CN109449374A - A kind of lithium-sulphur cell positive electrode, battery and preparation method using nitride/carbon nanotube as interlayer - Google Patents
A kind of lithium-sulphur cell positive electrode, battery and preparation method using nitride/carbon nanotube as interlayer Download PDFInfo
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Abstract
A kind of lithium-sulphur cell positive electrode, battery and preparation method using nitride/carbon nanotube as interlayer, including nitride/carbon nanotube interlayer is prepared on sulfur-bearing anode, form the lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer；Lithium-sulfur cell of the assembling acquisition using nitride/carbon nanotube as interlayer is carried out in an inert atmosphere；Lithium-sulfur cell using nitride/carbon nanotube as interlayer is followed successively by anode cover, using nitride/carbon nanotube as the lithium-sulphur cell positive electrode of interlayer, diaphragm, electrolyte, lithium anode and negative electrode casing from the bottom to top.There is the carbon nanotube of extremely strong electron transport ability and certain physical absorption ability improving the electric conductivity of anode, promoting lithium ion transport rate and reducing battery overall impedance by introducing, there is the nitride of extremely strong polysulfide chemical adsorption capacity by adding, the diffusion of polysulfide is effectively limited in interlayer, to achieve the purpose that shuttle effect is effectively relieved, improve cycle performance of battery.
Description
Technical field
The invention belongs to electrochemical technology field, in particular to a kind of lithium sulphur using nitride/carbon nanotube as interlayer
Anode, battery and preparation method.
Background technique
Due to the continuous aggravation of global energy shortage problem, the development and utilization of new energy technology is extremely urgent, thus promotees
Into the rapid development of electrochemical energy storage industry.And existing widely commercialized energy storage device-secondary battery capacity is not high enough, gradually
It is not able to satisfy ever-increasing market demand gradually.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, therefore is considered as
One of the secondary cell of the following most development potentiality.
Volume although lithium-sulfur cell development prospect is wide, in such as electronic isolation of sulphur, battery charge and discharge process
The shuttle effect that expansion, especially intermediate product polysulfide have is the weight for leading to battery capacity decaying, influencing cycle life
Factor is wanted, the problem of these are not yet fully solved all hampers its further commercialized development.
To solve the above-mentioned problems, many people carry out various carbon materials with sulphur compound, not only increase sulfur-bearing anode
Electric conductivity also limits volume expansion and shuttle effect using the porous structure of carbon material.Such as: 2009, Canada
Nazar group is successfully compound by CMK-3 ordered mesopore carbon and sulphur, and the mesh of limitation polysulfide migration is realized using meso-hole structure
, cycle performance (Ji X, Lee K T, the Nazar L F.A highly ordered of battery is effectively promoted
nanostructured carbon–sulphur cathode for lithium–sulphur batteries[J].Nature
materials,2009,8(6):500-506.)；Zhang etc. successfully prepares graphene oxide with Hummers method, then by its with it is more
Vulcanized sodium mixes in acid condition, obtains graphene oxide and sulphur composite material, can not only weaken polysulfide shuttle effect
It answers, also improves the electric conductivity (Z.Li, L.Yin, Nanoscale 2015,7,9597.) of anode.
Although above method all limits the dissolution 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.
Summary of the invention
Lithium-sulphur cell positive electrode, the battery that the purpose of the present invention is to provide a kind of using nitride/carbon nanotube as interlayer
And preparation method, to solve above-mentioned the problems of the prior art；Present invention process is simple, prepared lithium-sulfur cell significant effect,
The shuttle effect of polysulfide can effectively be inhibited and significantly improve the cycle performance of battery.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer, including positive plate and be located at positive plate on
Nitride/carbon nanotube interlayer；The positive plate is sulfur-bearing anode；Sulfur-bearing anode is prepared by following procedure: sulfur-bearing is living
Property substance, conductive agent, binder is with mass ratio (5~9): (1~4): (1~3) carries out material mixing, and being added in mixed process has
Solvent simultaneously stirs evenly acquisition slurry, slurry is uniformly coated on aluminium collector, vacuum drying, obtains sulfur-bearing anode.
A further improvement of the present invention lies in that the additional amount of organic solvent is 10~30 times of sulfur-bearing active material quality；
Conductive agent is conductive carbon black Ketjen black, Super P, Super C65, acetylene black, graphite, cavity carbon ball, carbon nanotube, biomass
One of carbon is a variety of；Bonding agent is Kynoar；Be coated on the slurry on aluminium collector with a thickness of 100~400 μm.
A further improvement of the present invention lies in that sulfur-bearing active material is elemental sulfur, inorganic sulphide, organic sulfur compound, work
Property charcoal/sulfur compound, microporous carbon/sulfur compound, mesoporous carbon/sulfur compound, mesoporous carbon/sulfur compound, macropore carbon/sulphur are compound
Object, mesoporous microporous carbon/sulfur compound, macropore microporous carbon/sulfur compound, macropore mesoporous carbon/sulfur compound, the mesoporous micropore of macropore
Carbon/sulfur compound, fibrous carbon/sulfur compound, cavity carbon ball/sulfur compound, graphene/sulfur compound, carbon nanotube/sulphur are compound
Object, carbon nano-fiber/sulfur compound, biomass carbon/sulfur compound, Ketjen black/sulfur compound, acetylene black/sulfur compound,
Super P/ sulfur compound, Super C65/ sulfur compound, metal oxide/sulfur compound, in conducting polymer/sulfur compound
It is one or more；The mass fraction of sulphur is 20%~100% in sulfur-bearing active material.
A further improvement of the present invention lies in that inorganic sulphide is lithium sulfide, cobalt sulfide, molybdenum sulfide, artificial gold, vulcanization
Tungsten, titanium sulfide, zinc sulphide or iron sulfide；Organic sulfur compound is 2,5- dimercapto -1,3,4- thiadiazoles.
