CN104518219B - Application of the porous carbon materials in positive electrode of lithium thionyl chloride battery - Google Patents
Application of the porous carbon materials in positive electrode of lithium thionyl chloride battery Download PDFInfo
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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
- H01M4/02—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
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- 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
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
Abstract
Application of the porous carbon materials in positive electrode of lithium thionyl chloride battery, carbon material particles particle diameter is 1 30um, and in itself in the class cellular structures being made up of carbon plate layer, pore volume is 0.5~5cm to particle3/ g, it is internal including two kinds of holes, and a kind of is the staggeredly through hole being made up of as hole wall carbon plate layer, and another hole is the hole being uniformly distributed in hole wall；Staggeredly 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 the 80% of through hole pore volume, and the two pore volume ratio is 1:10~10：1, carbon lamellar spacing is 2 50nm；Predominantly pore diameter range is the hole of 1~10nm in hole wall, accounts for more than the 90% of hole wall internal pore volume.The carbon material is used in positive electrode of lithium thionyl chloride battery, space availability ratio of the carbon material in discharge process can be to greatest extent improved, the energy density and power density of battery is effectively improved.
Description
Technical field
The invention belongs to one-shot battery field, and in particular to porous carbon materials answering in lithium-thionyl chloride battery positive pole
With.
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 current lithium
A kind of battery of discharge voltage highest in one-shot battery；Battery specific energy is high, can reach 500Wh/kg's and 1000Wh/L at present
Level；Specific power is big, can be with 10~50mA/cm2Electric discharge, high-power torpedo battery is up to 140W/kg；Operating temperature range is wide；
Battery is without internal pressure, and voltage accuracy is high；Battery self discharge rate is low（Year self-discharge rate≤2%）, storage life was up to 10~15 years；Electricity
Pond is with low cost.
The GND is metal Li, and positive pole is prepared using porous carbon materials, and electrolyte generally uses LiAlCl4As molten
Agent, SOCl2As solvent, while as active material absorption in positive pole.In discharge process, cathode oxidation is lithium ion, and
In positive pole, SOCl2It is reduced, its product is S and LiCl.Positive discharge product does not dissolve in electrolyte, and deposition occupies electrode hole
Road is until electric discharge terminates.Accordingly, as electrochemical reaction occur place, carbon material pore structure physical parameter to battery performance,
Especially discharge capacity has important influence.
Porous carbon with pore volume high can provide more storage areas for the product generated in discharge process, so that table
Reveal specific capacity high.But, solid product deposition certainly will influence lithium ion transmission wherein to occupying for electrode duct, enter
And increase ion transmission resistance, particularly in electric discharge latter stage, the carrying out of serious restriction electrode reaction is unfavorable for specific capacity on the contrary
Improve.Generally, in order to avoid the excessive blocking in electrode duct, can be using the carbon material rich in macroporous structure, such as acetylene black.So
And, the material specific surface area is relatively low, due to, the specific surface area of material directly determines the size at its electrochemical reaction interface, because
This is unfavorable for the heavy-current discharge performance of battery；Meanwhile, its pore volume is also smaller, so as to be unfavorable for obtaining discharge capacity higher.
On the other hand, when using the carbon material with large specific surface area and pore volume, such as Ketjen black, now due to its contained macropore ratio
It is relatively low, therefore electrode duct easily blocks in discharge process, therefore, it is not suitable for being applied to lithium-thionyl chloride battery.
As can be seen here, traditional granular pattern carbon material, is built because its duct space is main by intergranular space, larger
Grain diameter is conducive to obtaining larger aperture, but its specific surface area and pore volume are relatively low；Although however, less grain diameter
Larger specific surface area and pore volume can be obtained, but its macropore content is relatively low.Therefore, cannot be in height using the carbon material of the type
Specific surface area, realizes balance between pore volume high and macropore.
Therefore, to solve this problem it is necessary to be broken through in terms of the hole Forming Mechanism of material.
The content of the invention
It is an object of the invention to provide application of the porous carbon materials in lithium-thionyl chloride battery positive pole.
