CN106299287A - A kind of carbonization Bombyx mori L./MILs composite sulfur positive electrode and preparation method thereof - Google Patents
A kind of carbonization Bombyx mori L./MILs composite sulfur positive electrode and preparation method thereof Download PDFInfo
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Abstract
Open a kind of carbonization Bombyx mori L./MILs composite sulfur positive electrode of the present invention and preparation method thereof.First MILs is grown into carbonization Bombyx mori L. and obtains high-ratio surface carbonization Bombyx mori L. CS MILs；It is then placed in quartz ampoule, then pours sulfur powder into and enter in quartz ampoule, directly do not contact with CS MILs；Put into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, take out after then constant temperature keeps 8～20h and naturally cool to room temperature, obtain CS MILs/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 CS MILs/S composite in drying.The present invention uses vapour-liquid diffusion method to load sulfur, and beneficially sulfur is in the CS MILs duct of strong adsorption potential, is remarkably improved sulfur adsorption and uniform dispersion on carrier, improves the cycle life of anode.
Description
Technical field
The invention belongs to materials chemistry and technical field of electrochemistry, be specifically related to porous material and lithium-sulfur cell material thereof and
Its preparation method.
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 carbonization Bombyx mori L./MILs composite sulfur positive electrode and preparation method thereof, utilizes gas phase gas-liquid diffusion method by sulfur group
Divide and be supported in carbonization Bombyx mori L. duct with nano particle size, it is thus achieved that the charcoal-MILs sulfur composite that high dispersive and strong absorption combine.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of the carbonization Bombyx mori L. of the present invention/MILs composite sulfur positive electrode, comprises the steps,
(1) preparation of carbonization Bombyx mori L.: the preparation of carbonization Bombyx mori L.: be placed in high temperature process furnances by Bombyx mori L., logical protective gas blows
After sweeping, according to the heating rate of 2～8 DEG C/min be heated to 500～1000 DEG C carry out high temperature cabonization reaction obtain carbonization silkworm
Sand, is designated as CS.
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier: first carbonization Bombyx mori L., metal nitrate and polyprotic acid are joined
Body is placed in 50mL aqueous solution, reacts 10-20h at 180-220 DEG C；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite wood
Material, is CS-MILs；
(3) CS-MILs uploads sulfur: first put in quartz ampoule by CS-MILs, then pours sulfur powder into and enter in quartz ampoule, not with CS-
MILs directly contacts；Putting into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, then constant temperature takes after keeping 8～20h
Go out to naturally cool to room temperature, obtain CS-MILs/S1Composite；
(4) secondary carries sulfur: by CS-MILs/S1Composite is placed in hypo solution standing, then it is molten to drip hydrochloric acid
Liquid carries out chemical deposition secondary and carries reaction of Salmon-Saxl 2～5h, after centrifugal filtration, obtains carbonization Bombyx mori L./MILs composite sulfur positive pole in drying
Material, is designated as CS-MILs/S composite.
Further preferred as scheme, in described step (1), the high temperature cabonization response time is 1～8h, protective gas
The noble gases such as nitrogen, argon can be used.
Further preferred as scheme, in described step (2), range of reaction temperature is 180-220 DEG C；Metal nitrate
It is (0.5-4) with the mass ratio of carbonization Bombyx mori L.: 1；Metal nitrate and polyprotic acid part mass ratio are 2～6:1.Metal nitrate
For chromic nitrate, ferric nitrate, aluminum nitrate any one；Polybasic carboxylic acid part can be terephthalic acids and trimesic acid any one；
Further preferred as scheme, controls vacuum≤100Pa in quartz ampoule in described step (3)., 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 CS-MILs/S in described step (4)1Composite
Mass ratio be 4～10:1, time of repose is 5～10h.
