CN108630889A - A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer - Google Patents
A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer Download PDFInfo
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Abstract
The present invention discloses a kind of lithium-sulfur cell using nitride/graphene as interlayer and its anode and preparation method, the lithium-sulfur cell are made of anode, diaphragm, electrolyte, cathode；Wherein positive sulfur-bearing, is coated on aluminium foil, is coated with one layer of interlayer based on nitride/graphene thereon；Due to the presence of nitride and graphene in the interlayer, not only so that the electric conductivity of battery gets a promotion, additionally it is possible to the diffusion for effectively inhibiting polysulfide, to which shuttle effect be effectively relieved and improve the chemical property of battery.
Description
Technical field
The invention belongs to electrochemical technology field, more particularly to a kind of lithium sulphur electricity using nitride/graphene as interlayer
Pond and its anode and preparation method.
Background technology
Due to the continuous aggravation of global energy shortage problem, the exploitation of new energy technology is extremely urgent, and what is developed therewith goes back
There is the potential market in the fields such as energy storage and electric vehicle.And existing commercialized secondary battery capacity is not high enough, cannot expire gradually
Sufficient ever-increasing market demand.And lithium-sulfur cell has superelevation specific capacity (1675mAhg-1) and high-energy-density (2600Wh/
Kg), and its raw material sulphur is abundant, cheap in the storage of the earth, and safety non-pollution, thus be considered as it is following most
There is one of the secondary cell of development potentiality.
Although lithium-sulfur cell development prospect is wide, also face an open question, as sulphur electronic isolation, in
Between product polysulfide there is shuttle effect, be easily dissolved in electrolyte and diffuse to cathode and lithium metal side reaction occurs,
This is also the main reason for the sharp-decay for causing cycle performance of battery.
In order to solve the capacity fade problem caused by shuttle effect in lithium-sulfur cell cyclic process, many people are by a variety of carbon
Material and sulphur progress are compound, not only increase the electric conductivity of sulfur-bearing anode, also utilize the porous structure of carbon material to polysulfide
Diffusion limited.Such as：2009, Canadian Nazar groups were successfully compound by CMK-3 ordered mesopore carbons and sulphur, utilized
Meso-hole structure realize limitation polysulfide migration purpose, effectively improve battery cycle performance (Ji X, Lee K T,
Nazar L F.Ahighly ordered nanostructured carbon–sulphur cathode for lithium–
sulphur batteries[J].Nature materials,2009,8(6):500-506.)；There is scholar to be introduced in anode again
Conducting polymer.Such as：Sun etc. is prepared for PPy (polypyrrole) and sulphur composite material, can not only weaken polysulfide shuttle
Effect also improves electric conductivity (Sun M, Zhang S, Jiang T, the et al.Nano-wire networks of of anode
sulfur–polypyrrole composite cathode materials for rechargeable lithium
batteries[J].Electrochemistry Communications,2008,10(12):1819-1822.)。
Although above method all limits the dissolving of polysulfide to a certain extent, the stable circulation of battery is improved
Property, but its technique often it is complicated it is cumbersome, working condition is harsh, and the problem of have not been able to well solve battery capacity decaying.
