CN104518225B - Porous carbon material for lithium air cell, preparation and application thereof - Google Patents
Porous carbon material for lithium air cell, preparation and application thereof Download PDFInfo
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- CN104518225B CN104518225B CN201310452147.XA CN201310452147A CN104518225B CN 104518225 B CN104518225 B CN 104518225B CN 201310452147 A CN201310452147 A CN 201310452147A CN 104518225 B CN104518225 B CN 104518225B
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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
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- 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
- C01B32/15—Nano-sized carbon materials
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/96—Carbon-based electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a porous carbon material for a lithium air cell. The porous carbon material is a metal-doped nitrogen-containing porous carbon material, is prepared through a one-step hard template process, has the specific surface area of 500-2000 m＜2＞*g＜-1＞ and the total pore volume of 0.8-5 cm＜3＞*g＜-1＞, the mesopore volume accounts for 50-90% of the total pore volume, the metal atom content is 0.5-5 wt.%, and the nitrogen atom content is 1-10 wt.%. Nitrogen atom and metal atoms, which are introduced in the forms of a nitrogen-containing carbon source and a metal salt solution, have catalytic effect, more active sites are provided in the charging/discharging process of the lithium air cell, the charge transfer impedance is effectively reduced, and the voltage of a discharge plateau is improved.
Description
Technical field
The present invention relates to lithium air battery positive electrode, particularly a kind of metal-classifying porous material of nitrogen/carbon and its in lithium air
Application on anode.
Background technology
The energy and environment are the two large problems of 21 century facing mankind.With the continuous development of economic society, the mankind are to energy
The demand in source is increasing.According to estimates, to the year two thousand fifty mankind, present twice can be reached to the demand of the energy, and to this century
Last then present three times can be reached.Traditional fossil energy one side reserves limited it is impossible to meet the demand of social development, another
Consuming excessively of aspect fossil energy brings serious environmental problem.In order to solve the dual difficulty of energy shortage and environmental pollution
Topic, the exploitation of reproducible clean energy resource is most important.Wherein, lithium ion battery has led battery industry with its unique advantage
Development, and be widely used in mobile phone, the mobile device such as notebook computer.However, the energy density of lithium ion battery is too low,
Limit its application in electric automobile field.Therefore theoretical energy density is far longer than the lithium-air battery of lithium ion battery and is subject to
Arrive extensive concern.
Lithium-air battery is proposed in 1976 first by littauer and tsai.Both positive and negative polarity active substance is lithium metal respectively
And oxygen, because oxygen can obtain from space outerpace, therefore positive electrode capacity is infinitely great in theory.Its theoretical energy density can
To reach 13000wh kg-1.
The element of lithium-air battery includes the lithium piece as negative pole, positive electrode, electrolyte and barrier film.Its
In, positive electrode is generally porous carbon materials, and its Main Function is to provide transmission channel for oxygen and is that electric discharge produces
li2o2Memory space is provided.Therefore, the aperture of positive pole material with carbon element and pore volume are to the discharge capacity of lithium-air battery and cycle performance
Play an important role.In discharge process, the mesoporous deposition most beneficial for discharging product of tens nanometer scope, and hundred nano-scale
Macropore then provides transmission channel for oxygen.Using business-like kb-600 carbon dust as the positive electrode of lithium-air battery, its specific volume
Amount can reach 3500mah.g-1Left and right, but because its pore-size distribution is unreasonable, lead to the space availability ratio of carbon dust not enough.
Zhang jiguang etc. using the classifying porous Graphene of functionalization as the positive electrode of lithium-air battery, in ethers electrolyte
Middle first circle specific discharge capacity can reach 15000mah.g-1, it is peak ([j] zhang of document report so far
Jiguang et al, nano lett.2011,11,5071-5078).But Graphene preparation process is complicated it is impossible to realization is big
Large-scale production, and expensive, it is unsuitable for large-scale commercial application.Additionally, research also demonstrates that metallic atom and nitrogen-atoms exist
Avtive spot can be served as, the raising to discharge performance plays an important role in lithium-air battery discharge process.
Content of the invention
It is an object of the invention to provide a kind of metal-classifying porous material of nitrogen/carbon and preparation method thereof being applied
In lithium air battery positive electrode.
For achieving the above object, the present invention adopt technical scheme as follows:
Described lithium air battery positive electrode material is a kind of metal-classifying porous material of nitrogen/carbon, and it is using a step die
Plate method is made, and specific surface area is 500-2000m2.g-1, total hole volume is 0.8-53.g-1, wherein mesoporous volume accounts for total hole volume
Ratio is 50-90, and metal atom content is 0.5%-5%, and nitrogen atom content is 1%-10%.
