CN109768323A - A kind of all solid lithium metal-sulfur cell and preparation method thereof - Google Patents
A kind of all solid lithium metal-sulfur cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of all solid lithium metal-sulfur cells and preparation method thereof.The disadvantages of all solid lithium metal-sulfur cell at present, there is solid electrolyte and positive and negative anodes contact resistance is big, solid electrolyte is blocked up, solid electrolyte batch production is difficult.The electrolyte that all solid lithium metal-sulfur cell of the invention uses is bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether@lithium ion battery separator film-type composite solid electrolyte；The material of sulphur anode includes sulphur powder, nano magnesia, carbon nanotube, Ketjen black and polyethylene glycol oxide；Sulphur anode pole piece surface is coated with bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether；Lithium an- ode surface is coated with bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether.Film-type composite solid electrolyte of the invention can be to avoid " the shuttle effect " of sulphur anode, all solid lithium metal-sulfur cell cyclical stability with higher of preparation.
Description
Technical field
The invention belongs to technical field of lithium batteries, specifically a kind of all solid lithium metal-sulfur cell and its preparation side
Method.
Background technique
According to China " energy conservation and new-energy automobile Technology Roadmap ", the year two thousand twenty power-type lithium ion battery specific energy reaches
300Wh/Kg；To the year two thousand thirty, specific energy will reach 500Wh/Kg, and conventional business type lithium ion battery is reaching 300Wh/
After kg, the theoretical ceiling that current material is limited is reached substantially to, the further specific energy for improving lithium ion battery is not only
It is highly difficult and be absolutely unsafe.Cooking stove is only separately found, the old frame and corresponding battery material of lithium ion battery are thoroughly reformed
Material is possible to the specific energy for significantly improving lithium battery under the premise that security is guaranteed.At present lithium metal-sulphur battery by
Extensive concern in the industry, reason are that lithium an- ode and elemental sulfur anode all have high theoretical specific capacity, in the industry
It is believed that lithium metal-sulphur battery specific energy is expected to more than 500Wh/kg.But use lithium metal-sulphur of liquid electrolyte
Battery faces two and is difficult to the difficulty overcome greatly.First, during the charging process, lithium is deposited on lithium an- ode table in a manner of dendrite
Face, being easy puncture diaphragm leads to the short circuit of battery, and there is serious security risks.Second, during discharge, sulphur and lithium from
Son reacts to form polysulfide small molecule, these polysulfide small molecules are easily soluble in electrolyte, then with electrolyte
It diffuses to cathode side and side reaction occurs for lithium metal, not only consume the active material of positive and negative anodes, it is most important that in lithium gold
Metal surface forms the extremely low Li of one layer of lithium ion conductivity2S, so as to cause the failure of cathode, here it is lithium metal-sulphur batteries to write
" the shuttle effect " of name.In order to thoroughly solve the two problems, using small with high Young's modulus and insoluble polysulfide
The solid electrolyte of molecule is a kind of thinking of great realistic meaning to replace the liquid electrolyte in current lithium-sulfur cell.
Nevertheless, at present all solid lithium metal-sulfur cell that there is also solid electrolyte and positive and negative anodes contact resistances is big,
The disadvantages of solid electrolyte is blocked up, solid electrolyte batch production is difficult.So a kind of solid electrolyte of film-type is developed, and
Have the advantages that, batch production good, at low cost to positive and negative anodes wetability is easy, will have broad application prospects and great reality
Border meaning.
Summary of the invention
It is an object of the invention to solve the problems, such as that existing all solid lithium metal-sulfur cell exists, provide a kind of using new
The all solid lithium metal-sulfur cell of type film-type composite solid electrolyte.
For this purpose, the technical solution adopted by the present invention are as follows: a kind of all solid lithium metal-sulfur cell, the electrolyte used are
Bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether@lithium ion battery separator film-type complex solid
Electrolyte；The material of sulphur anode includes sulphur powder, nano magnesia, carbon nanotube, Ketjen black and polyethylene glycol oxide；Sulphur anode pole piece
Surface is coated with bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether；Lithium an- ode surface coating double three
Methyl fluoride sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether.
