CN104518219A - Applications of porous carbon material in lithium-thionyl chloride battery positive electrode - Google Patents
Applications of porous carbon material in lithium-thionyl chloride battery positive electrode Download PDFInfo
- Publication number
- CN104518219A CN104518219A CN201310460193.4A CN201310460193A CN104518219A CN 104518219 A CN104518219 A CN 104518219A CN 201310460193 A CN201310460193 A CN 201310460193A CN 104518219 A CN104518219 A CN 104518219A
- Authority
- CN
- China
- Prior art keywords
- carbon
- template
- holes
- hole
- kinds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
Abstract
The invention relates to applications of a porous carbon material in a lithium-thionyl chloride battery positive electrode, According to the present invention, the particle size of the carbon material particles is 1-30 [mu]m, the carbon particles have a honeycomb-like porous structure formed by carbon sheet layers, the pore volume is 0.5-5 cm<3>/g, the internal of the carbon particles are provided with two types of holes, the one type of the holes are staggered through holes formed by adopting the carbon sheet layer as the hole wall, the other type of the holes are uniformly distributed in the hole wall, the staggered through holes are mainly two classes of the holes respectively with pore sizes of 5-90 nm and 100-500 nm, the two classes of the holes account for more than 80% of the volume of the through holes, the volume ratio of the two classes of the holes is 1:10-10:1, the thickness of the carbon sheet layer is 2-50 nm, the holes in the hole wall are mainly the holes with a pore size of 1-10 nm, and the holes in the hole wall and with the pore size of 1-10 nm account for more than 90% of the volume of the pores in the hole wall. With the application of the carbon material of the present invention in the lithium-thionyl chloride battery positive electrode, the space utilization rate of the carbon material during the discharge process can be improved to the greatest extent, and the energy density and the power density of the battery can be effectively improved.
Description
Technical field
The invention belongs to primary cell field, be specifically related to the application of porous carbon materials in lithium-thionyl chloride battery positive pole.
Background technology
Lithium thionyl chloride cell discharge voltage is high and discharge curve is steady.The open circuit voltage of battery is 3.65V, is a kind of battery that in current lithium primary battery, discharge voltage is the highest; Battery specific energy is high, can reach the level of 500Wh/kg and 1000Wh/L at present; Specific power is large, can 10 ~ 50mA/cm
2electric discharge, high-power torpedo battery can reach 140W/kg; Operating temperature range is wide; Battery is without interior pressure, and voltage accuracy is high; Battery self discharge rate low (year self-discharge rate≤2%), storage life can reach 10 ~ 15 years; Battery is with low cost.
This battery cathode is metal Li, and positive pole adopts porous carbon materials preparation, and electrolyte adopts LiAlCl usually
4as solvent, SOCl
2as solvent, be adsorbed in positive pole as active material simultaneously.In discharge process, cathode oxidation is lithium ion, and in positive pole, SOCl
2be reduced, its product is S and LiCl.Positive discharge product is all insoluble to electrolyte, and deposition occupies electrode duct until electric discharge terminates.Therefore, as the place that electrochemical reaction occurs, material with carbon element pore structure physical parameter is to battery performance, and especially discharge capacity has important impact.
The porous carbon with high pore volume can provide more storage area for the product generated in discharge process, thus shows high specific capacity.But solid product deposition certainly will affect lithium ion transmission wherein to occupying of electrode duct, and then increases ion transfer resistance, particularly discharging latter stage, the carrying out of serious restriction electrode reaction, is unfavorable for the raising of specific capacity on the contrary.Usually, in order to avoid the excessive blocking in electrode duct, the material with carbon element being rich in macroporous structure can be adopted, such as acetylene black.But this material specific surface area is lower, due to, the specific area of material directly determines the size at its electrochemical reaction interface, is therefore unfavorable for the heavy-current discharge performance of battery; Meanwhile, its pore volume is also less, thus is unfavorable for obtaining higher discharge capacity.On the other hand, when adopting the material with carbon element had compared with Large ratio surface sum pore volume, as Ketjen black, now contained by it, macropore ratio is lower, and therefore electrode duct very easily blocks in discharge process, therefore, is not suitable for being applied to lithium-thionyl chloride battery.
As can be seen here, traditional granular pattern material with carbon element, because its space, duct builds primarily of intergranular space, larger grain diameter is conducive to obtaining larger aperture, but its specific area and pore volume lower; But although less grain diameter can obtain larger specific area and pore volume, its macropore content is lower.Therefore, the material with carbon element of the type is adopted at high-specific surface area, to realize between high pore volume and macropore balancing.
Therefore, in order to address this problem, need to break through from the Forming Mechanism aspect, hole of material.
Summary of the invention
The object of the present invention is to provide the application of porous carbon materials in lithium-thionyl chloride battery positive pole.