Prepared a further improvement of the present invention lies in that nitride/carbon nanotube interlayer passes through following procedure: by nitride and
Carbon nanotube ultrasonic disperse in ethanol, by being centrifugated out nitride/carbon mano-tube composite, the wherein matter of carbon nanotube
Amount score is nitride/carbon nanotube gross mass 10%~90%；Nitride/carbon mano-tube composite and binder are pressed into matter
Amount is than (7~9): (1~3) carries out material mixing, and organic solvent is added in mixed process and stirs evenly, obtains slurry, will starch
Material is uniformly coated on positive plate, is dried in vacuo, is obtained nitride/carbon nanotube interlayer.
A further improvement of the present invention lies in that the slurry being coated on positive plate with a thickness of 100~400 μm；
Nitride is lithium nitride, sodium nitride, aluminium nitride, CaCl2, nitrogenized manganese, tungsten nitride, magnesium nitride, copper nitride, nitridation
One of zirconium, titanium nitride, nitridation silver, tantalum nitride, vanadium nitride, phosphorus nitride, silicon nitride, boron nitride, carbonitride are a variety of；Nitridation
The mass fraction of nitride is 10%~90% in object/carbon nanotube interlayer；
Carbon nanotube is single-walled carbon nanotube, multi-walled carbon nanotube, lithium doping carbon nanotube, boron doping carbon nanotube, nitrogen
Doped carbon nanometer pipe, Fluorin doped carbon nanotube, silicon doped carbon nanometer pipe, sulfur doping carbon nanotube, potassium doped carbon nanometer pipe, transition
One of metal-doped carbon nanotube, aminated carbon nano tube, carboxylic carbon nano-tube, hydroxyl carbon nano tube are a variety of.
A further improvement of the present invention lies in that the additional amount of organic solvent is nitride/carbon mano-tube composite quality
10~30 times.
A further improvement of the present invention lies in that organic solvent is N-Methyl pyrrolidone, triethyl phosphate, N, N- dimethyl
Formamide or dimethyl sulfoxide.
A kind of lithium-sulfur cell of the lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer includes setting from the bottom to top
The anode cover set, using nitride/carbon nanotube as the lithium-sulphur cell positive electrode of interlayer, diaphragm, electrolyte, lithium metal negative film and negative
Pole shell.
A kind of preparation method of lithium-sulfur cell, comprising the following steps:
1) sulfur-bearing anode is prepared；
2) nitride/carbon nanotube interlayer is prepared on sulfur-bearing anode, is formed using nitride/carbon nanotube as interlayer
Lithium-sulphur cell positive electrode；
3) battery assembly: it is electric that the lithium sulphur that assembling is obtained using nitride/carbon nanotube as interlayer is carried out in an inert atmosphere
Pond；Lithium-sulfur cell using nitride/carbon nanotube as interlayer is followed successively by anode cover, from the bottom to top with nitride/carbon nanotube
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 following advantages: the present invention it is a kind of using nitride/carbon nanotube as
The lithium-sulfur cell and its anode and preparation method of interlayer have extremely strong electron transport ability and certain physical absorption energy by introducing
The carbon nanotube of power passes through addition improving the electric conductivity of anode, promoting lithium ion transport rate and reducing battery overall impedance
Nitride with extremely strong polysulfide chemical adsorption capacity, the diffusion of polysulfide is effectively limited in interlayer, to reach
To the purpose that shuttle effect is effectively relieved, improves cycle performance of battery；Secondly based on the positive interlayer of nitride/carbon nanotube
Preparation is simple, safe and reliable, is applicable to industrial mass production, has broad application prospects.
Detailed description of the invention
Fig. 1 is a kind of positive preparation process flow of the lithium-sulfur cell using nitride/carbon nanotube as interlayer of the present invention
Figure.
Fig. 2 is a kind of lithium-sulfur cell structural schematic diagram using nitride/carbon nanotube as interlayer of the present invention.
In figure: 1, negative electrode casing, 2, lithium piece, 3, diaphragm, 4, nitride/carbon nanotube interlayer, 5, positive plate, 6, anode cover.
Specific embodiment
Present invention will now be described in detail with reference to the accompanying drawings..
Lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer of the invention, including positive plate and be located at anode
The nitride of on piece/carbon nanotube interlayer；The positive plate is sulfur-bearing anode；
Referring to Fig. 1, sulfur-bearing anode the preparation method comprises the following steps: by sulfur-bearing active material, conductive agent, binder with mass ratio (5~
9): (1~4): (1~3) carries out material mixing, and organic solvent is added after mixing and stirs evenly acquisition slurry, and slurry is uniform
Be coated on aluminium collector, be coated on the slurry on positive plate with a thickness of 100~400 μm.By aluminium collector vacuum drying, obtain
To the sulfur-bearing anode of sulfur-bearing active material；Wherein, is sulfur-bearing active material quality is added in the additional amount of organic solvent be added
10~30 times；
Sulfur-bearing active material is elemental sulfur, inorganic sulphide, organic sulfur compound, active 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, carbon nano-fiber/sulfur compound, life
Substance carbon/sulfur compound, Ketjen black/sulfur compound, acetylene black/sulfur compound, Super P/ sulfur compound, Super C65/ sulphur
One of compound, metal oxide/sulfur compound, conducting polymer/sulfur compound are a variety of.
Inorganic sulphide is lithium sulfide, cobalt sulfide, molybdenum sulfide, artificial gold, tungsten sulfide, titanium sulfide, zinc sulphide or iron sulfide；
Organic sulfur compound is DMCT (2,5- dimercapto -1,3,4- thiadiazoles)；
Organic sulfur compound is 2,5- dimercapto -1,3,4- thiadiazoles.
