CN106207136A - A kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof - Google Patents
A kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof.First by Bombyx mori L. and ZnCl2Mixing is placed in high temperature process furnances, and after logical protective gas purging, reacting by heating obtains Bombyx mori L. multi-stage porous charcoal SPC；It is then placed in quartz ampoule, then pours sulfur powder into and enter in quartz ampoule, directly do not contact with SPC；Put into drying baker after evacuation, sealing, take out after being warming up to 120～160 DEG C of reactions and naturally cool to room temperature, obtain SPC/S1Composite；It is placed in hypo solution standing again, then drips hydrochloric acid solution and carry out chemical deposition secondary and carry reaction of Salmon-Saxl 2～5h, after centrifugal filtration, obtain SPC/S composite in drying.The present invention uses vacuum and steam method, chemical solution deposition to load sulfur, and beneficially sulfur is at the multi-stage porous charcoal hole wall deposition growing of strong adsorption potential, is remarkably improved sulfur adsorption and uniform dispersion on carrier, improves the electric specific capacity of anode.
Description
Technical field
The invention belongs to materials chemistry and technical field of electrochemistry, be specifically related to porous carbon material and lithium-sulfur cell material thereof
And preparation method thereof.
Background technology
Excessively 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 socioeconomic sustainable development are heavily threatened.Therefore, accelerate that particularly clean new forms of energy can be again
The development and utilization of the raw energy is human society in the top priority of the facing of new century and severe challenge.Circulation can use
Secondary cell is the excellent energy storage device of various regenerative resource (such as solar energy, wind energy, tide energy etc.), is that following cleaning can be again
The raw indispensable important composition of the energy, has great social need.
In recent years, lithium-sulfur cell receives much concern as the lithium secondary battery of a new generation's high-energy-density.Its theory compares energy
Amount may be up to 2600Wh/kg, exceeds 6-7 times than lithium ion battery energy density, sustainable kart continuation of the journey 500-
More than 800km, thus receive much concern, and be considered as one of the most promising energy-storage battery system in future.
In lithium-sulfur cell, the performance of sulfur positive electrode is the key determining lithium-sulfur cell quality height.But, it is limited to sulfur
And the electric conductivity that discharging product lithium sulfide is poor, and produce in the middle of a series of many lithium sulfides formed in charge and discharge process
Thing is soluble in the shortcomings such as organic electrolyte, and it is relatively low (particularly under high current density that lithium-sulfur cell still suffers from sulfur positive pole utilization rate
Discharge and recharge) and cycle performance difference etc. problem, become hinder the actual application of lithium-sulfur cell maximum bottleneck.
If can sulfur be homogeneously dispersed among the porous material that a kind of electric conductivity is good with small particle size form, a side
Face can be effectively improved the utilization rate of sulfur；On the other hand, the surface adsorption effect utilizing conductive carrier can effectively suppress again
Sulfur and the discharging product (many lithium sulfides) loss on anode pole piece thereof.Therefore, height can be prepared by compound to sulfur and material with carbon element
Capacity and the anode composite material of lithium sulfur battery of cycle performance excellence.Bombyx mori L. is the main garbage of Bombyxmori Linnaeus industry, at rural area warp
Chang Suiyi abandons and causes environmental pollution, understands it from Electron microscope observation and has natural three-dimensional drape structure and phosphorus content height,
High-ratio surface multiporous biological charcoal can be obtained through high temperature cabonization and activation.
At present, people's many employings one step melts diffusion method and the injection of sulfur component is carried formation lithium sulfur positive pole composite wood in sulfur materials
Material.There is following problem in this method: (1) sulfur is the best with the wellability of porous material hole wall in the molten state, it tends to be difficult to
Go deep into inside duct particularly in micropore hole, and block duct；(2) sulfur component is relatively low with porous material hole wall adhesion, dispersion
Uneven.These two aspects have impact on the high rate performance that composite is overall to a great extent, is easily caused composite simultaneously
Middle utilization efficiency is the highest, and the discharge capacity of battery reduces；In addition sulfur component is difficult to diffuse into micropore canals, reduces it and carries sulfur
The adsorption of material, the polysulfide causing reaction to generate is easier to be dissolved in organic electrolyte, accelerates lithium-sulfur cell
Capacity attenuation speed.