The concrete preparation method of its described metal-classifying porous material of nitrogen/carbon is as follows:
First, from suitably nitrogenous carbon source, macromolecule performed polymer is prepared according to selected carbon source.According to certain ratio
By two kinds of various sizes of silica template agent mix homogeneously of size.Then by performed polymer and template according to certain ratio
It is sufficiently mixed, in mixed solution, adds a certain amount of metal salt solution, cause polymerization by way of certain.By polymerizate
Filter, wash, be dried and sinter 1-3h in 700-900 DEG C under an inert atmosphere after removing moisture, wash drying.
By above-mentioned product, in mass fraction, the naoh solution for 5%-20% impregnates 24h to remove template at 30-60 DEG C
Agent, washs, filters, is dried.
Carbon source used in the present invention is polyaniline, melamine resin, polythiophene, polypropylene are fine or polypyrrole in
One or more.
Metal salt solution used herein is in ferrum, the sulfate of cobalt, nickel or zirconium, nitrate or Chloride Solution
Plant or several.
The ratio of two kinds of different size template used in the present invention is 10:1-1:10.
Performed polymer used in the present invention is 10:1-3:7 with the mol ratio of template.
Noble gases used in the present invention are nitrogen or argon.
Beneficial effects of the present invention:
1. in the present invention, in nitrogenous carbon source and metal salt solution, the nitrogen-atoms introducing and metallic atom have catalytic action,
Provide more avtive spots in lithium-air battery charge and discharge process, effectively reduce Charge-transfer resistance, improve electric discharge
Platform voltage.
2. metal-classifying porous material of nitrogen/carbon that the present invention provides is to be prepared with a step hard template method, and raw material is easy to get,
Cheap, preparation process is simple compared with Graphene is it is easy to large-scale production.
3. the present invention provide metal-classifying porous material of nitrogen/carbon using silicon dioxide gel as template, using nitrogenous
Macromolecule as carbon source, by dopand metals saline solution, introduce metallic atom and nitrogen-atoms in presoma situ, it is to avoid
Follow-up doping treatment, simplifies preparation process.
4. metal-classifying porous the material of nitrogen/carbon of preparation method preparation of the present invention is used for lithium air battery positive electrode work
During property material, there is very high discharge platform voltage and specific discharge capacity, its discharge performance is significantly better than various business-like carbon materials
Material.
5. present excellent electric discharge using the lithium-air battery of this metal-nitrogen/carbon classifying porous positive electrode assembling
Can, it is 30ma.g in electric current density-1When, first circle specific discharge capacity reaches 10567mah.g-1, discharge voltage is 2.75v.
6. the material with carbon element of the present invention, has that processability is excellent, process is simple, good process repeatability, low cost and an environment
Friendly the advantages of.
Brief description
Fig. 1 is the bet curve of metal-classifying porous material of nitrogen/carbon that embodiment 1 obtains.
Fig. 2 is first circle electric discharge in lithium-air battery for the metal-nitrogen/carbon classifying porous material positive pole that obtains of embodiment 2
Curve chart.
Specific embodiment
With reference to embodiment, the invention will be further described, but the enforcement of the present invention is not limited only to this.
In following examples, the assemble method of lithium-air battery is as follows:
Under room temperature, lithium-air battery is assembled in the glove box full of argon.First negative pole lithium piece is placed in end
Cover, be sequentially placed into barrier film, porous carbon positive pole, tetrafluoro set, currect collecting net, spring after Deca electrolyte, after sealing, produce glove box.
In following examples, lithium-air battery electrochemical test method is as follows:
Under room temperature, the lithium-air battery assembling is carried out in oxygen atmosphere charge-discharge performance test, oxygen pressure is
1.2 atmospheric pressure, charge and discharge system is constant current charge-discharge, and discharge and recharge is interval to be 4.7-2.0v.The conversion of specific capacity is many with positive pole
The quality of hole carbon is defined.Charging-discharge tester system is land.
