CN105161724B - Porous carbon sphere for lithium-sulfur battery and preparation method and application of porous carbon sphere - Google Patents
Porous carbon sphere for lithium-sulfur battery and preparation method and application of porous carbon sphere Download PDFInfo
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- CN105161724B CN105161724B CN201510456565.5A CN201510456565A CN105161724B CN 105161724 B CN105161724 B CN 105161724B CN 201510456565 A CN201510456565 A CN 201510456565A CN 105161724 B CN105161724 B CN 105161724B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a porous carbon sphere for a lithium-sulfur battery and a preparation method and an application of the porous carbon sphere. The porous carbon sphere for the lithium-sulfur battery is formed by disorderly winding a graphene ribbon. The preparation method comprises the following steps: (1) preparing Si-C-O particles; and (2) preparing the porous carbon sphere. The porous carbon sphere for the lithium-sulfur battery is suitable for preparation of a lithium-sulfur battery cathode material; the capacity and the cycling stability of the lithium-sulfur battery and the conductivity of a sulfur electrode can be improved; the preparation method is simple; the yield is relatively high; and the porous carbon sphere can be produced in batches.
Description
Technical field
The invention belongs to secondary power field of lithium, more particularly to a kind of positive material for lithium-sulfur battery and its preparation side
Method and application.
Background technology
Demand expanding day of the development of society to Fossil fuels such as oil, natural gass, however as Fossil fuel consumption
The increase of amount, the exhaustion trend of these non-renewable Fossil fuels is increasingly subject to extensive concern, while Fossil fuel is in burning
During caused by institute air pollution and greenhouse effect also just becoming global problem.In order to solve the traffic with fuel oil as power
Energy shortage and problem of environmental pollution produced by means of transport, electrokinetic cell is increasingly becoming focus of concern.Power current
Pond includes fuel cell, lead-acid battery, Ni-MH battery and lithium ion battery etc..Fuel cell needs to use rare noble metal platinum
As the PEM that catalyst and price are high, while producing for fuel hydrogen is difficult with accumulating.Lead-acid battery mass-energy density
Amount and specific power are relatively low, and cycle life is shorter, while the manufacture contaminative of lead-acid battery is larger.Although Ni-MH battery has realized business
Product, but its efficiency for charge-discharge is low, cycle life is poor, the low shortcoming of specific energy.By contrast lithium ion battery has energy
Density is high（It is 2~3 times of lead-acid battery and Ni-MH battery）, having extended cycle life, energy density is high, and self discharge is little, memoryless effect
Should, operating temperature range width the features such as, be a kind of best battery of current combination property.Therefore, lithium ion battery is recognized as
It is one of best electrokinetic cell solution within the following long term.
The positive electrode of the lithium ion battery of commercialization at present is mainly transition metal oxide such as LiCoO2、LiMnO2、
LiFePO4Deng its specific capacity is difficult to meet the demand of electrokinetic cell.Elemental sulfur is because of theoretical specific capacity (1672 mAh/g) and ratio
Energy height (2600 Wh/kg), is that one kind has very high exploitation while also having low cost, hypotoxicity, advantages of environment protection
The secondary power anode material of lithium battery of value and application prospect.But, elemental sulfur there is also some and asks as positive electrode
Topic, the intrinsic electronic isolation of one side elemental sulfur appears as electrochemistry passivity；In the electric discharge of another aspect sulfur electrode
Between product polysulfide there is higher dissolubility, easily cause the loss of active substance, and it is steady to destroy the circulation of battery system
It is qualitative.
In order to improve elemental sulfur chemical property in the battery, current most researchers are attempted sulfur and have high table
The porous carbon materials of area and high conductivity are combined as carrier and the elemental sulfur of sulfur, so as to increase positive electrode electric conductivity,
Electrochemical reaction active site is provided and suppresses discharging product Li2Sx(x>2) dissolving diffusion.So can not only improve negative electrode
Electronic and ionic transmission capacity, and enable reduction process produce many polysulfides of intermediate keep in the cathode, it is to avoid its
In being dissolved in organic electrolyte, so as to improve the capability retention of lithium-sulfur cell.At present conventional porous carbon materials mostly are carbon nanometer
Pipe, Graphene etc., make after battery after these nano materials are compound with sulfur, are susceptible to brokenly in electrode cycle charge and discharge process
It is bad, therefore cyclical stability is poor.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided one kind is being adapted to prepare lithium-sulfur cell just
Pole material, the lithium-sulfur cell porous carbon ball that lithium-sulfur cell capacity and cyclical stability can be improved, sulfur electrode electric conductivity is improved, also
A kind of preparation method of the lithium-sulfur cell porous carbon ball that method is simple, yield is higher, can be mass is provided, is correspondingly provided
Application of the porous carbon ball in lithium-sulfur cell is prepared.