Film-type composite solid electrolyte of the invention has ionic conductivity height, electrochemical window mouth width；It is negative to lithium metal
Pole stable circulation has good wetting effect to positive and negative anodes, small to positive and negative anodes contact resistance；Film-type complex solid of the invention
Electrolyte can be to avoid " the shuttle effect " of sulphur anode, all solid lithium metal-sulfur cell stable circulation with higher of preparation
Property；All solid lithium metal-sulfur cell of the invention has many advantages, such as that the internal resistance of cell is low, specific capacity is high.
As the supplement of above-mentioned all solid lithium metal-sulfur cell, bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetra-
In the film-type composite solid electrolyte of glycol dimethyl ether@lithium ion battery separator, bis trifluoromethyl sulfimide lithium and poly-
The monomer mole ratio of ethylene oxide is 1:5, bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether matter
Amount uses lithium ion battery separator as substrate than being 1:1, it is described lead lighium polymer electrolyte be coated on lithium ion battery every
Film surface.
As the supplement of above-mentioned all solid lithium metal-sulfur cell, the sulphur anode is received by sulphur powder, nano magnesia, carbon
Mitron, Ketjen black and polyethylene glycol oxide composition, wherein sulfur content 50wt-70wt%, as a positive electrode active material；It is nano oxidized
Magnesium 2wt-5wt%, the adsorbent as polysulfide；Carbon nanotube 5wt-10wt%, Ketjen black 10wt-20wt%, as leading
Electric network and conductive agent；Polyethylene glycol oxide 10wt-20wt%, as binder.
As the supplement of above-mentioned all solid lithium metal-sulfur cell, sulphur anode pole piece surface and the coating of lithium an- ode surface
Bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether, bis trifluoromethyl sulfimide lithium and polyoxygenated
The monomer mole ratio of ethylene is 1:1, bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether mass ratio
For 1:1.
It is a further object of the present invention to provide a kind of preparation methods of all solid lithium metal-sulfur cell comprising step: 1)
Under inert atmosphere protection, using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide and tetraethyleneglycol dimethyl ether as raw material, dissolution
Weak solution is configured in acetonitrile, then in lithium ion battery separator surface double spread, is subsequently dried；2) in inert atmosphere protection
Under, above-mentioned weak solution is coated uniformly on sulphur anode pole piece, vacuumizing penetrates into weak solution in sulphur anode micropore, then dry
It is dry；3) under inert atmosphere protection, above-mentioned weak solution is coated with lithium an- ode surface, is subsequently dried.
The preparation method of all solid lithium metal-sulfur cell of the present invention has preparation process simple, at low cost, is suitable for big
The advantages that technical scale metaplasia produces.
As the supplement of above-mentioned preparation method, step 1) and 2) in, the inert atmosphere is argon atmosphere or nitrogen atmosphere,
Water content in inert atmosphere is less than 1ppm, and oxygen content is less than 1ppm；In step 3), the inert atmosphere is argon atmosphere, lazy
Property atmosphere in water content be less than 1ppm, oxygen content be less than 1ppm.
As the supplement of above-mentioned preparation method, it is coated in the weak solution on lithium ion battery separator surface, bis trifluoromethyl
The monomer mole ratio of sulfimide lithium and polyethylene glycol oxide is 1:5, bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetrem
The mass ratio of glycol dimethyl ether is 1:1；Bis trifluoromethyl sulfimide lithium/total the matter of polyethylene glycol oxide/tetraethyleneglycol dimethyl ether
Score is measured within 5wt%.
As the supplement of above-mentioned preparation method, it is coated on the weak solution on sulphur anode pole piece surface and lithium an- ode surface
In, the monomer mole ratio of bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide is 1:1, and bis trifluoromethyl sulfimide lithium-is poly-
The mass ratio of ethylene oxide and tetraethyleneglycol dimethyl ether is 1:1；Bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetrem two
The total mass fraction of diethylene glycol dimethyl ether is within 5wt%.