Constituting the carbon particle of the carbon material has the cellular pore structure of class, and its particle size is 1~30um, preferred scope
It is 1-10um, gap can be used as macropore lithium ion transport passage between its particle；Meanwhile, interlocked insertion by carbon plate layer building inside it
Product deposition duct, 5~90nm of its pore diameter range, preferred scope is 10-60nm, and occurrence can prepare work by regulation and control carbon material
Skill parameter realizes that less aperture can be internally formed larger specific surface area and pore volume in particle.Further, at by post activation
Reason, can perform etching elimination to part carbon plate layer, so as to two grades of lithium ion transports that 100~500nm is internally formed in particle lead to
Road, makes full use of the solid product deposition space inside particle, improves the discharge performance of battery.Insertion in two pore diameter ranges
Hole accounts for more than the 80% of through hole cumulative volume, and the pore volume ratio in the hole of the 100~500nm of hole and aperture of 5~90nm of aperture is 1:
10~10：1, preferred scope is 1:3~5:1, carbon lamellar spacing is 2-50nm.By the carbon material using the structure, can be effective
Traditional structure carbon material problem encountered is solved, high-specific surface area, the balance between pore volume high and macropore structure is realized.
Carbon material pore volume of the present invention is 0.5~5cm3/g；Inside carbon particle except by carbon plate layer as hole wall structure
Into staggeredly there is the hole that is uniformly distributed in carbon plate layer hole wall outside through hole, also, the hole of wherein 1~10nm of aperture accounts for hole wall
More than the 90% of hole cumulative volume, the parameter of this partial hole depends primarily on the carbon source employed in carbon material preparation process.Meanwhile,
Described carbon plate layer surface can doping catalyst component in situ, including N, B, O, Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru,
One or two or more kinds of Nb, Y, Rh, Cr, Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V, are examined using x-ray photoelectron power spectrum
Survey, x-ray photoelectron spectroscopy detection scope is below carbon plate layer surface to carbon plate layer surface in 10 nanometer ranges, in detection range
The amount ratio that catalyst component accounts for the material of detection range all elements is 0.1~10%.The material is used to prepare lithium-thionyl
Chlorine anode, positive electrode composition includes carbon material and binding agent, and wherein carbon material mass content is 70%~95%；Institute
The binding agent stated is polytetrafluoroethylene (PTFE), polyvinyl alcohol, Kynoar, sodium carboxymethylcellulose, polyolefin, butadiene-styrene rubber, fluorine
Change rubber, one or more in polyurethane.
The carbon material is prepared from using two-step method,
Original carbon material is prepared using template first, post activation then is carried out to it, further inside its carbon particle
Build this cell channels that aperture is 100~500nm.
Prepared by original carbon material is mainly realized using template, can also be combined with metal salt catalyst activation or foaming.Tool
Body process is as follows：
During carbon matrix precursor and template are dissolved in into deionized water or organic solvent, 40~85 DEG C of heating water bath and mechanical agitation,
After after moisture or organic solvent evaporating completely in 60~80 DEG C of dryings；Dried product is carbonized, and carbonization gas are N2Or/
And Ar, at 500~1700 DEG C, preferred scope is 600~1100 DEG C to carburizing temperature scope, and carbonization time is controlled in 1~8h, is obtained
Template/carbon complex, removing template is removed with acid or aqueous slkali, through filtering, is dried, and obtains final product porous carbon materials.
Wherein described carbon matrix precursor include it is following in one or two or more kinds：
（1）Low molecular carbohydrate, including sucrose, starch, maltose, glucose, xylose or furfuryl alcohol；
（2）The organic matter of small molecule, including formaldehyde, phenol, ethene, acetylene, propylene, benzene；
（3）High molecular polymer, including mesophase pitch, polyethylene glycol, phenol formaldehyde resin or resorcinol formaldehyde tree
Fat, polyaniline, polypyridine, melamine.
The template is SiO2Colloidal sol, zeolite, Al2O3, mesoporous SiO2, magnesia, magnesium acetate, magnesium gluconate, oxidation
Copper, zinc oxide, ferrous oxide, di-iron trioxide, calcium carbonate, magnesium carbonate, ferroso-ferric oxide, tin ash, silica, oxidation
Aluminium, zirconium oxide, molybdenum trioxide, vanadium trioxide, nano titanium oxide powder, metal nickel hydroxide, metal iron hydroxide, gold
Belong to one or more in hydroxide, silicon dioxide microsphere, polystyrene microsphere, the poly (methyl methacrylate) micro-sphere of magnesium,
In 5~8000nm, preferred scope is 5-500nm to wherein template grain size scope.