To solve above-mentioned technical problem, the present invention is employed the following technical solutions：
A kind of lithium-sulfur cell porous carbon ball, the porous carbon ball is entwined by banding graphite is unordered.
In above-mentioned lithium-sulfur cell porous carbon ball, it is preferred that the banding graphite is made up of Multi-layer graphite piece, described many
The piece number of plies of layer graphite flake is 10~20 layers.
Used as a total technology design, the present invention also provides a kind of preparation method of lithium-sulfur cell porous carbon ball, wraps
Include following steps：
（1）Prepare Si-C-O granules：By silicon carbide heating and gasifying, then using low under inert gas shielding
Pressure chemical vapor deposition prepares Si-C-O granules；
（2）Prepare porous carbon ball：By step（1）Gained Si-C-O granules are carried out at high warm under inert gas shielding
Reason, to remove the Si-C-O granules in oxygen element and element silicon, obtain lithium-sulfur cell porous carbon ball.
In above-mentioned preparation method, it is preferred that the step（1）In, element silicon and carbon in the silicon carbide
The atomic ratio of element is 1: 2, and the number-average molecular weight of the silicon carbide is 500~2000.
In above-mentioned preparation method, it is preferred that the step（2）In, the temperature of the high-temperature heat treatment is 2600 DEG C~
2700 DEG C, temperature retention time is 1h~3h.
In above-mentioned preparation method, it is preferred that the step（1）In, the temperature of the low-pressure chemical vapor deposition is
1000 DEG C~1200 DEG C, sedimentation time is 0.5h~3h, and the pressure of the low-pressure chemical vapor deposition is not higher than 1000 Pa.
In above-mentioned preparation method, it is preferred that the step（1）In, the temperature of the silicon carbide heating and gasifying
Spend for 120 DEG C~180 DEG C.
Used as a total technology design, the present invention also provides a kind of above-mentioned lithium-sulfur cell porous carbon ball or above-mentioned
Application of the lithium-sulfur cell porous carbon ball in lithium-sulfur cell obtained in preparation method.
In above-mentioned application, it is preferred that the application includes mixing the lithium-sulfur cell porous carbon ball with sulphur powder, system
The positive electrode of standby lithium-sulfur cell.
In above-mentioned application, it is preferred that the lithium-sulfur cell porous carbon ball is 3: 2 with the mass ratio of the sulphur powder.
The step of preparation method of the present invention（1）In, the preferable nitrogen of noble gases, step（2）In, the guarantor of high-temperature heat treatment
The preferable argon of shield medium.
Compared with prior art, it is an advantage of the current invention that：
（1）The lithium-sulfur cell porous carbon ball of the present invention, is the graphite tape being made up of 10~20 layers of graphite flake in its structure
The unordered loose structure being entwined, because the piece number of plies of graphite flake contained by graphite tape is higher, stability is higher, thus is applied to
During battery, the holding that the long period is capable of in the charge and discharge process of battery is complete, therefore cyclical stability is higher.
（2）The preparation method of the lithium-sulfur cell porous carbon ball of the present invention, equipment investment is little, simple to operate, preparation cost
Low, yield is high, easily realizes batch production.
（3）The preparation method of the lithium-sulfur cell porous carbon ball of the present invention, because the preparation temperature of porous carbon ball is higher, ties
Defect on structure is less, and the follow-up lithium-sulfur cell performance for preparing is more excellent.
Description of the drawings
Fig. 1 is the principle schematic that low-pressure chemical vapor deposition of the present invention prepares Si-C-O granules.
Fig. 2 is the step of the embodiment of the present invention 1（1）The SEM microscopic appearance figures of prepared Si-C-O granules.
