be illustrated, and a part will be obvious from the description
Ground is drawn, or is learned by putting into practice.Objects and advantages of the present invention will be by referring specifically in appended claims
Element gone out and combinations thereof is realized and obtained.
It is to be understood that foregoing general description and following detailed description are only exemplary, but do not limit required
Embodiment.
The accompanying drawing for being incorporated into and forming the part of this specification shows some embodiments of the present invention, with specification
With reference to explain the present invention principle.
Brief description of the drawings
Fig. 1 is the acetylene carbon black not being modified（AB）And pass through HNO3And H2O2The AB of modification Fourier transform infrared
Spectrum（FTIR）Figure, corresponding to embodiment 1-6.
Fig. 2 is the acetylene carbon black not being modified（AB）And pass through HNO3And H2O2The AB of modification X-ray diffraction（XRD）
Figure, corresponding to embodiment 1-6.
Fig. 3 is shown：A) unmodified AB, C) chemical modification in embodiment 1 AB, and E) chemistry is repaiied in embodiment 4
The AB of decorations SEM pictures；And B）Unmodified AB, D）The AB of chemical modification in embodiment 1, and F）It is chemical in embodiment 4
The AB of modification power dissipation X-ray spectrum（EDX）Figure.
Fig. 4 is the AB for the AB and chemical modification not being modified sulfur content and the atom % of oxygen element, is corresponded to
Embodiment 1-6.
Fig. 5 is the AB and electrolyte for the AB and chemical modification not being modified（1M LiPF in PC6）Between angle of wetting,
Corresponding to embodiment 1-6.
Fig. 6 A are the graph of pore diameter distribution that the AB for the AB and chemical modification not being modified is determined by nitrogen De contamination, corresponding
In embodiment 1-6.
Fig. 6 B are that aperture is distributed in 0 enlarged drawing for arriving 20nm in Fig. 6 A.
Fig. 7 is the BET specific surface area that the AB for the AB and chemical modification not being modified is determined by nitrogen De contamination, corresponding
In embodiment 1-6.
Fig. 8 A are the AB for the AB and chemical modification not being modified impedance spectras, corresponding to embodiment 1-6.
Fig. 8 B are the enlarged drawings of Fig. 8 A middle impedance spectrograms.
Fig. 9 is the AB for the AB and chemical modification not being modified electro-static charging and discharging curve first, corresponding to embodiment 1-
6。
Embodiment
Details involved in embodiments of the present invention will be specifically described below, some examples are in the accompanying drawings
Detailed elaboration is carried out.Generally speaking, the reference being previously mentioned in accompanying drawing will correspondence in the text, represent it is identical or
Similar part.
Involved lithium-air battery term or its other similar appellation in the present invention, mean a kind of electrochemistry electricity
Pond, comprising a lithium base electrode, i.e. lithium base anode, a kind of electrolyte and a kind of porous electrode, i.e., porous negative electrode.
Involved this term of electrolyte or its other similar appellation in the present invention, refer to that a kind of permission lithium ion passes
Defeated material.
This term of proton inertia system lithium-air battery involved in the present invention or its other similar appellation, refer to one kind
Containing organic and/or nonaqueous solvents and the liquid electrolyte of at least a kind of soluble or partly soluble salt lithium air electricity
Pond.
Negative electrode involved in the present invention, air electrode or other similar appellations, refer to discharging in lithium-air battery
Reduction reaction occurs in journey, the electrode of oxygen is produced in charging process.Cathode thickness is about 50-500 μm.
Involved hetero atom in the present invention, based on heteroatomic group, heteroatom group or other similar appellations, it is
Refer to a kind of atom or atomic radical and comprise at least a kind of non-carbon element.
Involved three phase region or other similar appellations, refer to a kind of solid-liquid-vapor interface, by being catalyzed in the present invention
Agent carrier, electrolyte and oxygen composition.Discharge and recharge reaction in lithium-air battery occurs on three phase region.
In various exemplary embodiments mentioned in the present invention, the moon of carbon material after modification in lithium-air battery
Catalyst and carrier are used as in extremely simultaneously.Carbon material is modified by chemistry and/or physical method to introduce in carbon material surface
Hetero atom and/or based on heteroatomic group, so as to improve the BET specific surface area of carbon material, improves the oleophobic performance of carbon material,
And/or reduce the content of sulphur or other unfavorable impurity at cathode surface.
The hetero atom or be based on that the raising of carbon material catalytic activity will be at least partly due on carbon material surface after modification
The introducing of heteroatomic group.By the hetero atom for modifying that carbon material obtains with catalytic activity or based on heteroatomic group
It is scattered with atomic level in carbon material.In specific embodiment, the scattered of this atomic level will modify
More dispersed active site is introduced in carbon material afterwards, particularly with using traditional mixed method by metal or
Metal oxide catalyst is dispersed on carbon material carrier and compared.In various embodiments, the BET ratios of the carbon material after modification
Surface area all increases, so as to store more Li2O and/or Li2O2.In addition, carbon material oleophobic property carries after modification
Height will cause the increase of the contact angle between electrolyte in lithium-air battery.