The mass fraction of sulphur is 20%~100% in sulfur-bearing active material；
Nitride is lithium nitride, sodium nitride, aluminium nitride, CaCl2, nitrogenized manganese, tungsten nitride, magnesium nitride, copper nitride, nitridation
One of zirconium, titanium nitride, nitridation silver, tantalum nitride, vanadium nitride, phosphorus nitride, silicon nitride, boron nitride, carbonitride are a variety of.
The mass fraction of nitride is 10%~90% in nitride/carbon nanotube interlayer；
Carbon nanotube is single-walled carbon nanotube, multi-walled carbon nanotube, lithium doping carbon nanotube, boron doping carbon nanotube, nitrogen
Doped carbon nanometer pipe, Fluorin doped carbon nanotube, silicon doped carbon nanometer pipe, sulfur doping carbon nanotube, potassium doped carbon nanometer pipe, transition
One of metal-doped carbon nanotube, aminated carbon nano tube, carboxylic carbon nano-tube, hydroxyl carbon nano tube are a variety of.
Nitride/carbon nanotube interlayer is the preparation method comprises the following steps: in ethanol by nitride and carbon nanotube ultrasonic disperse, lead to
It crosses and is centrifugated out nitride/carbon mano-tube composite, wherein the mass fraction of carbon nanotube is the total matter of nitride/carbon nanotube
The 10%~90% of amount；By nitride/carbon mano-tube composite and binder (7~9) in mass ratio: it is mixed that (1~3) carries out material
It closes, organic solvent is added after mixing and stirs evenly acquisition slurry, slurry is uniformly coated on positive plate, aluminium afflux is coated on
Slurry on body with a thickness of 100~400 μm.40~70 DEG C of vacuum drying, obtain nitride/carbon nanotube interlayer；Wherein, institute
Be added the additional amount of solvent by 10~30 times of addition sulfur-bearing active material quality.
Conductive agent is conductive carbon black Ketjen black, Super P, Super C65, acetylene black, graphite, cavity carbon ball, carbon nanometer
One of pipe, biomass carbon are a variety of.
Bonding agent is PVDF (Kynoar)；
Organic solvent is one of ketone, alcohols, aldehydes, organic acid or a variety of.
The organic solvent used in the present invention specifically: NMP (N-Methyl pyrrolidone, TEP (triethyl phosphate), DMF
(n,N-Dimethylformamide) or DMSO (dimethyl sulfoxide).
A kind of lithium-sulfur cell using nitride/carbon nanotube as interlayer provided by the invention, including above-mentioned with nitridation
Lithium-sulphur cell positive electrode of the object/carbon nanotube as interlayer.
Referring to fig. 2, the above-mentioned lithium-sulfur cell using nitride/carbon nanotube as interlayer includes the anode of setting from the bottom to top
Shell 6, positive plate 5, nitride/carbon nanotube are as interlayer 4, diaphragm 3, electrolyte, lithium piece 2 and negative electrode casing 1.
The preparation method of the above-mentioned lithium-sulfur cell using nitride/carbon nanotube as interlayer, comprising:
1) sulfur-bearing anode, is prepared；
2) nitride/carbon nanotube interlayer, is prepared on sulfur-bearing anode, is formed using nitride/carbon nanotube as interlayer
Lithium-sulphur cell positive electrode；
3), battery assembly: it is electric that the lithium sulphur that assembling is obtained using nitride/carbon nanotube as interlayer is carried out in an inert atmosphere
Pond；The lithium-sulfur cell using nitride/carbon nanotube as interlayer is followed successively by anode cover from the bottom to top, is received with nitride/carbon
Mitron is as the lithium-sulphur cell positive electrode of interlayer, diaphragm, electrolyte, lithium anode and negative electrode casing.
Embodiment 1
Using nitride/carbon nanotube as the lithium-sulfur cell of positive interlayer, including sulfur-bearing active material anode, diaphragm, electricity
Solve liquid, lithium anode；One layer of nitrogenate/carbon mano-tube composite interlayer is coated on sulfur-bearing active material anode.
Sulfur-bearing active material anode the preparation method comprises the following steps: conductive carbon black Ketjen black/sulfur compound (conductive carbon black Ketjen black/
In sulfur compound the mass fraction of sulphur be 50%) be sulfur-bearing active material, acetylene black be conductive agent, binder (PVDF) with quality
Material mixing is carried out than 8:1:1, organic solvent N-Methyl pyrrolidone 3mL is added in mixed process, with medium speed 500r/
Min stirs 1h, obtains slurry；Then adjustable scraper is used, set application conditions: coating thickness is as 350 μm, coating width
Slurry is uniformly coated on aluminium collector by 400mm, collector is placed in 60 DEG C of vacuum oven and is dried for 24 hours, obtained
The positive electrode of sulfur-bearing active material.
Nitrogenate/carbon mano-tube composite interlayer the preparation method comprises the following steps: carbonitride/multi-walled carbon nanotube (carbonitride/
The mass fraction of multi-walled carbon nanotube is that in ethanol, then ultrasonic 30min stirs 6h for 30%) dispersion in multi-walled carbon nanotube,
By being centrifugated out nitride/carbon mano-tube composite.Nitride/carbon mano-tube composite and binder (PVDF) are pressed into matter
Amount carries out material mixing than 8:2, organic solvent N-Methyl pyrrolidone 2mL is added in mixed process, with medium speed 500r/
Min stirs 1h, then, is coated on sulfur-bearing anode in the method similar with sulfur-bearing anode preparation method, coating thickness is 350 μ
m；Then the dry 12h in 60 DEG C of vacuum ovens, obtains pole piece, then cuts and be dried in vacuo again, obtain nitrogenate/carbon
The interlayer of nanotube complex.