The carbon granule forming this material with carbon element has the cellular pore structure of class, and its particle size is 1 ~ 30um, and preferable range is 1-10um, and between its particle, gap can be used as macropore lithium ion transport passage; Simultaneously, the product deposition duct that its inside interlocks through by carbon plate layer building, its pore diameter range 5 ~ 90nm, preferable range is 10-60nm, occurrence can be realized by regulation and control material with carbon element preparation technology parameter, and less aperture can form larger specific area and pore volume in granule interior.Further, by rear activation processing, etching can be carried out to part carbon plate layer and eliminate, thus form the secondary lithium ion transport passage of 100 ~ 500nm in granule interior, make full use of the solid product deposition space of granule interior, improve the discharge performance of battery.Through hole in two pore diameter ranges accounts for more than 80% of through hole cumulative volume, and the pore volume ratio in the hole of aperture 5 ~ 90nm and the hole of aperture 100 ~ 500nm is 1:10 ~ 10:1, and preferable range is 1:3 ~ 5:1, and carbon plate layer thickness is 2-50nm.By adopting the material with carbon element of this structure, effectively can solve traditional structure material with carbon element institute problems faced, realizing high-specific surface area, the balance between high pore volume and macropore build.
Material with carbon element pore volume of the present invention is 0.5 ~ 5cm
3/ g; Carbon granule is inner except except the staggered through hole that carbon plate layer is formed as hole wall, also there is the hole be uniformly distributed in carbon plate layer hole wall, the hole of its mesoporous 1 ~ 10nm accounts for more than 90% of hole wall hole cumulative volume, and the parameter in this part hole depends primarily on the carbon source adopted in material with carbon element preparation process.Simultaneously, described carbon sheet surfaces can in-situ doped catalyst component, comprise one or two or more kinds of N, B, O, Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V, adopt x-ray photoelectron spectroscopy detection, x-ray photoelectron spectroscopy detection scope is in below carbon sheet surfaces to carbon sheet surfaces 10 nanometer range, and in detection range, catalyst component accounts for the amount of substance ratio of detection range all elements is 0.1 ~ 10%.By this material for the preparation of lithium-thionyl chloride battery positive pole, positive electrode composition comprises material with carbon element and binding agent, and wherein material with carbon element mass content is 70% ~ 95%; Described binding agent is one or more in polytetrafluoroethylene, polyvinyl alcohol, Kynoar, sodium carboxymethylcellulose, polyolefin, butadiene-styrene rubber, Viton, polyurethane.
This material with carbon element adopts two-step method to be prepared from,
First adopt the original material with carbon element of template synthesis, then carrying out rear activation to it, is this part duct of 100 ~ 500nm further in its carbon granule internal build aperture.
The realization of original material with carbon element preparation main employing template, also can activate with metal salt catalyst or foaming is combined.Detailed process is as follows:
Carbon matrix precursor and template are dissolved in deionized water or organic solvent, heating water bath 40 ~ 85 DEG C is mechanical agitation also, 60 ~ 80 DEG C of dryings after moisture or organic solvent evaporate completely; Dried product carries out carbonization, and carbonization gas is N
2or/and Ar, carburizing temperature scope is at 500 ~ 1700 DEG C, and preferable range is 600 ~ 1100 DEG C, and carbonization time controls at 1 ~ 8h, obtains template/carbon complex, removes template with acid or aqueous slkali, after filtration, dry, obtains porous carbon materials.
Wherein said carbon matrix precursor comprise following in one or two or more kinds:
(1) low molecular carbohydrate, comprises sucrose, starch, maltose, glucose, wood sugar or furfuryl alcohol;
(2) micromolecular organic substance, comprises formaldehyde, phenol, ethene, acetylene, propylene, benzene;
(3) high molecular polymer, comprises mesophase pitch, polyethylene glycol, phenol formaldehyde resin or resorcinol formaldehyde resin, polyaniline, polypyridine, melamine.
Described template is SiO
2colloidal sol, zeolite, Al
2o
3, mesoporous SiO
2, magnesium oxide, magnesium acetate, magnesium gluconate, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, calcium carbonate, magnesium carbonate, tri-iron tetroxide, tin ash, silicon dioxide, aluminium oxide, zirconia, molybdenum trioxide, vanadium trioxide, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, the hydroxide of magnesium metal, silicon dioxide microsphere, polystyrene microsphere, one or more in poly (methyl methacrylate) micro-sphere, wherein template grain size scope is at 5 ~ 8000nm, and preferable range is 5-500nm.
When with metal salt catalyst activation method in conjunction with time, its process is as follows:
Carbon matrix precursor is dissolved in deionized water or organic solvent, then slaine or metal hydroxides continuation dissolving dispersion is added, add template again and dissolve dispersion, heating water bath 40 ~ 85 DEG C is mechanical agitation also, 60 ~ 80 DEG C of dryings after moisture or organic solvent evaporate completely; Dried product carries out carbonization, and carburizing temperature scope is at 500 ~ 1700 DEG C, and preferable range is 600 ~ 1100 DEG C, carbonization time controls at 1 ~ 8h, obtains template/carbon complex, removes template and slaine or metal hydroxides with acid or aqueous slkali, after filtration, dry, obtain porous carbon materials;
Slaine or metal hydroxides presoma are containing one or two or more kinds of Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V; Slaine is one or two or more kinds in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound.Wherein, the mass percent scope of slaine or metal hydroxides and template is 1 ~ 15%.