Further preferred as scheme, in described step (4), 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 specific discharge capacity that the carbonization Bombyx mori L. of the present invention/MILs composite sulfur positive electrode circulates after 130 circles under 0.1C is high
Reaching 921-987mAh/g, its capability retention is up to more than 80%；Carry sulfur gained charcoal sulfur apparently higher than directly melted diffusion to be combined
Positive electrode, is also 2～3 times of conventional lithium-ion battery material specific capacity.
The principle of the present invention: by compound to MILs material and the carbonization Bombyx mori L. specific surface area that can significantly improve Carbon Materials, and
Being formed in duct and have metal position and the micropore canals of oxygen position in a large number, these adsorption sites can form strong absorption affinity, sulfur with sulfur
Strong adsorption and uniform load can be effectively improved the overall electric conductivity of composite and the utilization rate of sulfur simple substance, thus promote
The specific discharge capacity of composite sulfur positive electrode and long-acting cycle performance.
Compared with prior art, the present invention is advantageous in that:
(1) carrier used in the present invention is carbonization Bombyx mori L., belongs to twice laid, wide material sources and with low cost, directly
Carbonizatin method completes, and process is simple and environmental protection.
(2) utilize carbonization Bombyx mori L. abundant duct can with MILs Material cladding obtain specific surface area higher with metal
Position and the adsorption site position of oxygen position, can form strong absorption, can effectively suppress the loss of sulfur component sulfur and polysulfide thereof.
(3) present invention uses vapor diffusion active sulfur component to be carried on equably in the duct of CS-MILs, permissible
Make sulfur component occupy the strongest adsorption site and form little S crystal seed, more just more S can be supported on by chemical solution deposition
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 carbonization Bombyx mori L. of the present invention/MILs composite sulfur positive electrode has excellent cycle performance, presents well
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 carbonization Bombyx mori L. charcoal/MIL (Cr)；
Fig. 3 is CS-MIL of the present invention (Cr)/S composite and the thermogravimetric curve of MIL (Cr)-101/S；
Fig. 4 is the cycle performance figure of the 0.1C of CS-MIL of the present invention (Cr)/S composite；
Fig. 5 is the rate charge-discharge curve chart of CS-MIL of the present invention (Cr)/S composite；
Fig. 6 is the EIS curve of CS-MIL of the present invention (Cr)/S and MIL (Cr)-101/S composite.
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 the preparation method of a kind of CS-MILs/S positive electrode, comprises the steps,
(1) preparation of carbonization Bombyx mori L.
At N210.0g Faeces bombycis is raised to 500 DEG C with the heating rate of 5 DEG C/min by atmosphere, and at 500 DEG C, keeps 3h
Below cool to room temperature after, obtain carbonization Bombyx mori L., be designated as CS.
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier:
First 1.0 carbonization Bombyx mori L.s, 0.5g Chromium nitrate (Cr(NO3)3),nonahydrate and 0.17g terephthalic acids are placed in 50mL aqueous solution, 180
20h is reacted at DEG C；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite, are CS-MIL (Cr)；
(3) vacuum-steam method uploads sulfur at CS-MIL (Cr)
First 0.3g CS-MIL (Cr) powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.By 1g
Sulfur powder is poured in quartz ampoule, does not directly contact with CS-MIL (Cr)；Put after evacuation (vacuum is at≤100Pa), sealing
Entering and can be warming up to 120 DEG C according to the heating rate of 0.5 DEG C/min in the drying baker of temperature programmed control, constant temperature takes out after keeping 8h
Naturally cool to room temperature, obtain CS-MIL (Cr)/S1Composite.
(4) chemical solution deposition is at CS-MIL (Cr)/S1On composite, secondary carries sulfur
By 0.1g CS-MIL (Cr)/S1Composite is placed in the hypo solution of 100mL standing 5h, and sulfur is for sulfur
The concentration of acid sodium is at 0.03mol/L；Then the hydrochloric acid solution 12mL being slowly added dropwise concentration 3wt% fully reacts 2h；Centrifugal filtration
After, dry for standby at 80 DEG C, sample is labeled as CS-MIL (Cr)/S composite.