In some embodiments, electrolyte includes at least one organic solvent and at least one salt.Exemplary implementation
Mode includes at least one lithium salts.The nonrestrictive example of organic solvent includes polar solvent, such as propylene carbonate（“PC”）,
Ethylene carbonate（“EC”）, diethyl carbonate（“DEC”）, dimethyl carbonate（“DMC”）, 1,2- dimethoxy-ethane（“DME”）,
Methyl ethyl carbonate（“EMC”）, tetrahydrofuran（“THF”）, diethyl carbitol（" ethyl diglyme ", " EDG "）, four is sweet
Diethylene glycol dimethyl ether（" tetraethyleneglycol dimethyl ether ", " TEGDME "）, 1,2- diethoxyethane（“DEE”）, 1- tert-butoxy -2- ethoxies
Base ethane（“BEE”）, triglyme（" triglyme "）, DOX（“DOL”）, dimethyl sulfoxide
（“DMSO”）, tetramethylene sulfoxide（“TMSO”）, dipropyl carbonate（“DPC”）, CH3CN（" acetonitrile "）, tetramethylene sulfone（" ring
Fourth sulfone ", " TMS "）, gamma-butyrolacton（" γ-BL ", " GBL "）, 1-METHYLPYRROLIDONE（“NMP”）, 2- methyltetrahydrofurans
（“2-Me-THF”）, ionic liquid.
The nonrestrictive example of lithium salts includes LiPF6, LiBF4, LiBF3Cl, LiClO4, LiCF3SO3, lithium-bis-（Oxalic acid）
Borate（“Li-BOB”）, LiClO4, LiB (C2O4)2, and LiN (CF3SO2)2。
In an illustrative embodiments, electrolyte is included in the 1M LiPF in PC6Solution.
In various embodiments of the present invention, negative electrode includes porous material.Hole in porous cathode material allows oxygen to expand
Into/out lithium-air battery is dissipated, and stores and discharges Li2O and/or Li2O2, and also provided instead to be charged and discharged reaction
Answer site.
In some embodiments, negative electrode includes porous carbon materials.Carbon is conductive, and can have high surface
Product.
In some embodiments, carbon material is selected from amorphous carbon, polycrystalline carbon and crystalline carbon, such as acetylene carbon black, carbon black,
Activated carbon, charcoal, coke, mesoporous carbon, fibrous carbon, carbon gel, carbon foam, mesoporous carbon particulate, CNT, carbon nanocoils, carbon
Fiber, graphite, graphene and graphite alkene.
In order to assign the characteristic desired by carbon material, various embodiments include modifying by chemistry and/or physical method
Carbon.The modification of some embodiments includes chemistry and/or the physical treatment of at least one type.In various embodiments
In, modification includes the combination of the chemistry and/or physical method of two or more.In some embodiments, modified
Journey is situ process.Modification make it that following at least one performance of cathode material is improved：Li2O and/or Li2O2Deposit
Store up capacity, the contact angle with electrolyte, the distribution of active site, and/or the reduction of sulphur or other undesirable impurity.
The non-limitative example of physical method includes atmospheric treatment or Plasma-Modified.In some embodiments, gas
Body is selected from F2, Cl2, N2, NH3, CO2, O2, O3, and combinations thereof.
The non-limitative example of chemical method includes backflow, and/or is stirred with liquid chemical.In some embodiments
In, chemicals is selected from strong acid or the chemicals of strong oxidizing property, including F2, Cl2, Br2, I2, N2, nitric acid, hydrochloric acid, perchloric acid,
H3PO3, HF, hydrogen peroxide, sulfuric acid, HClO, NO2, chromium trioxide, manganese dioxide, VO3, thionyl chloride, SOCl2,（NH4）2S2O8,
Sodium hypochlorite, NaClO2, ammonia, cerous nitrate（IV）Ammonium, Isosorbide-5-Nitrae-benzoquinones, benzoyl peroxide, nitrosobenzene, potassium chlorate, permanganic acid
Potassium, potassium bromate, potassium bichromate, KNO3, and combinations thereof；And complex ion and metal with sufficiently high oxidizing potential
Cation, including Ag+, PdCl42-, Fe3+, and combinations thereof.
The effect of carbon modification can be controlled by manipulating the key parameter in modification, such as used chemicals
Type, the dosage for using chemicals, the concentration of chemicals, gas flow, modification temperature, modification time and their group
Close.In some embodiments, when the concentration of longer modification time, higher temperature and/or used chemicals is higher,
Obtain larger BET specific surface area, larger pore volume, more hetero atoms and/or based on heteroatomic group on carbon surface,
And/or less impurity.
In some embodiments, the modification time is at least 0.1 hour, at least 1 hour, at least 2 hours, at least 5 hours,
At least 7 hours, at least 10 hours, at least 12 hours, at least 24 hours, at least 48 hours, at least 72 hours, at least 100 hours,
Or at least 1000 hours.In the various exemplary embodiments, it is about 1 hour to modify the time.
In some embodiments, modification temperature is at least 273K, at least 290K, at least 350K, at least 500K, extremely
When being 800K, at least 1000K less, or at least 1500K.In the various exemplary embodiments, the temperature range of modification is from about
273K to about 1773K.
In some embodiments, the concentration for the chemical solution that modification uses is：At least 1wt.%, at least
5wt.%, at least 10wt.%, at least 20wt.%, at least 50wt.%, at least 75wt.%, or at least 95wt.%.Show various
In example property embodiment, the concentration range of chemical solution is from about 1wt.% to about 100wt.%, about 2wt.% to about 95wt.%,
About 3wt.% to about 75wt.%, about 4%wt.% are to about 50wt.%, or about 5wt.% to about 30wt.%.
Various embodiments are modified including the use of the method for chemicals, so as to be established between carbon material and chemicals good
Good contact.In some embodiments, chemicals is a kind of liquid, and is stirred in surface modification process and keep persistently stirring
Mix.In an illustrative embodiments, the hole of carbon material can be penetrated to ensure liquid chemical using vacuum, and assign whole
Individual carbon material is uniformly modified.