Battery assembly:
Positive plate is put into the glove box full of argon gas, using its be anode, lithium metal as cathode, Celgard film as
Diaphragm, two (trifluoromethane sulfonic acid acyl) imine lithiums are electrolyte, and 0.1mol/L lithium nitrate is additive, and solvent is that volume ratio is 1:
The mixture of 1 DOL (1,3- dioxolanes) and DME (glycol dimethyl ether).Battery assembly be followed successively by from the bottom to top anode cover,
Sulfur-bearing active material anode, diaphragm, electrolyte, lithium anode, negative electrode casing；It is finally assembling to button cell.
Battery performance test:
At room temperature, charge-discharge test is carried out to battery with Wuhan Lan electricity Co., Ltd blue electricity LANDCT2001A charge and discharge instrument,
Charging/discharging voltage range is 1.7V-2.6V, and 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 1423mAhg-1, 100 times circulation after specific capacity be 899mAhg-1。
Comparative example 1
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (mass fraction of sulphur is 50%) is sulfur-bearing active material, acetylene black is to lead
Electric agent, binder (PVDF) carry out material mixing with mass ratio 8:1:1, and organic solvent N-Methyl pyrrolidone is added in the process
3mL stirs 1h with medium speed 500r/min；Then, using adjustable scraper, set application conditions: coating thickness is 350 μ
Slurry is uniformly coated on aluminium collector by m, coating width 400mm, collector is placed in 60 DEG C of vacuum oven
Drying obtains the positive electrode of sulfur-bearing active material for 24 hours.Then it is cut into disk and obtains positive plate.
Battery assembly:
Positive plate is put into the glove box full of argon gas, using its be anode, lithium metal as cathode, Celgard film as
Diaphragm, two (trifluoromethane sulfonic acid acyl) imine lithiums are electrolyte, and 0.1mol/L lithium nitrate is additive, and solvent is that volume ratio is 1:
DOL (1,3- dioxolanes): DME (glycol dimethyl ether) of 1.Battery assembly 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 test:
At room temperature, charge-discharge test is carried out to battery with Wuhan Lan electricity Co., Ltd blue electricity LANDCT2001A charge and discharge instrument,
Charging/discharging voltage range is 1.7V-2.6V, and 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 circulation 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 (mass fraction of sulphur is 50% in conductive carbon black Ketjen black/sulfur compound)
It is conductive agent, binder (PVDF) with mass ratio 8:1:1 progress material mixing, mixed process for sulfur-bearing active material, acetylene black
Middle addition organic solvent N-Methyl pyrrolidone 3mL stirs 1h with medium speed 500r/min；Then, using adjustable scraper,
Set application conditions: slurry is uniformly coated on aluminium collector by coating thickness as 350 μm, coating width 400mm, will be collected
Fluid is placed in 60 DEG C of vacuum oven and dries the positive electrode for obtaining sulfur-bearing active material for 24 hours.
Interlayer preparation method:
By lithium nitride/multi-walled carbon nanotube, (mass fraction of multi-walled carbon nanotube is in lithium nitride/multi-walled carbon nanotube
40%) in ethanol, ultrasonic 30min stirs 6h afterwards, by being centrifugated out nitride/carbon mano-tube composite for dispersion.By nitrogen
Compound/carbon mano-tube composite and binder (PVDF) 8:2 in mass ratio carry out material mixing, and organic solvent N- is added in the process
Methyl pyrrolidone 2mL stirs 1h with medium speed 500r/min, then, in the method similar with sulfur-bearing anode preparation method
Coated on sulfur-bearing anode, coating thickness is 250 μm；Then dry 12h obtains pole piece in 60 DEG C of vacuum ovens, then cuts out
It cuts and is dried in vacuo again, obtain nitrogenate/carbon mano-tube composite interlayer.
Battery assembly and electrochemical property test are the same as embodiment 1；Battery initial specific capacities 1451.3mAhg-1, follow for 100 times
Specific capacity is 920.1mAhg after ring-1。
Embodiment 3
The preparation method of sulfur-bearing active material anode
Carbon nano-fiber/sulfur compound (mass fraction of sulphur is 50% in carbon nano-fiber/sulfur compound) is that sulfur-bearing is living
Property substance, acetylene black be that conductive agent, binder (PVDF) with mass ratio 8:1:1 carry out material mixing, being added in mixed process has
Solvent N-Methyl pyrrolidone 3mL stirs 1h with medium speed 500r/min；Then, using adjustable scraper, setting coating
Condition: coating thickness is 350 μm, and slurry is uniformly coated on aluminium collector, collector is placed by coating width 400mm
The positive electrode for obtaining sulfur-bearing active material for 24 hours is dried in 60 DEG C of vacuum oven.
Interlayer preparation method
By aluminium nitride/single-walled carbon nanotube, (mass fraction of single-walled carbon nanotube is in aluminium nitride/single-walled carbon nanotube
50%) in ethanol, ultrasonic 30min stirs 6h afterwards, by being centrifugated out nitride/carbon mano-tube composite for dispersion.By nitrogen
Compound/carbon mano-tube composite and binder (PVDF) 8:2 in mass ratio carry out material mixing, are added in mixed process organic molten
Agent N-Methyl pyrrolidone 2mL stirs 1h with medium speed 500r/min, then, with similar with sulfur-bearing anode preparation method
Method is coated on sulfur-bearing anode, and coating thickness is 400 μm；Then dry 12h obtains pole piece in 60 DEG C of vacuum ovens, so
After cut and be dried in vacuo again.
Battery assembly and electrochemical property test are the same as embodiment 1.Battery initial specific capacities 1420.2mAhg-1, follow for 100 times
Specific capacity is 962.2mAhg after ring-1。
Embodiment 4
The preparation method of sulfur-bearing active material anode
Multi-walled carbon nanotube/sulfur compound (mass fraction of sulphur is 50% in multi-walled carbon nanotube/sulfur compound) be containing
Sulphur active material, conductive carbon black Ketjen black are conductive agent, binder (PVDF) with mass ratio 8:1:1 progress material mixing, mixing
Organic solvent N-Methyl pyrrolidone 3mL is added in the process, 1h is stirred with medium speed 500r/min；Then, use is adjustable
Scraper sets application conditions: slurry is uniformly coated on aluminium collector by coating thickness as 350 μm, coating width 400mm,
Collector is placed in the positive electrode dried in 60 DEG C of vacuum oven and obtain sulfur-bearing active material for 24 hours.