Summary of the invention
The present invention is directed to existing porous material carry that sulfur is uneven and absorption affinity is weak and cause composite cycle performance difference etc.
Problem, it is provided that a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode and preparation method thereof, utilizes gas phase steam absorption-chemical solution
Sulfur component is supported in the duct of Bombyx mori L. multi-stage porous charcoal by the process of deposition with nano particle size, it is thus achieved that high dispersive and adsorb by force combination
Carbon sulfur composite.
The purpose of the present invention is achieved through the following technical solutions:
A kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, this material has mesopore (2～50nm) and micropore (< 2nm) two
Planting duct, its micropore has strong adsorption to sulfur molecule, and the discharging product that mesopore is electronics, ion and sulfur and sulfur carries
For quick diffusion admittance；The BET specific surface area of obtained SPC material is at 1250-1460m2/ g, micropore average pore size existsThe average pore size of mesopore existsObtained SPC/S composite is up to 630-at 6.0C discharge capacity
660mAh/g, and under high magnification 3.0C, circulate the specific discharge capacity after 120 circles be up to 623-655mAh/g, capability retention is high
Reach more than 86%.
The preparation method of the Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode of the present invention, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal: by Bombyx mori L. and ZnCl2Powder mixes, and is placed in high temperature process furnances, logical protection gas
After body purging, it is heated to 300-700 DEG C and carries out reaction and obtain Bombyx mori L. multi-stage porous charcoal；It is designated as SPC；
(2) Bombyx mori L. multi-stage porous charcoal uploads sulfur: first put in quartz ampoule by Bombyx mori L. multi-stage porous carbon powder, then pours sulfur powder into and enter stone
Ying Guanzhong, does not directly contact with Bombyx mori L. multi-stage porous charcoal；Put into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, then
Constant temperature takes out after keeping 8～20h and naturally cools to room temperature, obtains SPC/S1Composite；
(3) secondary carries sulfur: by SPC/S1Composite is placed in hypo solution standing, then drips hydrochloric acid solution and enter
Row chemical deposition secondary carries reaction of Salmon-Saxl 2～5h, after centrifugal filtration, obtains Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode in drying,
It is designated as SPC/S composite.
Further preferred as scheme, in described step (1), the high temperature cabonization response time is 0.5～5h, protectiveness gas
Body can use the noble gases such as nitrogen, argon；Range of reaction temperature is 300-700 DEG C；ZnCl2With the mass ratio of Bombyx mori L. be (1～
6):1；
Further preferred as scheme, controls vacuum≤100Pa in quartz ampoule in described step (2)., drying baker is adopted
With can temperature programmed control drying baker, concrete temperature control process:
(a) temperature-rise period: rise to 120～160 DEG C from room temperature with the heating rate of 0.5～2.0 DEG C/min；
(b) thermostatic process: be placed in 120～160 DEG C and keep 10～15h；
(c) temperature-fall period: thermostatic process takes out after terminating immediately in drying baker, naturally cools to room temperature.
Further preferred as scheme, hypo solution and SPC/S in described step (3)1The matter of composite
Amount ratio is 4～10:1, and time of repose is 5～10h.
Further preferred as scheme, in described step (3), hydrochloric acid is 3～11:1 with the mol ratio of sodium thiosulfate,
The concentration that can use sodium thiosulfate is 0.03～0.20mol/L, and concentration of hydrochloric acid is 3～10wt%.
The principle of the present invention: make gaseous sulfur Molecular Adsorption Bombyx mori L. multistage by vapor sorption mode the most under vacuum conditions
On the strongest adsorption site of hole Carbon Materials, the micropore canals of Bombyx mori L. multi-stage porous charcoal is formed sulfur microcrystals, obtains Bombyx mori L. multistage
Hole charcoal sulfur SPC/S1Composite.Recycling chemical solution deposition is by SPC/S1Composite is placed in Na2S2O3In solution, slowly
Dropping hydrochloric acid solution, makes sulfur slowly separate out on Bombyx mori L. multi-stage porous charcoal existing sulfur nucleus, forms sulfur Load Balanced and absorption affinity
Strong Bombyx mori L. multi-stage porous charcoal sulfur composite.The strong adsorption of sulfur and uniform load can be effectively improved overall the leading of composite
Electrically and the utilization rate of sulfur simple substance, thus promote the high rate capability of composite and long-acting cycle performance.
The Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode of the present invention circulates the specific discharge capacity after 120 circles up under 3.0C
660mAh/g, hence it is evident that carry sulfur gained charcoal sulfur composite positive pole higher than directly melted diffusion, be also 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 Bombyx mori L. multi-stage porous charcoal, belongs to twice laid, wide material sources and with low cost,
Carbonization reaming one-step method completes, and process is simple and environmental protection；
(2) structure utilizing the fold that Bombyx mori L. itself has is carbon source, can form three-dimensional network intercommunication by carbonization reaming
Hierarchical porous structure, micropore surface is conducive to improving absorption affinity to sulfur, and mesopore then can provide defeated for lithium ion and electrolyte
Send passage, reduce lithium ion and the diffusional resistance of electrolyte.
(3) present invention uses vapor diffusion active sulfur component to be carried on equably in the duct of SPC-MILs, can
So that sulfur component occupies the strongest adsorption site and forms little S crystal seed, more just more S can be loaded by chemical solution deposition
At strong adsorption potential, on the one hand this can be effectively improved the contact surface of sulfur component and the adhesive force of carrier and sulfur component and conduction hole wall
Long-pending, on the other hand also can be prevented effectively from melted diffusion method and bring duct blocking linear, and then improve the utilization ratio of sulfur, simultaneously
The cycle performance of long-acting circulation can be obtained.
(4) the Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode of the present invention has higher high rate performance and excellent cyclicity
Can, present good industrial applications prospect.
(5) preparation method of the present invention is simple to operation, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the SEM of Bombyx mori L.；
Fig. 2 is the SEM figure of Bombyx mori L. multi-stage porous charcoal；
Fig. 3 is the thermal gravimetric analysis curve figure of SPC/S composite of the present invention；
Fig. 4 is the 6.0C rate charge-discharge curve chart of SPC/S composite of the present invention；
After Fig. 5 embodiment of the present invention one SPC/S composite activates 2 circles under 0.5C (840mA/g), 3.0C (5040mA/
G) the cycle performance figure under multiplying power.
Detailed description of the invention
The present invention will be further described with embodiment below in conjunction with the accompanying drawings, but the scope of protection of present invention is not
It is confined to the scope of embodiment statement.
Embodiment 1
The preparation method of a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal
At 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
Cool to room temperature after keeping 0.5h at 300 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPC.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 0.3gSPC powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.1g sulfur powder is poured into
In quartz ampoule, directly do not contact with SPC；Evacuation (vacuum is at≤100Pa), seal after put it into can the baking of temperature programmed control
In dry case, being warming up to 120 DEG C according to the heating rate of 0.5 DEG C/min, constant temperature takes out after keeping 8h and naturally cools to room temperature,
To SPC/S1Composite.
(3) chemical solution deposition is at SPC/S1On composite, secondary carries sulfur
By 0.1g SPC/S1Composite is placed in the hypo solution of 100mL standing 5h, sodium thiosulfate dense
Degree is at 0.03mol/L；Then the hydrochloric acid solution 12mL being slowly added dropwise concentration 3wt% fully reacts 2h；After centrifugal filtration, at 80 DEG C
Lower dry for standby, sample is labeled as SPC/S composite.
Embodiment 2
The preparation method of a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal
At 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
Cool to room temperature after keeping 1.0h at 400 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPC.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 1.0g Bombyx mori L. multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.
The sulfur powder of 2g is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPC；Evacuation (vacuum is at≤100Pa), close
Being honored as a queen and put it into and can be warming up to 140 DEG C according to the heating rate of 1.0 DEG C/min in the drying baker of temperature programmed control, constant temperature is protected
Take out after holding 14h and naturally cool to room temperature, obtain SPC/S1Composite.