In some embodiments, the chemical solution and the volume ratio of carbon material used in modification is 0.001-
1000.In the various exemplary embodiments, the volume range of chemical solution and carbon material is about 0.001-1000, about
0.01-500, about 0.1-200, about 1-100, or about 5-50.
Various embodiments are including the use of the method for gas to reach uniform modification.In some embodiments, carbon materials
Material is completely dried under vacuo before modification, and the surface of carbon material can be reached to ensure to modify gas molecule.In an example
In property embodiment, carbon material is maintained at a soft fluffy state, to ensure uniformly to modify.
In various embodiments, modification is in the surface introducing hetero-atoms of the carbon material of modification and/or based on miscellaneous original
The group of son.Heteroatomic nonrestrictive example includes：H, B, P, O, N, S, F, Cl, Br, I, and combinations thereof.It is based on
The nonrestrictive example of heteroatomic group includes oxy radical, such as carboxyl, carbonyl, carboxylic acid anhydrides, phenolic hydroxyl group group, lactone
Base, phenolic group, quinonyl, xanthyl, ether, acyl chloride, methyl ester, diazomethane base, carboxylic acid group, peroxide group and super
Oxide groups；Nitrogen-containing group, for example, C=N, N-H and cyano group；And halohydrocarbyl, such as C-F, acyl chloride and sulfurous
Acyl chlorides.
It is superoxide ion based on heteroatomic group in an illustrative embodiments, O2 -。
In some embodiments, the hetero atom of the carbon material surface after modification and/or the amount based on heteroatomic group
Scope be 0.01-99.9%（Mole）, 0.1-90%（Mole）, 0.2-80%（Mole）, 0.3-50%（Mole）, 0.4-
40%（Mole）, or 0.5-30%（Mole）.
In some embodiments, the amount of the oxygen atom on the surface of the carbon material of modification is at least about 0.01%（Rub
You）, about 0.1%（Mole）, about 1%（Mole）, about 10%（Mole）, about 20%（Mole）, about 50%（Mole）, about 70%
（Mole）, about 90 moles of %, or about 99.9%（Mole）.In an illustrative embodiments, the surface of the carbon material of modification
On the amount of oxygen atom be at least about 0.15%（Mole）.In some embodiments, compared with unmodified carbon material, modification
The incrementss of oxygen atom on the surface of carbon material at least about 1%, about 5%, about 10%, about 20%, about 50%, about 70% afterwards,
About 90%, or about 99%.In some exemplary embodiments, compared with unmodified carbon material, the carbon material of modification
The amount increase at least about 10% of surface oxygen atoms.
Hetero atom on carbon surface and/or the amount based on heteroatomic group can be by using different chemical methodes
And/or physical method is adjusted.In chemistry and/or physical treatment method, hetero atom and/or can based on heteroatomic group
With（i）Physical absorption on the surface of carbon or（ii）Chemically reacted with carbon surface.
Oxygen reduction reaction in lithium-air battery discharge process（“ORR”）With the oxygen evolution reaction in charging process
（“OER”）During, the increase of the catalytic activity of the carbon material of modification can be attributed to surface hetero atom or based on hetero atom
Group., can be by changing on carbon material surface as the catalytic activity of the carbon material of the modification of the negative electrode of lithium-air battery
Hetero atom and/or type and quantity based on heteroatomic group be adjusted.
The catalytic activity allows the carbon material of modification while as the carrier and catalyst in the negative electrode of lithium-air battery.It is logical
Cross catalysis hetero atom that modification obtains and/or scattered on the carbon carrier with atomic level based on heteroatomic group.At certain
In a little embodiments, this may result in than on traditional carbon carrier-more uniform carbon material of metallic catalyst cathode material
The distribution of catalytic site.Being uniformly distributed for reaction site can make cathode material more efficient.
In various embodiments, the modification of carbon material adds its BET specific surface area and pore volume, is put so as to improve
Electric product Li2O and/or Li2O2Deposition and memory capacity.This helps to realize the lithium air electricity with high actual discharge capacity
Pond.
In some embodiments, compared with unmodified carbon material, the BET surface area of the carbon material after modification increases to
Few about 1%, about 5%, about 10%, about 20%, about 50%, about 70%, about 90%, or about 99%.In some exemplary implementations
In mode, the BET surface area of the carbon material of modification at least increases about 10% than unmodified carbon material.In some exemplary realities
To apply in mode, the BET specific surface area of the carbon material of modification is below about 200 meters squared per grams, and/or below about 100 meters squared per grams.
In some embodiments, by adjusting chemistry and/or physical modification method species, can adjust in modification
The type and/or size in hole formed, modification, and/or activation.Pore-size distribution, such as micropore, mesoporous and macropore, also may be used
To influence the performance of cathode material.As described herein, micropore have less than about 2nm aperture, mesoporous aperture be about 2nm- about
Between 50nm, the aperture of macropore is greater than about 50nm.
In various embodiments, modification adds the mesoporous quantity and/or ratio in carbon material.In various realities
Apply in mode, modification adds the quantity and/or ratio of the micropore in carbon material.In some illustrative embodiments,
The pore-size distribution of the carbon material of modification is：Mesoporous, and the about 0-70% micropore of at least about 30% macropore, about 0-70%.
In various embodiments, macropore accounts for about 30%, 40%, 50%, 60%, 70%, 80%, or about 90% total pore volume.In various realities
Apply in mode, it is mesoporous account for about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60% or 70% total pore volume.In various embodiments
In, micropore accounts for about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60% or 70% total pore volume.