Invention content
The lithium-sulfur cell and its anode and system that the purpose of the present invention is to provide a kind of using nitride/graphene as interlayer
Preparation Method, to solve the above technical problems.Present invention process is simple, prepared lithium-sulfur cell significant effect, can effectively inhibit
The shuttle effect of polysulfide and the cycle performance for significantly improving battery.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer, including positive plate and on positive plate
Nitride/graphene interlayer；The positive plate is sulfur-bearing anode；
The preparation method of sulfur-bearing anode is：By sulfur-bearing active material, conductive agent, binder with mass ratio (5~9):(1~
4):(1~3) material mixing is carried out, organic solvent is added in the process and stirs evenly acquisition slurry, slurry is uniformly coated on aluminium
On collector, collector vacuum drying is obtained into the sulfur-bearing anode of sulfur-bearing active material；Prepare sulfur-bearing anode be added it is organic molten
The addition of agent by addition binder quality 1/10-1/5；
Sulfur-bearing active material is elemental sulfur, inorganic sulphide, organic sulfur compound, activated carbon/sulfur compound, microporous carbon/sulphur
It is compound, mesoporous carbon/sulfur compound, mesoporous carbon/sulfur compound, macropore carbon/sulfur compound, mesoporous microporous carbon/sulfur compound, big
Hole microporous carbon/sulfur compound, macropore mesoporous carbon/sulfur compound, the mesoporous microporous carbon/sulfur compound of macropore, fibrous carbon/sulphur are compound
Object, cavity carbon ball/sulfur compound, graphene/sulfur compound, carbon nanotube/sulfur compound, biomass carbon/sulfur compound, section's qin
Black/sulfur compound, acetylene black/sulfur compound, Super P/ sulfur compounds, Super C65/ sulfur compounds, metal oxide/sulphur
Compound, conducting polymer/sulfur compound are one such or a variety of, and the mass fraction of sulphur is in the sulfur-bearing active material
20%~100%；
The nitride be lithium nitride, sodium nitride, aluminium nitride, CaCl2, nitrogenized manganese, tungsten nitride, magnesium nitride, copper nitride,
Zirconium nitride, titanium nitride, nitridation silver, tantalum nitride, nitridation alum, phosphorus nitride, silicon nitride, boron nitride, carbonitride are one such or more
Kind, the mass fraction of the nitride is 10%~90%；
Further, the preparation method of nitride/graphene interlayer is：By nitride and graphene ultrasonic disperse in ethyl alcohol
In, by centrifuging out nitride/graphene complex, wherein graphene account for nitride/graphene gross mass 10%~
90%；By nitride/graphene complex and binder in mass ratio 7~9:1~3 carries out material mixing, and be added has in the process
Solvent simultaneously stirs evenly acquisition slurry, and slurry is uniformly coated on positive plate, and vacuum drying is obtained with nitride/graphite
Lithium-sulphur cell positive electrode of the alkene as interlayer；In the preparation process of nitride/graphene interlayer, the addition of solvent be added is
The 1/10-1/5 of binder quality be added.
Further, the conductive agent be conductive carbon black Ketjen black, Super P, Super C65, acetylene black, graphite,
Cavity carbon ball, graphene, biomass carbon are one such or a variety of.
Further, the organic solvent is one or more in ketone, alcohols, aldehydes, organic acid.
Further, it is 15~40 μm that slurry, which is uniformly coated on the thickness on positive plate,.
Further, it is 15~40 μm that slurry, which is uniformly coated on the thickness on aluminium collector,.
Further, the organic solvent be N-Methyl pyrrolidone, dimethyl toluidine, dimethylacetylamide it is a kind of or
It is a variety of.
Further, the binder used in the preparation of nitride/graphene interlayer and the preparation of sulfur-bearing anode is
PVDF。
Further, in the preparation of nitride/graphene interlayer, in ethanol by nitride and graphene dispersion, ultrasound
10min-100min stirs 2h-10h afterwards, by centrifuging out nitride/graphene complex.
Further, in the preparation of nitride/graphene interlayer, nitride/graphene complex and binder are pressed into matter
Measure ratio 7~9:1~3 carries out material mixing, and organic solvent is added in the process, and 0.5h-2h is stirred with medium speed.
Further, in the preparation of nitride/graphene interlayer, after slurry is uniformly coated on positive plate, at 40-70 DEG C
Dry 12-24h in vacuum drying chamber.
Further, in the preparation method of sulfur-bearing anode, slurry is uniformly coated on aluminium collector, collector is placed
12-24h is dried in 40~70 DEG C of vacuum drying chamber obtains the positive electrode of sulfur-bearing active material.
A kind of lithium-sulfur cell using nitride/graphene as interlayer, including it is described using nitride/graphene as every
The lithium-sulphur cell positive electrode of layer.