Embodiment 2
The preparation method of the preparation method of a kind of CS-MILs/S positive electrode, comprises the steps,
(1) preparation of carbonization Bombyx mori L.
At N210.0g Faeces bombycis is raised to 600 DEG C with the heating rate of 2 DEG C/min by atmosphere, and at 600 DEG C, keeps 8h
After cool to room temperature, to carbonization Bombyx mori L., be designated as CS.
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier:
First 1.0 carbonization Bombyx mori L.s, 1.0g Chromium nitrate (Cr(NO3)3),nonahydrate and 0.2g terephthalic acids are placed in 50mL aqueous solution, 190
10h is reacted at DEG C；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite, are CS-MIL (Cr)；
(3) vacuum-steam method uploads sulfur at CS-MIL (Cr)
First 1.0g CS-MIL (Cr) powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.By 2g
Sulfur powder pour in quartz ampoule, directly do not contact with CS-MIL (Cr)；By it after evacuation (vacuum is at≤100Pa), sealing
Putting into and can be warming up to 140 DEG C according to the heating rate of 2.0 DEG C/min in the drying baker of temperature programmed control, constant temperature takes after keeping 14h
Go out to naturally cool to room temperature, obtain CS-MIL (Cr)/S1Composite.
(4) chemical solution deposition is at CS-MIL (Cr)/S1On composite, secondary carries sulfur
By 0.6g CS-MIL (Cr)/S1Composite is placed in the hypo solution of 200mL standing 7h, and sulfur is for sulfur
The concentration of acid sodium is at 0.12mol/L；Then the hydrochloric acid solution 120mL being slowly added dropwise concentration 6wt% fully reacts 4h；Centrifugal filtration
After, dry for standby at 80 DEG C, sample is labeled as CS-MIL (Cr)/S composite.
Embodiment 3
The preparation method of the preparation method of a kind of CS-MILs/S positive electrode, comprises the steps,
(1) preparation of carbonization Bombyx mori L.
At N210.0g Faeces bombycis is raised to 1000 DEG C with the heating rate of 8 DEG C/min by atmosphere, and keeps at 1000 DEG C
Cool to room temperature after more than 1h, obtain carbonization Bombyx mori L., be designated as CS.
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier:
First 1.0 carbonization Bombyx mori L.s, 2.0g ferric nitrate and 0.6g trimesic acid are placed in 50mL aqueous solution, anti-at 200 DEG C
Answer 13h；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite, are CS-MIL (Fe)；
(3) vacuum-steam method uploads sulfur at CS-MIL (Fe)
First 2.0g CS-MIL (Fe) powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.By one
Quantitative sulfur powder is poured in quartz ampoule, does not directly contact with CS-MIL (Fe)；After evacuation (vacuum is at≤100Pa), sealing
Putting it into and can be warming up to 160 DEG C according to the heating rate of 2.0 DEG C/min in the drying baker of temperature programmed control, constant temperature keeps 20h
Rear taking-up naturally cools to room temperature, obtains CS-MIL (Fe)/S1Composite.
(4) chemical solution deposition is at CS-MIL (Fe)/S1On composite, secondary carries sulfur
By 1.0g CS-MIL (Fe)/S1Composite is placed in the hypo solution of 300mL standing 10h, and sulfur is for sulfur
The concentration of acid sodium is at 0.20mol/L；Then the hydrochloric acid solution 240mL being slowly added dropwise concentration 10wt% fully reacts 5h；It was centrifuged
After filter, dry for standby at 80 DEG C, sample is labeled as CS-MIL (Fe)/S composite.
Embodiment 4
The preparation method of the preparation method of a kind of CS-MILs/S positive electrode, comprises the steps,
(1) preparation of carbonization Bombyx mori L.
At N210.0g Faeces bombycis is raised to 700 DEG C with the heating rate of 4 DEG C/min by atmosphere, and at 700 DEG C, keeps 4h
Below cool to room temperature after, obtain carbonization Bombyx mori L., be designated as CS.