As the supplement of above-mentioned preparation method, the sulphur anode is by sulphur powder, nano magnesia, carbon nanotube, Ketjen black
It is formed with polyethylene glycol oxide, wherein sulfur content 50wt-70wt%, as a positive electrode active material；Nano magnesia 2wt-5wt%,
Adsorbent as polysulfide；Carbon nanotube 5wt-10wt%, Ketjen black 10wt-20wt%, as conductive network and conduction
Agent；Polyethylene glycol oxide 10wt-20wt%, as binder.
As the supplement of above-mentioned preparation method, sulphur anode the preparation method is as follows: by sulphur powder, nano magnesia, carbon nanometer
Pipe, Ketjen black and polyethylene glycol oxide are raw material, and slurry is configured using N- methyl pyrrole network alkanone as solvent, and subsequent mechanical stirring is made
Uniform sizing material, is coated on aluminium foil surface, and vacuum drying removes N-Methyl pyrrolidone；Then with bis trifluoromethyl sulfimide
Lithium, polyethylene glycol oxide and tetraethyleneglycol dimethyl ether are that raw material is configured to dilute molten in an inert atmosphere using acetonitrile as organic solvent
This weak solution is then coated on sulphur anode pole piece surface in an inert atmosphere by liquid, is subsequently vacuumed out in favor of weak solution infiltration
Into in anode pole piece surface pore, finally dry.
The device have the advantages that as follows: film-type composite solid electrolyte of the invention can be to avoid sulphur anode
" shuttle effect ", all solid lithium metal-sulfur cell cyclical stability with higher of preparation；All solid lithium gold of the invention
Category-sulphur battery has many advantages, such as that the internal resistance of cell is low, specific capacity is high.The preparation method of all solid lithium metal-sulfur cell of the present invention, tool
The advantages that having preparation process simple, at low cost, being suitable for large-scale industrial production.
Detailed description of the invention
Fig. 1 (a) and (b) are business type lithium ion battery separator and bis trifluoromethyl sulfimide in the embodiment of the present invention 1
The optical microscopy of lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether@lithium ion battery separator film-type composite solid electrolyte
Photo；Fig. 1 (c) and (d), which are that the sulphur of sulphur anode and adhering film type composite solid electrolyte is positive in the embodiment of the present invention 1, to be swept
Retouch electron microscope picture.
Fig. 2 (a) is the impedance spectra at room temperature of all solid lithium metal-sulfur cell in the embodiment of the present invention 1；Fig. 2 (b) is complete
The charge and discharge electrograph of solid-state lithium metal-sulphur battery at room temperature, multiplying power 0.1C；Fig. 2 (c) and (d) are then all solid lithium metal-sulfur
The capacity and coulombic efficiency of the charge and discharge of battery at room temperature summarize；
Fig. 3 (a) is the charge and discharge electrograph of all solid lithium metal-sulfur cell at room temperature in the embodiment of the present invention 2, and multiplying power is
0.2C；Fig. 3 (b) and (c) then summarize for the capacity of the charge and discharge of all solid lithium metal-sulfur cell at room temperature and coulombic efficiency；
Fig. 4 (a) is charge and discharge electrograph of all solid lithium metal-sulfur cell at 40 DEG C in the embodiment of the present invention 3, and multiplying power is
0.1C；Fig. 4 (b) then summarizes for the capacity of the charge and discharge of all solid lithium metal-sulfur cell at room temperature；
Fig. 5 (a) is the impedance spectra at room temperature of all solid lithium metal-sulfur cell in comparative example 1 of the present invention；Fig. 5 (b) is complete
The charge and discharge electrograph of solid-state lithium metal-sulphur battery at room temperature, multiplying power 0.1C；
Fig. 6 is the charge and discharge electrograph in comparative example 2 of the present invention using lithium metal-sulphur battery of liquid electrolyte at room temperature,
Multiplying power is 0.1C.
Specific embodiment
The present invention is further elaborated and is illustrated with specific embodiment with reference to the accompanying drawings of the specification.
Embodiment 1
It is organic molten with acetonitrile using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide, tetraethyleneglycol dimethyl ether as raw material
Agent is configured to weak solution in an inert atmosphere, wherein the monomer mole ratio of bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide
For 1:5, the mass ratio of bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether is 1:1.In membrane surface
Double spread vacuumizes and 1 hour dry at 60 DEG C.
