CN106207136B - A kind of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof - Google Patents
A kind of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof Download PDFInfo
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- CN106207136B CN106207136B CN201610813685.0A CN201610813685A CN106207136B CN 106207136 B CN106207136 B CN 106207136B CN 201610813685 A CN201610813685 A CN 201610813685A CN 106207136 B CN106207136 B CN 106207136B
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a kind of silkworm excrement multi-stage porous charcoal composite sulfur positive electrodes and preparation method thereof.First by silkworm excrement and ZnCl2Mixing is placed in high temperature process furnances, and after leading to protective gas purging, heating reaction obtains silkworm excrement multi-stage porous charcoal SPC；It is then placed in quartz ampoule, then pours into sulphur powder into quartz ampoule, do not contacted directly with SPC；Vacuumize, seal after be put into drying box, be warming up to 120~160 DEG C reaction after take out cooled to room temperature, obtain SPC/S1Composite material；It places it in hypo solution and stands again, then hydrochloric acid solution is added dropwise and carries out the secondary load 2~5h of reaction of Salmon-Saxl of chemical deposition, after centrifugal filtration, obtain SPC/S composite material in drying.The present invention loads sulphur using vacuum-steam method, chemical solution deposition, is conducive to sulphur in the multi-stage porous charcoal hole wall deposition growing of strong adsorption potential, is remarkably improved sulphur adsorption and uniform dispersion on carrier, improves the electric specific capacity of anode.
Description
Technical field
The invention belongs to materials chemistries and electrochemical technology field, and in particular to porous carbon material and its lithium-sulfur cell material
And preparation method thereof.
Background technique
The excessive exploitation and a large amount of consumption of fossil energy have caused increasingly serious global energy crisis and environmental problem, sternly
The living environment of the mankind and the sustainable development of social economy have been threatened again.Therefore, accelerate that especially clean to new energy can be again
The development and utilization of the raw energy is top priority and severe challenge of the human society in the facing of new century.It recycles available
Secondary cell is the excellent energy storage device of various renewable energy (such as solar energy, wind energy, tide energy), is that the following cleaning can be again
The raw indispensable important composition of the energy, there is great social demand.
In recent years, lithium-sulfur cell is concerned as the lithium secondary battery of high-energy density of new generation.Its theory compares energy
Amount may be up to 2600Wh/kg, be higher by 6-7 times than lithium ion battery energy density, can support a kart continuation of the journey 500-
800km or more, thus be concerned, and be considered as one of following most promising energy-storage battery system.
The performance of sulphur positive electrode is the key that determine lithium-sulfur cell quality height in lithium-sulfur cell.However, being limited to sulphur
And its it is produced among the electric conductivity that discharging product lithium sulfide is poor, and a series of more lithium sulfides formed in charge and discharge process
Object is soluble in the disadvantages of organic electrolyte, and that there are still sulphur anode utilization rates is lower (especially under high current density for lithium-sulfur cell
Charge and discharge) and the problems such as poor circulation, become the maximum bottleneck for hindering lithium-sulfur cell practical application.
If sulphur can be homogeneously dispersed in the form of small particle size among a kind of porous material with good conductivity, a side
Face can effectively improve the utilization rate of sulphur；On the other hand, can effectively be inhibited again using the adsorption effect of conductive carrier
The loss of sulphur and its discharging product (more lithium sulfides) on anode pole piece.Therefore, by sulphur with carbon material is compound can prepare height
Capacity and the excellent anode composite material of lithium sulfur battery of cycle performance.Silkworm excrement is the main waste of silkworm industry, is passed through in rural area
Chang Suiyi discarding lead to environmental pollution, from Electron microscope from known to its with natural three-dimensional drape structure and phosphorus content height,
High-ratio surface multiporous biological charcoal can be obtained through high temperature cabonization and activation.