When with foaming in conjunction with time, its process is as follows:
Carbon matrix precursor, template and blowing agent are dissolved in deionized water or organic solvent, heating water bath 40 ~ 85 DEG C is mechanical agitation also, 60 ~ 80 DEG C of dryings after moisture or organic solvent evaporate completely; Dried product carries out carbonization, and carbonization gas is N
2or/and Ar, carburizing temperature scope is at 500 ~ 1700 DEG C, preferable range is 600 ~ 1100 DEG C, carbonization time controls at 1 ~ 8h, obtain template/carbon complex, remove template with acid or aqueous slkali, after filtration, dry, obtain porous carbon materials, wherein the mass percent scope of blowing agent and carbon matrix precursor is 5 ~ 100%.
Wherein, blowing agent is one or more in citric acid, ammonium carbonate, carbonic hydroammonium, calcium carbonate, magnesium carbonate, sodium acid carbonate, sodium carbonate, lauryl sodium sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol, pentane, n-hexane, normal heptane, benzinum.
In material with carbon element preparation process, the mass percent of template and carbon matrix precursor is 600 ~ 10%; The concentration of carbon matrix precursor in deionized water or organic solvent is 0.05 ~ 0.4g/ml; Organic solvent is one or two or more kinds in ethanol, isopropyl alcohol, acetone, N-N dimethyl formamide, N-N dimethylacetylamide or 1-METHYLPYRROLIDONE; The acid solution removing template use is 0.5 ~ 3M hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, and aqueous slkali is 0.5 ~ 3M sodium hydroxide solution.
Rear activation processing is carried out to original carbon prepared by said process:
Steam, CO is passed into porous carbon materials
2, NH
3in one or two or more kinds or one or two or more kinds that can produce in the compound of above-mentioned three kinds of arbitrary gases activate; Activation temperature controls at 400 ~ 1300 DEG C, and preferable range is 600 ~ 900 DEG C, and soak time controls at 10min ~ 5h, and charge flow rate controls at 2 ~ 100ml/min;
Or by even for the porous carbon materials ground and mixed of activating reagent and described template synthesis, activating reagent is 10 ~ 300% of material with carbon element quality, and activation temperature controls at 300 ~ 900 DEG C, and soak time controls at 10min ~ 5h; After activation, material with carbon element spends deionized water and drying; Described activating reagent comprises bases activating reagent KOH, acids activating reagent H
3pO
4, salt activating reagent is ZnCl
2, K
2cO
3or Na
2cO
3.
By this material for the preparation of lithium-thionyl chloride battery positive pole, lithium-thionyl chloride battery positive electrode composition comprises porous carbon materials and binding agent, and wherein material with carbon element mass content is 70% ~ 95%; Described binding agent is one or more in polytetrafluoroethylene, polyvinyl alcohol, Kynoar, sodium carboxymethylcellulose, polyolefin, butadiene-styrene rubber, Viton, polyurethane.
Take binding agent as polytetrafluoroethylene be example, can realize according to the following procedure:
By material and ptfe emulsion (mass fraction is 5%) blended in solvent, obtain electrode slurry, wherein solid matter and solvent ratios are 10 ~ 30mg solid/ml solvent; Adopt the mode of blade coating, spraying or roll-in, prepare pellet electrode, dry obtained electrode in 40-80 degree Celsius, wherein binder content is 70% ~ 95%.
Wherein solvent is alcohol, water or alcohol-water mixture, and in alcohol-water mixture, alcohol and water quality are than being 1:4-4:1; Wherein, alcohol comprises ethanol, isopropyl alcohol, ethylene glycol, one or more in glycerol etc.
Beneficial effect of the present invention:
1. material with carbon element of the present invention, its structure had both had the deposition hole of applicable discharging product deposition, had again wide-aperture ion transfer hole.Each performs its own functions in two kinds of holes, do not interfere with each other, and can optimize to greatest extent it respectively, realizes the balance of product deposition and ion transfer.
2. by the anode of this material members, both there is the macropore ion transfer main channel built by intergranular space, there is again the secondary ion transmission channel that granule interior hundred nano-scale duct builds, two kinds of passages organically combine, thus build three-dimensional high-effect ionic transmission space network, significantly improve battery space utilance.
Embodiment
Embodiment 1
With nano-calcium carbonate magnesium powder for Template preparation hierarchical porous structure porous carbon materials.Precise 5g glucose, adding 15ml deionized water for stirring to dissolving completely, then adding 3g citric acid, 5g magnesium carbonate, and under 80 DEG C of water bath condition, heating also mechanical agitation, makes it disperse completely, put into 80 DEG C of dry 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances charing, atmosphere is nitrogen, and gas flow controls at 30ml/min.Take out through carbonization 2h at 800 DEG C and obtain nano particle/carbon complex, then add appropriate 2M watery hydrochloric acid removal nano-calcium carbonate magnesium, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, carry out rear activation, pass into steam to porous carbon materials to it, activation temperature controls at 800 DEG C, and soak time controls at 1h, and charge flow rate controls at 10ml/min.