Fig. 3 is the step of the embodiment of the present invention 1（1）The XRD material phase analysis figures of prepared Si-C-O granules.
Fig. 4 is the step of the embodiment of the present invention 1（2）The SEM microscopic appearance figures of prepared lithium-sulfur cell porous carbon ball.
Fig. 5 is the step of the embodiment of the present invention 1（2）The XRD material phase analysis figures of prepared lithium-sulfur cell porous carbon ball.
Fig. 6 is the step of the embodiment of the present invention 2（1）The SEM microscopic appearance figures of prepared Si-C-O granules.
Fig. 7 is the step of the embodiment of the present invention 2（1）The XRD material phase analysis figures of prepared Si-C-O granules.
Fig. 8 is the step of the embodiment of the present invention 2（2）The SEM microscopic appearance figures of prepared lithium-sulfur cell porous carbon ball.
Fig. 9 is the step of the embodiment of the present invention 2（2）The XRD material phase analysis figures of prepared lithium-sulfur cell porous carbon ball.
Figure 10 is the step of the embodiment of the present invention 3（1）The SEM microscopic appearance figures of prepared Si-C-O granules.
Figure 11 is the step of the embodiment of the present invention 3（1）The XRD material phase analysis figures of prepared Si-C-O granules.
Figure 12 is the step of the embodiment of the present invention 3（2）The SEM microscopic appearance figures of prepared lithium-sulfur cell porous carbon ball.
Figure 13 is the step of the embodiment of the present invention 3（2）The XRD material phase analysis figures of prepared lithium-sulfur cell porous carbon ball.
Figure 14 is the step of the embodiment of the present invention 3（2）The transmission electron microscope picture of prepared lithium-sulfur cell porous carbon ball；Wherein
A figures are the images of transmissive electron microscope of multiple granules, and b figures are the high-resolution-ration transmission electric-lens image of individual particle, and c figures are individual particle office
The high-resolution-ration transmission electric-lens image in portion.
Figure 15 is the charging and discharging curve of lithium-sulfur cell prepared by the embodiment of the present invention 3.
Figure 16 is the cycle life figure of lithium-sulfur cell prepared by the embodiment of the present invention 3.
Figure 17 is the high rate performance of lithium-sulfur cell prepared by the embodiment of the present invention 3.
Marginal data：
1st, silicon carbide；2nd, there-necked flask；3rd, thermometer；4th, heating mantle；5th, tube furnace；6th, graphite boat；7th, nitrogen
Gas tank；8th, vacuum pump.
Specific embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Embodiment 1：
A kind of lithium-sulfur cell porous carbon ball of the present invention, is entwined by banding graphite is unordered.Banding graphite is by 10
~20 graphite flake compositions.
A kind of preparation method of the lithium-sulfur cell porous carbon ball of above-mentioned the present embodiment, comprises the following steps：
（1）Prepare Si-C-O granules：With silicon carbide（The atomic ratio of number-average molecular weight Mn about 700, Si and C
For 1: 2）Heating and gasifying is carried out for raw material, in N2Si-C-O is prepared under atmosphere protection by low-pressure chemical vapor deposition process
Grain.Equipment principle schematic diagram used in low-pressure chemical vapor deposition is as shown in figure 1, concrete grammar is as follows：By low molecular weight polycaprolactone carbon
Silane 1（Special Resin）In being placed in there-necked flask 2, three mouths of there-necked flask 2 connect respectively the admission line of nitrogen pot 7, pipe
One end of formula stove 5 and thermometer 3, the other end connection vacuum pump 8 of tube furnace 5, are placed with graphite boat 6 in tube furnace 5.Open true
Empty pump 8, and tube furnace 5 is heated, the heating up process intermediate pump 8 of tube furnace 5 runs always, treats the temperature of tube furnace 5
Degree is risen to after depositing temperature, connects nitrogen, and opens there-necked flask heating mantle 4, by the low molecular weight polycaprolactone carbon silicon in there-necked flask 2
Alkane 1 is heated to design temperature.Draught head causes to volatilize gaseous state silicon carbide in there-necked flask 2 and enters into tube furnace 5
In, these gaseous state silicon carbides are cracked to form Si-C-O granules and are deposited on graphite boat 6 in the high-temperature region of tube furnace 5
On.During the low-pressure chemical vapor deposition, being passed through the purpose of nitrogen mainly has two aspects, and one is to provide Special Resin and splits
Protective atmosphere needed for solution, it two is that gaseous state Special Resin is transported in tube furnace 5.Therefore, the flow of nitrogen can also root
It is adjusted according to the amount of Si-C-O granules to be prepared.At the end of low-pressure chemical vapor deposition process, nitrogen and vacuum are closed
Pump, stops heated Tube-furnace, and stops heating Special Resin immediately.