Sulphur powder, nano oxidized magnesium powder, carbon nanotube, Ketjen black, polyethylene glycol oxide will be distilled for raw material, with N- methylpyrrole
Alkanone configures slurry as solvent, and then 24 hours obtained uniform sizing materials of subsequent mechanical stirring are coated on aluminium foil surface, at 60 DEG C
It is dried in vacuo 24 hours removing N- methyl pyrrole network alkanones.Then with bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide, tetrem two
Diethylene glycol dimethyl ether is raw material, using acetonitrile as organic solvent, weak solution is configured in an inert atmosphere, then in an inert atmosphere by this
Weak solution is coated on anode pole piece surface, is subsequently vacuumed out so that weak solution penetrates into anode pole piece surface pore, finally
It is 1 hour dry at 60 DEG C.One layer of above-mentioned weak solution, dry 1 hour last dress at subsequent 60 DEG C are coated on lithium an- ode surface
It is made into lithium-sulphur button cell (CR2032), tests the internal resistance of cell and cycle efficieny.
Fig. 1 a is the photo that the optical microscopy of business type lithium ion battery separator is shot, and Fig. 1 b is manufactured in the present embodiment
Bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether@lithium ion battery separator film-type solid electrolytic
Matter optical microscopy claps to obtain picture, as can be seen from the figure has one layer of polymeric to be adhered on lithium ion battery separator.Fig. 1 c is
The scanning electron microscope diagram piece of sulphur anode manufactured in the present embodiment, and Fig. 1 d is then that double fluoroforms have been adhered in the present embodiment
Base sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether sulphur anode scanning electron microscope diagram piece, clearly can be with
See polymer dielectric on the surface of anode pole piece.
Fig. 2 a is the impedance spectra of all solid lithium metal-sulfur button cell manufactured in the present embodiment at room temperature, wherein semicircle
Be 58.6 Ω with the intercept of x-axis, representative be film-type solid electrolyte resistance；What half diameter of a circle represented is solid electrolytic
The contact resistance summation of matter and positive and negative anodes, all-in resistance are about 260 Ω, as can be seen from the figure the either resistance of solid electrolyte
Or contact resistance is all smaller, also indicates that the wetability of solid electrolyte film and positive and negative anodes is preferable.Fig. 2 b is the present embodiment
The multiplying power of the charging and discharging curve of all solid lithium metal-sulfur button cell of preparation at room temperature, charge and discharge is 0.1C, and Fig. 2 c is shown often
The charge/discharge capacity of one circle summarizes, and Fig. 2 d is then summarizing for the coulombic efficiency of corresponding each circle.First circle charging capacity is
550mAh/gS, discharge capacity 460mAh/gS；After 50 circles, charging capacity is about 420mAh/gS, discharge capacity is about
335mAh/gS。
Embodiment 2
It is organic molten with acetonitrile using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide, tetraethyleneglycol dimethyl ether as raw material
Agent is configured to weak solution in an inert atmosphere, wherein the monomer mole ratio of bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide
For 1:5, the mass ratio of bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether is 1:1.In membrane surface
Double spread vacuumizes and 1 hour dry at 60 DEG C.
Sulphur powder, nano oxidized magnesium powder, carbon nanotube, Ketjen black, polyethylene glycol oxide will be distilled for raw material, with N- methylpyrrole
Alkanone configures slurry as solvent, and then 24 hours obtained uniform sizing materials of subsequent mechanical stirring are coated on aluminium foil surface, at 60 DEG C
It is dried in vacuo 24 hours removing N- methyl pyrrole network alkanones.Then with bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide, tetrem two
Diethylene glycol dimethyl ether is raw material, using acetonitrile as organic solvent, weak solution is configured in an inert atmosphere, then in an inert atmosphere by this
Weak solution is coated on anode pole piece surface, is subsequently vacuumed out so that weak solution penetrates into anode pole piece surface pore, finally
It is 1 hour dry at 60 DEG C.It is coated with one layer of above-mentioned weak solution on lithium an- ode surface, drying 1 hour, finally fills at subsequent 60 DEG C
It is made into lithium-sulphur button cell (CR2032), tests the internal resistance of cell and cycle efficieny.