When with metal salt catalyst activation method combination, its process is as follows：
During carbon matrix precursor is dissolved in into deionized water or organic solvent, then adds slaine or metal hydroxides continues molten
Solution dispersion, adds template dissolving dispersion, 40~85 DEG C of heating water bath and mechanical agitation, treats moisture or organic solvent evaporating completely
Afterwards in 60~80 DEG C of dryings；Dried product is carbonized, and at 500~1700 DEG C, preferred scope is 600 to carburizing temperature scope
~1100 DEG C, carbonization time control in 1~8h, obtain template/carbon complex, with acid or aqueous slkali go removing template and slaine or
Metal hydroxides, through filtering, dries, and obtains final product porous carbon materials；
Slaine or metal hydroxides presoma containing Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr,
One or two or more kinds of Zr, Ce, Ti, Mo, Mn, Zn, W, Sn, La and V；Slaine is nitrate, carbonate, the sulfuric acid of metal
Salt, acetate, halide, dinitroso diamine salts, acetylacetonate or big ring complex compound and porphyrin compound, phthalein mountain valley with clumps of trees and bamboo compound
In one or two or more kinds.Wherein, slaine or metal hydroxides and the mass percent scope of template are 1~15%.
When with foaming combination, its process is as follows：
During carbon matrix precursor, template and foaming agent are dissolved in into deionized water or organic solvent, 40~85 DEG C of heating water bath and machine
Tool stir, after after moisture or organic solvent evaporating completely in 60~80 DEG C of dryings；Dried product is carbonized, carbonization gas
It is N2Or/and Ar, at 500~1700 DEG C, preferred scope is 600~1100 DEG C to carburizing temperature scope, carbonization time control 1~
8h, obtains template/carbon complex, and removing template is removed with acid or aqueous slkali, through filtering, dries, and porous carbon materials is obtained final product, wherein foaming
The mass percent scope of agent and carbon matrix precursor is 5~100%.
Wherein, foaming agent is citric acid, ammonium carbonate, ammonium hydrogen carbonate, calcium carbonate, magnesium carbonate, sodium acid carbonate, sodium carbonate, ten
One or two in sodium dialkyl sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol, pentane, n-hexane, normal heptane, petroleum ether
More than.
In carbon material preparation process, template is 600~10% with the mass percent of carbon matrix precursor；Carbon matrix precursor go from
Concentration in sub- water or organic solvent is 0.05~0.4g/ml；Organic solvent is ethanol, isopropanol, acetone, N-N dimethyl methyls
One or two or more kinds in acid amides, N-N dimethylacetylamides or 1-METHYLPYRROLIDONE；The acid solution for going removing template to use is
0.5~3M hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, aqueous slkali are 0.5~3M sodium hydroxide solutions.
Post activation treatment is carried out to original carbon prepared by said process：
Vapor, CO are passed through to porous carbon materials2、NH3In one or two or more kinds or can produce above-mentioned three kinds appoint
One or two or more kinds in the compound of one gas is activated；At 400~1300 DEG C, preferred scope is for activation temperature control
600~900 DEG C, soak time control is controlled in 2~100ml/min in 10min~5h, charge flow rate；
Or, the porous carbon materials ground and mixed that activating reagent is prepared with the template is uniform, and activating reagent is carbon
The 10~300% of quality of materials, at 300~900 DEG C, soak time is controlled in 10min~5h for activation temperature control；Carbon after activation
Material is washed with deionized and dries；Described activating reagent includes bases activating reagent KOH, acids activating reagent H3PO4,
Salt activating reagent is ZnCl2、K2CO3Or Na2CO3。
The material is used to prepare lithium-thionyl chloride battery positive pole, lithium-thionyl chloride battery positive electrode composition bag
Porous carbon materials and binding agent are included, wherein carbon material mass content is 70%~95%；Described binding agent is polytetrafluoroethylene (PTFE), gathers
One kind in vinyl alcohol, Kynoar, sodium carboxymethylcellulose, polyolefin, butadiene-styrene rubber, Viton, polyurethane or two
More than kind.
So that binding agent is as polytetrafluoroethylene (PTFE) as an example, can realize according to the following procedure：
By material and ptfe emulsion（Mass fraction is 5%）It is blended in solvent, obtains electrode slurry, wherein solid
Body material is 10~30mg solids/ml solvents with solvent ratios；By the way of blade coating, spraying or roll-in, sheet is prepared
Electrode, electrode is obtained in 40-80 degrees Celsius of drying, and wherein binder content is 70%~95%.