Further, including the anode cover, lithium-sulphur cell positive electrode, diaphragm, electrolyte, the lithium metal negative film and negative that set gradually
Pole shell.
A kind of preparation method of lithium-sulfur cell using nitride/graphene as interlayer, including：
1) sulfur-bearing anode, is prepared；
2) nitride/graphene interlayer, is prepared on sulfur-bearing anode, forms the lithium using nitride/graphene as interlayer
Sulphur cell positive electrode；
3), battery assembles：It is electric that the lithium sulphur that assembling is obtained using nitride/graphene as interlayer is carried out in an inert atmosphere
Pond；The lithium-sulfur cell using nitride/graphene as interlayer is followed successively by anode cover, with nitride/graphene from the bottom to top
As the lithium-sulphur cell positive electrode of interlayer, diaphragm, electrolyte, lithium anode and negative electrode casing.
Compared with the existing technology, the invention has the advantages that：It is of the invention a kind of using nitride/graphene as every
The lithium-sulfur cell and its anode and preparation method of layer have preferable conductive capability, extremely strong physics and chemisorption energy by introducing
Power nitride/graphene interlayer so that the electric conductivity of sulfur-bearing anode is improved, and can effectively limit the expansion of polysulfide
It dissipates, to achieve the purpose that be effectively relieved shuttle effect, improve cycle performance of battery.Just secondly based on nitride/graphene
The preparation of pole interlayer is simple, safe and reliable, is applicable to industrial mass production, has broad application prospects.
Description of the drawings
Fig. 1 is a kind of positive preparation technology flow chart of lithium-sulfur cell using nitride/graphene as interlayer of the invention.
Fig. 2 is a kind of lithium-sulfur cell structural schematic diagram using nitride/graphene as interlayer of the invention.In figure：1, it bears
Pole electrode shell, 2, lithium piece, 3, diaphragm, 4, nitride/graphene interlayer, 5, positive plate, 6, anode electrode shell.
Specific implementation mode
Embodiment 1
Using nitride/graphene as the lithium-sulfur cell of positive interlayer, including sulfur-bearing active material anode, diaphragm, electrolysis
Liquid, lithium anode；In sulfur-bearing active material anode, it is coated with the interlayer of one layer of nitrogenate/graphene complex.
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (sulphur accounts for 50%) is sulfur-bearing active material, acetylene black is conductive agent, binder
(PVDF) with mass ratio 8:1:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with middle constant speed
Degree stirring 1h；Then adjustable scraper is used, application conditions are set：Coating thickness is 35 μm, and coating width 400mm will be starched
Material is uniformly coated on aluminium collector, collector is positioned over to dry in 60 DEG C of vacuum drying chamber obtains sulfur-bearing active matter for 24 hours
The positive electrode of matter.
Interlayer preparation method
In ethanol by carbonitride/graphene (graphene accounts for 30%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 8:2 carry out
Material mix, in the process be added organic solvent N-Methyl pyrrolidone 2ml, with medium speed stir 1h, then, with sulfur-bearing just
Preparation method similar method in pole is coated on sulfur-bearing anode, and coating thickness is 35 μm；Then it is done in 60 DEG C of vacuum drying chambers
Dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles
Positive plate is put into the glove box full of argon gas, using its be anode, lithium metal as cathode, Celgard films as
Diaphragm, two (trifluoromethane sulfonic acid acyl) imine lithiums are electrolyte, and 0.1mol/L lithium nitrates are additive, and solvent is that volume ratio is 1:
1 DOL (1,3- dioxolanes)：DME (glycol dimethyl ether).Battery assembling is followed successively by anode cover, sulfur-bearing activity from the bottom to top
Substance anode, diaphragm, electrolyte, lithium anode, negative electrode casing.It is finally assembling to button cell.