Interlayer preparation method
By carbonitride/single-walled carbon nanotube, (mass fraction of single-walled carbon nanotube is in carbonitride/single-walled carbon nanotube
60%) in ethanol, ultrasonic 30min stirs 6h afterwards, by being centrifugated out nitride/carbon mano-tube composite for dispersion.By nitrogen
Compound/carbon mano-tube composite and binder (PVDF) 8:2 in mass ratio carry out material mixing, are added in mixed process organic molten
Agent N-N dimethylformamide 2mL stirs 1h with medium speed 500r/min, then, with similar with sulfur-bearing anode preparation method
Method is coated on sulfur-bearing anode, and coating thickness is 350 μm；Then dry 12h obtains pole piece in 60 DEG C of vacuum ovens, so
After cut and be dried in vacuo again.
Battery assembly and electrochemical property test are the same as embodiment 1；Battery initial specific capacities 1502.4mAhg-1, follow for 100 times
Specific capacity is 953.2mAhg after ring-1。
Embodiment 5
The preparation method of sulfur-bearing active material anode
Super C65/ sulfur compound (mass fraction of sulphur is 50% in Super C65/ sulfur compound) is sulfur-bearing activity
Substance, acetylene black are that conductive agent, binder (PVDF) with mass ratio 8:1:1 carry out material mixing, are added in mixed process organic
Solvent N-methyl pyrilidone 3mL stirs 1h with medium speed 500r/min；Then, using adjustable scraper, setting applies cloth
Part: coating thickness is 350 μm, and slurry is uniformly coated on aluminium collector, collector is placed in by coating width 400mm
The positive electrode for obtaining sulfur-bearing active material for 24 hours is dried in 60 DEG C of vacuum oven.
Interlayer preparation method
By boron nitride/nitrogen-doped carbon nanometer pipe, (quality of nitrogen-doped carbon nanometer pipe is divided in boron nitride/nitrogen-doped carbon nanometer pipe
For 70%) dispersion, in ethanol, ultrasonic 30min stirs 6h to number afterwards, by being centrifugated out nitride/carbon mano-tube composite.
Nitride/carbon mano-tube composite and binder (PVDF) 8:2 in mass ratio are subjected to material mixing, being added in mixed process has
Solvent N-Methyl pyrrolidone and N-N dimethylformamide 2mL, with medium speed 500r/min stir 1h, then, with contain
The similar method of sulphur anode preparation method is coated on sulfur-bearing anode, and coating thickness is 350 μm；Then in 60 DEG C of vacuum ovens
Middle dry 12h obtains pole piece, then cuts and is dried in vacuo again.
Battery assembly and electrochemical property test are the same as 1. battery initial specific capacities 1311.5mAhg of embodiment-1, follow for 100 times
Specific capacity is 835.6mAhg after ring-1。
Embodiment 6
The preparation method of sulfur-bearing active material anode
Acetylene black/sulfur compound (mass fraction of sulphur is 20% in acetylene black/sulfur compound) be sulfur-bearing active material,
Super P and Super C65 are that conductive agent, binder (PVDF) with mass ratio 7:2:1 carry out material mixing, in mixed process plus
Enter organic solvent N-Methyl pyrrolidone 3mL, 1h is stirred with medium speed 500r/min；Then, using adjustable scraper, setting
Application conditions: coating thickness is 350 μm, and slurry is uniformly coated on aluminium collector by coating width 400mm, by collector
It is placed in the positive electrode dried in 60 DEG C of vacuum oven and obtain sulfur-bearing active material for 24 hours.
Interlayer preparation method
By titanium nitride and magnesium nitride/nitrogen-doped carbon nanometer pipe (titanium nitride and magnesium nitride/nitrogen-doped carbon nanometer pipe mixture
The mass fraction of middle nitrogen-doped carbon nanometer pipe is that in ethanol, ultrasonic 30min stirs 6h afterwards, passes through centrifuge separation for 40%) dispersion
Nitride/carbon mano-tube composite out.Nitride/carbon mano-tube composite and binder (PVDF) 8:2 in mass ratio are carried out
Material mixes, and organic solvent N-Methyl pyrrolidone 2mL is added in mixed process, stirs 1h with medium speed 500r/min, so
Afterwards, it is coated on sulfur-bearing anode in the method similar with sulfur-bearing anode preparation method, coating thickness is 250 μm；Then at 60 DEG C
Dry 12h obtains pole piece in vacuum oven, then cuts and is dried in vacuo again.
Battery assembly and electrochemical property test are the same as 1. battery initial specific capacities 1326.5mAhg of embodiment-1, follow for 100 times
Specific capacity is 914.5mAhg after ring-1。
Embodiment 7
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (mass fraction of sulphur is 70% in conductive carbon black Ketjen black/sulfur compound)
It is conductive agent, binder (PVDF) with mass ratio 8:1:1 progress material mixing for sulfur-bearing active material, carbon nanotube, mixed
Organic solvent N-Methyl pyrrolidone 3mL is added in journey, 1h is stirred with medium speed 500r/min；Then, it is scraped using adjustable
Knife sets application conditions: slurry is uniformly coated on aluminium collector by coating thickness as 400 μm, coating width 400mm, will
Collector is placed in 60 DEG C of vacuum oven and dries the positive electrode for obtaining sulfur-bearing active material for 24 hours.