In some embodiments, compared with unmodified carbon material, the specific capacity increase of the carbon material after modification is at least
About 5%, about 10%, about 20%, about 50%, about 75%, about 100%, about 150%, about 200%, about 500%, about 750%, or
About 1000%.In some exemplary embodiments, compared to unmodified carbon material, the specific capacity of the carbon material after modification increases
Add at least about 20%.In some exemplary embodiments, the specific capacity of the carbon material after modification is at least about 900mAh/g,
1000mAh/g, 1500mAh/g, and/or 2000mAh/g.
In some embodiments, compared to unmodified carbon material, the cycle efficieny increase of the carbon material of modification is at least about
5%, about 10%, about 15%, about 20%, about 50%, about 75%, about 100%, about 150%, about 200%, about 500%, about
750%, or about 1000%.In some exemplary embodiments, compared with unmodified carbon material, following for carbon material is modified
Ring efficiency increase at least about 15%.
In some exemplary embodiments, compared with unmodified carbon material, the Li of the carbon material of modification2O and/or
Li2O2Specific capacity at least about 60%, 65%, 70%, 75%, and/or 80%.
In some embodiments, modification adds the polarity and oleophobic performance of carbon surface.It is organic that this can play increase
The effect of angle of wetting of the electrolyte on the carbon material of modification, then increase the quantity of three phase region in discharge and recharge reaction at negative electrode
And/or quality.The negative electrode of carbon material including modification can provide the specific capacity higher than traditional carbon support material and circulation
Efficiency, this is due to the improvement of the angle of wetting between the carbon material of modification and electrolyte.
In an exemplary embodiment, angle of wetting of the electrolyte on the carbon surface of modification is about between 10-90 °.
In some embodiments, chemistry and/or physical modification process can be reduced undesirable miscellaneous on carbon material surface
Matter.For example, in various embodiments, after modification, sulphur on carbon material surface and/or grey amount be reduced.
In some embodiments, after modification, the amount of the sulphur atom on carbon material surface is below about 1%（Mole）, about
0.7%（Mole）, about 0.5%（Mole）, about 0.2%（Mole）, about 0.1%（Mole）, about 0.07%（Mole）, about 0.05%
（Mole）, about 0.02 mole of %, or about 0.01%（Mole）.In some exemplary embodiments, after modification, carbon material
The amount of sulphur atom on surface is below about 0.2%（Mole）.In some embodiments, compared to unmodified carbon material, modification
Carbon material surface on sulphur atom amount reduce at least about 5%（Mole）, about 10%（Mole）, about 20%（Mole）, about
30%（Mole）, about 40%（Mole）, about 50 moles of %, about 75%（Mole）, about 90%（Mole）, or about 100%（Mole）.
In some exemplary embodiments, the amount of the sulphur atom on the carbon material surface of modification is reduced compared to unmodified carbon material
At least about 40%（Mole）.
In various embodiments, modification does not dramatically increase the contact resistance or transfer resistance of carbon material.Therefore,
Modification not adversely affects for the electrical property of the carbon material.
In an exemplary embodiment, it is chemically modified increase carbon material BET with 20% hydrogen peroxide and compares table
Area, pore volume and mesoporous ratio, reduce the sulphur impurity on carbon material surface and assign carbon material surface oxy radical.
Element described herein and limiting factor, Yi Jiren can be included according to the composition of present invention and method
What he or optional be described herein or otherwise known or for composition in the art, part or limit
System, is made up of, or be made up of substantially them them.
The embodiment of following dispersion liquid and composition be for illustrate according to the present invention exemplary embodiment, without
Therefore limitation scope.Percentage is provided based on weight.
Embodiment
Embodiment 1
Acetylene carbon black（AB）Powder 0.5g is immersed in 20% HNO3Beaker in and magnetic agitation 6 hours.Modification
It is washed with deionized after AB filterings, and is dried in vacuo 12 hours under 100 °C.By regarding the AB of modification as carrier and gathering
Vinylidene fluoride（PVDF）Slurry is blended together coated in preparing air electrode on cathode current collector as adhesive.The AB of modification and
PVDF weight ratio is 11:15.Air electrode is pressed into thickness as 150 ± 2 μm.Unmodified AB compares as " preceding ".As a result
As shown in table 1.
Embodiment 2
Acetylene carbon black（AB）Powder 0.5g is immersed in 20%HNO3Beaker in and magnetic agitation 24 hours.Modification
It is washed with deionized after AB filterings, and is dried in vacuo 12 hours under 100 °C.By regarding the AB of modification as carrier and gathering
Vinylidene fluoride（PVDF）Slurry is blended together coated in preparing air electrode on cathode current collector as adhesive.The AB of modification and
PVDF weight ratio is 11:15.Air electrode is pressed into thickness as 150 ± 2 μm.Unmodified AB compares as " preceding ".As a result
As shown in table 1.
Embodiment 3
Acetylene carbon black（AB）Powder 0.5g is immersed in 20% HNO3Beaker in and magnetic agitation 72 hours.Modification
AB filterings after be washed with deionized, and be dried in vacuo 12 hours under 100 °C.By by the AB of modification be used as conductive agent with
And polyvinylidene fluoride（PVDF）Slurry is blended together coated in preparing air electrode on cathode current collector as adhesive.The AB of modification
Weight ratio with PVDF is 11:15.Air electrode is pressed into thickness as 150 ± 2 μm.Unmodified AB compares as " preceding ".Knot
Fruit is as shown in table 1.