Fig. 3 a is the charging and discharging curve of all solid lithium metal-sulfur button cell manufactured in the present embodiment at room temperature, charge and discharge
Multiplying power be 0.2C, Fig. 3 b shows summarizing for the charge/discharge capacity of each circle, and Fig. 3 c is then the coulombic efficiency of corresponding each circle
Summarize.First circle charging capacity is 419mAh/gS, discharge capacity 361mAh/gS；After 100 circles, charging capacity is about
343mAh/gS, discharge capacity is about 293mAh/gS。
Embodiment 3
It is organic molten with acetonitrile using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide, tetraethyleneglycol dimethyl ether as raw material
Agent is configured to weak solution in an inert atmosphere, wherein the monomer mole ratio of bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide
For 1:5, the mass ratio of bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether is 1:1.In membrane surface
Double spread vacuumizes and 1 hour dry at 60 DEG C.
Sulphur powder, nano oxidized magnesium powder, carbon nanotube, Ketjen black, polyethylene glycol oxide will be distilled for raw material, with N- methylpyrrole
Alkanone configures slurry as solvent, and then 24 hours obtained uniform sizing materials of subsequent mechanical stirring are coated on aluminium foil surface, at 60 DEG C
It is dried in vacuo 24 hours removing N- methyl pyrrole network alkanones.Then with bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide, tetrem two
Diethylene glycol dimethyl ether is raw material, using acetonitrile as organic solvent, weak solution is configured in an inert atmosphere, then in an inert atmosphere by this
Weak solution is coated on anode pole piece surface, is subsequently vacuumed out so that weak solution penetrates into anode pole piece surface pore, finally
It is 1 hour dry at 60 DEG C.One layer of above-mentioned weak solution, dry 1 hour last dress at subsequent 60 DEG C are coated on lithium an- ode surface
It is made into lithium-sulphur button cell (CR2032), tests the internal resistance of cell and cycle efficieny.
Fig. 4 a is the charging and discharging curve at 40 DEG C of all solid lithium metal-sulfur button cell manufactured in the present embodiment, charge and discharge
Multiplying power be 0.1C, Fig. 4 b shows summarizing for the charge/discharge capacity of each circle.First circle charging capacity is 795mAh/gS, electric discharge appearance
Amount is 662mAh/gS；After 12 circles, charging capacity is about 778mAh/gS, discharge capacity is about 620mAh/gS, almost without declining
Subtract.
Comparative example 1
Using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide as raw material, using acetonitrile as organic solvent, in an inert atmosphere
It is configured to weak solution, no tetraethyleneglycol dimethyl ether makees plasticiser, wherein bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide
Monomer mole ratio is 1:5.In membrane surface double spread, vacuumize and 1 hour dry at 60 DEG C.
Sulphur powder, nano oxidized magnesium powder, carbon nanotube, Ketjen black, polyethylene glycol oxide will be distilled for raw material, with N- methylpyrrole
Alkanone configures slurry as solvent, and then 24 hours obtained uniform sizing materials of subsequent mechanical stirring are coated on aluminium foil surface, at 60 DEG C
It is dried in vacuo 24 hours removing N- methyl pyrrole network alkanones.Then using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide as raw material,
Using acetonitrile as organic solvent, it is configured to weak solution in an inert atmosphere, is then in an inert atmosphere coated on this weak solution just
Pole pole piece is subsequently vacuumed out so that weak solution penetrates into anode pole piece surface pore, and dry 1 is small at last 60 DEG C
When.It is coated with one layer of above-mentioned weak solution on lithium an- ode surface, is finally assembled into lithium-sulphur button within dry 1 hour at subsequent 60 DEG C
Battery (CR2032) tests the internal resistance of cell and cycle efficieny.