Currently, people, which mostly use step melting diffusion method to inject sulphur component, carries formation lithium sulphur anode composite wood in sulfur materials
Material.There are the following problems for the method: (1) sulphur is bad with the wellability of porous material hole wall in the molten state, it tends to be difficult to
Go deep into inside duct in especially micropore hole, and blocks duct；(2) sulphur component and porous material hole wall binding force are lower, dispersion
Unevenly.These two aspects largely affects the high rate performance of composite material entirety, while being easy to cause composite material
Middle utilization efficiency is not high, and the discharge capacity of battery reduces；Furthermore sulphur component is not easy to diffuse into micropore canals, reduces it and carries sulphur
The adsorption of material, the polysulfide for causing reaction to generate are easier to be dissolved into organic electrolyte, accelerate lithium-sulfur cell
Capacity attenuation speed.
Summary of the invention
The present invention carries that sulphur is uneven and adsorption capacity is weak for existing porous material and leads to composite material poor circulation etc.
Problem provides a kind of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof, utilizes gas phase steam absorption-chemical solution
Sulphur component is supported in the duct of silkworm excrement multi-stage porous charcoal by the process of deposition with nano particle size, obtains high dispersive and strong absorption combines
Carbon sulphur composite material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, the material have mesoporous (2~50nm) and micropore (< 2nm) two
Kind duct, micropore has strong adsorption to sulfur molecule, and mesoporous mentions for the discharging product of electronics, ion and sulphur and sulphur
For quick diffusion admittance；The BET specific surface area of obtained SPC material is in 1250-1460m2/ g, micropore average pore size existThe average pore size of mesoporous existsObtained SPC/S composite material is up to 630- in 6.0C discharge capacity
660mAh/g, and the specific discharge capacity at high magnification 3.0C after 120 circle of circulation is up to 623-655mAh/g, capacity retention ratio is high
Up to 86% or more.
The preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode of the invention, includes the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal: by silkworm excrement and ZnCl2Powder mixing, is placed in high temperature process furnances, leads to protection gas
After body purging, it is heated to 300-700 DEG C and is reacted to obtain silkworm excrement multi-stage porous charcoal；It is denoted as SPC；
(2) silkworm excrement multi-stage porous charcoal uploads sulphur: first silkworm excrement multi-stage porous carbon powder being put into quartz ampoule, then pours into sulphur powder into stone
Ying Guanzhong is not contacted directly with silkworm excrement multi-stage porous charcoal；Vacuumize, seal after be put into drying box, be warming up to 120~160 DEG C, then
Constant temperature takes out cooled to room temperature after keeping 8~20h, obtains SPC/S1Composite material；
(3) secondary load sulphur: by SPC/S1Composite material is placed in hypo solution and stands, then be added dropwise hydrochloric acid solution into
Row chemical deposition secondary load 2~5h of reaction of Salmon-Saxl after centrifugal filtration, obtains silkworm excrement multi-stage porous charcoal composite sulfur positive electrode in drying,
It is denoted as SPC/S composite material.
As the further preferred of scheme, step (1) the high temperature carburizing reagent time is 0.5~5h, protectiveness gas
Nitrogen, the inert gases such as argon gas can be used in body；Range of reaction temperature is 300-700 DEG C；ZnCl2With the mass ratio of silkworm excrement be (1~
6):1；
As the further preferred of scheme, vacuum degree≤100Pa in control quartz ampoule in the step (2)., drying box adopts
With can temperature programmed control drying box, specific temperature control process:
(a) 120~160 DEG C temperature-rise period: are risen to from room temperature with the heating rate of 0.5~2.0 DEG C/min；
(b) 120~160 DEG C of 10~15h of holding thermostatic process: are placed in；
(c) temperature-fall period: taking out out of drying box immediately after thermostatic process, cooled to room temperature.
As the further preferred of scheme, hypo solution and SPC/S in the step (3)1The matter of composite material
For amount than being 4~10:1, time of repose is 5~10h.
As the further preferred of scheme, the molar ratio of hydrochloric acid and sodium thiosulfate is 3~11:1 in the step (3),
The concentration that sodium thiosulfate can be used is 0.03~0.20mol/L, and concentration of hydrochloric acid is 3~10wt%.