Embodiment 4
Acetylene carbon black（AB）Powder 0.5g is immersed in 20% H2O2Beaker in and magnetic agitation 6 hours.Modification
It is washed with deionized after AB filterings, and is dried in vacuo 12 hours under 100 °C.By regarding the AB of modification as carrier and gathering
Vinylidene fluoride（PVDF）Slurry is blended together coated in preparing air electrode on cathode current collector as adhesive.The AB of modification and
PVDF weight ratio is 11:15.Air electrode is pressed into thickness as 150 ± 2 μm.Unmodified AB compares as " preceding ".As a result
As shown in table 1.
Embodiment 5
Acetylene carbon black（AB）Powder 0.5g is immersed in 20%H2O2Beaker in and magnetic agitation 24 hours.The AB of modification
It is washed with deionized after filtering, and is dried in vacuo 12 hours under 100 °C.By regarding the AB of modification as carrier and gathering inclined
Difluoroethylene（PVDF）Slurry is blended together coated in preparing air electrode on cathode current collector as adhesive.The AB and PVDF of modification
Weight ratio be 11:15.Air electrode is pressed into thickness as 150 ± 2 μm.Unmodified AB compares as " preceding ".As a result such as table 1
It is shown.
Embodiment 6
Acetylene carbon black（AB）Powder 0.5g is immersed in 20%H2O2Beaker in and magnetic agitation 72 hours.The AB of modification
It is washed with deionized after filtering, and is dried in vacuo 12 hours under 100 °C.By regarding the AB of modification as carrier and gathering inclined
Difluoroethylene（PVDF）Slurry is blended together coated in preparing air electrode on cathode current collector as adhesive.The AB and PVDF of modification
Weight ratio be 11:15.Air electrode is pressed into thickness as 150 ± 2 μm.The AB of modification compares as " preceding ".As a result such as the institute of table 1
Show.
It will be assembled into these embodiments 1-6 by the unmodified AB and AB of the chemical modification negative electrodes prepared by symmetrical negative electrode
Composition, and by2025 button cells that 2400 barrier films (Celgard, LLC, Charlotte, NC) separate, are handed over
Flow impedance is tested.
The negative electrode prepared in embodiment 1-6 by the unmodified AB and AB of chemical modification is used in lithium-air battery.With
It is to be based on one kind in the lithium-air battery that electro-static charging and discharging is testedBattery design, by lithium metal anode（Diameter
14mm, thickness 0.25mm）, electrolyte（(1M LiPF6It is dissolved in PC, Jiangsu Cathay Huarong Chemical Group）,2400 every
Film and the porous cathode prepared are formed.Battery assembles in the glove box of oxygen and water content less than 1ppm.Except
For porous cathode to be exposed to the stainless (steel) wire window of electrolyte-saturation oxygen atmosphere, battery tool air-tightness.Battery is 1atm's
Worked in the container of electrolyte-saturation oxygen.
As shown in table 1, HNO in embodiment 1-63And H2O2The AB air electrodes of chemical modification are than unmodified AB air electricity
Pole shows significantly higher specific capacity and cycle efficieny.
Table 1
Fig. 1 shows the Fourier transform infrared spectroscopy of the AB through chemical modification in unmodified AB and embodiment 1-6
（FTIR）.Embodiment 1-6 FTIR composes the surface polarity oxy radical that more unmodified AB samples show enhancing.According to Fig. 1
In correspond to C=O stretchings (ν C=O), C-O stretchings (ν C-O), the peak confirmation of O-H stretchings (ν O-H) and O-H bendings (δ O-H) can be
By HNO3And H2O2The presence of C=O, C-O, and O-H group is confirmed in the AB of modification.In addition, O2 -Also can be in H2O2In the AB of modification
It was found that as shown in corresponding to the peak of O-O vibrations (ν O-O) in Fig. 1.For given method of modifying, the increase for modifying the time can
Cause the obvious increase of polarity oxy radical amount.
Fig. 2 shows the X-ray diffraction of the AB through chemical modification in unmodified AB and embodiment 1-6（XRD）Figure.Implement
Example 1-6 XRD shows the raising of graphite crystallization, and this is advantageous to occur in the charge discharge reaction at negative electrode
Electronics conducts.
Fig. 3 is shown：A）Unmodified AB, C）The AB and E of chemical modification in embodiment 1）Chemical modification in embodiment 4
AB stereoscan photograph（SEM）, and B）Unmodified AB, D）The AB and F of chemical modification in embodiment 1）Change in embodiment 4
Learn the AB of modification X-ray energy dispersion（EDX）Spectrum.Fig. 3 A, 3C and 3E SEM photograph show the AB for unmodified sample
And the AB of the chemical modification of embodiment 1 and 4 is uniformly distributed.The granularity of all AB samples is about 100nm.Shown in Fig. 3 B
EDX spectrums show only three kinds of elements（C, O, S）It is present in untreated AB.Fig. 3 D and 3F are shown：D）6 hours HNO3And F）6
Hour H2O2In chemical modification do not change element type in AB samples.However, the distribution of weight of three kinds of elements is repaiied in chemistry
Changed after decorations, Fig. 3 D and 3F show the reduction relative to Fig. 3 B sulfur content and the increase of oxygen content.