Contrast before and after activation, in material, carbon granule pore volume is by 1.5cm
3/ g is promoted to 2.3cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 4:1.
By prepared material with carbon element and ptfe emulsion (mass fraction is 5%) blended in ethanol, obtain electrode slurry, wherein solid matter and solvent ratios are 20mg solid/ml solvent; Adopt the mode of blade coating, spraying or roll-in, prepare pellet electrode, dry obtained electrodes in 60 degrees Celsius, wherein binder content is 80%, and electrode carbon material face density is 7mg/cm
2.
Adopt KB600, acetylene black is sample as a comparison, prepares carbon positive pole according to said process.
With the LiAlCl of 1M
4/ SOCl
2for electrolyte, porous polypropylene is as barrier film, and lithium metal, as negative pole, is evaluated prepared carbon positive pole.Result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 60% compared to KB600 capacity, improve 110% compared to acetylene black capacity; 10mA/cm
2under, improve 280% compared to KB600 capacity, improve 130% compared to acetylene black capacity.
Embodiment 2
With SiO
2colloidal sol is Template preparation hierarchical porous structure porous carbon materials.Precise 5g glucose, 0.2716g cabaltous nitrate hexahydrate add 15ml deionized water for stirring to dissolving completely, then add 5g SiO
2colloidal sol, mechanical agitation makes it disperse completely, and under 80 DEG C of water bath condition, heating also mechanical agitation, puts into 80 DEG C of vacuumize 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances charing, atmosphere is nitrogen, and gas flow controls at 30ml/min.900 DEG C obtain Nano-meter SiO_2 through carbonization 3h taking-up
2/ carbon complex, then add appropriate 1M HF removal SiO
2with the cobalt oxide generated, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, carry out rear activation, pass into ammonia to porous carbon materials to it, activation temperature controls at 800 DEG C, and soak time controls at 1h, and charge flow rate controls at 10ml/min.
Contrast before and after activation, in material, carbon granule pore volume is by 1.6cm
3/ g is promoted to 2.4cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 3:1.
Adopt the technique identical with embodiment 1 and parameter, material with carbon element is evaluated in preparation, and result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 65% compared to KB600 capacity, improve 120% compared to acetylene black capacity; 10mA/cm
2under, improve 270% compared to KB600 capacity, improve 130% compared to acetylene black capacity.
Embodiment 3
With nano-calcium carbonate calcium powder for Template preparation hierarchical porous structure porous carbon materials.It is complete to dispersion that precise 5g glucose, 2g nickel hydroxide add 10ml deionized water for stirring, then adds 3g calcium carbonate, and under 80 DEG C of water bath condition, heating also mechanical agitation, makes it disperse completely, put into 80 DEG C of vacuumize 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances charing, atmosphere is nitrogen, and gas flow controls at 20ml/min.Obtain nano particle/carbon complex at 900 DEG C through carbonization 2h taking-up, then remove nano-calcium carbonate and nickel oxide with appropriate 2M watery hydrochloric acid, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, carry out rear activation, pass into carbon dioxide to porous carbon materials to it, activation temperature controls at 800 DEG C, and soak time controls at 1h.
Contrast before and after activation, in material, carbon granule pore volume is by 1.4cm
3/ g is promoted to 2.1cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 3.2:1.
Adopt the technique identical with embodiment 1 and parameter, material with carbon element is evaluated in preparation, and result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 65% compared to KB600 capacity, improve 120% compared to acetylene black capacity; 10mA/cm
2under, improve 240% compared to KB600 capacity, improve 110% compared to acetylene black capacity.
Embodiment 4
Take Nano-sized Alumina Powder as Template preparation hierarchical porous structure porous carbon materials.It is complete to dispersion that precise 5g sucrose adds 10ml deionized water for stirring, then adds 8g aluminium oxide, and under 80 DEG C of water bath condition, heating also mechanical agitation, makes it disperse completely, put into 80 DEG C of vacuumize 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances charing, N
2in 800 DEG C process 3h, change CO
2800 DEG C purge 1h, then change N
2purge to room temperature, obtain nano particle/carbon complex, then remove aluminium oxide with appropriate 2M watery hydrochloric acid, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, carry out rear activation to it, it mixed with mass ratio 1:1 with KOH, at 700 DEG C of activation 2h, after activation, material with carbon element spends deionized water and drying.
Contrast before and after activation, in material, carbon granule pore volume is by 1.5cm
3/ g is promoted to 2.3cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 2:1.
Adopt the technique identical with embodiment 1 and parameter, material with carbon element is evaluated in preparation, and result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 50% compared to KB600 capacity, improve 100% compared to acetylene black capacity; 10mA/cm
2under, improve 270% compared to KB600 capacity, improve 130% compared to acetylene black capacity.
Embodiment 5
With silicon dioxide microsphere powder for Template preparation hierarchical porous structure porous carbon materials.The manganese nitrate aqueous solution of precise 5g sucrose, 0.358g50% adds 15ml deionized water for stirring to disperseing completely, then 6g silicon dioxide microsphere is added, under 60 DEG C of water bath condition, heating also mechanical agitation, makes it disperse completely, puts into 80 DEG C of vacuumize 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances carbonization, N
2in 850 DEG C process 3h, change steam 850 DEG C purge 0.5h, then change N
2purge to room temperature, obtain nano particle/carbon complex, then use appropriate 1M HF eccysis silicon dioxide and manganese oxide, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, rear activation is carried out to it, by itself and H
3pO
4mix with mass ratio 1:1.5, activation temperature controls at 650 DEG C, and soak time controls at 3h.