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier:
First 1.0 carbonization Bombyx mori L.s, 3.0g aluminum nitrate and 1.4g terephthalic acids are placed in 50mL aqueous solution, anti-at 210 DEG C
Answer 16h；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite, are CS-MIL (Al)；
(3) vacuum-steam method uploads sulfur at CS-MIL (Al)
First 0.6g carbonization Bombyx mori L. CS powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.By one
Quantitative sulfur powder is poured in quartz ampoule, does not directly contact with CS-MIL (Al)；After evacuation (vacuum is at≤100Pa), sealing
Putting it into and can be warming up to 130 DEG C according to the heating rate of 1.0 DEG C/min in the drying baker of temperature programmed control, constant temperature keeps 10h
Rear taking-up naturally cools to room temperature, obtains CS-MIL (Al)/S1Composite.
(4) chemical solution deposition is at CS-MIL (Al)/S1On composite, secondary carries sulfur
By 0.3g CS-MIL (Al)/S1Composite is placed in the hypo solution of 150mL standing 6h, and sulfur is for sulfur
The concentration of acid sodium is at 0.07mol/L；Then the hydrochloric acid solution 60mL being slowly added dropwise concentration 4wt% fully reacts 3h；Centrifugal filtration
After, dry for standby at 80 DEG C, sample is labeled as CS-MIL (Al)/S composite.
Embodiment 5
The preparation method of the preparation method of a kind of CS-MILs/S positive electrode, comprises the steps,
(1) preparation of carbonization Bombyx mori L.
At N210.0g Faeces bombycis is raised to 900 DEG C with the heating rate of 6 DEG C/min by atmosphere, and at 900 DEG C, keeps 2h
Below cool to room temperature after, obtain carbonization Bombyx mori L., be designated as CS.
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier:
First 1.0 carbonization Bombyx mori L.s, 4.0g Chromium nitrate (Cr(NO3)3),nonahydrate and 0.7g trimesic acid are placed in 50mL aqueous solution, 220
8h is reacted at DEG C；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite, are CS-MIL (Cr-100)；
(3) vacuum-steam method uploads sulfur at CS-MIL (Cr-100)
First 1.5g CS-MIL (Cr-100) 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 CS-MIL (Cr-100)；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 CS-MIL (Cr-100)/S1Composite.
(4) chemical solution deposition is at CS-MIL (Cr-100)/S1On composite, secondary carries sulfur
By 0.8g CS-MIL (Cr-100)/S1Composite is placed in the hypo solution of 250mL standing 9h, sulfur
The concentration of sodium thiosulfate is at 0.18mol/L；Then the hydrochloric acid solution 190mL being slowly added dropwise concentration 9wt% fully reacts 4h；Centrifugal
After filtration, dry for standby at 80 DEG C, sample is labeled as CS-MIL (Cr-100)/S composite.
Material properties test:
(1) surface topography of CS-MIL (Cr) composite
CS-MIL (Cr) composite present invention prepared and Bombyx mori L. carry out electron-microscope scanning, obtain the SEM of Fig. 1～Fig. 2
Figure.
Fig. 1 is the SEM photograph of Faeces bombycis, and Fig. 2 is the SEM photograph of CS-MIL (Cr) composite.
Comparison diagram 1 with in Fig. 2 it can be seen that compared with Faeces bombycis, carbonization Bombyx mori L. wrinkled surface fades away, and occurs in that non-
The abundantest channel design, channel interior is coated with tiny MIL (Cr) crystal grain, presents netted point of duct, multiple aperture
Cloth general layout.This structure is advantageous to load and the absorption of S.
(2) CS-MIL (Cr) composite and the pore structure parameter of CS-MIL (Cr)/S composite
Use the ASAP-2020 specific surface pore-size distribution instrument that Micro company of the U.S. produces to CS-MIL (Cr) composite
Characterizing with the pore structure of CS-MIL (Cr)/S composite, result is as shown in table 1.