Fig. 4 shows in unmodified AB and embodiment 1-6 the atomic percent of sulphur and oxygen in the AB through chemical modification.Phase
For unmodified AB, HNO is used3And H2O2The AB of chemical modification shows the reduction of sulfur content and the increase of oxygen content.For
Given method of modifying, substantially reducing and surface oxygen atoms content for surface sulphur atom content can be caused by modifying the increase of time
Dramatically increase.Fig. 4 is further demonstrated that, in the case where identical modifies time and concentration, H2O2In the AB carbon surface oxygen atoms of increase modification
Aspect is compared with HNO3More effectively.
Fig. 5 shows 1M LiPF6PC electrolyte is dissolved in repair on unmodified AB and in embodiment 1-6 through chemistry
Angle of wetting between on the AB of decorations.Flat electrolysis drop on surface shows less angle of wetting, and formed on surface it is spherical more
Obvious drop then shows bigger angle of wetting.Use HNO3And H2O2The AB of chemical modification has bigger relative to unmodified AB
Angle of wetting.For given method of modifying, the increase of angle of wetting can be caused by modifying the increase of time.Fig. 5 further demonstrates that,
Identical is modified under time and concentration, H2O2Relative to HNO3Can more effectively it increase between electrolyte and the AB carbon surfaces of modification
Angle of wetting.
Fig. 6 A show the AB through chemical modification in the unmodified AB and embodiment 1-6 measured by nitrogen adsorption desorption method
Pore-size distribution.Fig. 6 B are the enlarged drawings according to the pore-size distribution that Fig. 6 A aperture is 0-20nm.As shown in figures 6 a-6b, with 20%
HNO3The Ab of modification has the micropore of the about 3nm diameters of greater proportion, and uses 20%H2O2The AB of modification 7nm, 10nm and 50nm
The mesoporous ratio of diameter has increase.For given method of modifying, modify the increase of time can cause hole obvious increase and
Boring ratio example with certain size range significantly increases.
Fig. 7 shows that being inhaled with nitrogen of the AB through chemical modification in unmodified AB and embodiment 1-6-desorption method measures
BET surface area.Use HNO3And H2O2The AB that the AB of chemical modification is more unmodified has bigger BET specific surface area.For what is given
Method of modifying, the obvious increase of BET specific surface area can be caused by modifying the increase of time.Fig. 7 further shows to modify in identical
In the case of time and concentration, HNO3Compared with H in terms of the BET specific surface area of the AB carbon of increase modification2O2More effectively.
Fig. 8 A show the AC impedance figure of the AB of chemical modification in unmodified AB and embodiment 1-6.Fig. 8 B are bases
Fig. 8 A AC impedance figure enlarged drawing.Use HNO3And H2O2The AB of chemical modification has similar contact resistance to unmodified AB
And transfer resistance.This shows that AB modification does not have anticathode electrical property and had a negative impact.The phase shown in embodiment 1-6
Slight increase for unmodified AB contact resistance may be due to polarity oxy radical and low pole on the AB surfaces through modification
Unfavorable contact between property organic electrolyte causes.
Fig. 9 shows that the static discharge first of the AB through chemical modification and charging are bent in unmodified AB and embodiment 1-6
Line.Use HNO3And H2O2The AB of chemical modification has the bigger specific capacities and cycle efficieny of more unmodified AB.Repaiied for given
Decorations method, the obvious increase of specific capacity and cycle efficieny can be caused by modifying the increase of time.Fig. 9 show further to be repaiied identical
In the case of adoring time and concentration, H2O2Compare HNO in terms of increase specific capacity and cycle efficieny3More effectively.
Embodiment 7
Activated carbon is flowed back 12 hours with 2M HCl solution, then washed 6 hours with distilled water backflow, with the steaming of boiling
It is 5.5 that distilled water, which is washed to the pH of washing lotion, to modify.As a result it is as shown in table 2.
Embodiment 8
Activated carbon is washed 12 hours with 2M HCl solution backflow, it is therefore an objective to sulphur removal and some dusts are gone, then with distillation
Water backflow washing 6 hours.Then it is dried overnight under 383K.Carbon 5%O2–95%N2Gaseous mixture is modified 10 hours in 723K and is used in combination
The pH of the distillation water washing of boiling to washing lotion is 5.5.As a result it is as shown in table 2.
Embodiment 9
Activated carbon is washed 12 hours with 2M HCl solution backflow, it is therefore an objective to sulphur removal and some dusts are gone, then with distillation
Water backflow washing 6 hours.Then it is dried overnight under 383K.Carbon directly uses 5M HNO3Solution modify 3 hours and with seethe with excitement steaming
It is 5.5 that distilled water, which is washed to the pH of washing lotion,.As a result it is as shown in table 2.
Embodiment 10
The corona treatment of carbon black produces plasma using radio frequency and carried out.For produce frequency 13.56MHz grade from
Power needed for daughter is 60W.The gas phase composition of plasma is the CF of 10% volume4-He。10%CF4- He gases are subsequently introduced into
Cavity, while hydrocarbon black powder is by RF Plasma-Modifieds 60 minutes that power is 100W.The volume flow rate of gas is 24sccm.Knot
Fruit is as shown in table 2.
Embodiment 11
The corona treatment modification of carbon fiber is wireless for 13.56MHz by using power 60W power supply tranmitting frequency
Electricity, to produce plasma to realize.The gas phase composition of plasma is the CF of 10% volume4-He.By 10% CF4- He is introduced
To cavity, carbon black powder plasma is modified 60 minutes by power 100W radio frequency plasma.The volume flow rate of gas is
40sccm.The results are shown in table 2.
Embodiment 12
30 grams of Vulcan XC-72R carbon is added in 60 milliliters of 60% hydrogenperoxide steam generator.Obtained suspension stirs
After mixing 48 hours, the solid of recovery, and dried 24 hours at 120 DEG C.The results are shown in table 2.