Interlayer preparation method
By titanium nitride/silicon doped carbon nanometer pipe, (quality of silicon doped carbon nanometer pipe is divided in titanium nitride/silicon doped carbon nanometer pipe
For 80%) dispersion, in ethanol, ultrasonic 30min stirs 6h to number afterwards, by being centrifugated out nitride/carbon mano-tube composite.
Nitride/carbon mano-tube composite and binder (PVDF) 8:2 in mass ratio are subjected to material mixing, being added in mixed process has
Solvent N-Methyl pyrrolidone 2mL, with medium speed 500r/min stir 1h, then, with sulfur-bearing anode preparation method class
As method be coated on sulfur-bearing anode on, coating thickness be 150 μm；Then dry 12h obtains pole in 60 DEG C of vacuum ovens
Then piece cuts and is dried in vacuo again.
Battery assembly and electrochemical property test are the same as 1. battery initial specific capacities 1330.5mAhg of embodiment-1, follow for 100 times
Specific capacity is 960.6mAhg after ring-1。
Embodiment 8
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (mass fraction of sulphur is 50% in conductive carbon black Ketjen black/sulfur compound)
It is conductive agent, binder (PVDF) with mass ratio 5:2:3 progress material mixing, mixed process for sulfur-bearing active material, Super P
Middle addition organic solvent N-Methyl pyrrolidone 3mL stirs 1h with medium speed 500r/min；Then, using adjustable scraper,
Set application conditions: slurry is uniformly coated on aluminium collector by coating thickness as 100 μm, coating width 400mm, will be collected
Fluid is placed in 60 DEG C of vacuum oven and dries the positive electrode for obtaining sulfur-bearing active material for 24 hours.
Interlayer preparation method
By silicon nitride/silicon doped carbon nanometer pipe, (quality of silicon doped carbon nanometer pipe is divided in silicon nitride/silicon doped carbon nanometer pipe
For 90%) dispersion, in ethanol, ultrasonic 30min stirs 6h to number afterwards, by being centrifugated out nitride/carbon mano-tube composite.
Nitride/carbon mano-tube composite and binder (PVDF) 9:1 in mass ratio are subjected to material mixing, being added in mixed process has
Solvent N-Methyl pyrrolidone 2mL, with medium speed 500r/min stir 1h, then, with sulfur-bearing anode preparation method class
As method be coated on sulfur-bearing anode on, coating thickness be 350 μm；Then dry 12h obtains pole in 60 DEG C of vacuum ovens
Then piece cuts and is dried in vacuo again.
Battery assembly and electrochemical property test are the same as embodiment 1；Battery initial specific capacities 1488.2mAhg-1, follow for 100 times
Specific capacity is 953.2mAhg after ring-1。
Embodiment 9
The preparation method of sulfur-bearing active material anode
Conductive carbon black Ketjen black/sulfur compound (mass fraction of sulphur is 50% in conductive carbon black Ketjen black/sulfur compound)
It is that conductive agent, binder (PVDF) carry out material mixing with mass ratio 7:1:2 for sulfur-bearing active material, graphite, in mixed process
Organic solvent dimethyl sulfoxide 3mL is added, 1h is stirred with medium speed 500r/min；Then, using adjustable scraper, setting is applied
Cloth condition: coating thickness is 350 μm, and slurry is uniformly coated on aluminium collector, collector is put by coating width 400mm
It is placed in the positive electrode dried in 60 DEG C of vacuum oven and obtain sulfur-bearing active material for 24 hours.
Interlayer preparation method
By silicon nitride/aminated carbon nano tube, (quality of aminated carbon nano tube is divided in silicon nitride/aminated carbon nano tube
For 10%) dispersion, in ethanol, ultrasonic 30min stirs 6h to number afterwards, by being centrifugated out nitride/carbon mano-tube composite.
Nitride/carbon mano-tube composite and binder (PVDF) 7:3 in mass ratio are subjected to material mixing, being added in mixed process has
Solvent N-Methyl pyrrolidone 2mL, with medium speed 500r/min stir 1h, then, with sulfur-bearing anode preparation method class
As method be coated on sulfur-bearing anode on, coating thickness be 200 μm；Then dry 12h obtains pole in 60 DEG C of vacuum ovens
Then piece cuts and is dried in vacuo again.
Battery assembly and electrochemical property test are the same as embodiment 1, battery initial specific capacities 1423.6mAhg-1, follow for 100 times
Specific capacity is 946.5mAhg after ring-1。
Embodiment 10
Using nitride/carbon nanotube as the lithium-sulfur cell of positive interlayer, including sulfur-bearing active material anode, diaphragm, electricity
Solve liquid, lithium anode；One layer of nitrogenate/carbon mano-tube composite interlayer is coated on sulfur-bearing active material anode.
Sulfur-bearing active material anode the preparation method comprises the following steps: elemental sulfur is sulfur-bearing active material, Super P and cavity carbon ball
Mixture is that conductive agent, binder (PVDF) with mass ratio 5:4:2 carry out material mixing, and organic solvent phosphorus is added in mixed process
Triethylenetetraminehexaacetic acid ester stirs 1h with medium speed 500r/min, obtains slurry；Then adjustable scraper is used, application conditions are set: being applied
With a thickness of 350 μm, slurry is uniformly coated on aluminium collector cloth by coating width 400mm, and collector is placed in 60 DEG C
The positive electrode for obtaining sulfur-bearing active material for 24 hours is dried in vacuum oven.The additional amount of organic solvent triethyl phosphate be containing
10 times of sulphur active material quality.
Nitrogenate/carbon mano-tube composite interlayer the preparation method comprises the following steps: nitride/carbon nanotube (nitride/carbon is received
The mass fraction of carbon nanotube is that in ethanol, then ultrasonic 30min stirs 6h, pass through centrifuge separation for 10%) dispersion in mitron
Nitride/carbon mano-tube composite out.Nitride/carbon mano-tube composite and binder (PVDF) 9:3 in mass ratio are carried out
Material mixing, organic solvent triethyl phosphate is added in mixed process, stirs 1h with medium speed 500r/min, then, with
The similar method of sulfur-bearing anode preparation method is coated on sulfur-bearing anode, and coating thickness is 100 μm；Then it is dried in vacuo at 60 DEG C
Dry 12h, obtains pole piece, then cuts and be dried in vacuo again, obtain nitrogenate/carbon mano-tube composite interlayer in case.