Table 1CS-MIL (Cr) composite and the pore structure parameter of CS-MIL (Cr)/S composite
As can be seen from Table 1, carbonization Bombyx mori L./MIL (Cr) composite has higher specific surface area, its Langmuir and
BET specific surface area is respectively 2060 and 1502m2/ g, total pore volume is 1.36cm3/g.This illustrates after crystal growth, composite wood
Specific surface area and the pore volume of material have and the most significantly promote, and this illustrates MIL (Cr) successful growth in CS material.This material is one
Kind there is high-ratio surface and the composite of metal/oxygen adsorption site, wherein micropore, metal/oxygen position can be to sulfur and vulcanize more
Thing forms stronger adsorption, is favorably improved the cyclical stability of sulfur composite, improves the cycle performance of battery.
Significantly being declined by the specific surface area of CS-MIL (Cr)/S after carrying sulfur, Langmuir specific surface area is the most surplus
252m2/g；Its pore volume the most significantly declines, the 22% of only CS pore volume；Additionally, Micropore volume and micropore specific area are the most significantly
Degree declines, and this surface sulfur component is diffused into endoporus from the exit orifice of carbonization Bombyx mori L. (macropore or mesoporous of connection particle exterior surface)
Among.
(3) thermogravimetric curve of CS-MIL (Cr)/S composite
The STA449C structural synthesis thermal analyzer using NETZSCH company of Germany to produce is multiple to the CS/S prepared by the present invention
Condensation material and XF/S (one-step method melts the composite that evaporation obtains) carry out heat stability testing, and test condition is: nitrogen is protected
Protecting, heating rate is 10 DEG C/min, and temperature elevating range is 50～600 DEG C.Test result is as shown in Figure 3.MIL-101 (Cr) in experiment
The synthesis of metal-organic framework materials: MIL-101 (Cr) crystal prepared by method described in prior art.
From figure 3, it can be seen that CS-MIL prepared by the present invention (Cr)/S composite starts the first rank under 473K
Section is weightless, no longer changes to weight during 598K, remains to 648K, is about 63.1% by the weight-loss ratio before 577K,
This weight is about the content of S, and weightlessness later for 577K is then that MIL (Cr)-101 crystal decomposes.From this figure it can be seen that S
The temperature disengaged from CS-MIL (Cr)/S composite will less than the evaporating temperature of pure S, this is important be because CS-MIL (Cr)/
S in S composite exists with the state of little molecule, and crystal size is less, and this makes the evaporation temperature of the relatively large S of evaporating temperature of S
Degree step-down is caused.As can be seen here, preparation method of the present invention is conducive to raising sulfur to be combined at CS-MIL (Cr)/S
Dispersion in material.
(4) chemical property of CS-MIL (Cr)/S composite
Fig. 4 shows the circulation under 0.1C (168mA/g) multiplying power of embodiment of the present invention 1CS-MIL (Cr)/S composite
Performance map.As it can be seen, the composite prepared by the present invention circulates 130 circles under 0.1C under discharge-rate after, its ratio that discharges
Capacity is kept at 966mAh/g, and coulombic efficiency is up to 93.3%, and its capability retention is up to 80.5%.Table 2 shows five
Plant embodiment gained CS-MILs/S composite under 0.1C, circulate discharge performance and reversible capacity conservation rate.As shown in Table 2,
Five kinds of composites after 130 circle circulations, specific discharge capacity at 921-987mAh/g, its capability retention 80-87.1% it
Between, all show preferable cycle performance.