Embodiment 13
Carbon is in ammonia（Flow velocity is 200 cc/mins）In with 3 DEG C/min of speed be heated to 800 °C, and at 800 °C
Insulation 3 hours, then proceedes to be cooled to room temperature in ammonia.Carbon material is extracted with water, and removes the ammonia of residual and any water solubility
Material.The sample of modification is dried under the conditions of 75 DEG C of vacuum, and the results are shown in table 2.
Embodiment 14
Carbon flows back 48 hours first in 7.5M nitric acid and is oxidized.Then, the oxidized carbon obtained is in ammonia（Flow velocity is
200 cc/mins）In with 3 DEG C/min of speed be heated to 800 °C, and be incubated 3 hours at 800 °C, then proceed to
Room temperature is cooled in ammonia.Carbon is extracted with water, and removes the ammonia of residual and any water-soluble material.The sample of modification is in 75 DEG C of vacuum
Under the conditions of dry, the results are shown in table 2.
Embodiment 15
Wood activated charcoal uses N2Modify to introduce nitrogen groups.Carbon is in N2It is heated in atmosphere using speed as 10 DEG C/min
450 DEG C, and in this temperature 0.5 hour.Carbon after modification is washed with water, to remove any excessive catabolite.It is tied
Fruit is shown in Table 2.
Embodiment 16
In this embodiment, the carbon black of measurement atmosphere Plasma-Modified.By the way that carbon black is incorporated into Atmosphere Plasma
Realized at single nozzle, this nozzle is connected on a 280V generator（Plasma Treat GmbH）.Then air is used
Plasma is with 1.5 bars, 2000 ls/h of flow velocity treated carbon black.The results are shown in table 2.
Embodiment 17
In this embodiment, the carbon black of measurement atmosphere Plasma-Modified.This be by by carbon black be incorporated into atmosphere etc. from
Realized at the single nozzle of daughter, this nozzle is connected on a 280V generator（Plasma Treat GmbH）.Then use
Nitrogen gas plasma is with 1.5 bars, 2000 ls/h of flow velocity treated carbon black.The results are shown in table 2.
Embodiment 18
3g carbon nano-fibers（“CNF”）By first using 400 milliliters of 2.5M HCl solution to enter within 18 hours in 120 DEG C of backflows
The pre- modification of row, then washs the carbon 8 hours in the deionized water of 400 milliliters of boilings.Further functionalization CNF is by by 1 gram
The CNF modified in advance concentrates 1 at 400 milliliters:1 nitric acid：The mixture of sulfuric acid handles what is realized within 4 hours at 120 DEG C.In acid treatment
Afterwards, then the carbon sample with the thorough washing function of deionized water, and it is dried overnight in 60-70 DEG C of vacuum drying oven.Its result
It is shown in table 2.
Embodiment 19
Graphite particle is dispersed in the three-necked flask equipped with 1000 milliliter 5% of nitric acid.By mixture at 120 DEG C next time
Stream 12 hours, then the particle filtering that will be treated, are washed 15 minutes with the deionized water continuously flowed, finally existed in an oven
Dried 12 hours at 110 DEG C.The results are shown in table 2.
Embodiment 20
Carbon in 30% nitric acid by boiling 3 hours with pre-oxidation.The modification of carbon is by by the carbon of pre-oxidation treatment
Reacted 2.5 hours at 230 DEG C in excess of ammonia stream with ammonia.Carbon is then under nitrogen flowing with 10 DEG C of min-1Speed heating rise
Temperature, and isothermal holding 10 minutes at 400 DEG C.The results are shown in table 2.
Embodiment 21
Modified carbon is 3.96mmol NH3g by carbon and flow velocity-1Ammonia-air Mixture of carbon is reacted at 420 DEG C to be obtained.
Ammonia：The ratio of air is 0.2, NH3Volume be 240 milliliters.The results are shown in table 2.
As shown in table 2, the carbon sample modified using different method of modifying is confirmed on the carbon material surface of modification
Hetero atom and/or based on heteroatomic group.
Table 2
Predict embodiment
Predict embodiment 1
It is carbon nano-tube modified（“CNT”）Material can be by the way that CNT be immersed in the inorganic acid of oxidisability, then violent
Obtained within 3 hours in 80-90 DEG C of backflow under stirring.After being isolated by filtration, treated CNT is washed with deionized,
And drying in 5 hours at 120 DEG C in atmosphere.Pretreatment can use the inorganic acid of three types, include 30% nitric acid, mixing
98% H2SO4+ 70% nitric acid, and 98% H2SO4+ 0.4M potassium bichromate solution.
Predict embodiment 2
Hot method can also be used to remove the compound on surface.For example, carbon material in a vacuum at about 1000 DEG C of temperature plus
Heat, or in inert gas, or include at least 80% N2Under atmosphere, completely or generally whole existing surface chemical combination is decomposed
Thing.After the carbon of this heating is cooled to room temperature, exposed to dry oxygen, some oxygen can carry out chemisorbed.By this carbon
After being immersed in aqueous acid, the oxygen of same amount of chemisorbed also occurs, and the oxygen atom of each chemisorbed can be simultaneously
The acid of equivalent about 1 equivalent.