(3) chemical solution deposition is at SPC/S1On composite, secondary carries sulfur
By 0.6g SPC/S1Composite is placed in the hypo solution of 200mL standing 7h, sodium thiosulfate dense
Degree is at 0.12mol/L；Then the hydrochloric acid solution 120mL being slowly added dropwise concentration 6wt% fully reacts 4h；After centrifugal filtration, 80
Dry for standby at DEG C, sample is labeled as SPC/S composite.
Embodiment 3
The preparation method of a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal
At 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
Cool to room temperature after keeping 2.0h at 500 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPC.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 2.0g Bombyx mori L. multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.
A certain amount of sulfur powder is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPC；Evacuation (vacuum≤
100Pa), put it into after sealing and the drying baker of temperature programmed control can be warming up to 160 according to the heating rate of 2.0 DEG C/min
DEG C, constant temperature takes out after keeping 20h and naturally cools to room temperature, obtains SPC/S1Composite.
(3) chemical solution deposition is at SPC/S1On composite, secondary carries sulfur
By 1.0g SPC/S1Composite is placed in the hypo solution of 300mL standing 10h, sodium thiosulfate
Concentration is at 0.20mol/L；Then the hydrochloric acid solution 240mL being slowly added dropwise concentration 10wt% fully reacts 5h；After centrifugal filtration,
Dry for standby at 80 DEG C, sample is labeled as SPC/S composite.
Embodiment 4
The preparation method of a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal
At 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
Cool to room temperature after keeping 3.0h at 600 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPC.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 0.6g Bombyx mori L. multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.
A certain amount of sulfur powder is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPC；Evacuation (vacuum≤
100Pa), put it into after sealing and the drying baker of temperature programmed control can be warming up to 130 according to the heating rate of 1.0 DEG C/min
DEG C, constant temperature takes out after keeping 10h and naturally cools to room temperature, obtains SPC/S1Composite.
(3) chemical solution deposition is at SPC/S1On composite, secondary carries sulfur
By 0.3g SPC/S1Composite is placed in the hypo solution of 150mL standing 6h, sodium thiosulfate dense
Degree is at 0.07mol/L；Then the hydrochloric acid solution 60mL being slowly added dropwise concentration 4wt% fully reacts 3h；After centrifugal filtration, at 80 DEG C
Lower dry for standby, sample is labeled as SPC/S composite.
Embodiment 5
The preparation method of a kind of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal
At 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
Cool to room temperature after keeping 5.0h at 700 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPC.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 1.5g Bombyx mori L. multi-stage porous charcoal SPC powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.
A certain amount of sulfur powder is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPC；Evacuation (vacuum≤
100Pa), put it into after sealing and the drying baker of temperature programmed control can be warming up to 150 according to the heating rate of 2.0 DEG C/min
DEG C, constant temperature takes out after keeping 18h and naturally cools to room temperature, obtains SPC/S1Composite.
(3) chemical solution deposition is at SPC/S1On composite, secondary carries sulfur
By 0.8g SPC/S1Composite is placed in the hypo solution of 250mL standing 9h, sodium thiosulfate dense
Degree is at 0.18mol/L；Then the hydrochloric acid solution 190mL being slowly added dropwise concentration 9wt% fully reacts 4h；After centrifugal filtration, 80
Dry for standby at DEG C, sample is labeled as SPC/S composite.
Material properties test:
(1) surface topography of SPC/S composite
The Bombyx mori L. multi-stage porous charcoal present invention prepared and Bombyx mori L. carry out electron-microscope scanning, obtain the SEM figure of Fig. 1～Fig. 2.
Fig. 1 is the SEM photograph of Faeces bombycis, and Fig. 2 is the SEM photograph of Bombyx mori L. multi-stage porous charcoal SPC.
Comparison diagram 1 with in Fig. 2 it can be seen that compared with Faeces bombycis, Bombyx mori L. multi-stage porous charcoal wrinkled surface fades away, occur
Very abundant duct and channel design, channel interior is also may be seen indistinctly the most tiny duct, presents multiple pore
Road net distribution general layout.This structure is advantageous to the load of S.
(2) Bombyx mori L. multi-stage porous charcoal, SPC/S1And the pore structure parameter of SPC/S composite
Use the ASAP-2020 specific surface pore-size distribution instrument that Micro company of the U.S. produces to Bombyx mori L. multi-stage porous SPC, SPC/
S1And the pore structure of SPC/S composite characterizes, result is as shown in table 1.