Fig. 5 show embodiment 1CS-MIL (Cr)/S composite different discharge-rate 0.1C, 0.2C, 0.4C,
High rate performance figure under 0.8C, 1.6C, 2.4C and 3.0C.As shown in Figure 5, battery at 0.1C, 0.2C, 0.4C, 0.8C, 2.4C and
Specific discharge capacity under 3.0C is followed successively by 1123,963,816,762,601,506 and 460mAh/g；When discharge-rate subtracts from 3.0
Little for 0.1C time, the specific discharge capacity of material increases to 1103mAh/g from 460mAh/g.Meanwhile, along with the increase of discharge-rate,
The coulombic efficiency of material has the trend of increase.As can be seen here, material is put down at tested multiplying power change procedure, the cyclic curve of material
Surely, discharge capacity is restorative good, sufficiently embodies the high specific discharge capacity of this material and excellent high rate performance.
Fig. 6 shows that embodiment 1CS-MIL (Cr)/S composite and MIL-101 (Cr)/S composite fill at battery
Discharge the AC impedance figure tested after 10 times.It is clear from the figure that the total impedance of CS-MIL (Cr)/S composite is only
The 35% of MIL-101 (Cr)/S material total impedance, after this explanation CS Yu MILs crystal is compound, the electric conductivity of sulfur positive pole obtains
It is obviously improved.
2 five kinds of embodiment gained CS-MILs/S composites of table circulate discharge performance under 0.1C and reversible capacity keeps
Rate
Claims (10)
1. the preparation method of carbonization Bombyx mori L./MILs composite sulfur positive electrode, it is characterised in that: comprise the steps,
(1) preparation of carbonization Bombyx mori L.: be placed in high temperature process furnances by Bombyx mori L., after logical protective gas purging, is heated to 500～1000
DEG C carry out high temperature cabonization reaction and obtain carbonization Bombyx mori L.；
(2) preparation of carbonization Bombyx mori L./MILs composite material carrier: first carbonization Bombyx mori L., metal nitrate and polyprotic acid part are put
In aqueous solution, at 180-220 DEG C, react 8-20h；Sucking filtration drying obtain carbonization Bombyx mori L./MILs composite, are CS-
MILs；
(3) CS-MILs uploads sulfur: first put in quartz ampoule by CS-MILs, then pours sulfur powder into and enter in quartz ampoule, not with CS-MILs
Directly contact；Put into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, take out certainly after then constant temperature keeps 8～20h
So it is cooled to room temperature, obtains CS-MILs/S1Composite；
(4) secondary carries sulfur: by CS-MILs/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 CS-MILs/S positive electrode in drying.
The preparation method of carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
Stating the high temperature cabonization response time in step (1) is 1～8h.
The preparation method of carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
Stating the mass ratio of metal nitrate and carbonization Bombyx mori L. in step (2) is 0.5-4:1；Metal nitrate and polyprotic acid part mass ratio
It is 2～6:1.
The preparation method of carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
State metal nitrate in step (2) be in chromic nitrate, ferric nitrate, aluminum nitrate any one；Polybasic carboxylic acid part is terephthalic acids
Or benzenetricarboxylic acid.
The preparation method of carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
State in step (2) vacuum≤100Pa in quartz ampoule.
The preparation method of carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
State in step (3) 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 carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
State hypo solution and CS-MILs/S in step (4)1The mass ratio of composite is 4～10:1.
The preparation method of carbonization Bombyx mori L. the most according to claim 1/MILs composite sulfur positive electrode, it is characterised in that: institute
Stating the mol ratio of hydrochloric acid and sodium thiosulfate in step (4) is 3～11:1.
The preparation method of carbonization Bombyx mori L. the most according to claim 8/MILs composite sulfur positive electrode, it is characterised in that: institute
Stating the concentration of sodium thiosulfate in step (4) is 0.03～0.20mol/L, in described step (4) concentration of hydrochloric acid be 3～
10wt%.
10. obtain according to the preparation method of the arbitrary described carbonization Bombyx mori L./MILs composite sulfur positive electrode of claim 1～9
Material, it is characterised in that: this material is after cycle charge-discharge 130 times, and its reversible discharge specific capacity is maintained at 921-987mAh/g,
Its capability retention is up to more than 80%.
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