Fig. 5 a is the impedance spectra of all solid lithium metal-sulfur button cell manufactured in the present embodiment at room temperature, wherein semicircle
Be 140 Ω with the intercept of x-axis, representative be film-type solid electrolyte resistance；What half diameter of a circle represented is solid electrolytic
The contact resistance summation of matter and positive and negative anodes, resistance are about 700 Ω, and as can be seen from the figure either the resistance of solid electrolyte is also
It is that contact resistance is all bigger, also indicates that the wetability of solid electrolyte film and positive and negative anodes is very poor.Fig. 5 b is the present embodiment system
The charging and discharging curve of standby all solid lithium metal-sulfur button cell at room temperature, the multiplying power of charge and discharge are 0.1C.First circle charging capacity
For 150mAh/gS, discharge capacity 96mAh/gS；After 40 circles, charging capacity is about 79mAh/gS, discharge capacity is about
73mAh/gS, population size plays all very poor.
Comparative example 2
It using bis trifluoromethyl sulfimide lithium as solute, is dissolved in glycol dinitrate ether solvents, in an inert atmosphere, matches
It is set to 1 mole every liter of liquid-type electrolyte.To distil sulphur powder, nano oxidized magnesium powder, carbon nanotube, Ketjen black, polyoxyethylene
Alkene is raw material, the configuration slurry using N-Methyl pyrrolidone as solvent, 24 hours obtained uniform sizing materials of subsequent mechanical stirring, then
It is coated on aluminium foil surface, 24 hours removing N- methyl pyrrole network alkanones are dried in vacuo at 60 DEG C.It is then sub- with bis trifluoromethyl sulphonyl
Amine lithium, polyethylene glycol oxide are configured to weak solution, then in indifferent gas using acetonitrile as organic solvent for raw material in an inert atmosphere
This weak solution is coated on anode pole piece surface in atmosphere, is subsequently vacuumed out so that weak solution penetrates into anode pole piece surface pore
In, it is 1 hour dry at last 60 DEG C.It is coated with one layer of above-mentioned weak solution on lithium an- ode surface, drying 1 hour at subsequent 60 DEG C
It is finally assembled into lithium-sulphur button cell (CR2032), tests the internal resistance of cell and cycle efficieny.
Fig. 6 is that the charge and discharge of the lithium metal using liquid electrolyte-sulphur button cell manufactured in the present embodiment at room temperature are bent
Line, the multiplying power of charge and discharge are 0.1C.First circle charging capacity is 1107mAh/gS, discharge capacity 756mAh/gS；After 10 circles, fill
Capacitance is about 464mAh/gS, discharge capacity is about 217mAh/gS, population size decaying it is unusual fast, reason be using
There is shuttle effects for liquid-type electrolyte.
Claims (10)
1. a kind of all solid lithium metal-sulfur cell, which is characterized in that
Its electrolyte used is bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether@lithium ion battery
The film-type composite solid electrolyte of diaphragm；The material of sulphur anode include sulphur powder, nano magnesia, carbon nanotube, Ketjen black and
Polyethylene glycol oxide；Sulphur anode pole piece surface is coated with bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether；
Lithium an- ode surface is coated with bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether.
2. all solid lithium metal-sulfur cell according to claim 1, which is characterized in that bis trifluoromethyl sulfimide lithium/
In polyethylene glycol oxide/tetraethyleneglycol dimethyl ether@lithium ion battery separator film-type composite solid electrolyte, bis trifluoromethyl sulphur
The monomer mole ratio of imide li and polyethylene glycol oxide is 1:5, bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetrem two
The mass ratio of diethylene glycol dimethyl ether is 1:1, uses lithium ion battery separator as substrate, the lighium polymer electrolyte of leading is coated on
Lithium ion battery separator surface.
3. all solid lithium metal-sulfur cell according to claim 1 or 2, which is characterized in that the sulphur anode is by sulphur
Powder, nano magnesia, carbon nanotube, Ketjen black and polyethylene glycol oxide composition, wherein sulfur content 50wt-70wt%, as anode
Active material；Nano magnesia 2wt-5wt%, the adsorbent as polysulfide；Carbon nanotube 5wt-10wt%, Ketjen black
10wt-20wt%, as conductive network and conductive agent；Polyethylene glycol oxide 10wt-20wt%, as binder.