Battery performance is tested
At room temperature, charge-discharge test is carried out to battery with Wuhan Lan electricity Co., Ltds blue electricity LANDCT2001A charge and discharge instrument,
Charging/discharging voltage ranging from 1.7V-2.6V, time of repose is 1h before charge and discharge, and time of repose is 1min, charge and discharge between charge and discharge
Electric current is 0.1C.Battery first discharge specific capacity is 1533.1mAhg-1, 100 times cycle after specific capacity be 1043.4mAhg-1。
Comparative example 1
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (sulphur accounts for 50%) is sulfur-bearing active material, acetylene black is conductive agent, binder
(PVDF) with mass ratio 8:1:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with middle constant speed
Degree stirring 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 35 μm, and coating width 400mm will be starched
Material is uniformly coated on aluminium collector, collector is positioned over to dry in 60 DEG C of vacuum drying chamber obtains sulfur-bearing active matter for 24 hours
The positive electrode of matter.Then it is cut into disk and obtains positive plate.
Battery assembles
Positive plate is put into the glove box full of argon gas, using its be anode, lithium metal as cathode, Celgard films as
Diaphragm, two (trifluoromethane sulfonic acid acyl) imine lithiums are electrolyte, and 0.1mol/L lithium nitrates are additive, and solvent is that volume ratio is 1:
1 DOL (1,3- dioxolanes)：DME (glycol dimethyl ether).Battery assembling is followed successively by anode cover, sulfur-bearing activity from the bottom to top
Substance anode, diaphragm, electrolyte, lithium anode, negative electrode casing.It is finally assembling to button cell.
Battery performance is tested
At room temperature, charge-discharge test is carried out to battery with Wuhan Lan electricity Co., Ltds blue electricity LANDCT2001A charge and discharge instrument,
Charging/discharging voltage ranging from 1.7V-2.6V, time of repose is 1h before charge and discharge, and time of repose is 1min, charge and discharge between charge and discharge
Electric current is 0.1C.Battery first discharge specific capacity is 1322.2mAhg-1, 100 times cycle after specific capacity be 689.7mAhg-1。
Embodiment 2
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (sulphur accounts for 50%) is sulfur-bearing active material, acetylene black is conductive agent, binder
(PVDF) with mass ratio 8:1:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with middle constant speed
Degree stirring 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 35 μm, and coating width 400mm will be starched
Material is uniformly coated on aluminium collector, collector is positioned over to dry in 60 DEG C of vacuum drying chamber obtains sulfur-bearing active matter for 24 hours
The positive electrode of matter.
Interlayer preparation method
In ethanol by lithium nitride/graphene (graphene accounts for 40%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 8:2 carry out
Material mix, in the process be added organic solvent N-Methyl pyrrolidone 2ml, with medium speed stir 1h, then, with sulfur-bearing just
Preparation method similar method in pole is coated on sulfur-bearing anode, and coating thickness is 25 μm；Then it is done in 60 DEG C of vacuum drying chambers
Dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1617.2mAhg of embodiment-1, follow for 100 times
Specific capacity is 985.9mAhg after ring-1。
Embodiment 3
The preparation method of sulfur-bearing active material anode
Elemental sulfur, acetylene black are conductive agent, binder (PVDF) with mass ratio 8:1:1 carries out material mixing, adds in the process
Enter organic solvent N-Methyl pyrrolidone 3ml, 1h is stirred with medium speed；Then, using adjustable scraper, setting applies cloth
Part：Coating thickness is 35 μm, coating width 400mm, and slurry is uniformly coated on aluminium collector, collector is positioned over 60
DEG C vacuum drying chamber in dry the positive electrode for obtaining sulfur-bearing active material for 24 hours.