In the present embodiment, the design temperature of the heating of silicon carbide 1 is 120 DEG C（That is heating and gasifying temperature）, low pressure
Chemical vapor deposition temperature is 1000 DEG C, and pressure is 1000 Pa, and sedimentation time is 1h.Si-C-O prepared by the present embodiment
The SEM microscopic appearances of grain are as shown in Figure 2, it is seen that the Si-C-O particle surfaces prepared by 1000 DEG C of low-pressure chemical vapor depositions are in ball
Shape, particle surface is smooth, is connected with each other between granule.The constituent content of prepared Si-C-O granules is as shown in table 1, it is known that
Granule prepared by 1000 DEG C of low-pressure chemical vapor depositions is mainly elementary composition by silicon, carbon, three kinds of oxygen.Prepared Si-C-O
The XRD material phase analysis of grain in XRD spectra as shown in figure 3, can only observe the corresponding diffraction maximum of graphite-phase, and cannot observe
SiC corresponding diffraction maximum, this is low mainly due to preparation temperature, and SiC phases are difficult to crystallize, and silicon atom can only be former with carbon in local
Sub- bonding and/or with oxygen atom bonding, be not enough to form single phase.
Table 1：The step of embodiment 1（1）The constituent content table of prepared Si-C-O granules
| Element | Percentage by weight % | Atomic percent % |
| C | 82.78 | 89.74 |
| O | 06.49 | 05.28 |
| Si | 10.73 | 04.97 |
（2）Prepare porous carbon ball：Step will be loaded with（1）The graphite crucible of gained Si-C-O granules is placed in graphite heater furnace
In, argon protection under carry out high-temperature heat treatment, to remove Si-C-O granules in element silicon and oxygen element, obtain lithium-sulfur cell
Use porous carbon ball.In the present embodiment, high-temperature heat treatment temperature is 2700 DEG C, and temperature retention time is 1h.Prepared lithium-sulfur cell is used
The SEM microscopic appearances of porous carbon ball are as shown in Figure 4, it is seen that the Si-C-O particle surfaces after 2700 DEG C of heat treatments are still smooth, and
In spherical.The material phase analysis of prepared lithium-sulfur cell porous carbon ball are as shown in figure 5, granule obtained by after 2700 DEG C of heat treatments
XRD diffraction patterns show it containing only graphite-phase.The content of prepared lithium-sulfur cell porous carbon ball is as shown in table 2, it is known that
Gained granule comprises only carbon after 2700 DEG C of heat treatments.This illustrates Si-C-O granules in 2700 DEG C of high-temperature heat treatment process,
Si-C and Si-O bond fissions, element silicon and oxygen element are with gaseous state SiO, CO, CO2Etc. form effusion, atom level size is produced then
Hole, remaining C element crystalline becomes band and graphite and presents the loose structure being intertwined.
Table 2：The step of embodiment 1（2）The constituent content table of prepared lithium-sulfur cell porous carbon ball
| Element | Percentage by weight % | Atomic percent % |
| C | 100.00 | 100.00 |
Embodiment 2：
A kind of lithium-sulfur cell porous carbon ball of the present invention, is entwined by banding graphite is unordered.Banding graphite is by 10
~20 graphite flake compositions.