4. all solid lithium metal-sulfur cell according to claim 1 or 2, which is characterized in that sulphur anode pole piece surface and lithium
Bis trifluoromethyl sulfimide lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether of metal negative electrode surface coating, bis trifluoromethyl sulphur
The monomer mole ratio of imide li and polyethylene glycol oxide is 1:1, bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetrem two
The mass ratio of diethylene glycol dimethyl ether is 1:1.
5. a kind of preparation method of all solid lithium metal-sulfur cell, which is characterized in that comprising steps of 1) in inert atmosphere protection
Under, using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide and tetraethyleneglycol dimethyl ether as raw material, be dissolved in acetonitrile configure it is dilute
Solution is subsequently dried then in lithium ion battery separator surface double spread；It 2), will be above-mentioned dilute molten under inert atmosphere protection
Liquid is coated uniformly on sulphur anode pole piece, and vacuumizing penetrates into weak solution in sulphur anode micropore, is subsequently dried；3) in inert atmosphere
Under protection, above-mentioned weak solution is coated with lithium an- ode surface, is subsequently dried.
6. the preparation method of all solid lithium metal-sulfur cell according to claim 5, which is characterized in that step 1) and 2)
In, the inert atmosphere is argon atmosphere or nitrogen atmosphere, and the water content in inert atmosphere is less than 1ppm, and oxygen content is less than
1ppm；In step 3), the inert atmosphere is argon atmosphere, and the water content in inert atmosphere is less than 1ppm, and oxygen content is less than
1ppm。
7. the preparation method of all solid lithium metal-sulfur cell according to claim 5, which is characterized in that be coated on lithium from
In the weak solution on sub- battery diaphragm surface, the monomer mole ratio of bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide is 1:5, double
The mass ratio of lithium trifluoromethanesulp,onylimide-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether is 1:1；Bis trifluoromethyl sulfimide
Lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether total mass fraction≤5wt%.
8. the preparation method of all solid lithium metal-sulfur cell according to claim 5, which is characterized in that be coated on sulphur just
In pole pole piece and the weak solution on lithium an- ode surface, the monomer of bis trifluoromethyl sulfimide lithium and polyethylene glycol oxide rubs
, than being 1:1, the mass ratio of bis trifluoromethyl sulfimide lithium-polyethylene glycol oxide and tetraethyleneglycol dimethyl ether is 1:1 for you；Double trifluoros
Sulfonyloxy methyl imine lithium/polyethylene glycol oxide/tetraethyleneglycol dimethyl ether total mass fraction≤5wt%.
9. the preparation method of all solid lithium metal-sulfur cell according to claim 5, which is characterized in that the sulphur is just
Pole is made of sulphur powder, nano magnesia, carbon nanotube, Ketjen black and polyethylene glycol oxide, wherein sulfur content 50wt-70wt% makees
For positive active material；Nano magnesia 2wt-5wt%, the adsorbent as polysulfide；Carbon nanotube 5wt-10wt%, section
The black 10wt-20wt% of qin, as conductive network and conductive agent；Polyethylene glycol oxide 10wt-20wt%, as binder.
10. the preparation method of all solid lithium metal-sulfur cell according to claim 9, which is characterized in that the system of sulphur anode
Preparation Method is as follows:
By sulphur powder, nano magnesia, carbon nanotube, Ketjen black and polyethylene glycol oxide be raw material, using N- methyl pyrrole network alkanone as
Solvent configures slurry, and uniform sizing material is made in subsequent mechanical stirring, is coated on aluminium foil surface, and vacuum drying removes N- crassitude
Ketone；It is organic molten with acetonitrile then using bis trifluoromethyl sulfimide lithium, polyethylene glycol oxide and tetraethyleneglycol dimethyl ether as raw material
Agent is configured to weak solution in an inert atmosphere, this weak solution is then coated on sulphur anode pole piece surface in an inert atmosphere, with
After vacuumize so that weak solution penetrates into anode pole piece surface pore, finally dry.
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