Interlayer preparation method
In ethanol by nitride aluminum/graphite alkene (graphene accounts for 50%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 8:2 carry out
Material mix, in the process be added organic solvent N-Methyl pyrrolidone 2ml, with medium speed stir 1h, then, with sulfur-bearing just
Preparation method similar method in pole is coated on sulfur-bearing anode, and coating thickness is 40 μm；Then it is done in 60 DEG C of vacuum drying chambers
Dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as embodiment 1.Battery initial specific capacities 1592.6mAhg-1, follow for 100 times
Specific capacity is 920.3mAhg after ring-1。
Embodiment 4
The preparation method of sulfur-bearing active material anode
Carbon nanotube/sulfur compound (sulphur accounts for 50%) is sulfur-bearing active material, conductive carbon black Ketjen black is conductive agent, bonding
Agent (PVDF) is with mass ratio 8:1:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with medium
Speed stirs 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 35 μm, coating width 400mm, will
Slurry is uniformly coated on aluminium collector, collector is positioned in 60 DEG C of vacuum drying chamber dry obtain for 24 hours sulfur-bearing activity
The positive electrode of substance.
Interlayer preparation method
In ethanol by carbonitride/graphene (graphene accounts for 60%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 8:2 carry out
Material mixes, and organic solvent dimethyl toluidine 2ml is added in the process, and 1h is stirred with medium speed, then, with positive with sulfur-bearing
The similar method of preparation method is coated on sulfur-bearing anode, and coating thickness is 35 μm；Then dry in 60 DEG C of vacuum drying chambers
12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1479.2mAhg of embodiment-1, follow for 100 times
Specific capacity is 825.2mAhg after ring-1。
Embodiment 5
The preparation method of sulfur-bearing active material anode
Super C65/ sulfur compounds (sulphur accounts for 50%) are sulfur-bearing active material, acetylene black is conductive agent, binder
(PVDF) with mass ratio 8:1:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with middle constant speed
Degree stirring 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 35 μm, and coating width 400mm will be starched
Material is uniformly coated on aluminium collector, collector is positioned over to dry in 60 DEG C of vacuum drying chamber obtains sulfur-bearing active matter for 24 hours
The positive electrode of matter.
Interlayer preparation method
In ethanol by boron nitride/graphene (graphene accounts for 70%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 8:2 carry out
Material mixes, and organic solvent N-Methyl pyrrolidone and dimethylacetylamide 2ml are added in the process, and 1h is stirred with medium speed,
Then, it is coated on sulfur-bearing anode in the method similar with sulfur-bearing anode preparation method, coating thickness is 35 μm；Then at 60 DEG C
Dry 12h obtains pole piece in vacuum drying chamber, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1460.7mAhg of embodiment-1, follow for 100 times
Specific capacity is 815.9mAhg after ring-1。
Embodiment 6
The preparation method of sulfur-bearing active material anode
Acetylene black/sulfur compound (sulphur accounts for 20%) is sulfur-bearing active material, Super P and Super C65 are conductive agent, viscous
Agent (PVDF) is tied with mass ratio 8:2:2 carry out material mixing, organic solvent N-Methyl pyrrolidone 3ml are added in the process, in
Uniform velocity stirs 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 35 μm, coating width 400mm,
Slurry is uniformly coated on aluminium collector, collector is positioned in 60 DEG C of vacuum drying chamber dry obtain for 24 hours sulfur-bearing work
The positive electrode of property substance.
Interlayer preparation method
In ethanol by titanium nitride and magnesium nitride/graphene (graphene accounts for 40%) dispersion, ultrasonic 30min stirs 6h afterwards,
By centrifuging out nitride/graphene complex.In mass ratio by nitride/graphene complex and binder (PVDF)
8:2 carry out material mixing, and organic solvent N-Methyl pyrrolidone 2ml is added in the process, and 1h is stirred with medium speed, then, with
The method similar with sulfur-bearing anode preparation method is coated on sulfur-bearing anode, and coating thickness is 25 μm；Then dry in 60 DEG C of vacuum
Dry 12h obtains pole piece in dry case, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1416.4mAhg of embodiment-1, follow for 100 times
Specific capacity is 905.6mAhg after ring-1。
Embodiment 7
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (sulphur accounts for 80%) is sulfur-bearing active material, graphene is conductive agent, binder
(PVDF) with mass ratio 8:1:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with middle constant speed
Degree stirring 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 40 μm, and coating width 400mm will be starched
Material is uniformly coated on aluminium collector, collector is positioned over to dry in 60 DEG C of vacuum drying chamber obtains sulfur-bearing active matter for 24 hours
The positive electrode of matter.