Embodiment 1
The tripolycyanamide of 3.15g is added in 5ml formaldehyde and the mixed solution of 12.5ml water, with mass concentration 10%
naco3Solution ph is adjusted to 8.5 about by solution.Said mixture is placed in 20min in 85 DEG C of water-baths and obtains settled solution, cold
But the silicon dioxide gel solution being 5% with 30ml mass concentration under agitation to after 40 DEG C mixes, wherein tripolycyanamide with
The mol ratio of silicon dioxide granule is 1:1, and silicon dioxide gel solution is the dioxy containing two kinds of different sizes (20nm, 200nm)
SiClx colloidal sol by silicon dioxide granule mol ratio 1:1 form (mass concentration 5%), in above-mentioned mixed solution add quality dense
The feso of degree 5%4Solution, feso4Mol ratio with tripolycyanamide is 1:20.The ph to 4 adjusting solution with the hcl solution of 2m is left
The right side, standing 3h obtains white precipitate material.Filter, washing, be dried after be placed in tube furnace under nitrogen atmosphere in 950 DEG C of roastings
2h.Then by above-mentioned product mass fraction be 40% naoh solution at 40 DEG C dipping 24h to remove template, wash
Wash, filter, being dried.
Its specific surface area of products therefrom is 1130m2.g-1, total hole volume is 3.1cm3.g-1, mesoporous volume accounts for total hole volume
Ratio is 67, and metal atom content is 0.7wt.%, and nitrogen atom content is 6.5wt.%.Nitrogenous classification as shown in Figure 1 is many
The bet curve of hole material with carbon element shows that it has abundant meso-hole structure, aperture integrated distribution in 23nm, big pore volume and conjunction
Suitable pore-size distribution is conducive to accommodating more discharging product.
Embodiment 2
The tripolycyanamide of 3.15g is added in 5ml formaldehyde and the mixed solution of 12.5ml water, with 10% naco3Molten
Solution ph is adjusted to 8.5 about by liquid.Said mixture is placed in 20min in 85 DEG C of water-baths and obtains settled solution, be cooled to 40
The silicon dioxide gel solution being 10% with 22.5ml mass concentration under agitation after DEG C mixes, wherein tripolycyanamide and two
The mol ratio of silicon oxide particle be 2:3, the silicon dioxide gel of two kinds of different sizes (20nm, 100nm) consist of 2:1, to
The feso that mass concentration is 10% is added in above-mentioned mixed solution4Solution, feso4Mol ratio with tripolycyanamide is 1:10.Use 2m
Hcl solution adjust solution ph to 4 about, standing 3h obtain white precipitate material.Filter, washing, be dried after be placed in tubular type
In 900 DEG C of roasting 3h under argon gas atmosphere in stove.Then by above-mentioned product mass fraction be 40% naoh solution in 40
To remove template at DEG C, wash, filter, be dried.
Its specific surface area of products therefrom is 768m2.g-1, total hole volume is 2.8cm3.g-1, mesoporous volume accounts for total hole volume ratio
Example is 76, and metal atom content is 0.6wt.%, and nitrogen atom content is 7.3wt.%.The gold of present invention preparation is adopted in Fig. 2
The lithium air battery positive electrode of genus-nitrogen/carbon classifying porous material preparation presents very big first circle specific discharge capacity:
10567mah.g-1.Discharge voltage is stablized in 2.75v, illustrates that the metal-classifying porous material of nitrogen/carbon of present invention preparation is empty in lithium
Excellent discharge performance is shown in pneumoelectric pond.
Embodiment 3
3g pvp is added in the mixed solution of second alcohol and water, after stirring 30min, the mixing of addition 10ml aniline and hcl is molten
Liquid (wherein aniline containing 2.5ml and 1.5ml hcl).Be 20% with 51ml mass concentration under agitation after stirring 30min two
Silica sol mixes, and wherein aniline and the mol ratio of silicon dioxide are 1:1, the dioxy of two kinds of different sizes (20nm, 100nm)
SiClx colloidal sol consist of 1:1, in above-mentioned mixed solution add mass concentration be 5% feso4Solution, feso4With aniline
Mol ratio is 1:20..Then it is added dropwise over the nh of 25ml0.1m4s2o8Cause polymerization, filter, washing, be dried after be placed in tube furnace
In under nitrogen atmosphere in 800 DEG C of roasting 2h.Then by above-mentioned product in the naoh solution being 40% in mass fraction 40
At DEG C, dipping 24h, to remove template, washs, filters, is dried.
Its specific surface area of products therefrom is 934m2.g-1, total hole volume is 2.5cm3.g-1, mesoporous volume accounts for total hole volume ratio
Example is 83, and metal atom content is 1wt.%, and nitrogen atom content is 5.2wt.%.