The principle of the present invention: keep gaseous sulfur Molecular Adsorption silkworm excrement multistage by vapor sorption mode under vacuum conditions first
On the most strong adsorption site of hole Carbon Materials, sulphur microcrystals is formed in the micropore canals of silkworm excrement multi-stage porous charcoal, obtains silkworm excrement multistage
Hole charcoal sulphur SPC/S1Composite material.Recycle chemical solution deposition by SPC/S1Composite material is placed in Na2S2O3In solution, slowly
Hydrochloric acid solution is added dropwise, sulphur is precipitated slowly on the existing sulphur nucleus of silkworm excrement multi-stage porous charcoal, forms sulphur Load Balanced and adsorption capacity
Strong silkworm excrement multi-stage porous charcoal sulphur composite material.The strong adsorption and uniform load of sulphur can effectively improve leading for composite material entirety
Electrical and sulphur simple substance utilization rate, to promote the high rate capability and long-acting cycle performance of composite material.
Silkworm excrement multi-stage porous charcoal composite sulfur positive electrode of the invention recycled at 3.0C 120 circle after specific discharge capacity be up to
660mAh/g, hence it is evident that be higher than directly melting diffusion and carry charcoal sulphur composite positive pole obtained by sulphur and conventional lithium-ion battery material
2~3 times of specific capacity.
Compared with prior art, the present invention is advantageous in that:
(1) carrier used in the present invention is silkworm excrement multi-stage porous charcoal, belongs to waste utilization, from a wealth of sources and low in cost,
The reaming one-step method that is carbonized is completed, and process is simple and environmentally friendly；
(2) structure for the fold having using silkworm excrement itself is carbon source, and by being carbonized, reaming can form three-dimensional network intercommunication
Hierarchical porous structure, micropore surface is conducive to improve the adsorption capacity to sulphur, and mesoporous can then provide defeated for lithium ion and electrolyte
Channel is sent, the diffusional resistance of lithium ion and electrolyte is reduced.
(3) active sulphur component can be equably carried in the duct of SPC-MILs by the present invention using vapor diffusion, can
So that sulphur component occupies most strong adsorption site and forms small S crystal seed, then more S can be loaded by chemical solution deposition
In strong adsorption potential, this aspect can effectively improve the adhesive force of sulphur component and carrier and the contact surface of sulphur component and conductive hole wall
On the other hand product also can effectively avoid melting diffusion method from bringing duct blocking linear, and then improve the utilization efficiency of sulphur, simultaneously
The cycle performance of long-acting circulation can be obtained.
(4) silkworm excrement multi-stage porous charcoal composite sulfur positive electrode high rate performance with higher of the invention and excellent cyclicity
Can, present good industrial applications prospect.
(5) preparation method of the invention is simple to operation, is suitble to large-scale industrial production.
Detailed description of the invention
Fig. 1 is the SEM of silkworm excrement；
Fig. 2 is the SEM figure of silkworm excrement multi-stage porous charcoal；
Fig. 3 is the thermal gravimetric analysis curve figure of SPC/S composite material of the present invention；
Fig. 4 is the 6.0C rate charge-discharge curve graph of SPC/S composite material of the present invention；
After one SPC/S composite material of Fig. 5 embodiment of the present invention activates 2 circles at 0.5C (840mA/g), 3.0C (5040mA/
G) cycle performance figure under multiplying power.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
A kind of preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, includes the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal
In N2By 10.0g Faeces bombycis and 10.0g ZnCl in atmosphere2Powder is raised to 300 DEG C with the heating rate of 2 DEG C/min, and
Room temperature is cooled to after keeping 0.5h at 300 DEG C, silkworm excrement multi-stage porous charcoal is obtained, is denoted as SPC.