Interlayer preparation method
In ethanol by titanium nitride/graphene (graphene accounts for 80%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 8:2 carry out
Material mix, in the process be added organic solvent N-Methyl pyrrolidone 2ml, with medium speed stir 1h, then, with sulfur-bearing just
Preparation method similar method in pole is coated on sulfur-bearing anode, and coating thickness is 15 μm；Then it is done in 60 DEG C of vacuum drying chambers
Dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1632.4mAhg of embodiment-1, follow for 100 times
Specific capacity is 1005.6mAhg after ring-1。
Embodiment 8
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (sulphur accounts for 50%) is sulfur-bearing active material, Super P are conductive agent, bonding
Agent (PVDF) is with mass ratio 5:2:3 carry out material mixing, organic solvent N-Methyl pyrrolidone 3ml are added in the process, with medium
Speed stirs 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 10 μm, coating width 400mm, will
Slurry is uniformly coated on aluminium collector, collector is positioned in 60 DEG C of vacuum drying chamber dry obtain for 24 hours sulfur-bearing activity
The positive electrode of substance.
Interlayer preparation method
In ethanol by silicon nitride/graphene (graphene accounts for 90%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 9:1 carries out
Material mix, in the process be added organic solvent N-Methyl pyrrolidone 2ml, with medium speed stir 1h, then, with sulfur-bearing just
Preparation method similar method in pole is coated on sulfur-bearing anode, and coating thickness is 35 μm；Then it is done in 60 DEG C of vacuum drying chambers
Dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1587.8mAhg of embodiment-1, follow for 100 times
Specific capacity is 965.7mAhg after ring-1。
Embodiment 9
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (sulphur accounts for 50%) is sulfur-bearing active material, graphite is conductive agent, binder
(PVDF) with mass ratio 9:4:1 carries out material mixing, organic solvent N-Methyl pyrrolidone 3ml is added in the process, with middle constant speed
Degree stirring 1h；Then, using adjustable scraper, application conditions are set：Coating thickness is 35 μm, and coating width 400mm will be starched
Material is uniformly coated on aluminium collector, collector is positioned over to dry in 60 DEG C of vacuum drying chamber obtains sulfur-bearing active matter for 24 hours
The positive electrode of matter.
Interlayer preparation method
In ethanol by silicon nitride/graphene (graphene accounts for 10%) dispersion, ultrasonic 30min stirs 6h afterwards, passes through centrifugation
Isolate nitride/graphene complex.By nitride/graphene complex and binder (PVDF) in mass ratio 7:3 carry out
Material mix, in the process be added organic solvent N-Methyl pyrrolidone 2ml, with medium speed stir 1h, then, with sulfur-bearing just
Preparation method similar method in pole is coated on sulfur-bearing anode, and coating thickness is 20 μm；Then it is done in 60 DEG C of vacuum drying chambers
Dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembles and electrochemical property test is the same as 1. battery initial specific capacities 1511.6mAhg of embodiment-1, follow for 100 times
Specific capacity is 933.6mAhg after ring-1。
Claims (9)
1. a kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer, which is characterized in that including positive plate and positioned at just
Nitride/graphene interlayer on pole piece；The positive plate is sulfur-bearing anode；
The preparation method of sulfur-bearing anode is：By sulfur-bearing active material, conductive agent, binder with mass ratio (5~9):(1~4):(1
~3) material mixing is carried out, organic solvent is added in the process and stirs evenly acquisition slurry, slurry is uniformly coated on aluminium afflux
On body, collector vacuum drying is obtained into the sulfur-bearing anode of sulfur-bearing active material；Prepare sulfur-bearing anode organic solvent be added
Addition by addition binder quality 1/10-1/5；
Sulfur-bearing active material is that elemental sulfur, inorganic sulphide, organic sulfur compound, activated carbon/sulfur compound, microporous carbon/sulphur are compound