Claims (9)
1. a kind of lithium-air battery porous carbon materials it is characterised in that: described porous carbon materials are metal-doped nitrogenous
Porous carbon materials, are prepared from by a step hard template method, and its specific surface area is 500-2000 .g-1, total hole volume is 0.8-5
㎝3.g-1, it is 50-90% that mesoporous volume accounts for total hole volume ratio, and metal atom content is 0.5-5wt.%, and nitrogen atom content is
1-10wt.%；
Described porous carbon materials are prepared from using following steps,
Two kinds are contained the silicon dioxide gel solution of different size silicon dioxide granule, press the mass ratio of wherein silicon dioxide granule
10:1-1:10 mixes；
In silicon dioxide gel solution, the size of silicon dioxide granule is respectively 10-30nm and 100-300nm；
Then nitrogenous carbon source performed polymer with template silicon dioxide gel solution, by the mol ratio of performed polymer and silicon dioxide is
10:1-3:7 is sufficiently mixed, and adds metal salt solution in mixed solution, causes polymerization, polymerizate is filtered, washs, and is dried
1-3h is sintered in 700-900 DEG C under an inert atmosphere after removing moisture；
By above-mentioned product, in mass fraction, the naoh solution for 5%-20% impregnates more than 24h to remove template at 30-60 DEG C
Agent, washs, filters, is dried.
2. porous carbon materials described in a kind of claim 1 preparation method it is characterised in that: described porous carbon materials are using such as
Lower step is prepared from,
Two kinds are contained the silicon dioxide gel solution of different size silicon dioxide granule, press the mass ratio of wherein silicon dioxide granule
10:1-1:10 mixes；
In silicon dioxide gel solution, the size of silicon dioxide granule is respectively 10-30nm and 100-300nm；
Then nitrogenous carbon source performed polymer with template silicon dioxide gel solution, by the mol ratio of performed polymer and silicon dioxide is
10:1-3:7 is sufficiently mixed, and adds metal salt solution in mixed solution, causes polymerization, polymerizate is filtered, washs, and is dried
1-3h is sintered in 700-900 DEG C under an inert atmosphere after removing moisture；
By above-mentioned product, in mass fraction, the naoh solution for 5%-20% impregnates more than 24h to remove template at 30-60 DEG C
Agent, washs, filters, is dried.
3. preparation method according to claim 2 is it is characterised in that described carbon source is polyaniline, melamino-formaldehyde tree
One of fat, polythiophene or polypyrrole or two or more.
4. preparation method according to claim 2 is it is characterised in that contain the silicon dioxide gel solution of silicon dioxide granule
Mass concentration be 5%-40%.
5. preparation method according to claim 2 it is characterised in that: described metal salt solution be ferrum, the sulfur of cobalt, nickel or zirconium
One of hydrochlorate, nitrate or Chloride Solution or two or more, metal salt solution mass concentration is 5%-20%.
6. preparation method according to claim 2 it is characterised in that: described ionizable metal salt with the mol ratio of template is
40:1-1:1.
7. preparation method according to claim 2 it is characterised in that: described inert atmosphere be nitrogen atmosphere or argon gas
Atmosphere.
8. preparation method according to claim 2 it is characterised in that: when carbon source used be polyaniline, melamino-formaldehyde
When resin, polythiophene or polypyrrole, initiation method used respectively adds nh4s2o8, adjust ph to 4.5, add alcl3, add
fecl3Cause polymerization.
9. the porous carbon materials application described in a kind of claim 1 is it is characterised in that described porous carbon materials are used for lithium air electricity
Pond positive pole.
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| CN114643074B (en) * | 2022-04-28 | 2023-10-27 | 扬州工业职业技术学院 | Nitrogen-doped composite carbon material and application thereof |
| CN114933334A (en) * | 2022-06-02 | 2022-08-23 | 深圳职业技术学院 | Lithium ion battery PANI/Fe 2 O 3 Preparation method of composite negative electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356507A (en) * | 2009-03-18 | 2012-02-15 | 昭和电工株式会社 | Catalyst for air battery, and air battery using same |
| CN102646839A (en) * | 2012-03-30 | 2012-08-22 | 中国科学院青岛生物能源与过程研究所 | Carbon material and carbon composite material used for air electrode of lithium air battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356507A (en) * | 2009-03-18 | 2012-02-15 | 昭和电工株式会社 | Catalyst for air battery, and air battery using same |
| CN102646839A (en) * | 2012-03-30 | 2012-08-22 | 中国科学院青岛生物能源与过程研究所 | Carbon material and carbon composite material used for air electrode of lithium air battery |
Non-Patent Citations (1)
| Title |
|---|
| "Nitrogen enriched mesoporous carbon as a high capacity cathode in lithium–oxygen batteries";Hongjiao Nie;《Nanoscale》;20130710;第5卷;第8484-8487页 * |
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