(2) vacuum-steam method uploads sulphur in silkworm excrement multi-stage porous charcoal
First 0.3gSPC powder is laid in Noah's ark, and Noah's ark is slowly pushed into the middle part of quartz ampoule.1g sulphur powder is poured into
In quartz ampoule, do not contacted directly with SPC；Vacuumize (vacuum degree is in≤100Pa), sealing after put it into can temperature programmed control baking
In dry case, 120 DEG C are warming up to according to the heating rate with 0.5 DEG C/min, constant temperature takes out cooled to room temperature after keeping 8h, obtains
To SPC/S1Composite material.
(3) chemical solution deposition is in SPC/S1Secondary load sulphur on composite material
By 0.1g SPC/S1Composite material, which is placed in the hypo solution of 100mL, stands 5h, sodium thiosulfate it is dense
Degree is in 0.03mol/L；Then the hydrochloric acid solution 12mL that concentration 3wt% is slowly added dropwise sufficiently reacts 2h；After centrifugal filtration, at 80 DEG C
Under be dried for standby, sample be labeled as SPC/S composite material.
Embodiment 2
A kind of preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, includes the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal
In N2By 10.0g Faeces bombycis and 30.0g ZnCl in atmosphere2Powder is raised to 400 DEG C with the heating rate of 5 DEG C/min, and
Room temperature is cooled to after keeping 1.0h at 400 DEG C, silkworm excrement multi-stage porous charcoal is obtained, is denoted as SPC.
(2) vacuum-steam method uploads sulphur in silkworm excrement multi-stage porous charcoal
First 1.0g silkworm excrement multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed into the middle part of quartz ampoule.
The sulphur powder of 2g is poured into quartz ampoule, is not contacted directly with silkworm excrement multi-stage porous charcoal SPC；It vacuumizes (vacuum degree is in≤100Pa), close
It is honored as a queen and puts it into and can be warming up to 140 DEG C according to the heating rate with 1.0 DEG C/min, constant temperature is protected in the drying box of temperature programmed control
Cooled to room temperature is taken out after holding 14h, obtains SPC/S1Composite material.
(3) chemical solution deposition is in SPC/S1Secondary load sulphur on composite material
By 0.6g SPC/S1Composite material, which is placed in the hypo solution of 200mL, stands 7h, sodium thiosulfate it is dense
Degree is in 0.12mol/L；Then the hydrochloric acid solution 120mL that concentration 6wt% is slowly added dropwise sufficiently reacts 4h；After centrifugal filtration, 80
It is dried for standby at DEG C, sample is labeled as SPC/S composite material.
Embodiment 3
A kind of preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, includes the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal
In N2By 10.0g Faeces bombycis and 40.0g ZnCl in atmosphere2Powder is raised to 500 DEG C with the heating rate of 3 DEG C/min, and
Room temperature is cooled to after keeping 2.0h at 500 DEG C, silkworm excrement multi-stage porous charcoal is obtained, is denoted as SPC.
(2) vacuum-steam method uploads sulphur in silkworm excrement multi-stage porous charcoal
First 2.0g silkworm excrement multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed into the middle part of quartz ampoule.
A certain amount of sulphur powder is poured into quartz ampoule, is not contacted directly with silkworm excrement multi-stage porous charcoal SPC；Vacuumize (vacuum degree≤
100Pa), 160 can be warming up to according to the heating rate with 2.0 DEG C/min in the drying box of temperature programmed control by putting it into after sealing
DEG C, constant temperature takes out cooled to room temperature after keeping 20h, obtains SPC/S1Composite material.
(3) chemical solution deposition is in SPC/S1Secondary load sulphur on composite material
By 1.0g SPC/S1Composite material, which is placed in the hypo solution of 300mL, stands 10h, sodium thiosulfate
Concentration is in 0.20mol/L；Then the hydrochloric acid solution 240mL that concentration 10wt% is slowly added dropwise sufficiently reacts 5h；After centrifugal filtration,
It is dried for standby at 80 DEG C, sample is labeled as SPC/S composite material.
Embodiment 4
A kind of preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, includes the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal
In N2By 10.0g Faeces bombycis and 50.0g ZnCl in atmosphere2Powder is raised to 600 DEG C with the heating rate of 6 DEG C/min, and
Room temperature is cooled to after keeping 3.0h at 600 DEG C, silkworm excrement multi-stage porous charcoal is obtained, is denoted as SPC.