Wherein, nitride is the mixture of CaCl2 and nitrogenized manganese, and carbon nanotube is lithium doping carbon nanotube and boron doping carbon nanotube
Mixture；The additional amount of organic solvent triethyl phosphate is 30 times of nitride/carbon mano-tube composite quality.
Battery assembly is the same as embodiment 1.
Embodiment 11
Using nitride/carbon nanotube as the lithium-sulfur cell of positive interlayer, including sulfur-bearing active material anode, diaphragm, electricity
Solve liquid, lithium anode；One layer of nitrogenate/carbon mano-tube composite interlayer is coated on sulfur-bearing active material anode.
Sulfur-bearing active material anode the preparation method comprises the following steps: tungsten sulfide is sulfur-bearing active material, carbon nanotube and biomass carbon
Mixture be that conductive agent, binder (PVDF) with mass ratio 9:2:1 carry out material mixing, organic solvent is added in mixed process
N,N-Dimethylformamide stirs 1h with medium speed 500r/min, obtains slurry；Then adjustable scraper is used, setting applies
Cloth condition: coating thickness is 100 μm, and slurry is uniformly coated on aluminium collector, collector is put by coating width 400mm
The positive electrode dried and obtain sulfur-bearing active material for 24 hours is placed in 60 DEG C of vacuum oven.The additional amount of organic solvent be containing
30 times of sulphur active material quality.
Nitrogenate/carbon mano-tube composite interlayer the preparation method comprises the following steps: nitride/carbon nanotube (nitride/carbon is received
The mass fraction of carbon nanotube is that in ethanol, then ultrasonic 30min stirs 6h, pass through centrifuge separation for 90%) dispersion in mitron
Nitride/carbon mano-tube composite out.Nitride/carbon mano-tube composite and binder (PVDF) 7:1 in mass ratio are carried out
Material mixes, and organic solvent n,N-Dimethylformamide is added in mixed process, stirs 1h with medium speed 500r/min, so
Afterwards, it is coated on sulfur-bearing anode in the method similar with sulfur-bearing anode preparation method, coating thickness is 200 μm；Then at 60 DEG C
Dry 12h, obtains pole piece, then cuts and be dried in vacuo again, obtain nitrogenate/carbon mano-tube composite in vacuum oven
Interlayer.Wherein, nitride is the mixture of tantalum nitride, vanadium nitride, phosphorus nitride and silicon nitride, and carbon nanotube is that sulfur doping carbon is received
Mitron, potassium doped carbon nanometer pipe, transient metal doped carbon nanotube and aminated carbon nano tube mixture；Organic solvent adds
Entering amount is 30 times of nitride/carbon mano-tube composite quality.
Battery assembly is the same as embodiment 1.
Embodiment 12
Using nitride/carbon nanotube as the lithium-sulfur cell of positive interlayer, including sulfur-bearing active material anode, diaphragm, electricity
Solve liquid, lithium anode；One layer of nitrogenate/carbon mano-tube composite interlayer is coated on sulfur-bearing active material anode.
Sulfur-bearing active material anode the preparation method comprises the following steps: the mesoporous microporous carbon/sulfur compound of macropore, fibrous carbon/sulfur compound,
Cavity carbon ball/sulfur compound, graphene/sulfur compound, carbon nanotube/sulfur compound and carbon nano-fiber/sulfur compound are mixed
Closing the mixture that object is sulfur-bearing active material, acetylene black and graphite is conductive agent, binder (PVDF) with mass ratio 7:1:3 progress
Material mixes, and organic solvent dimethyl sulfoxide is added in mixed process, stirs 1h with medium speed 500r/min, obtains slurry；
Then adjustable scraper is used, set application conditions: coating thickness uniformly applies slurry as 400 μm, coating width 400mm
Collector is placed in the anode dried in 60 DEG C of vacuum oven and obtain sulfur-bearing active material for 24 hours on aluminium collector by cloth
Material.The additional amount of organic solvent is 20 times of sulfur-bearing active material quality.
Nitrogenate/carbon mano-tube composite interlayer the preparation method comprises the following steps: nitride/carbon nanotube (nitride/carbon is received
The mass fraction of carbon nanotube is that in ethanol, then ultrasonic 30min stirs 6h, pass through centrifuge separation for 50%) dispersion in mitron
Nitride/carbon mano-tube composite out.Nitride/carbon mano-tube composite and binder (PVDF) 8:1 in mass ratio are carried out
Material mixes, and organic solvent n,N-Dimethylformamide is added in mixed process, stirs 1h with medium speed 500r/min, so
Afterwards, it is coated on sulfur-bearing anode in the method similar with sulfur-bearing anode preparation method, coating thickness is 300 μm；Then at 60 DEG C
Dry 12h, obtains pole piece, then cuts and be dried in vacuo again, obtain nitrogenate/carbon mano-tube composite in vacuum oven
Interlayer.Wherein, nitride is the mixture of zirconium nitride, titanium nitride, nitridation silver, tantalum nitride and vanadium nitride, and carbon nanotube is lithium
Doped carbon nanometer pipe, boron doping carbon nanotube, nitrogen-doped carbon nanometer pipe and Fluorin doped carbon nanotube mixture；Organic solvent
Additional amount is 20 times of nitride/carbon mano-tube composite quality.
Battery assembly is the same as embodiment 1.