Contrast before and after activation, in material, carbon granule pore volume is by 1.8cm
3/ g is promoted to 2.9cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 4.2:1.
Adopt the technique identical with embodiment 1 and parameter, material with carbon element is evaluated in preparation, and result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 75% compared to KB600 capacity, improve 130% compared to acetylene black capacity; 10mA/cm
2under, improve 200% compared to KB600 capacity, improve 80% compared to acetylene black capacity.
Embodiment 6
With nickel hydroxide powder for Template preparation hierarchical porous structure porous carbon materials.Precise 5g starch, 1g carbonic hydroammonium, add 15ml deionized water for stirring to dissolving completely, under 80 DEG C of water bath condition, heating also mechanical agitation, makes it disperse completely, puts into 80 DEG C of dry 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances charing, atmosphere is nitrogen, and gas flow controls at 50ml/min.Take out through carbonization 4h at 900 DEG C and obtain nano particle/carbon complex, then add appropriate 2M dust technology removal nickel oxide, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, rear activation is carried out to it, by itself and Na
2cO
3mix with mass ratio 1:2, activation temperature controls at 850 DEG C, and soak time controls at 2h.
Contrast before and after activation, in material, carbon granule pore volume is by 1.5cm
3/ g is promoted to 2.7cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 5:1.
Adopt the technique identical with embodiment 1 and parameter, material with carbon element is evaluated in preparation, and result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 90% compared to KB600 capacity, improve 150% compared to acetylene black capacity; 10mA/cm
2under, improve 160% compared to KB600 capacity, improve 60% compared to acetylene black capacity.
Embodiment 7
With nickel hydroxide powder for Template preparation hierarchical porous structure porous carbon materials.Precise 5g sucrose, add 10ml deionized water for stirring to disperseing completely, then to add 10g nickel hydroxide powder, under 80 DEG C of water bath condition, heating also mechanical agitation, makes it disperse completely, puts into 80 DEG C of vacuumize 24h after moisture evaporates completely.Then dried product is put into high temperature process furnances charing, in Ar, 800 DEG C of process 3h, change CO
2800 DEG C purge 1h, and then change Ar and purge to room temperature, obtain nano particle/carbon complex, then remove nickel oxide with appropriate 2M dust technology, 80 DEG C of vacuumize 24h, obtain hierarchical porous structure porous carbon materials after filtering.
Further, rear activation is carried out to it, by itself and K
2cO
3mix with mass ratio 1:2, activation temperature controls at 850 DEG C, and soak time controls at 2h.
Contrast before and after activation, in material, carbon granule pore volume is by 1.7cm
3/ g is promoted to 2.4cm
3/ g, the pore volume of pore diameter range in the hole of 5 ~ 90nm and 100 ~ 500nm is than being 3.3:1.
Adopt the technique identical with embodiment 1 and parameter, material with carbon element is evaluated in preparation, and result shows, the carbon positive pole 2mA/cm prepared by the present invention
2under, improve 45% compared to KB600 capacity, improve 90% compared to acetylene black capacity; 10mA/cm
2under, improve 240% compared to KB600 capacity, improve 110% compared to acetylene black capacity.
Claims (10)
1. the application of porous carbon materials in lithium-thionyl chloride battery positive pole, is characterized in that: described carbon material particles particle diameter is 1-30um, and particle itself is in the class cellular structures be made up of carbon plate layer, and pore volume is 0.5 ~ 5cm
3/ g, its inside comprises two kinds of holes, and wherein a kind of is the staggered through hole be made up of as hole wall carbon plate layer, and another kind of hole is the hole be uniformly distributed in hole wall;
Staggered through hole is mainly the hole that two class pore diameter ranges are respectively 5 ~ 90nm and 100 ~ 500nm, and the two accounts for more than 80% of through hole pore volume, and the two pore volume ratio is 1:10 ~ 10:1, and carbon plate layer thickness is 2-50nm; Hole in hole wall is mainly the hole that pore diameter range is 1 ~ 10nm, accounts for more than 90% of hole wall internal pore volume.
2. according to application according to claim 1, it is characterized in that: the carbon plate layer surface in situ doping catalyst component in carbon granule, described catalyst component comprises N, B, O, Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, one or two or more kinds of La and V, adopt x-ray photoelectron spectroscopy detection, x-ray photoelectron spectroscopy detection scope is in below carbon sheet surfaces to carbon sheet surfaces 10 nanometer range, in detection range, catalyst component accounts for the amount of substance ratio of detection range all elements is 0.1 ~ 10%.