Wherein solvent is alcohol, water or alcohol-water mixture, and alcohol and water quality ratio are 1 in alcohol-water mixture:4-4:1；Wherein, alcohol
Including ethanol, isopropanol, ethylene glycol, one or more in glycerine etc..
Beneficial effects of the present invention：
1. carbon material of the present invention, its structure both has the deposition hole for being adapted to discharging product deposition, and with large aperture
Ion transmission hole.Each performs its own functions in two kinds of holes, does not interfere with each other, and it can be optimized to greatest extent respectively, realizes that product sinks
The balance that product is transmitted with ion.
2. by the anode of the material members in, both there is the big ionic porogen transmission built by intergranular space main logical
, there is the secondary ion transmission channel that particle inside hundred nano-scale duct builds in road again, and two kinds of passages are organically combined, so as to build vertical
The high-effect ionic transmission space network of body, greatly improves battery space utilization rate.
Specific embodiment
Embodiment 1
Hierarchical porous structure porous carbon materials are prepared by template of nano-calcium carbonate magnesium powder body.Precise 5g glucose, adds
Stirring is complete to dissolving in 15ml deionized waters, is subsequently adding 3g citric acids, 5g magnesium carbonate, is heated simultaneously under 80 DEG C of water bath conditions
Mechanical agitation, is completely dispersed it, and 24h is dried after being put into 80 DEG C after moisture evaporating completely.Then dried product is put into
High temperature process furnances are carbonized, and atmosphere is nitrogen, and gas flow is controlled in 30ml/min.Taken out through the 2h that is carbonized at 800 DEG C and obtain nanometer
Particle/carbon complex, then add appropriate 2M watery hydrochloric acid removal nano-calcium carbonate magnesium, 80 DEG C of vacuum drying 24h, obtain final product classification after filtering
Pore structure porous carbon materials.
Further, post activation is carried out to it, vapor is passed through to porous carbon materials, activation temperature is controlled at 800 DEG C, activation
Time control is controlled in 10ml/min in 1h, charge flow rate.
Contrast before and after activation, carbon particle pore volume is by 1.5cm in material3/ g is promoted to 2.3cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 4:1.
By prepared carbon material and ptfe emulsion（Mass fraction is 5%）It is blended in ethanol, obtains electrode slurry
Material, wherein solid matter are 20mg solids/ml solvents with solvent ratios；By the way of blade coating, spraying or roll-in, prepare
Pellet electrode, electrode is obtained in 60 degrees Celsius of drying, and wherein binder content is 80%, and electrode carbon material surface density is 7mg/
cm2。
Using KB600, acetylene black sample as a comparison prepares carbon positive pole as procedure described above.
With the LiAlCl of 1M4/SOCl2Be electrolyte, porous polypropylene as barrier film, lithium metal as negative pole, to prepared
Carbon positive pole is evaluated.Result shows, the carbon positive pole 2mA/cm prepared by the present invention2Under, 60% is improved compared to KB600 capacity,
110% is improved compared to acetylene black capacity；10mA/cm2Under, 280% is improved compared to KB600 capacity, compared to acetylene black capacity
Improve 130%.
Embodiment 2
With SiO2Colloidal sol prepares hierarchical porous structure porous carbon materials for template.Precise 5g glucose, the water of 0.2716g six
Close stirring during cobalt nitrate adds 15ml deionized waters and extremely dissolve complete, be subsequently adding 5g SiO2Colloidal sol, mechanical agitation makes its complete
Dispersion, heating and mechanical agitation under 80 DEG C of water bath conditions are vacuum dried 24h after being put into 80 DEG C after moisture evaporating completely.Then
Dried product is put into high temperature process furnances charing, atmosphere is nitrogen, and gas flow is controlled in 30ml/min.900 DEG C through carbon
Change 3h taking-ups and obtain Nano-meter SiO_22/ carbon complex, then add appropriate 1M HF removals SiO2With the cobalt oxide of generation, after filtering 80 DEG C
Vacuum drying 24h, obtains final product hierarchical porous structure porous carbon materials.
Further, post activation is carried out to it, ammonia is passed through to porous carbon materials, activation temperature is controlled at 800 DEG C, during activation
Between control in 1h, charge flow rate control in 10ml/min.
Contrast before and after activation, carbon particle pore volume is by 1.6cm in material3/ g is promoted to 2.4cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 3:1.
Using technique and parameter same as Example 1, prepare and evaluate carbon material, as a result show, prepared by the present invention
Carbon positive pole 2mA/cm2Under, 65% is improved compared to KB600 capacity, improve 120% compared to acetylene black capacity；10mA/cm2Under, phase
270% is improved compared with KB600 capacity, 130% is improved compared to acetylene black capacity.
Embodiment 3
Hierarchical porous structure porous carbon materials are prepared by template of nano-calcium carbonate calcium powder.Precise 5g glucose, 2g hydrogen
Stirring is complete to disperseing during nickel oxide adds 10ml deionized waters, is subsequently adding 3g calcium carbonate, is heated under 80 DEG C of water bath conditions
And mechanical agitation, it is completely dispersed, it is vacuum dried 24h after being put into 80 DEG C after moisture evaporating completely.Then by dried product
Product are put into high temperature process furnances charing, and atmosphere is nitrogen, and gas flow is controlled in 20ml/min.Taken out through the 2h that is carbonized at 900 DEG C
To nano particle/carbon complex, then nano-calcium carbonate and nickel oxide are removed with appropriate 2M watery hydrochloric acid, 80 DEG C of vacuum are done after filtering
Dry 24h, obtains final product hierarchical porous structure porous carbon materials.
Further, post activation is carried out to it, carbon dioxide is passed through to porous carbon materials, activation temperature is controlled at 800 DEG C, living
Change time control in 1h.
Contrast before and after activation, carbon particle pore volume is by 1.4cm in material3/ g is promoted to 2.1cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 3.2:1.
Using technique and parameter same as Example 1, prepare and evaluate carbon material, as a result show, prepared by the present invention
Carbon positive pole 2mA/cm2Under, 65% is improved compared to KB600 capacity, improve 120% compared to acetylene black capacity；10mA/cm2Under, phase
240% is improved compared with KB600 capacity, 110% is improved compared to acetylene black capacity.
Embodiment 4
Hierarchical porous structure porous carbon materials are prepared by template of Nano-sized Alumina Powder.Precise 5g sucrose adds 10ml
Stirring is complete to disperseing in deionized water, is subsequently adding 8g aluminum oxide, and heating and mechanical agitation, make it under 80 DEG C of water bath conditions
It is completely dispersed, 24h is vacuum dried after being put into 80 DEG C after moisture evaporating completely.Then dried product is put into high temperature process furnances
Charing, N2In 800 DEG C treatment 3h, change CO2800 DEG C of purging 1h, then change N2Purging obtains nano particle/carbon and is combined to room temperature
Thing, then alumina is gone with appropriate 2M watery hydrochloric acid, 80 DEG C of vacuum drying 24h, obtain final product hierarchical porous structure porous carbon after filtering
Material.
Further, post activation is carried out to it, by its with KOH with mass ratio 1:1 mixing, 2h, carbon after activation are activated at 700 DEG C
Material is washed with deionized and dries.
Contrast before and after activation, carbon particle pore volume is by 1.5cm in material3/ g is promoted to 2.3cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 2:1.
Using technique and parameter same as Example 1, prepare and evaluate carbon material, as a result show, prepared by the present invention
Carbon positive pole 2mA/cm2Under, 50% is improved compared to KB600 capacity, improve 100% compared to acetylene black capacity；10mA/cm2Under, phase
270% is improved compared with KB600 capacity, 130% is improved compared to acetylene black capacity.
Embodiment 5
Hierarchical porous structure porous carbon materials are prepared by template of silicon dioxide microsphere powder.Precise 5g sucrose,
Stirring is complete to disperseing during the manganese nitrate aqueous solution of 0.358g50% adds 15ml deionized waters, is subsequently adding 6g silica micro-
Ball, heating and mechanical agitation, are completely dispersed it under 60 DEG C of water bath conditions, are done after 80 DEG C of vacuum are put into after moisture evaporating completely
Dry 24h.Then dried product is put into high temperature process furnances carbonization, N2In 850 DEG C for the treatment of 3h, change 850 DEG C of vapor purging
0.5h, then changes N2Purging obtains nano particle/carbon complex, then remove silica and oxidation with appropriate 1M HF to room temperature
Manganese, 80 DEG C of vacuum drying 24h, obtain final product hierarchical porous structure porous carbon materials after filtering.
Further, post activation is carried out to it, by itself and H3PO4With mass ratio 1:1.5 mixing, activation temperature is controlled 650
DEG C, soak time is controlled in 3h.
Contrast before and after activation, carbon particle pore volume is by 1.8cm in material3/ g is promoted to 2.9cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 4.2:1.
Using technique and parameter same as Example 1, prepare and evaluate carbon material, as a result show, prepared by the present invention
Carbon positive pole 2mA/cm2Under, 75% is improved compared to KB600 capacity, improve 130% compared to acetylene black capacity；10mA/cm2Under, phase
200% is improved compared with KB600 capacity, 80% is improved compared to acetylene black capacity.
Embodiment 6
Hierarchical porous structure porous carbon materials are prepared by template of nickel hydroxide powder.Precise 5g starch, 1g bicarbonates
Ammonium, stirring is complete to dissolving in adding 15ml deionized waters, and heating and mechanical agitation, make it divide completely under 80 DEG C of water bath conditions
Dissipate, 24h is dried after being put into 80 DEG C after moisture evaporating completely.Then dried product is put into high temperature process furnances charing, atmosphere
It is nitrogen, gas flow is controlled in 50ml/min.Taken out through the 4h that is carbonized at 900 DEG C and obtain nano particle/carbon complex, then added suitable
Amount 2M dust technology removal nickel oxide, 80 DEG C of vacuum drying 24h, obtain final product hierarchical porous structure porous carbon materials after filtering.
Further, post activation is carried out to it, by itself and Na2CO3With mass ratio 1:2 mixing, activation temperature is controlled at 850 DEG C,
Soak time is controlled in 2h.
Contrast before and after activation, carbon particle pore volume is by 1.5cm in material3/ g is promoted to 2.7cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 5:1.
Using technique and parameter same as Example 1, prepare and evaluate carbon material, as a result show, prepared by the present invention
Carbon positive pole 2mA/cm2Under, 90% is improved compared to KB600 capacity, improve 150% compared to acetylene black capacity；10mA/cm2Under, phase
160% is improved compared with KB600 capacity, 60% is improved compared to acetylene black capacity.
Embodiment 7
Hierarchical porous structure porous carbon materials are prepared by template of nickel hydroxide powder.Precise 5g sucrose, adds 10ml
Stirring is complete to disperseing in deionized water, is subsequently adding 10g nickel hydroxide powders, is heated under 80 DEG C of water bath conditions and machinery is stirred
Mix, be completely dispersed it, 24h are vacuum dried after being put into 80 DEG C after moisture evaporating completely.Then dried product is put into height
Warm tube furnace charing, 800 DEG C for the treatment of 3h, change CO in Ar2800 DEG C of purging 1h, then change Ar and purge to room temperature, obtain nanometer
Grain/carbon complex, then nickel oxide is removed with appropriate 2M dust technologies, 80 DEG C of vacuum drying 24h, obtain final product hierarchical porous structure after filtering
Porous carbon materials.
Further, post activation is carried out to it, by itself and K2CO3With mass ratio 1:2 mixing, activation temperature is controlled at 850 DEG C,
Soak time is controlled in 2h.
Contrast before and after activation, carbon particle pore volume is by 1.7cm in material3/ g is promoted to 2.4cm3/ g, pore diameter range 5~
The pore volume ratio in the hole of 90nm and 100~500nm is 3.3:1.
Using technique and parameter same as Example 1, prepare and evaluate carbon material, as a result show, prepared by the present invention
Carbon positive pole 2mA/cm2Under, 45% is improved compared to KB600 capacity, improve 90% compared to acetylene black capacity；10mA/cm2Under, compare
240% is improved in KB600 capacity, 110% is improved compared to acetylene black capacity.
Claims (10)
1. application of the porous carbon materials in lithium-thionyl chloride battery positive pole, it is characterised in that：The carbon material particles particle diameter is
1-30um, in itself in the class cellular structures being made up of carbon plate layer, pore volume is 0.5~5cm to particle3/ g, includes inside it
Two kinds of holes, one of which is the staggeredly through hole being made up of as hole wall carbon plate layer, and another hole is to be uniformly distributed in hole wall
Interior hole；
Staggeredly through hole is mainly the hole that two class pore diameter ranges are respectively 5~90nm and 100~500nm, and the two accounts for through hole hole
More than the 80% of volume, the two pore volume ratio is 1:10~10：1, carbon lamellar spacing is 2-50nm；Hole in hole wall is mainly
Pore diameter range is the hole of 1~10nm, accounts for more than the 90% of hole wall internal pore volume.
2. according to the application described in claim 1, it is characterised in that：Carbon plate layer surface doping catalysis group in situ in carbon particle
Point, described catalyst component include N, B, O, Fe, Co, Ni, Cu, Ag, Pt, Pd, Au, Ir, Ru, Nb, Y, Rh, Cr, Zr, Ce, Ti,
One or two or more kinds of Mo, Mn, Zn, W, Sn, La and V, using x-ray photoelectron spectroscopy detection, the inspection of x-ray photoelectron power spectrum
It is that catalyst component accounts for detection range institute in detection range below carbon plate layer surface to carbon plate layer surface in 10 nanometer ranges to survey scope
The amount ratio for having the material of element is 0.1~10%.
3. according to the application described in claim 1, it is characterised in that：Described carbon material is prepared from using two-step method,
Prepare original carbon material according to the following procedure using template first, post activation then is carried out to it, inside its carbon particle
Build the duct that described aperture is 100~500nm；
(1) template preparation process is as follows：
During carbon matrix precursor and template are dissolved in into deionized water or organic solvent, 40~85 DEG C of heating water bath and mechanical agitation treat water
Point or organic solvent evaporating completely after in 60~80 DEG C of dryings；Dried product is carbonized, and carbonization gas are N2Or/and
Ar, at 500~1700 DEG C, carbonization time is controlled in 1~8h carburizing temperature scope, obtains template/carbon complex, with acid or alkali soluble
Liquid removes removing template, through filtering, dries, and obtains final product porous carbon materials；
(2) post activation process is as follows：
Porous carbon materials prepared by the template are passed through vapor, CO2、NH3In one or two or more kinds or can produce
One or two or more kinds in the compound of the above-mentioned three kinds of any gas of life is activated；Activation temperature is controlled 400~1300
DEG C, soak time control is controlled in 2~100ml/min in 10min~5h, charge flow rate；
Or, the porous carbon materials ground and mixed that activating reagent is prepared with the template is uniform, and activating reagent is carbon material
The 10~300% of quality, at 300~900 DEG C, soak time is controlled in 10min~5h for activation temperature control；Carbon material after activation
It is washed with deionized and dries；Described activating reagent includes bases activating reagent KOH, acids activating reagent H3PO4, salt
Activating reagent is ZnCl2、K2CO3Or Na2CO3In one kind.
4. application according to claim 3, it is characterised in that：The carbon matrix precursor include it is following in one kind or two kinds with
On：
(1) one kind in low molecular carbohydrate, including sucrose, starch, maltose, glucose, xylose or furfuryl alcohol；
(2) one kind in the organic matter of small molecule, including formaldehyde, phenol, ethene, acetylene, propylene, benzene；
(3) high molecular polymer, including it is mesophase pitch, polyethylene glycol, phenol formaldehyde resin or resorcinol formaldehyde resin, poly-
One kind in aniline, polypyridine, melamine.
5. application according to claim 3, it is characterised in that：The template is zeolite, magnesia, magnesium acetate, glucose
Sour magnesium, cupric oxide, zinc oxide, ferrous oxide, di-iron trioxide, calcium carbonate, magnesium carbonate, ferroso-ferric oxide, tin ash, dioxy
SiClx, aluminum oxide, zirconium oxide, molybdenum trioxide, vanadium trioxide, nano titanium oxide powder, metal nickel hydroxide, metallic iron hydrogen
One or more in oxide, the hydroxide of magnesium metal, polystyrene microsphere, poly (methyl methacrylate) micro-sphere,
Wherein template grain size scope is in 5~8000nm.
6. application according to claim 3, it is characterised in that：
Original carbon material in the preparation process can be also prepared from using template combination catalytic activation method, and its process is such as
Under：
During carbon matrix precursor is dissolved in into deionized water or organic solvent, then adds slaine or metal hydroxides continues dissolving point
Dissipate, add template dissolving dispersion, 40~85 DEG C of heating water bath and mechanical agitation, after after moisture or organic solvent evaporating completely
60~80 DEG C of dryings；Dried product is carbonized, carburizing temperature scope at 500~1700 DEG C, carbonization time control 1~
8h, obtains template/carbon complex, and removing template and slaine or metal hydroxides are removed with acid or aqueous slkali, through filtering, dries,
Obtain final product porous carbon materials；
In the preparation process of the template combination catalytic activation method, carbon matrix precursor is added into presoma in course of dissolution and is contained
One kind 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 or
More than two kinds slaines or metal hydroxides；Slaine is nitrate, carbonate, sulfate, acetate, the halogenation of metal
One or two or more kinds in thing, dinitroso diamine salts, acetylacetonate or big ring complex compound, wherein slaine or gold
Category hydroxide is 1~15% with the mass percent scope of template.
7. application according to claim 3, it is characterised in that：
Original carbon material in the preparation process can be also according to the following procedure prepared from using template combination foaming：
During carbon matrix precursor, template and foaming agent are dissolved in into deionized water or organic solvent, simultaneously machinery is stirred 40~85 DEG C of heating water bath
Mix, after after moisture or organic solvent evaporating completely in 60~80 DEG C of dryings；Dried product is carbonized, and carbonization gas are N2
Or/and Ar, at 500~1700 DEG C, carbonization time is controlled in 1~8h carburizing temperature scope, template/carbon complex is obtained, with acid
Or aqueous slkali removes removing template, through filtering, dry, obtain final product porous carbon materials, the wherein mass percent of foaming agent and carbon matrix precursor
Scope is 5~100%.
8. application according to claim 7, it is characterised in that：The foaming agent be citric acid, ammonium carbonate, ammonium hydrogen carbonate,
Calcium carbonate, magnesium carbonate, sodium acid carbonate, sodium carbonate, lauryl sodium sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol, pentane, just
One or more foaming agents in hexane, normal heptane, petroleum ether.
9. the application according to claim 3,6 or 7, it is characterised in that：The mass percent of the template and carbon matrix precursor
It is 600~10%；Concentration of the carbon matrix precursor in deionized water or organic solvent is 0.05~0.4g/ml；Organic solvent is second
One kind in alcohol, isopropanol, acetone, N-N dimethylformamides, N-N dimethylacetylamides or 1-METHYLPYRROLIDONE or two kinds
More than；It is 0.5~3M hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid to remove the acid solution that removing template is used, and aqueous slkali is 0.5~3M hydrogen-oxygens
Change sodium solution.
10. application according to claim 1, it is characterised in that：Porous carbon materials are used to prepare lithium-thionyl chloride battery just
Pole；Lithium-thionyl chloride battery positive electrode composition includes porous carbon materials and binding agent, and wherein carbon material mass content is
70%~95%；Described binding agent is polytetrafluoroethylene (PTFE), polyvinyl alcohol, Kynoar, sodium carboxymethylcellulose, polyene
One or more in hydrocarbon, butadiene-styrene rubber, Viton, polyurethane.
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| CN104909363B (en) * | 2015-05-18 | 2017-03-08 | 陕西科技大学 | A kind of preparation method of meshed nano structure material with carbon element |
| CN105271176A (en) * | 2015-11-17 | 2016-01-27 | 南通绿业中试技术研究院有限公司 | Mesoporous carbon material and manufacturing method thereof |
| 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 |
| 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 |
| 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 |
| CN109742338B (en) * | 2018-12-13 | 2021-04-20 | 温州大学 | Preparation method of G-quadruplex/heme enzyme/carbon nanotube composite material and application of G-quadruplex/heme enzyme/carbon nanotube composite material in lithium-sulfur battery |
| CN110746602B (en) * | 2019-10-29 | 2021-04-20 | 大连理工大学 | Metal cobalt porphyrin-based porous organic polymer and preparation method and application thereof |
| CN111239215B (en) * | 2020-01-19 | 2020-11-24 | 江西农业大学 | Preparation method of phosphorus-doped porous carbon microsphere as niclosamide oxidase sensor |
| TWI799810B (en) | 2021-03-11 | 2023-04-21 | 國立清華大學 | Rechargeable transition metal 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 |
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