Table 1 SPC, SPC/S1Pore structure parameter with SPC/S
As can be seen from Table 1, Bombyx mori L. multi-stage porous charcoal SPC has higher specific surface area, itself Langmuir and BET specific surface
Long-pending respectively 955 and 1202m2/ g, total pore volume is 0.42cm3/g.This explanation is after high-temperature activation reacts, in Faeces bombycis duct
Oxy radical and some tar components be removed, activator ZnCl simultaneously2There is strong taking hydrogen by force and take oxygen function by force, by Bombyx mori L.
The multi-stage porous pore passage structure of micropore and mesopore is etched on internal channel.This material is that one has multi-stage porous (in/micropore) carbon material
Material, wherein micropore can form stronger adsorption to sulfur and polysulfide, is favorably improved the circulation of sulfur composite
Stability；Hollow sections then can provide transfer passage for lithium ion and electrolyte, reduces lithium ion and the diffusion of electrolyte
Resistance, improves the high rate performance of battery.
After carrying sulfur by steaming process and further chemical solution deposition, the specific surface area of SPC/S significantly declines,
Langmuir specific surface area only remains 199m2/g；Its pore volume the most significantly declines, the 26% of only SPC pore volume；Additionally, micropore hole
Holding and micropore specific area the most significantly declines, this surface sulfur component (connects granule from the exit orifice of Bombyx mori L. multi-stage porous charcoal
The macropore or mesoporous on surface) it is diffused among endoporus.
(3) thermogravimetric curve of SPC/S composite
The STA449C structural synthesis thermal analyzer using NETZSCH company of Germany to produce is multiple to the SPC/S prepared by the present invention
Condensation material carries out heat stability testing, and test condition is: nitrogen protect, heating rate is 10 DEG C/min, temperature elevating range be 100～
450℃.Test result is as shown in Figure 3.
From figure 3, it can be seen that SPC/S composite prepared by the present invention starts weightlessness to occur, to 385 DEG C at 305 DEG C
Shi Chongliang no longer changes, and weightlessness terminates, and its weight-loss ratio is about 72.0%.Weight-loss ratio corresponds to the sulfur content of composite,
The i.e. sulfur content of this composite is about 72.0%.As can be seen here, preparation method of the present invention is conducive to obtaining high-sulfur
The composite positive pole of content, the S of the higher explanation of the evaporating temperature of S simultaneously is stronger with the adsorption of Bombyx mori L. multi-stage porous charcoal.
(4) chemical property of SPC/S composite
Fig. 4 shows anode SPC/S composite positive pole filling under ultra-high magnifications 6.0C (1C=1680mAh/g)
Discharge curve.From the charging and discharging curve of battery it can be seen that the discharge platform of battery remain two (～2.2V and～
1.8V), illustrate the Stability Analysis of Structures of SPC/S composite positive pole, be conducive to keeping the high-energy-density of battery.
After Fig. 5 shows that the embodiment of the present invention one SPC/S composite activates 2 circles under 0.5C (840mA/g), 3.0C
(5040mA/g) the cycle performance figure under multiplying power.As it can be seen, after material circulates 120 circles under 3.0C, its specific discharge capacity is still
Up to 651mAh/g, its capability retention is up to 86.6%.Table 2 shows that five kinds of embodiment gained SPC/C composites exist
Discharge performance and reversible capacity conservation rate is circulated under 3.0C.SPC/S composite is respectively provided with higher storehouse in the condition tested
Human relations efficiency, this also illustrates that the combination of S and carrier Bombyx mori L. multi-stage porous charcoal is more tight, and Bombyx mori L. multi-stage porous charcoal also shows more simultaneously
Excellent electric conductivity.