(2) vacuum-steam method uploads sulphur in silkworm excrement multi-stage porous charcoal
First 0.6g silkworm excrement multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed into the middle part of quartz ampoule.
A certain amount of sulphur powder is poured into quartz ampoule, is not contacted directly with silkworm excrement multi-stage porous charcoal SPC；Vacuumize (vacuum degree≤
100Pa), 130 can be warming up to according to the heating rate with 1.0 DEG C/min in the drying box of temperature programmed control by putting it into after sealing
DEG C, constant temperature takes out cooled to room temperature after keeping 10h, obtains SPC/S1Composite material.
(3) chemical solution deposition is in SPC/S1Secondary load sulphur on composite material
By 0.3g SPC/S1Composite material, which is placed in the hypo solution of 150mL, stands 6h, sodium thiosulfate it is dense
Degree is in 0.07mol/L；Then the hydrochloric acid solution 60mL that concentration 4wt% is slowly added dropwise sufficiently reacts 3h；After centrifugal filtration, at 80 DEG C
Under be dried for standby, sample be labeled as SPC/S composite material.
Embodiment 5
A kind of preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, includes the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal
In N2By 10.0g Faeces bombycis and 60.0g ZnCl in atmosphere2Powder is raised to 700 DEG C with the heating rate of 4 DEG C/min, and
Room temperature is cooled to after keeping 5.0h at 700 DEG C, silkworm excrement multi-stage porous charcoal is obtained, is denoted as SPC.
(2) vacuum-steam method uploads sulphur in silkworm excrement multi-stage porous charcoal
First 1.5g silkworm excrement multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed into the middle part of quartz ampoule.
A certain amount of sulphur powder is poured into quartz ampoule, is not contacted directly with silkworm excrement multi-stage porous charcoal SPC；Vacuumize (vacuum degree≤
100Pa), 150 can be warming up to according to the heating rate with 2.0 DEG C/min in the drying box of temperature programmed control by putting it into after sealing
DEG C, constant temperature takes out cooled to room temperature after keeping 18h, obtains SPC/S1Composite material.
(3) chemical solution deposition is in SPC/S1Secondary load sulphur on composite material
By 0.8g SPC/S1Composite material, which is placed in the hypo solution of 250mL, stands 9h, sodium thiosulfate it is dense
Degree is in 0.18mol/L；Then the hydrochloric acid solution 190mL that concentration 9wt% is slowly added dropwise sufficiently reacts 4h；After centrifugal filtration, 80
It is dried for standby at DEG C, sample is labeled as SPC/S composite material.
Material properties test:
(1) surface topography of SPC/S composite material
Silkworm excrement multi-stage porous charcoal prepared by the present invention and silkworm excrement are subjected to electron-microscope scanning, obtain the SEM figure of FIG. 1 to FIG. 2.
Fig. 1 is the SEM photograph of Faeces bombycis, and Fig. 2 is the SEM photograph of silkworm excrement multi-stage porous charcoal SPC.
It can be seen that compared with Faeces bombycis in comparison diagram 1 and Fig. 2, silkworm excrement multi-stage porous charcoal wrinkled surface fades away, and occurs
Duct and channel design very rich, channel interior are also may be seen indistinctly more tiny duct, and multiple aperture hole is showed
Road net distribution pattern.This structure is advantageous to the load of S.
(2) silkworm excrement multi-stage porous charcoal, SPC/S1And the pore structure parameter of SPC/S composite material
Using the ASAP-2020 specific surface pore-size distribution instrument of Micro company of U.S. production to silkworm excrement multi-stage porous SPC, SPC/
S1And the pore structure of SPC/S composite material is characterized, the results are shown in Table 1.