3. according to application according to claim 1, it is characterized in that: described material with carbon element adopts two-step method to be prepared from,
First adopt template to prepare original material with carbon element according to the following procedure, then carry out rear activation to it, the aperture described in its carbon granule internal build is the duct of 100 ~ 500nm;
(1) template synthesis process is as follows:
Carbon matrix precursor and template are dissolved in deionized water or organic solvent, heating water bath 40 ~ 85 DEG C is mechanical agitation also, 60 ~ 80 DEG C of dryings after moisture or organic solvent evaporate completely; Dried product carries out carbonization, and carbonization gas is N
2or/and Ar, carburizing temperature scope is at 500 ~ 1700 DEG C, and carbonization time controls at 1 ~ 8h, obtains template/carbon complex, removes template with acid or aqueous slkali, after filtration, dry, obtains porous carbon materials;
(2) activation process is as follows afterwards:
The porous carbon materials of described template synthesis is passed into steam, CO
2, NH
3in one or two or more kinds or one or two or more kinds that can produce in the compound of above-mentioned three kinds of arbitrary gases activate; Activation temperature controls at 400 ~ 1300 DEG C, and soak time controls at 10min ~ 5h, and charge flow rate controls at 2 ~ 100ml/min;
Or by even for the porous carbon materials ground and mixed of activating reagent and described template synthesis, activating reagent is 10 ~ 300% of material with carbon element quality, and activation temperature controls at 300 ~ 900 DEG C, and soak time controls at 10min ~ 5h; After activation, material with carbon element spends deionized water and drying; Described activating reagent comprises bases activating reagent KOH, acids activating reagent H
3pO
4, salt activating reagent is ZnCl
2, K
2cO
3or Na
2cO
3in one.
4. application according to claim 3, is characterized in that: described carbon matrix precursor comprise following in one or two or more kinds:
(1) low molecular carbohydrate, comprises sucrose, starch, maltose, glucose, wood sugar or furfuryl alcohol;
(2) micromolecular organic substance, comprises formaldehyde, phenol, ethene, acetylene, propylene, benzene;
(3) high molecular polymer, comprises mesophase pitch, polyethylene glycol, phenol formaldehyde resin or resorcinol formaldehyde resin, polyaniline, polypyridine, melamine.
5. application according to claim 3, is characterized in that: described template is SiO
2colloidal sol, zeolite, Al
2o
3, mesoporous SiO
2, magnesium oxide, magnesium acetate, magnesium gluconate, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, calcium carbonate, magnesium carbonate, tri-iron tetroxide, tin ash, silicon dioxide, aluminium oxide, zirconia, molybdenum trioxide, vanadium trioxide, nano titanium oxide powder, metallic nickel hydroxide, metallic iron hydroxide, the hydroxide of magnesium metal, silicon dioxide microsphere, polystyrene microsphere, one or more in poly (methyl methacrylate) micro-sphere, wherein template grain size scope is at 5 ~ 8000nm.
6. application according to claim 3, is characterized in that:
Original material with carbon element in described preparation process also can adopt template to be prepared from conjunction with catalytic activation method, and its process is as follows:
Carbon matrix precursor is dissolved in deionized water or organic solvent, then slaine or metal hydroxides continuation dissolving dispersion is added, add template again and dissolve dispersion, heating water bath 40 ~ 85 DEG C is mechanical agitation also, 60 ~ 80 DEG C of dryings after moisture or organic solvent evaporate completely; Dried product carries out carbonization, and carburizing temperature scope is at 500 ~ 1700 DEG C, and carbonization time controls at 1 ~ 8h, obtains template/carbon complex, removes template and slaine or metal hydroxides with acid or aqueous slkali, after filtration, dry, obtains porous carbon materials;
In the preparation process of described template in conjunction with catalytic activation method, carbon matrix precursor is added in course of dissolution one or two or more kinds slaine or metal hydroxides that presoma contains Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V; Slaine is one or two or more kinds in the nitrate of metal, carbonate, sulfate, acetate, halide, dinitroso diamine salts, acetylacetonate or large ring complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound, and wherein the mass percent scope of slaine or metal hydroxides and template is 1 ~ 15%.
7. application according to claim 3, is characterized in that:
Original material with carbon element in described preparation process also can adopt template to be prepared from according to the following procedure in conjunction with foaming:
Carbon matrix precursor, template and blowing agent are dissolved in deionized water or organic solvent, heating water bath 40 ~ 85 DEG C is mechanical agitation also, 60 ~ 80 DEG C of dryings after moisture or organic solvent evaporate completely; Dried product carries out carbonization, and carbonization gas is N
2or/and Ar, carburizing temperature scope is at 500 ~ 1700 DEG C, and carbonization time controls at 1 ~ 8h, obtain template/carbon complex, remove template with acid or aqueous slkali, after filtration, dry, obtain porous carbon materials, wherein the mass percent scope of blowing agent and carbon matrix precursor is 5 ~ 100%.
8. application according to claim 7, is characterized in that: described blowing agent is one or more blowing agents in citric acid, ammonium carbonate, carbonic hydroammonium, calcium carbonate, magnesium carbonate, sodium acid carbonate, sodium carbonate, lauryl sodium sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol, pentane, n-hexane, normal heptane, benzinum.