From Table 2, it can be seen that the SPC/S composite obtained by scope of experiment involved in the present invention is using
After 120 circles, its reversible capacity conservation rate is positively retained at more than 86%.This shows, the cycle performance of SPC/S composite is excellent,
Under the discharging condition under high magnification, particularly it still is able to keep higher specific capacity.As can be seen here, first it is melted in silkworm with steam
Load little crystal grain sulfur on husky multi-stage porous charcoal, then sulfur component can be evenly spread to SPC's by chemical solution deposition load sulfur
Micropore surface, on the one hand can be effectively improved the utilization rate of sulfur, and then improve the specific discharge capacity of composite；On the other hand again can
Formed sulfur and the active adsorption of polysulfide that generated thereof, reduce the capacity attenuation rate that Shuttle effect is brought, improve
The cyclical stability of composite.
Table 3 shows the five kinds of embodiment gained SPC/S composites of present invention discharge capacity under different multiplying.From
Understanding in table, SPC/S composite high rate performance obtained in scope of experiment involved in the present invention is the most excellent.Electricity
Pond specific discharge capacity under 3.0 and 6.0C is up to 747-794 and 605-660mAh/g respectively；As can be seen here, material is being surveyed
The cyclo-stationary of material in examination multiplying power change procedure, has higher specific discharge capacity under high magnification.This is with sulfur-donor silkworm
The big passage of husky multi-stage porous charcoal is relevant with the quickly conduction of electronics to lithium ion.
2 five kinds of embodiment gained SPC/S composites of table circulate discharge performance and reversible capacity conservation rate under 0.5C
The 3 five kinds of embodiment gained SPC/S composites of table discharge capacity under different multiplying
Claims (10)
1. a Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode, it is characterised in that: the duct inner height of this material is dispersed with little point
Sub-sulfur；Obtained Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode SPC/S composite circulates the electric discharge after 120 circles under 3.0C
Specific capacity is 622-655mAh/g, and capability retention is up to more than 86%.
2. the preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode as claimed in claim 1, it is characterised in that: include as
Lower step,
(1) preparation of Bombyx mori L. multi-stage porous charcoal: by Bombyx mori L. and ZnCl2Powder mixes, and is placed in high temperature process furnances, and logical protective gas blows
After sweeping, reacting by heating obtains Bombyx mori L. multi-stage porous charcoal；
(2) Bombyx mori L. multi-stage porous charcoal uploads sulfur: first put in quartz ampoule by Bombyx mori L. multi-stage porous charcoal, then pours sulfur powder into and enter in quartz ampoule,
Directly do not contact with Bombyx mori L. multi-stage porous charcoal；Putting into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, then constant temperature is protected
Take out after holding 8～20h and naturally cool to room temperature, obtain SPC/S1Composite；
(3) secondary carries sulfur: by SPC/S1Composite is placed in hypo solution standing, then drips hydrochloric acid solution
Learn deposition secondary and carry reaction of Salmon-Saxl 2～5h, after centrifugal filtration, obtain Bombyx mori L. multi-stage porous composite sulfur positive electrode in drying.
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 1, it is characterised in that: described
Reacting by heating temperature 300～700 DEG C in step (1), the response time is 0.5-5h.
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 1, it is characterised in that: described
ZnCl in step (1)2It is 1～6:1 with the mass ratio of Bombyx mori L..
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 1, it is characterised in that: described
Vacuum≤100Pa in quartz ampoule in step (2).
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 1, it is characterised in that: described
In step (2) drying baker use can temperature programmed control drying baker, concrete temperature control process:
(a) temperature-rise period: rise to 120～160 DEG C from room temperature with the heating rate of 0.5～2.0 DEG C/min；
(b) thermostatic process: be placed in 120～160 DEG C and keep 10～15h；
(c) temperature-fall period: thermostatic process takes out after terminating immediately in drying baker, naturally cools to room temperature.
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 1, it is characterised in that: described
Hypo solution and SPC/S in step (3)1The mass ratio of composite is 4～10:1.
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 1 or 5, it is characterised in that:
In described step (3), hydrochloric acid is 3～11:1 with the mol ratio of sodium thiosulfate.
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 8, it is characterised in that: described
In step (3), the concentration of sodium thiosulfate is 0.03～0.20mol/L.
The preparation method of Bombyx mori L. multi-stage porous charcoal composite sulfur positive electrode the most according to claim 8, it is characterised in that: institute
Stating concentration of hydrochloric acid in step (3) is 3～10wt%.
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