As used herein, term " one ", " one kind ", and "the" are intended to comprising plural number and singulative.In other words, only for
It is convenient for reference, term " one " or " one kind " or "the" can be with used herein above, such as " carbon material ", and " organic electrolyte " is " cloudy
Pole " etc., but purpose is, unless explicitly stated otherwise, in contrast, refer to " at least one ", such as " at least one carbon material ", " at least one
Kind organic electrolyte ", " at least one negative electrode " etc..If term " at least one " is used in one example, and " one " or " one
Kind " or "the" use in another example, such as in same paragraph or chapters and sections, this is correct.It is in addition, used herein
, phrase " at least one " refers to one or more, thus including single component and their mixtures/combinations.
Term " comprising " used herein（And its grammatical variants）For comprising meaning, can replace with " having " makes
With.These terms be not necessarily to be construed as being used in it is exclusive in the sense that " consist of ", unless clearly so recording.
Except explicitly indicating that, all numerals represent the composition and/or reaction condition of quantity, it can be understood as by so-called
" in all cases " is modified with term " about ".This includes such as " all " or "None" and its variant.Repair as used herein
In the range of the limitation that decorations language " about " refers to, those skilled in the art can it is expected and define specific quantity, and this is probably, for example, each
In kind embodiment, ± the 10% of the quantity of instruction, ± the 5% of the quantity of instruction, ± the 2% of the quantity of instruction, the number of instruction
± the 1% of amount, ± the 0.5% of the quantity of instruction, or ± the 0.1% of the quantity of instruction.
In addition, the position provided in scope, it is it should be understood that define other embodiment with the end points of scope
In, the subrange includes what those were not expressly recited, also including other embodiment.
As used herein, " by ... formed ", " being generated by .. " and its variant, represent to derive from chemical reaction, wherein, it is described
" chemical reaction " include chemical reaction of spontaneous chemical reaction and induction.As used herein, phrase " by ... formed " and
" by ... produce " it is open, not those components listed of limit combination.
Element described herein and limitation, and this paper institutes can be included according to composition disclosed by the invention and method
Description is otherwise known in the art any extra or optional compositions, component or limitation, is made up of them, or
Person is made up of them substantially.
, otherwise, the step of various methods described herein can be with any suitable it should be appreciated that unless expressly stated otherwise,
Sequence is performed, and not all steps have to carry out, but this method is still intended that in the scope of the present disclosure.
It is to be understood that disclosed above and other features and function, or the variant of its substitute, it can also combine
Into many other different features and function.It is wherein various not predict or unexpected alternative solution at present, modification, change or
Improvement can be obtained then by those skilled in the art, also be fallen in the range of following claims includes.
Claims (5)
1. a kind of method for preparing lithium-air battery electrode, this method include：
Carbon material is modified to introduce at least one heteroatom group on the surface of carbon material, the heteroatom group be selected from carboxyl,
Carbonyl, carboxylic acid anhydrides, phenolic hydroxyl group, lactone group, phenolic group, quinonyl, xanthyl, ether, acyl chloride, methyl ester, diazomethane base
Group, hydroxy-acid group, peroxide-based, superoxides base, C=N, N-H, cyano group, halogeno-group, C-F, thionyl chloride, and
Combinations thereof, the modification include：
Unmodified carbon material is handled with chemicals, plasma or Technology for Heating Processing to form the carbon material of modification, its
In, the chemicals includes 20 weight % H2O2Solution；
Form the carbon material of modification and the slurry of binding agent；
Slurry is cast in cathode current collector, to form electrode；And
The electrode is pressed to required thickness；
This method washs the carbon material before or after being optionally included in processing.
2. the method as described in claim 1, it is characterised in that chemical solutions and the volume ratio of carbon material are 5-1000.
3. the method as described in claim 1, it is characterised in that include backflow with chemical treatments, stirring and theirs is mixed
Close, processing time is 1-72 hours.
4. the method as described in claim 1, it is characterised in that when with chemical treatments, this method further comprises 25
Dry at DEG C -120 DEG C up to 12 hours, optionally carry out in a vacuum.
5. the method as described in claim 1, it is characterised in that the plasma is generated using radio frequency, selected from CF4-
He plasmas, nitrogen ion body and air plasma.
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| KR102484887B1 (en) * | 2016-12-23 | 2023-01-04 | 현대자동차주식회사 | A lithium air battery comprising quinone-based soluble catalyst inducing discharge in solution |
| CN108281723B (en) * | 2017-12-26 | 2020-02-18 | 桂林理工大学 | Direct activation method for organic electrolyte system lithium air battery |
| CN110350152B (en) * | 2018-04-02 | 2021-01-26 | 中国科学院化学研究所 | Graphite alkyne/manganese dioxide nanosheet array material and preparation method and application thereof |
| CN110391401A (en) * | 2019-06-25 | 2019-10-29 | 肇庆理士电源技术有限公司 | OMC based combined electrode and lead-acid battery |
| CN110407188A (en) * | 2019-06-26 | 2019-11-05 | 肇庆理士电源技术有限公司 | Passivation modified processing method, hydrophilic ordered mesopore carbon and its application of order mesoporous carbon surface |
| CN110416502A (en) * | 2019-06-27 | 2019-11-05 | 肇庆理士电源技术有限公司 | OMC/ sponge Pb sandwich lead plaster and its preparation method and application |
| CN110668436B (en) * | 2019-11-04 | 2021-06-29 | 北京科技大学 | Preparation method of ultrathin nanoscale graphite alkyne film |
| KR102143610B1 (en) * | 2020-03-31 | 2020-08-11 | 한국해양대학교 산학협력단 | Method for producing nitrogen-carbon aggregate having hierarchical pore structure, nitrogen-carbon aggregate produced therefrom, and sodium ion battery including the same |
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