9. the application according to claim 3,6 or 7, is characterized in that: the mass percent of described template and carbon matrix precursor is 600 ~ 10%; The concentration of carbon matrix precursor in deionized water or organic solvent is 0.05 ~ 0.4g/ml; Organic solvent is one or two or more kinds in ethanol, isopropyl alcohol, acetone, N-N dimethyl formamide, N-N dimethylacetylamide or 1-METHYLPYRROLIDONE; The acid solution removing template use is 0.5 ~ 3M hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, and aqueous slkali is 0.5 ~ 3M sodium hydroxide solution.
10. application according to claim 1, is characterized in that: porous carbon materials is for the preparation of lithium-thionyl chloride battery positive pole; Lithium-thionyl chloride battery positive electrode composition comprises porous carbon materials and binding agent, and wherein material with carbon element mass content is 70% ~ 95%; Described binding agent is one or more in polytetrafluoroethylene, polyvinyl alcohol, Kynoar, sodium carboxymethylcellulose, polyolefin, butadiene-styrene rubber, Viton, polyurethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310460193.4A CN104518219B (en) | 2013-09-29 | 2013-09-29 | Application of the porous carbon materials in positive electrode of lithium thionyl chloride battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310460193.4A CN104518219B (en) | 2013-09-29 | 2013-09-29 | Application of the porous carbon materials in positive electrode of lithium thionyl chloride battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104518219A true CN104518219A (en) | 2015-04-15 |
| CN104518219B CN104518219B (en) | 2017-06-16 |
Family
ID=52793188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310460193.4A Active CN104518219B (en) | 2013-09-29 | 2013-09-29 | Application of the porous carbon materials in positive electrode of lithium thionyl chloride battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104518219B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909363A (en) * | 2015-05-18 | 2015-09-16 | 陕西科技大学 | Preparation method of network-like nanostructured carbon material |
| WO2017084251A1 (en) * | 2015-11-17 | 2017-05-26 | 南通绿业中试技术研究院有限公司 | Mesoporous carbon material and manufacturing method therefor |
| CN106848185A (en) * | 2017-02-27 | 2017-06-13 | 华南师范大学 | A kind of positive electrode of sulfur-bearing nitrogen-doped graphene, positive pole and lithium/thinly chloride battery |
| CN108455565A (en) * | 2018-05-15 | 2018-08-28 | 江汉大学 | A kind of preparation method of N doping graphitization nano carbon cage |
| CN108584915A (en) * | 2018-06-03 | 2018-09-28 | 湖南科技大学 | A kind of cellular carbon nanomaterial of regular hexagon and preparation method thereof |
| CN108630454A (en) * | 2018-04-28 | 2018-10-09 | 辽宁大学 | A kind of method that combined techniques prepare super capacitor carbon electrode material |
| CN109449372A (en) * | 2018-11-01 | 2019-03-08 | 贵州梅岭电源有限公司 | A kind of preparation method and applications of lithium-thionyl chloride porous anode |
| CN109742338A (en) * | 2018-12-13 | 2019-05-10 | 温州大学 | Tetra- serobilas of G-/hemachrome enzyme/carbon nano tube compound material preparation method and its application in lithium-sulfur cell |
| CN110746602A (en) * | 2019-10-29 | 2020-02-04 | 大连理工大学 | Metal cobalt porphyrin-based porous organic polymer and preparation method and application thereof |
| CN111239215A (en) * | 2020-01-19 | 2020-06-05 | 江西农业大学 | Preparation method of phosphorus-doped porous carbon microsphere as niclosamide oxidase sensor |
| CN114914406A (en) * | 2022-05-27 | 2022-08-16 | 武汉昊诚锂电科技股份有限公司 | Preparation method of positive pole piece and lithium sub-power battery |
| US11848445B2 (en) | 2021-03-11 | 2023-12-19 | National Tsing Hua University | Rechargeable transition metal battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
| CN101454243A (en) * | 2006-05-31 | 2009-06-10 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
-
2013
- 2013-09-29 CN CN201310460193.4A patent/CN104518219B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454243A (en) * | 2006-05-31 | 2009-06-10 | 促进科学E.V.麦克斯-普朗克公司 | Porous carbon electrode with conductive polymer coating |
| CN101284223A (en) * | 2007-04-13 | 2008-10-15 | 中国科学院金属研究所 | Magnetic porous carbon adsorbent and preparation method thereof |
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
Non-Patent Citations (1)
| Title |
|---|
| SANGJIN HAN ET AL.: "The effect of silica template structure on the pore structure of mesoporous carbons", 《CARBON》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909363A (en) * | 2015-05-18 | 2015-09-16 | 陕西科技大学 | Preparation method of network-like nanostructured carbon material |
| WO2017084251A1 (en) * | 2015-11-17 | 2017-05-26 | 南通绿业中试技术研究院有限公司 | Mesoporous carbon material and manufacturing method therefor |
| CN106848185A (en) * | 2017-02-27 | 2017-06-13 | 华南师范大学 | A kind of positive electrode of sulfur-bearing nitrogen-doped graphene, positive pole and lithium/thinly chloride battery |