Claims (10)
1. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer, which is characterized in that including positive plate and be located at
Nitride/carbon nanotube interlayer on positive plate；The positive plate is sulfur-bearing anode；Sulfur-bearing anode is prepared by following procedure:
By sulfur-bearing active material, conductive agent, binder with mass ratio (5~9): (1~4): (1~3) carries out material mixing, mixed process
Middle addition organic solvent simultaneously stirs evenly acquisition slurry, slurry is uniformly coated on aluminium collector, vacuum drying obtains sulfur-bearing
Anode.
2. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 1, feature exist
In the additional amount of organic solvent is 10~30 times of sulfur-bearing active material quality；Conductive agent is conductive carbon black Ketjen black, Super
P, one of SuperC65, acetylene black, graphite, cavity carbon ball, carbon nanotube, biomass carbon or a variety of；Bonding agent is poly- inclined
Vinyl fluoride；Be coated on the slurry on aluminium collector with a thickness of 100~400 μm.
3. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 2, feature exist
It is that elemental sulfur, inorganic sulphide, organic sulfur compound, active carbon/sulfur compound, microporous carbon/sulphur are compound in, sulfur-bearing active material
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, carbon nano-fiber/sulfur compound, biomass
Carbon/sulfur compound, Ketjen black/sulfur compound, acetylene black/sulfur compound, Super P/ sulfur compound, Super C65/ sulphur are compound
One of object, metal oxide/sulfur compound, conducting polymer/sulfur compound are a variety of；The matter of sulphur in sulfur-bearing active material
Measuring score is 20%~100%.
4. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 3, feature exist
In inorganic sulphide is lithium sulfide, cobalt sulfide, molybdenum sulfide, artificial gold, tungsten sulfide, titanium sulfide, zinc sulphide or iron sulfide；It is organic
Sulfide is 2,5- dimercapto -1,3,4- thiadiazoles.
5. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 1, feature exist
In nitride/carbon nanotube interlayer is prepared by following procedure: in ethanol by nitride and carbon nanotube ultrasonic disperse, leading to
It crosses and is centrifugated out nitride/carbon mano-tube composite, wherein the mass fraction of carbon nanotube is the total matter of nitride/carbon nanotube
The 10%~90% of amount；By nitride/carbon mano-tube composite and binder (7~9) in mass ratio: it is mixed that (1~3) carries out material
It closes, organic solvent is added in mixed process and stirs evenly, obtain slurry, slurry is uniformly coated on positive plate, vacuum is dry
It is dry, obtain nitride/carbon nanotube interlayer.
6. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 5, feature exist
In, be coated on the slurry on positive plate with a thickness of 100~400 μm；
Nitride is lithium nitride, sodium nitride, aluminium nitride, CaCl2, nitrogenized manganese, tungsten nitride, magnesium nitride, copper nitride, zirconium nitride, nitrogen
Change one of titanium, nitridation silver, tantalum nitride, vanadium nitride, phosphorus nitride, silicon nitride, boron nitride, carbonitride or a variety of；Nitride/carbon
The mass fraction of nitride is 10%~90% in nanotube interlayer；
Carbon nanotube is single-walled carbon nanotube, multi-walled carbon nanotube, lithium doping carbon nanotube, boron doping carbon nanotube, N doping
Carbon nanotube, Fluorin doped carbon nanotube, silicon doped carbon nanometer pipe, sulfur doping carbon nanotube, potassium doped carbon nanometer pipe, transition metal
One of doped carbon nanometer pipe, aminated carbon nano tube, carboxylic carbon nano-tube, hydroxyl carbon nano tube are a variety of.
7. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 5, feature exist
In the additional amount of organic solvent is 10~30 times of nitride/carbon mano-tube composite quality.
8. a kind of lithium-sulphur cell positive electrode using nitride/carbon nanotube as interlayer according to claim 5, feature exist
In organic solvent is N-Methyl pyrrolidone, triethyl phosphate, n,N-Dimethylformamide or dimethyl sulfoxide.
9. a kind of lithium-sulphur cell positive electrode based on any one of claim 1-8 using nitride/carbon nanotube as interlayer
Lithium-sulfur cell, which is characterized in that anode cover, the lithium sulphur using nitride/carbon nanotube as interlayer for including setting from the bottom to top
Anode, diaphragm, electrolyte, lithium metal negative film and negative electrode casing.
10. a kind of preparation method based on lithium-sulfur cell as claimed in claim 9, which comprises the following steps:
1) sulfur-bearing anode is prepared；
2) nitride/carbon nanotube interlayer is prepared on sulfur-bearing anode, forms the lithium sulphur using nitride/carbon nanotube as interlayer
Anode；
3) battery assembly: lithium-sulfur cell of the assembling acquisition using nitride/carbon nanotube as interlayer is carried out in an inert atmosphere；With
Nitride/carbon nanotube as the lithium-sulfur cell of interlayer be followed successively by from the bottom to top anode cover, using nitride/carbon nanotube as every
Lithium-sulphur cell positive electrode, diaphragm, electrolyte, lithium anode and the negative electrode casing of layer.
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| CN113131095A (en) * | 2021-04-16 | 2021-07-16 | 清华大学深圳国际研究生院 | Isolation layer, preparation method thereof and lithium-sulfur battery |
| CN113675406A (en) * | 2021-08-20 | 2021-11-19 | 西南大学 | Metal nitride loaded nitrogen-doped carbon network structure composite material and preparation method and application thereof |
| CN113470865A (en) * | 2021-09-06 | 2021-10-01 | 西安宏星电子浆料科技股份有限公司 | Environment-friendly silver conductor paste for aluminum nitride |
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| CN115566157A (en) * | 2022-08-31 | 2023-01-03 | 隆能科技(南通)有限公司 | Long cycle life power battery |
| CN115566157B (en) * | 2022-08-31 | 2023-09-15 | 阜阳隆能科技有限公司 | Long cycle life power battery |
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Application publication date: 20190308 |