Table 1 SPC, SPC/S1With the pore structure parameter of SPC/S
As can be seen from Table 1, silkworm excrement multi-stage porous charcoal SPC specific surface area with higher, Langmuir and BET specific surface
Product is respectively 955 and 1202m2/ g, total pore volume 0.42cm3/g.This explanation is after high-temperature activation reacts, in Faeces bombycis duct
Oxygen-containing group and some tar components be removed, while activator ZnCl2Have it is strong take hydrogen by force and take oxygen function by force, by silkworm excrement
The multi-stage porous cellular structure of micropore and mesoporous is etched on internal channel.The material is that a kind of have multi-stage porous (in/micropore) carbon materials
Material, wherein micropore can form stronger adsorption to sulphur and polysulfide, help to improve the circulation of sulphur composite material
Stability；Hollow sections then can provide transfer passage for lithium ion and electrolyte, reduce the diffusion of lithium ion and electrolyte
Resistance improves the high rate performance of battery.
Significantly declined by the specific surface area of SPC/S after steaming process and further chemical solution deposition load sulphur,
Langmuir specific surface area only remains 199m2/g；Its Kong Rong also sharp fall, the only hole SPC hold 26%；In addition, micropore hole
Hold and the equal sharp fall of micropore specific area, this surface sulphur component (are connected to outside particle from the exit orifice of silkworm excrement multi-stage porous charcoal
The macropore on surface is mesoporous) it is diffused among inner hole.
(3) thermogravimetric curve of SPC/S composite material
It is multiple to SPC/S prepared by the present invention using the STA449C pattern synthesis thermal analyzer of German NETZSCH company production
Condensation material carry out heat stability testing, test condition are as follows: nitrogen protection, heating rate be 10 DEG C/min, temperature elevating range be 100~
450℃.Test results are shown in figure 3.
From figure 3, it can be seen that weightlessness takes place at 305 DEG C in SPC/S composite material prepared by the present invention, to 385 DEG C
Shi Chongliang is no longer changed, and weightlessness terminates, and weight-loss ratio is about 72.0%.Weight-loss ratio corresponds to the sulfur content of composite material,
That is the sulfur content of the composite material is about 72.0%.It can be seen that preparation method of the present invention help to obtain high-sulfur
The composite positive pole of content, while the higher adsorption for illustrating S and silkworm excrement multi-stage porous charcoal of evaporating temperature of S is stronger.
(4) chemical property of SPC/S composite material
Fig. 4 shows anode SPC/S composite positive pole filling at ultra-high magnifications 6.0C (1C=1680mAh/g)
Discharge curve.The discharge platform that can be seen that battery from the charging and discharging curve of battery remain two (~2.2V and~
1.8V), it illustrates the stable structure of SPC/S composite positive pole, is conducive to the high-energy-density for keeping battery.
Fig. 5 show one SPC/S composite material of the embodiment of the present invention activated at 0.5C (840mA/g) 2 circle after, 3.0C
Cycle performance figure under (5040mA/g) multiplying power.As shown, specific discharge capacity is still after material recycles 120 circles at 3.0C
Up to 651mAh/g, capacity retention ratio are up to 86.6%.Table 2 shows SPC/C composite material obtained by five kinds of embodiments and exists
Discharge performance and reversible capacity conservation rate are recycled under 3.0C.SPC/S composite material all has higher library in the condition tested
Human relations efficiency, this also illustrates that the combination of S and carrier silkworm excrement multi-stage porous charcoal is more close, while silkworm excrement multi-stage porous charcoal is also shown more
Excellent electric conductivity.
From Table 2, it can be seen that obtained SPC/S composite material is using in scope of experiment according to the present invention
After 120 circles, reversible capacity conservation rate is positively retained at 86% or more.This shows that the cycle performance of SPC/S composite material is excellent,
It still especially is able to keep higher specific capacity under the discharging condition under high magnification.It can be seen that being first melted in silkworm with steam
Little crystal grain sulphur is loaded on husky multi-stage porous charcoal, then carry sulphur by chemical solution deposition sulphur component can be evenly spread to SPC's
On the one hand micropore surface can effectively improve the utilization rate of sulphur, and then improve the specific discharge capacity of composite material；Another aspect and energy
Effective absorption to sulphur and its polysulfide generated is formed, capacity attenuation rate brought by Shuttle effect is reduced, is improved
The cyclical stability of composite material.
Discharge capacity of the SPC/S composite material under different multiplying obtained by five kinds of embodiments of the present invention is shown in table 3.From
It is found that obtained SPC/S composite material high rate performance is more excellent in scope of experiment according to the present invention in table.Electricity
Specific discharge capacity of the pond under 3.0 and 6.0C is up to 747-794 and 605-660mAh/g respectively；It can be seen that material is being surveyed
Try the cyclo-stationary of material in multiplying power change procedure, the specific discharge capacity with higher under high magnification.This and sulfur-donor silkworm
The big channel of husky multi-stage porous charcoal is related to the quickly conduction of lithium ion with electronics.
SPC/S composite material obtained by 2 five kinds of embodiments of table recycles discharge performance and reversible capacity conservation rate at 0.5C
Discharge capacity of the SPC/S composite material under different multiplying obtained by 3 five kinds of embodiments of table
Claims (9)
1. a kind of preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode, it is characterised in that: include the following steps,
(1) preparation of silkworm excrement multi-stage porous charcoal: by silkworm excrement and ZnCl2Powder mixing, is placed in high temperature process furnances, logical protective gas is blown
After sweeping, heating reaction obtains silkworm excrement multi-stage porous charcoal；
(2) silkworm excrement multi-stage porous charcoal uploads sulphur: first silkworm excrement multi-stage porous charcoal is put into quartz ampoule, then pours into sulphur powder into quartz ampoule,
It is not contacted directly with silkworm excrement multi-stage porous charcoal；Vacuumize, seal after be put into drying box, be warming up to 120~160 oC, then constant temperature protect
Cooled to room temperature is taken out after holding 8~20 h, obtains SPC/S1Composite material；
(3) secondary load sulphur: by SPC/S1Composite material is placed in hypo solution and stands, then hydrochloric acid solution is added dropwise
It learns and deposits secondary 2~5 h of load reaction of Salmon-Saxl, after centrifugal filtration, then dry to obtain silkworm excrement multi-stage porous composite sulfur positive electrode；The material
Duct inner height be dispersed with small molecule sulphur；Obtained silkworm excrement multi-stage porous charcoal composite sulfur positive electrode SPC/S composite material exists
Specific discharge capacity under 3.0 C after 120 circle of circulation is 622-655 mAh/g, and capacity retention ratio is up to 86% or more.
2. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 1, it is characterised in that: described
300 ~ 700 oC of reaction temperature is heated in step (1), the reaction time is 0.5-5 h.
3. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 1, it is characterised in that: described
ZnCl in step (1)2Mass ratio with silkworm excrement is 1~6: 1.
4. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 1, it is characterised in that: described
Vacuum degree≤100 Pa in quartz ampoule in step (2).
5. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 1, it is characterised in that: described
In step (2) drying box using can temperature programmed control drying box, specific temperature control process:
(a) 120~160 oC temperature-rise period: are risen to from room temperature with the heating rate of 0.5~2.0 oC/min；
(b) thermostatic process: 120~160 oC are placed in and keep 10~15 h；
(c) temperature-fall period: taking out out of drying box immediately after thermostatic process, cooled to room temperature.
6. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 1, it is characterised in that: described
Hypo solution and SPC/S in step (3)1The mass ratio of composite material is 4 ~ 10: 1.
7. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 1 or 4, it is characterised in that:
The molar ratio of hydrochloric acid and sodium thiosulfate is 3~11:1 in the step (3).
8. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 7, it is characterised in that: described
The concentration of sodium thiosulfate is 0.03~0.20mol/L in step (3).
9. the preparation method of silkworm excrement multi-stage porous charcoal composite sulfur positive electrode according to claim 7, it is characterised in that: described
Concentration of hydrochloric acid is 3~10 wt% in step (3).
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