A kind of preparation method of the lithium-sulfur cell porous carbon ball of above-mentioned the present embodiment, comprises the following steps：
（1）Prepare Si-C-O granules：The present embodiment prepares the raw material and method and the basic phase of embodiment 1 of Si-C-O granules
Together, it is different only in that：In the present embodiment, the design temperature of silicon carbide heating is 150 DEG C, and low pressure chemical phase sinks
Accumulated temperature degree is 1100 DEG C, and pressure is 1000Pa, and sedimentation time is 1h.SEM microscopic appearances such as Fig. 6 of prepared Si-C-O granules
It is shown, it is seen that the Si-C-O particle surfaces prepared by 1100 DEG C of low-pressure chemical vapor depositions are in spherical, and particle surface is dispersed with few
Granular projection is measured, spherical particle is connected with each other.The constituent content of prepared Si-C-O granules is as shown in table 3, it is known that 1100 DEG C
Granule prepared by low-pressure chemical vapor deposition is mainly elementary composition by silicon, carbon, three kinds of oxygen.The thing of prepared Si-C-O granules
Facies analyses in XRD spectra as shown in fig. 7, can only observe the corresponding diffraction maximum of graphite-phase, and cannot observe that SiC is corresponding
Diffraction maximum, this is low mainly due to preparation temperature, and SiC phases are difficult to crystallize, thus are difficult to observe by the corresponding diffraction of SiC
Peak.
Table 3：The step of embodiment 2（1）The constituent content table of prepared Si-C-O granules
| Element | Percentage by weight % | Atomic percent % |
| C | 88.29 | 92.26 |
| O | 07.41 | 05.82 |
| Si | 04.30 | 01.92 |
（2）Prepare porous carbon ball：Step will be loaded with（1）The graphite crucible of gained Si-C-O granules is placed in graphite heater furnace
In, argon protection under carry out high-temperature heat treatment, to remove Si-C-O granules in element silicon and oxygen element, obtain lithium-sulfur cell
Use porous carbon ball.In the present embodiment, high-temperature heat treatment temperature is 2600 DEG C, and temperature retention time is 1h.Prepared lithium-sulfur cell is used
The SEM microscopic appearances of porous carbon ball are as shown in Figure 8, it is seen that the Si-C-O particle surfaces after 2600 DEG C of heat treatments are smooth, and in ball
Shape.The material phase analysis of prepared lithium-sulfur cell porous carbon ball are as shown in figure 9, the XRD of granule obtained by after 2600 DEG C of heat treatments
Diffraction patterns show it containing only the corresponding diffraction maximum of graphite-phase.The content of the prepared lithium-sulfur cell porous carbon ball such as institute of table 4
Show, it is known that gained granule comprises only carbon after 2600 DEG C of heat treatments.This explanation Si-C-O granule is in 2700 DEG C of high-temperature heat treatments
During, Si-C and Si-O bond fissions, element silicon and oxygen element are with gaseous state SiO, CO, CO2Etc. form effusion, atom is produced then
Level size hole, remaining C element crystalline becomes band and graphite and presents the loose structure being intertwined.
Table 4：The step of embodiment 2（2）The constituent content table of prepared lithium-sulfur cell porous carbon ball
| Element | Percentage by weight % | Atomic percent % |
| C | 100.00 | 100.00 |
Embodiment 3：
A kind of lithium-sulfur cell porous carbon ball of the present invention, is entwined by banding graphite is unordered.Banding graphite is by 10
~20 graphite flake compositions.
A kind of preparation method of the lithium-sulfur cell porous carbon ball of above-mentioned the present embodiment, comprises the following steps：
（1）Prepare Si-C-O granules：The present embodiment prepares the raw material and method and the basic phase of embodiment 1 of Si-C-O granules
Together, it is different only in that：In the present embodiment, the design temperature of silicon carbide heating is 180 DEG C, and low pressure chemical phase sinks
Accumulated temperature degree is 1200 DEG C, and pressure is 1000 Pa, and sedimentation time is 1h.The SEM microscopic appearances of prepared Si-C-O granules are as schemed
Shown in 10, it is seen that the Si-C-O granules of 1200 DEG C of low-pressure chemical vapor deposition synthesis are in still spherical, but its surface platelets is convex
Rise.The constituent content of prepared Si-C-O granules is as shown in table 5, it is known that prepared by 1200 DEG C of low-pressure chemical vapor depositions
Grain is mainly elementary composition by silicon, carbon, three kinds of oxygen.As shown in figure 11,1200 DEG C low for the material phase analysis of prepared Si-C-O granules
The diffraction maximum and SiC phases of graphite-phase can be substantially observed in the XRD spectra of the Si-C-O granules prepared by pressure chemical deposition
Diffraction maximum.