| CN108630454A (en) * | 2018-04-28 | 2018-10-09 | 辽宁大学 | A kind of method that combined techniques prepare super capacitor carbon electrode material |
| CN108455565B (en) * | 2018-05-15 | 2020-10-09 | 江汉大学 | Preparation method of nitrogen-doped graphitized nano carbon cage |
| CN108455565A (en) * | 2018-05-15 | 2018-08-28 | 江汉大学 | A kind of preparation method of N doping graphitization nano carbon cage |
| CN108584915B (en) * | 2018-06-03 | 2021-09-14 | 湖南科技大学 | Regular hexagonal honeycomb-shaped carbon nano material and preparation method thereof |
| CN108584915A (en) * | 2018-06-03 | 2018-09-28 | 湖南科技大学 | A kind of cellular carbon nanomaterial of regular hexagon and preparation method thereof |
| CN109449372B (en) * | 2018-11-01 | 2020-07-14 | 贵州梅岭电源有限公司 | Preparation method and application of lithium thionyl chloride porous anode |
| CN109449372A (en) * | 2018-11-01 | 2019-03-08 | 贵州梅岭电源有限公司 | A kind of preparation method and applications of lithium-thionyl chloride porous anode |
| CN109742338A (en) * | 2018-12-13 | 2019-05-10 | 温州大学 | Tetra- serobilas of G-/hemachrome enzyme/carbon nano tube compound material preparation method and its application in lithium-sulfur cell |
| CN110746602A (en) * | 2019-10-29 | 2020-02-04 | 大连理工大学 | Metal cobalt porphyrin-based porous organic polymer and preparation method and application thereof |
| CN111239215A (en) * | 2020-01-19 | 2020-06-05 | 江西农业大学 | Preparation method of phosphorus-doped porous carbon microsphere as niclosamide oxidase sensor |
| US11848445B2 (en) | 2021-03-11 | 2023-12-19 | National Tsing Hua University | Rechargeable transition metal battery |
| CN114914406A (en) * | 2022-05-27 | 2022-08-16 | 武汉昊诚锂电科技股份有限公司 | Preparation method of positive pole piece and lithium sub-power battery |
| CN114914406B (en) * | 2022-05-27 | 2024-01-30 | 武汉昊诚锂电科技股份有限公司 | Preparation method of positive electrode plate and lithium-ion power battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104518219B (en) | 2017-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104518219A (en) | Applications of porous carbon material in lithium-thionyl chloride battery positive electrode | |
| CN104518218A (en) | Applications of porous carbon material in lithium-thionyl chloride battery positive electrode | |
| CN103855366B (en) | A kind of porous carbon materials of lithium-air battery positive pole N doping | |
| CN103855413B (en) | A kind of lithium-air battery positive pole porous carbon materials | |
| CN104518226B (en) | A kind of lithium air or lithium-oxygen battery positive pole porous carbon materials | |
| CN108461694B (en) | Double-effect composite diaphragm for lithium-sulfur battery and preparation method thereof | |
| Tao et al. | Kinetically-enhanced polysulfide redox reactions by Nb 2 O 5 nanocrystals for high-rate lithium–sulfur battery | |
| Zhang et al. | Double-shelled hollow carbon sphere with microporous outer shell towards high performance lithium-sulfur battery | |
| Wu et al. | Fabricating three-dimensional hierarchical porous N-doped graphene by a tunable assembly method for interlayer assisted lithium-sulfur batteries | |
| CN107623103B (en) | Lithium-sulfur battery cell electrode | |
| CN103855367B (en) | The porous carbon materials of lithium-air battery positive pole N doping | |
| WO2016107564A1 (en) | Composite positive material for lithium-sulphur battery with high rate performance and preparation method | |
| Wang et al. | Conductive RuO2 stacking microspheres as an effective sulfur immobilizer for lithium–sulfur battery | |
| WO2020164353A1 (en) | Porous carbon nanocomposite material doped with metal atoms and preparation method therefor and use thereof | |
| CN105731416A (en) | Porous carbon membrane for lithium-sulfur batteries and application of porous carbon membrane | |
| KR20100113553A (en) | Porous electrodes and associated methods | |
| CN103855412B (en) | Lithium-air battery positive pole porous carbon materials | |
| CN104882594A (en) | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof | |
| CN103855365B (en) | Lithium-air battery positive pole uses the porous carbon materials of N doping | |
| CN104916828A (en) | Three dimensional graphene/hollow carbon sphere/sulfur composite material, preparation method thereof, and application in lithium-sulfur batteries | |
| CN104269543A (en) | Graphene-cladded sulfur/microporous carbon sphere composite cathode material | |
| WO2019024313A1 (en) | Lithium sulfur battery and assembly thereof, and application of functional material layer in lithium sulfur battery | |
| CN103855394B (en) | Lithium-air battery positive pole uses porous carbon materials | |
| Yang et al. | Efficient polysulfides trapping and redox enabled by Co/N-carbon implanted Li+-montmorillonite for advanced lithium-sulfur batteries | |
| Liang et al. | CNT threaded porous carbon nitride nanoflakes as bifunctional hosts for lithium sulfide cathode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |