CN106299298A - A kind of preparation method of sulfur/porous carbon composite positive pole - Google Patents
A kind of preparation method of sulfur/porous carbon composite positive pole Download PDFInfo
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- CN106299298A CN106299298A CN201610839198.1A CN201610839198A CN106299298A CN 106299298 A CN106299298 A CN 106299298A CN 201610839198 A CN201610839198 A CN 201610839198A CN 106299298 A CN106299298 A CN 106299298A
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides the preparation method of a kind of sulfur/porous carbon composite positive pole, comprises the following steps: the pre-carbonization of (1) hydro-thermal: organic nitrogen source and organic carbon source is mixed and prepares N doping presoma through hydro-thermal reaction；(2) activation: prepare doping nitrogen porous carbon materials through high-temperature calcination after being mixed with expanding agent by N doping presoma；(3) prepared by sulfur/porous carbon composite positive pole: reacting a period of time with porous carbon after being mixed by sulfur polished obtains sulfur/porous carbon composite positive pole.The present invention is by using glucose as carbon source, acetamide is as organic nitrogen source, material with carbon element pattern is controlled, it is ensured that sulfur granules is adsorbed in material with carbon element duct, improves the chemical property of electrode by serial of methods such as the pre-carbonization of hydro-thermal, expanding agent reaming, watery fusion methods.There is good reversibility and cyclical stability.Thus, the most worth expanded.
Description
[technical field]
The present invention relates to dynamic lithium battery positive electrode field, the system of a kind of sulfur/porous carbon composite positive pole
Preparation Method.
[background technology]
Along with society's high speed development increase day by day to demand for energy, and the exhaustion of reserves and Fossil fuel are to environment
Pollution so that the demand of novel alternative energy source is increased by people day by day.Traditional lithium ion battery is as novel alternative energy
Source and be widely studied, yet with general lithium ion battery energy density be difficult to break through 300Wh/kg, limit its
The extensive application in the fields such as pure electric vehicle and hybrid vehicles.Therefore low cost, high-energy-density are sought
Regenerative resource is the key solving lithium battery development problem.Elemental sulfur owing to cheap, density is relatively light, environmental friendliness and
Height ratio capacity is it is considered to be a kind of excellent anode material of lithium battery.Using elemental sulfur as positive pole, lithium metal is as the lithium of negative pole
Sulfur battery, theoretical energy density is up to 2500Wh/kg (volume energy density is up to 2800Wh/L).It is that one is the most potential
Secondary battery positive electrode material.
The research of lithium-sulfur cell system is concentrated mainly on two aspects: one, sulfur positive electrode is modified, improve material to electronics and
The conducting power of ion, such as porous carbon-sulfur composite, polymer-sulfur composite, CNT-sulfur composite；Two,
The optimization of sulfur content in lithium-sulfur cell system, it is ensured that the utilization rate of active substance sulfur and electrochemical stability.At material structure
On, first consider it is to adsorb on porous material skeleton, elemental sulfur for example with porous carbon, activated carbon, CNT, graphite
The material with carbon elements such as alkene are combined with sulfur, prevent the polysulfide produced in course of reaction to be dissolved in electrolyte, and are expanded by electrolyte
Dissipate, so contribute to minimizing and shuttle back and forth effect and self-discharge phenomenon.But the general specific surface area of traditional porous material is less, aperture chi
Very little single, structural integrity is poor, aperture is difficult to regulate and control, material adsorption activity material sulfur limited in one's ability, causes the compound of preparation
Sulfur content in positive electrode is relatively low, skewness, and electric conductivity is poor, is assembled into circulating battery after a few, still has a large amount of
Active substance can dissolve from material structure duct, causes the loss of active substance, this make lithium-sulfur cell energy density be difficult to into
One step improves.
In consideration of it, real be necessary to provide the preparation method of a kind of novel sulfur/porous carbon composite positive pole overcome with
Upper defect.
[summary of the invention]
It is an object of the invention to provide the preparation method of a kind of novel sulfur/porous carbon composite positive pole, the method is grasped
Make simple, relatively low to equipment requirements, and sulfur granules can be made to adsorb by the sulfur/porous carbon composite positive pole obtained by the method
In material with carbon element duct, improve the chemical property of electrode.
The present invention provides the preparation method of a kind of sulfur/porous carbon composite positive pole, comprises the following steps:
(1) the pre-carbonization of hydro-thermal: weigh a certain amount of glucose and be dissolved in deionized water, adds organic nitrogen and comes from solution
Transfer in reactor after stirring, mix homogeneously, after hydro-thermal reaction a period of time at a certain temperature, take after being cooled to room temperature
Go out, again with absolute ethanol washing, 50 DEG C of forced air drying 24h after deionized water filtration washing, prepare N doping presoma.
(2) activation: N doping presoma obtained in step 1 is mixed with certain mass ratio with expanding agent, add from
Sub-water, stirs at 70 DEG C, is put in porcelain boat in thick rear taking-up and is dried.Last inert gas shielding in high temperature process furnances
After lower calcining certain time, cooling is taken out.With a certain amount of deionized water ultrasonic after to add dehydrated alcohol more ultrasonic, final sucking filtration dries
Dry obtain adulterate nitrogen porous carbon materials.
(3) prepared by sulfur/porous carbon composite positive pole: mixed with different mol ratio from doping nitrogen porous carbon materials by sulfur
Close, in vacuum drying oven dried, be subsequently placed in the politef reactor of full noble gas, 158 DEG C of holdings
12h, now the mobility of sulfur is higher.Open reactor heat treatment at a certain temperature some hours, remove conductive black surface
Unnecessary sulfur.Reaction is ground after terminating and is i.e. obtained sulfur/porous carbon composite positive pole.
In a preferred embodiment, described organic nitrogen source is acetamide.
In a preferred embodiment, the temperature of described hydro-thermal reaction is 200～220 DEG C；Response time is 4～6h.
In a preferred embodiment, described expanding agent is KOH.
In a preferred embodiment, described N doping presoma is 1:3～1:4 with the mass ratio of expanding agent.
In a preferred embodiment, the temperature of described high temperature process furnances is 500～700 DEG C；Calcination time be 2～
4h。
In a preferred embodiment, described noble gas is N2。
In a preferred embodiment, described sulfur is 1:1～1:2 with the mol ratio of porous carbon.
In a preferred embodiment, described heat treatment temperature is 200 DEG C, and described heat treatment time is 2～3h.
The Advantageous Effects of the present invention is: the present invention is by using glucose as carbon source, and acetamide is as organic nitrogen
Source, controls material with carbon element pattern by serial of methods such as the pre-carbonization of hydro-thermal, expanding agent reaming, watery fusion methods, it is ensured that sulfur granules
It is adsorbed in material with carbon element duct, improves the chemical property of electrode.There is good reversibility and cyclical stability.
[Figure of description]
Fig. 1 is the SEM figure of nitrogen-doped porous carbon material corresponding to the embodiment of the present invention 1,2,3,4.
Fig. 2 is the N2 adsorption distribution curve of nitrogen-doped porous carbon material corresponding to the embodiment of the present invention 1,2,3,4.
Fig. 3 is the pore size distribution curve of nitrogen-doped porous carbon material corresponding to the embodiment of the present invention 1,2,3,4.
Fig. 4 is nitrogen-doped porous carbon material prepared by the embodiment of the present invention 2 and the XRD figure of sulfur/porous carbon composite thereof.
Fig. 5 is that the battery made of the sulfur prepared by the embodiment of the present invention 2/porous carbon composite positive pole is under 0.2C multiplying power
Charging and discharging curve figure.
Fig. 6 is that the battery made of the sulfur prepared by the embodiment of the present invention 2/porous carbon composite positive pole is under 0.2C multiplying power
Cyclic curve figure.
[detailed description of the invention]
The invention provides the preparation method of a kind of novel sulfur/porous carbon composite positive pole, comprise the following steps:
(1) the pre-carbonization of hydro-thermal: weigh a certain amount of glucose and be dissolved in deionized water, add organic nitrogen come from solution stir, mixed
Transfer in reactor after closing uniformly, after hydro-thermal reaction certain time at a certain temperature, take out after being cooled to room temperature, through go from
Again with absolute ethanol washing, 50 DEG C of forced air drying 24h after sub-water filtration washing, prepare N doping presoma.
(2) activation: N doping presoma obtained in step 1 is mixed with certain mass ratio with expanding agent, add from
Sub-water, stirs at 70 DEG C, is put in porcelain boat in thick rear taking-up and is dried.Last inert gas shielding in high temperature process furnances
After lower calcining certain time, cooling is taken out.With a certain amount of deionized water ultrasonic after to add dehydrated alcohol more ultrasonic, final sucking filtration dries
Dry obtain adulterate nitrogen porous carbon materials.
(3) prepared by sulfur/porous carbon composite positive pole: mixed with different mol ratio from doping nitrogen porous carbon materials by sulfur
Close, in vacuum drying oven dried, be subsequently placed in the politef reactor of full noble gas, 158 DEG C of holdings
12h, now the mobility of sulfur is higher.Open reactor heat treatment at a certain temperature some hours, remove conductive black surface
Unnecessary sulfur.Reaction is ground after terminating and is i.e. obtained sulfur/porous carbon composite positive pole.
N doping presoma described in step (1) is the product that organic carbon source and organic nitrogen source prepare after hydro-thermal reaction
Thing.In the present embodiment, described glucose is organic carbon source；Described organic nitrogen source is acetamide.In other embodiments,
The Organic substance of the carbon containings such as described organic carbon source can also be other saccharides, fatty acid, oil；Described organic nitrogen source can make acetyl
Amine, hexamethylene diamine, Methanamide etc. are containing amino compound.
The temperature of described hydro-thermal reaction is 200 DEG C～220 DEG C, and the response time is 4～6h.In optimum embodiment, institute
The temperature stating hydro-thermal reaction is 220 DEG C, and the response time is 5h.
Described deionized water can be redistilled water, ultra-pure water or other eliminate interference metal ion water quality；Institute
State dehydrated alcohol to replace with acetone, ether etc.；
The nitrogen porous carbon materials that adulterates described in step (2) is described N doping presoma with described expanding agent in high-temperature calcination
The minute aperture material with carbon element of rear formation.In the present embodiment, described expanding agent is KOH, in other embodiments, and described reaming
Agent can also be NaOH, H3PO4、ZnCl2One of which.Described N doping presoma mixes in deionized water with expanding agent
Time, described N doping presoma is 1:3～1:4 with the mass ratio of expanding agent.In optimum embodiment, described N doping forerunner
Body is 1:4 with the mass ratio of expanding agent；Before the relationship between quality of described N doping presoma and described deionized water is 1g N doping
Drive addition 20ml deionized water in body；
High-temperature calcination reaction temperature in described high temperature process furnances is 500～700 DEG C；Calcination time is 2～4h.At optimum
In embodiment, described high-temperature calcination reaction temperature is 600 DEG C, and calcination time is 2h.In the present embodiment, described indifferent gas
Body is N2, in other embodiments, described noble gas can also be helium, argon etc..
Elemental sulfur after sulfur is subliming by heating described in step (3)；Described sulfur/porous carbon composite positive pole is distillation
After sulfur mixes with certain proportion with porous carbon, after vacuum drying oven dried, the product of heat treatment gained.
Described Sublimed Sulfur is 1:1～1:2 with the mol ratio of porous carbon；The temperature of described heat treatment is 200 DEG C, described heat
The time processed is 2～3h.In optimum embodiment, described Sublimed Sulfur is 1:1 with the mol ratio of porous carbon；At described heat
Reason temperature is 200 DEG C, and described heat treatment time is 2h.
Below in conjunction with specific embodiment, the present invention is elaborated:
Embodiment 1:
(1) glucose weighing 16.0g is dissolved in the deionized water of 40.0mL, adds 1.5g acetamide and stirs in solution
Mix in the reactor that 50mL is transferred in mixing, take out after the cooling of hydro-thermal reaction 5h room temperature at 200 DEG C, cross diafiltration through deionized water
Again with absolute ethanol washing, 50 DEG C of forced air drying 24h after washing, prepare N doping presoma.
(2) N doping presoma is added a certain amount of deionized water with KOH 1:3 in mass ratio and be mixed in 70 DEG C of stirrings (before 1g
Drive body and add 20mL deionized water), it is put in 80 DEG C of dry 24h in porcelain boat in thick rear taking-up.Last at N2Protect lower 500 DEG C of pipes
After calcining 2h in formula stove, cooling is taken out.Add the ultrasonic 30min of dehydrated alcohol after adding the ultrasonic 30min of a certain amount of deionized water again, take out
Filter drying obtains nitrogen-doped porous carbon material.
(3) Sublimed Sulfur is mixed with 1:1 mol ratio with nitrogen-doped porous carbon material, put in crucible, in 50 DEG C of vacuum
Drying baker processes 12h, and after drying, the politef reactor of full nitrogen put into by sample, and 158 DEG C keep 12h.Beat subsequently
Open 200 DEG C of heat treatment 3h of reactor, remove the sulfur of conductive black excess surface.Grind after being finally cooled to room temperature i.e. obtain sulfur/
Porous carbon composite positive pole.
Embodiment 2:
(1) glucose weighing 16.0g is dissolved in the deionized water of 40.0mL, adds 2.0g acetamide and stirs in solution
Mix in the reactor that 50mL is transferred in mixing, take out after the cooling of hydro-thermal reaction 5h room temperature at 220 DEG C, cross diafiltration through deionized water
Again with absolute ethanol washing, 50 DEG C of forced air drying 24h after washing, prepare N doping presoma.
(2) N doping presoma is added a certain amount of deionized water with KOH 1:4 in mass ratio and be mixed in 70 DEG C of stirrings (before 1g
Drive body and add 20mL deionized water), it is put in 80 DEG C of dry 24h in porcelain boat in thick rear taking-up.Last at N2Protect lower 600 DEG C of pipes
After calcining 2h in formula stove, cooling is taken out.Add the ultrasonic 30min of dehydrated alcohol after adding the ultrasonic 30min of a certain amount of deionized water again, take out
Filter drying obtains nitrogen-doped porous carbon material.
(3) Sublimed Sulfur is mixed with 1:1 mol ratio with nitrogen-doped porous carbon material, put in crucible, in 50 DEG C of vacuum
Drying baker processes 12h, and after drying, the politef reactor of full nitrogen put into by sample, and 158 DEG C keep 12h.Beat subsequently
Open 200 DEG C of heat treatment 2h of reactor, remove the sulfur of conductive black excess surface.Grind after being finally cooled to room temperature i.e. obtain sulfur/
Porous carbon composite positive pole.
Embodiment 3:
(1) glucose weighing 16.0g is dissolved in the deionized water of 40.0mL, adds 2.5g acetamide and stirs in solution
Mix in the reactor that 50mL is transferred in mixing, take out after the cooling of hydro-thermal reaction 5h room temperature at 220 DEG C, cross diafiltration through deionized water
Again with absolute ethanol washing, 50 DEG C of forced air drying 24h after washing, prepare N doping presoma.
(2) N doping presoma is added a certain amount of deionized water with KOH 1:3 in mass ratio and be mixed in 70 DEG C of stirrings (before 1g
Drive body and add 20mL deionized water), it is put in 80 DEG C of dry 24h in porcelain boat in thick rear taking-up.Last at N2Protect lower 600 DEG C of pipes
After calcining 2h in formula stove, cooling is taken out.Add the ultrasonic 30min of dehydrated alcohol after adding the ultrasonic 30min of a certain amount of deionized water again, take out
Filter drying obtains nitrogen-doped porous carbon material.
(3) Sublimed Sulfur is mixed with 1:2 mol ratio with nitrogen-doped porous carbon material, put in crucible, in 50 DEG C of vacuum
Drying baker processes 12h, and after drying, the politef reactor of full nitrogen put into by sample, and 158 DEG C keep 12h.Beat subsequently
Open 200 DEG C of heat treatment 2h of reactor, remove the sulfur of conductive black excess surface.Grind after being finally cooled to room temperature i.e. obtain sulfur/
Porous carbon composite positive pole.
Embodiment 4:
(1) glucose weighing 16.0g is dissolved in the deionized water of 40.0mL, adds 3.0g acetamide and stirs in solution
Mix in the reactor that 50mL is transferred in mixing, take out after the cooling of hydro-thermal reaction 5h room temperature at 220 DEG C, cross diafiltration through deionized water
Again with absolute ethanol washing, 50 DEG C of forced air drying 24h after washing, prepare N doping presoma.
(2) N doping presoma is added a certain amount of deionized water with KOH 1:4 in mass ratio and be mixed in 70 DEG C of stirrings (before 1g
Drive body and add 20mL deionized water), it is put in 80 DEG C of dry 24h in porcelain boat in thick rear taking-up.Last at N2Protect lower 700 DEG C of pipes
After calcining 2h in formula stove, cooling is taken out.Add the ultrasonic 30min of dehydrated alcohol after adding the ultrasonic 30min of a certain amount of deionized water again, take out
Filter drying obtains nitrogen-doped porous carbon material.
(3) Sublimed Sulfur is mixed with 1:2 mol ratio with nitrogen-doped porous carbon material, put in crucible, in 50 DEG C of vacuum
Drying baker processes 12h, and after drying, the politef reactor of full nitrogen put into by sample, and 158 DEG C keep 12h.Beat subsequently
Open 200 DEG C of heat treatment 3h of reactor, remove the sulfur of conductive black excess surface.Grind after being finally cooled to room temperature i.e. obtain sulfur/
Porous carbon composite positive pole.
It is above specific embodiment provided by the present invention, it should be pointed out that the application of the present invention is not limited to above-mentioned
Citing, can be improved according to the above description or be converted, and all these modifications and variations all should belong to right appended by the present invention
The protection domain required.
By to tetra-kinds of different nitrogen of C1, C2, C3 and C4 obtained in the present invention four different embodiment steps (2)
Doped porous carbon material is scanned its surface topography of electron microscopic observation respectively, obtains nitrogen-doped porous carbon material as shown in Figure 1
SEM figure.By Fig. 1 it is recognised that the uniform pore diameter of C1, C2, C3 sample, based on the frame structure of mesoporous type.The hole of C2
Footpath is uniform, regular appearance is better than C1, C3.On the contrary, C4 is too high due to nitrogen content, reunites serious between granule, and pore-size distribution is uneven.
By above-mentioned analysis it is found that the pattern of C2 material is preferable, more conducively proton or the quick deintercalation of ion, have this shape
The material of looks may have more preferable electrochemical properties.
By to the N doping porous carbon different for C1, C2, C3, C4 etc. four kinds obtained by four different embodiments of the present invention
Material carries out N2 adsorption and pore-size distribution test respectively, obtain nitrogen-doped porous carbon material as shown in Figure 2 N2 adsorption curve,
The N2 adsorption of the nitrogen-doped porous carbon material shown in the pore size distribution curve figure of the nitrogen-doped porous carbon material shown in Fig. 3 and table 1
Curve and pore size distribution data table.The feature of the sample Adsorption and desorption isotherms that nitrogen content is different is low-pressure area as can be seen from Figure 2
Adsorbance is big, and along with the increase of pressure, absorption increment is little, and formation one, close to horizontal platform, is i.e. adsorbed and is desorbed same
Shi Jinhang, and adsorbance is close to desorption rate；Illustrate that these nitrogen-doped porous carbon material central hole structures are mainly with the form of micropore
Exist.The adsorption isotherm of sample is the transitional region occurring between 0-0.1 tilting at relative pressure, and is more than at relative pressure
Less time stagnant ring occurs when 0.6, shows that these nitrogen-doped porous carbon materials also have multilamellar absorption to occur, i.e. there is some
Aperture and mesopore.From Fig. 3 and table 1 pore analysis it can be seen that the aperture of sample is mainly distributed on about 2nm, this explanation is ground
The nitrogen-doped porous carbon material studying carefully preparation is a kind of existing micropore, is also enriched in the carbon material of middle macropore.Wherein sample C2 adsorbance
Maximum, specific surface area can reach 880/g；The loose structure of nitrogen-doped porous carbon material makes electrolyte can be easier to penetrate into material
Inside material granule, shorten the solid-state diffusion path of lithium ion, reduce its diffusional resistance, be ideal nitrogen-doped porous carbon
Material.
The N2 adsorption curve of nitrogen-doped porous carbon material corresponding to table 1 embodiment of the present invention 1,2,3,4 and pore-size distribution number
According to
According to Fig. 1, Fig. 2 and Fig. 3 it is concluded that, we use the N doping of reaction condition gained in embodiment 2
Porous carbon materials as object of study, to the sulfur prepared by its nitrogen-doped porous carbon material and this nitrogen-doped porous carbon material thereof/
Porous carbon composite (C2-S) carries out X-ray diffraction analysis, obtains XRD figure as shown in Figure 4.From fig. 4, it can be seen that C2
XRD diffraction spectrogram have a wider diffraction maximum at 25 °, corresponding (002) crystal face, illustrate that it has graphited architectural feature.C2-
S diffraction maximum near 23 ° is element sulphur diffraction maximum, and peak type is shallower, illustrate sulfur with little molecular dispersion in the duct of mesoporous carbon
In, sulfur/porous carbon composite surface sulfur content is relatively low, and this is favorably improved sulfur/porous carbon composite chemical property.
Sulfur/porous carbon composite positive pole that we use embodiment 2 to prepare is active substance, and Super-P is conductive electrode,
Segregation fluorothene (PVDF) is binding agent.Successively according to active substance: Super-P: the ratio of segregation fluorothene=80:10:10
Slurry is obtained after mixing with N-Methyl pyrrolidone (NMP) and grind.Slurry is coated in current collector aluminum foil, after vacuum drying
Punching, prepares the positive pole disk of a diameter of 10mm.
Test Selection of Battery CR2032 button cell, negative pole selects the metal lithium sheet of diameter 14mm, electrolyte selection 1mol/
L LiTFSI/DOL+DME (1:1, the V/V) LiNO Han 0.4mol/L3, it is electrolysed with negative electrode casing shell fragment pad lithium sheet
Battery is packaged by the order of liquid barrier film positive plate pad anode cover, and whole process is all being filled with the glove of argon
Case completes.
Test equipment choosing new prestige Neware BTS tests system, discharge and recharge blanking voltage scope 1.5～3.0V, test temperature
Spend 25 DEG C, the discharge capacity first of record battery.The battery making sulfur/porous carbon composite positive pole is in the last fortnight discharge and recharge
Test obtains charging and discharging curve as shown in Figure 5, and sulfur/porous carbon composite positive pole is made battery and followed under 0.2C multiplying power
Ring test, obtains cyclic curve figure as shown in Figure 6.The electricity as can be seen from Figure 5 sulfur/porous carbon composite positive pole made
Pond occurs two voltage platforms near 2.3V and 2.1V, meets lithium-sulfur cell two step exoelectrical reaction, but theoretical lithium-sulfur cell is put
Level platform should be at 2.4V and 2.1V, and first voltage platform of this battery is on the low side, and main cause is sulfur/porous carbon anode composite material
Little molecular sulfur is had stronger absorbability can cause certain polarization phenomena by the microcellular structure of material, occurs that voltage platform is delayed,
But have no effect on its functional effect as electrode material.Fig. 6 is following the battery that sulfur/porous carbon composite positive pole is made
Ring performance curve, this sulfur/porous carbon composite positive pole head week discharge capacity 892mAh/g, after circulating 50 weeks, discharge capacity can also
Keeping 642mAh/g, capability retention is 72%, and loop attenuation is shallower；Visible sulfur/porous carbon anode composite composite tool
There are good reversibility and cyclical stability.
It is above to make the purpose of the present invention, technical scheme and Advantageous Effects become apparent from understanding, in conjunction with accompanying drawing
And detailed description of the invention, the present invention is further elaborated.It should be appreciated that the concrete reality described in this specification
The mode of executing is only used to explain the present invention, is not intended to limit the present invention.
Claims (9)
1. a preparation method for sulfur/porous carbon composite positive pole, comprises the steps:
(1) the pre-carbonization of hydro-thermal: weigh a certain amount of glucose and be dissolved in deionized water, add certain mass organic nitrogen source in
Solution is transferred in reactor after stirring, mix homogeneously, after hydro-thermal reaction a period of time at a certain temperature, is cooled to room temperature
Rear taking-up, again with absolute ethanol washing, 50 DEG C of forced air drying 24h after deionized water filtration washing, prepares N doping forerunner
Body；
(2) activation: N doping presoma obtained in step 1 is mixed with certain mass ratio with expanding agent, adds deionized water,
Stir at 70 DEG C, be put in porcelain boat in thick rear taking-up and be dried；Finally forge under inert gas shielding in high temperature process furnances
After burning certain time, cooling is taken out；With a certain amount of deionized water ultrasonic after to add dehydrated alcohol more ultrasonic, final sucking filtration is dried
To doping nitrogen porous carbon materials；
(3) prepared by sulfur/porous carbon composite positive pole: mixed with different mol ratio from doping nitrogen porous carbon materials by sulfur,
Vacuum drying oven dried, is subsequently placed in the politef reactor of full noble gas, and 158 DEG C keep 12h, now
The mobility of sulfur is higher；Open reactor heat treatment at a certain temperature some hours, remove the sulfur of conductive black excess surface；
Reaction is ground after terminating and is i.e. obtained sulfur/porous carbon composite positive pole.
2. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described organic nitrogen
Source is acetamide.
3. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described hydro-thermal is anti-
The temperature answered is 200～220 DEG C；Response time is 4～6h.
4. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described expanding agent
For KOH.
5. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described N doping
Presoma is 1:3～1:4 with the mass ratio of expanding agent.
6. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described high-temperature pipe
The temperature of formula stove is 500～700 DEG C；Calcination time is 2～4h.
7. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described indifferent gas
Body is N2。
8. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described sulfur with mix
The mol ratio of miscellaneous nitrogen porous carbon materials is 1:1～1:2.
9. the preparation method of sulfur/porous carbon composite positive pole as claimed in claim 1, it is characterised in that: described heat treatment
Temperature be 200 DEG C, the time of described heat treatment is 2～3h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107572523A (en) * | 2017-09-11 | 2018-01-12 | 桂林电子科技大学 | A kind of classifying porous carbosphere of N doping and its preparation method and application |
| CN107591528A (en) * | 2017-09-26 | 2018-01-16 | 珠海光宇电池有限公司 | Carbon sulphur composite for lithium-sulphur cell positive electrode and preparation method thereof |
| CN107887586A (en) * | 2017-11-06 | 2018-04-06 | 陈少华 | A kind of preparation method of ion cathode material lithium |
| CN109037664A (en) * | 2018-07-05 | 2018-12-18 | 华南理工大学 | A kind of carbon-coated Mo of N doping2The preparation method of C/C functional composite material and its application in lithium-sulfur cell |
| CN109354004A (en) * | 2018-10-17 | 2019-02-19 | 西安理工大学 | A method of classifying porous carbon material is prepared using fish scale |
| CN109473647A (en) * | 2018-11-01 | 2019-03-15 | 东莞市迈科新能源有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN109734083A (en) * | 2019-01-30 | 2019-05-10 | 河南工程学院 | Micro- mesoporous carbon of a kind of high-graphitized boron doping " dumbbell shape " and preparation method thereof |
| CN109961965A (en) * | 2017-12-22 | 2019-07-02 | 中国电子科技集团公司第十八研究所 | Preparation method of nitrogen-doped porous carbon material for chemical capacitor |
| CN109980217A (en) * | 2019-03-26 | 2019-07-05 | 华南理工大学 | A kind of flexible self-supporting lithium-sulphur cell positive electrode and preparation method thereof based on natural fiber |
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| CN114583146A (en) * | 2022-05-06 | 2022-06-03 | 湖南大学 | Preparation method of sodium-sulfur battery positive electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107572523A (en) * | 2017-09-11 | 2018-01-12 | 桂林电子科技大学 | A kind of classifying porous carbosphere of N doping and its preparation method and application |
| CN107591528A (en) * | 2017-09-26 | 2018-01-16 | 珠海光宇电池有限公司 | Carbon sulphur composite for lithium-sulphur cell positive electrode and preparation method thereof |
| CN107887586A (en) * | 2017-11-06 | 2018-04-06 | 陈少华 | A kind of preparation method of ion cathode material lithium |
| CN109961965A (en) * | 2017-12-22 | 2019-07-02 | 中国电子科技集团公司第十八研究所 | Preparation method of nitrogen-doped porous carbon material for chemical capacitor |
| CN109037664A (en) * | 2018-07-05 | 2018-12-18 | 华南理工大学 | A kind of carbon-coated Mo of N doping2The preparation method of C/C functional composite material and its application in lithium-sulfur cell |
| CN109037664B (en) * | 2018-07-05 | 2021-11-19 | 华南理工大学 | N-doped carbon-coated Mo2Preparation method of C/C functional composite material and application of C/C functional composite material in lithium-sulfur battery |
| CN109354004B (en) * | 2018-10-17 | 2021-06-15 | 西安理工大学 | Method for preparing hierarchical porous carbon material by using fish scales |
| CN109354004A (en) * | 2018-10-17 | 2019-02-19 | 西安理工大学 | A method of classifying porous carbon material is prepared using fish scale |
| CN109473647A (en) * | 2018-11-01 | 2019-03-15 | 东莞市迈科新能源有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN109734083A (en) * | 2019-01-30 | 2019-05-10 | 河南工程学院 | Micro- mesoporous carbon of a kind of high-graphitized boron doping " dumbbell shape " and preparation method thereof |
| CN109980217A (en) * | 2019-03-26 | 2019-07-05 | 华南理工大学 | A kind of flexible self-supporting lithium-sulphur cell positive electrode and preparation method thereof based on natural fiber |
| CN111554891A (en) * | 2020-04-24 | 2020-08-18 | 天津大学 | Method for preparing lithium-sulfur battery cathode material from three-dimensional mesoporous biochar |
| CN112563449A (en) * | 2021-01-05 | 2021-03-26 | 齐鲁工业大学 | Preparation method of double-layer electrode material of lithium-sulfur battery |
| CN114583146A (en) * | 2022-05-06 | 2022-06-03 | 湖南大学 | Preparation method of sodium-sulfur battery positive electrode material |
| CN114583146B (en) * | 2022-05-06 | 2022-07-29 | 湖南大学 | Preparation method of sodium-sulfur battery positive electrode material |
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