Table 5：The step of embodiment 3（1）The constituent content table of prepared Si-C-O granules
| Element | Percentage by weight % | Atomic percent % |
| C | 71.20 | 83.34 |
| O | 5.95 | 5.22 |
| Si | 22.85 | 11.44 |
（2）Prepare porous carbon ball：Step will be loaded with（1）The graphite crucible of gained Si-C-O granules is placed in graphite heater furnace
In, argon protection under carry out high-temperature heat treatment, to remove Si-C-O granules in element silicon and oxygen element, obtain lithium-sulfur cell
Use porous carbon ball.In the present embodiment, high-temperature heat treatment temperature is 2700 DEG C, and temperature retention time is 1h.Prepared lithium-sulfur cell is used
The SEM microscopic appearances of porous carbon ball are as shown in figure 12, it is seen that after 2700 DEG C of heat treatments, and granule is in still spherical, and
Grain surface sheet projection is still present.Figure 14 is the transmission electron microscope picture of prepared lithium-sulfur cell porous carbon ball, and wherein b schemes
Can clearly find out with C figures, gained lithium-sulfur cell porous carbon ball is a kind of porous formed by the unordered winding of banding graphite
Structure, the gap between banding graphite constitutes the hole of porous carbon ball.The content of prepared lithium-sulfur cell porous carbon ball
As shown in table 6, it is known that gained granule comprises only carbon after 2700 DEG C of heat treatments.Prepared lithium-sulfur cell porous carbon ball
Material phase analysis only exist as shown in figure 13, after 2700 DEG C of heat treatments that graphite-phase is corresponding to spread out in the XRD spectra of gained granule
Peak is penetrated, Si-C-O granules is illustrated in 2700 DEG C of high-temperature heat treatment process, Si-C and Si-O bond fissions, element silicon and oxygen element escape
Go out, produce atom level size hole then, remaining C element crystalline becomes band and graphite and presents the porous being intertwined
Structure.
Table 6：The step of embodiment 3（2）The constituent content table of prepared lithium-sulfur cell porous carbon ball
| Element | Percentage by weight % | Atomic percent % |
| C | 100.0 | 100.0 |
A kind of application of the lithium-sulfur cell porous carbon ball of the present embodiment in lithium-sulfur cell preparation, the application is referred to will be upper
The lithium-sulfur cell porous carbon ball and sulphur powder for stating the present embodiment is mixed for preparing the positive electrode of lithium-sulfur cell, and lithium-sulfur cell is used
Porous carbon ball is 3: 2 with the mass ratio of sulphur powder.The preparation method of the positive electrode is as follows：First porous carbon ball is ground into broken, and
Mix by 3: 2 ratio of mass ratio with sulfur powder；Subsequently, mixed-powder is heated to into 155 DEG C, is then incubated 10h, obtain many
Hole carbon ball-sulfur composite；Finally, by the PVDF of the porous carbon ball of 80wt%-sulfur composite, 10wt% superconductions carbon and 10wt%
Slurry is mixed into, is coated on aluminium foil, under 60 DEG C of vacuum 24h is dried, obtain the positive electrode.
It is assembled in above-mentioned positive electrode as positive plate on lithium-sulfur cell, the lithium-sulfur cell is in 0.2C (1C=1672mA/
G) the 1st time, the 2nd time, the 3rd time and the 50th time charging and discharging curve is as shown in figure 15, it can be seen that discharge curve first
Two stable discharge platforms are shown, S is corresponded to respectivelysTo many sulphion Li2SxConversion, and many sulphions are to Li2S's enters one
Step reduction.The present embodiment with porous carbon ball-lithium-sulfur cell of the sulfur composite as positive pole, first discharge capacity is up to 950mAh/
G, and the discharge capacity first of commercialization lithium-sulfur cell typically only 700~800mAh/g at present, therefore, the lithium sulfur electricity of the present embodiment
Pond has reasonable discharge capacity first.Cycle life such as Figure 16 institute of the lithium-sulfur cell in 0.2C (1C=1672mA/g)
Show, it can be seen that the capacity of battery can be maintained at 93.9% after 100 cycles（Relative to the 5th charge and discharge electric capacity
Amount, similarly hereinafter）, the capacity of battery can be maintained at 83% Jing after 200 cycles, and the capacity of battery can be maintained at Jing after 300 cycles
71.1%, the capacity of battery can be maintained at 65% Jing after 400 cycles, and the capacity of battery can be maintained at 55% Jing after 500 cycles.