Object, mesoporous carbon/sulfur compound, mesoporous carbon/sulfur compound, macropore carbon/sulfur compound, mesoporous microporous carbon/sulfur compound, macropore are micro-
Hole carbon/sulfur compound, macropore mesoporous carbon/sulfur compound, the mesoporous microporous carbon/sulfur compound of macropore, fibrous carbon/sulfur compound, sky
Chamber carbon ball/sulfur compound, graphene/sulfur compound, carbon nanotube/sulfur compound, biomass carbon/sulfur compound, Ketjen black/sulphur
Compound, acetylene black/sulfur compound, Super P/ sulfur compounds, Super C65/ sulfur compounds, metal oxide/sulphur are compound
Object, conducting polymer/sulfur compound are one such or a variety of, and the mass fraction of sulphur is 20% in the sulfur-bearing active material
~100%；
The nitride is lithium nitride, sodium nitride, aluminium nitride, CaCl2, nitrogenized manganese, tungsten nitride, magnesium nitride, copper nitride, nitridation
Zirconium, titanium nitride, nitridation silver, tantalum nitride, nitridation alum, phosphorus nitride, silicon nitride, boron nitride, carbonitride are one such or a variety of, institute
The mass fraction for the nitride stated is 10%~90%.
2. a kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer according to claim 1, feature exist
In the preparation method of nitride/graphene interlayer is：In ethanol by nitride and graphene ultrasonic disperse, pass through centrifugation point
Nitride/graphene complex is separated out, wherein graphene accounts for the 10%~90% of nitride/graphene gross mass；By nitride/
Graphene complex and binder in mass ratio 7~9:1~3 carries out material mixing, and organic solvent is added in the process and stirs equal
Even acquisition slurry, slurry is uniformly coated on positive plate, and vacuum drying obtains the lithium using nitride/graphene as interlayer
Sulphur cell positive electrode；In the preparation process of nitride/graphene interlayer, is binder matter is added in the addition of solvent be added
The 1/10-1/5 of amount.
3. a kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer according to claim 1, feature exist
In the conductive agent is conductive carbon black Ketjen black, Super P, Super C65, acetylene black, graphite, cavity carbon ball, graphite
Alkene, biomass carbon are one such or a variety of.
4. a kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer according to claim 1, feature exist
In the organic solvent is one or more in ketone, alcohols, aldehydes, organic acid.
5. a kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer according to claim 2, feature exist
In it is 15~40 μm that slurry, which is uniformly coated on the thickness on positive plate,.
6. a kind of lithium-sulphur cell positive electrode using nitride/graphene as interlayer according to claim 2, feature exist
In it is 15~40 μm that slurry, which is uniformly coated on the thickness on aluminium collector,.
7. a kind of lithium-sulfur cell using nitride/graphene as interlayer, which is characterized in that including any in claim 1 to 6
The lithium-sulphur cell positive electrode using nitride/graphene as interlayer described in.
8. a kind of lithium-sulfur cell using nitride/graphene as interlayer according to claim 7, which is characterized in that packet
Include the anode cover set gradually, lithium-sulphur cell positive electrode, diaphragm, electrolyte, lithium metal negative film and negative electrode casing.
9. a kind of preparation method of lithium-sulfur cell using nitride/graphene as interlayer according to any one of claims 8, feature exist
In, including：
1) sulfur-bearing anode, is prepared；
2) nitride/graphene interlayer, is prepared on sulfur-bearing anode, forms the lithium sulphur electricity using nitride/graphene as interlayer
Pond anode；
3), battery assembles：Lithium-sulfur cell of the assembling acquisition using nitride/graphene as interlayer is carried out in an inert atmosphere；Institute
State the lithium-sulfur cell using nitride/graphene as interlayer be followed successively by from the bottom to top anode cover, using nitride/graphene as every
Lithium-sulphur cell positive electrode, diaphragm, electrolyte, lithium anode and the negative electrode casing of layer.
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