And at present commercialization lithium-sulfur cell after 100 circulations, its capacity retention rate only has 60%~70%, illustrate the present embodiment with many
Hole carbon ball-sulfur composite has preferable cyclical stability for the lithium-sulfur cell of positive pole.In porous carbon ball-sulfur compound,
Porous carbon ball is not only able to provide effective conductive channel for sulfur electrode, and can buffer and cause in sulfur electrode charge and discharge process
Change in volume, and the microcellular structure in porous carbon ball can effectively suppress in charge and discharge process produce polysulfide exist
Dissolving in electrolyte, therefore battery capacity conservation rate is greatly improved.The lithium-sulfur cell of the present embodiment is with porous carbon ball
By the unordered loose structure being entwined of graphite tape, its graphite tape is by multilamellar（10~20 layers）Graphite flake is constituted, due to graphite
The piece number of plies with contained graphite flake is more, and stability is higher, thus the not cracky in the charge and discharge process of battery, can be longer
The holding of time is complete, therefore the relatively current commercialization lithium-sulfur cell of cyclical stability is higher.Figure 17 is combined by porous carbon ball-sulfur
Material constitutes the high rate performance of positive pole, and as can be seen from the figure porous carbon ball-sulfur composite composition just has preferably
High rate performance, capacity is 750 mAh/g under 0.1C, under different multiplying after 30 circulations, still can in 4C discharge capacities
500 mAh/g are enough reached, the electric conductivity of the raising sulfur electrode that this explanation porous carbon ball can be larger.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned enforcement
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of lithium-sulfur cell porous carbon ball, it is characterised in that the porous carbon ball is entwined by banding graphite is unordered,
The banding graphite is made up of Multi-layer graphite piece, and the piece number of plies of the Multi-layer graphite piece is 10~20 layers.
2. a kind of preparation method of lithium-sulfur cell porous carbon ball, comprises the following steps：
（1）Prepare Si-C-O granules：By silicon carbide heating and gasifying, low pressure is then adopted under inert gas shielding
Learn vapour deposition and prepare Si-C-O granules；
（2）Prepare porous carbon ball：By step（1）Gained Si-C-O granules carry out high-temperature heat treatment under inert gas shielding, with
The oxygen element and element silicon in the Si-C-O granules is removed, lithium-sulfur cell porous carbon ball is obtained；
The step（2）In, the temperature of the high-temperature heat treatment is 2600 DEG C~2700 DEG C, and temperature retention time is 1h~3h.
3. preparation method according to claim 2, it is characterised in that the step（1）In, the silicon carbide
The atomic ratio of middle element silicon and carbon is 1: 2, and the number-average molecular weight of the silicon carbide is 500~2000.
4. the preparation method according to Claims 2 or 3, it is characterised in that the step（1）In, the low pressure chemical gas
Mutually the temperature of deposition is 1000 DEG C~1200 DEG C, and sedimentation time is 0.5h~3h, and the pressure of the low-pressure chemical vapor deposition is not
Higher than 1000 Pa.
5. the preparation method according to Claims 2 or 3, it is characterised in that the step（1）In, the low molecular weight polycaprolactone carbon
The temperature of silane heating and gasifying is 120 DEG C~180 DEG C.
6. a kind of lithium-sulfur cell porous carbon ball as claimed in claim 1 or as any one of claim 2~5
Application of the lithium-sulfur cell porous carbon ball in lithium-sulfur cell obtained in preparation method.
7. application according to claim 6, it is characterised in that the application is included the lithium-sulfur cell porous carbon ball
Mix with sulphur powder, prepare the positive electrode of lithium-sulfur cell.
8. application according to claim 7, it is characterised in that the matter of the lithium-sulfur cell porous carbon ball and the sulphur powder
Amount is than being 3: 2.
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