CN106865495B - Lithium sulphur battery electrode material and lithium-sulfur cell is prepared using this kind of electrode material - Google Patents

Lithium sulphur battery electrode material and lithium-sulfur cell is prepared using this kind of electrode material Download PDF

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CN106865495B
CN106865495B CN201710255948.5A CN201710255948A CN106865495B CN 106865495 B CN106865495 B CN 106865495B CN 201710255948 A CN201710255948 A CN 201710255948A CN 106865495 B CN106865495 B CN 106865495B
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lithium
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CN106865495A (en
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不公告发明人
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Ningxia and Hsing carbon based materials Co., Ltd.
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • B82—NANOTECHNOLOGY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

Lithium-sulfur cell is prepared the present invention relates to a kind of lithium sulphur battery electrode material and using this kind of electrode material, wherein negative electrode material is made of in terms of mass fraction following feedstock composition: 5-10 parts of stable state lithium powder, 3-7 parts of carbon materials, 1 part of binder and solvent.The present invention has especially selected stable state lithium powder and carbon nanospheres, carbon nanotube and mesoporous carbon to prepare cathode mixed slurry as the carbon material in cathode for the mixture that 5:2:1 is mixed according to mass ratio, so that the lithium-sulfur cell negative electrode material has superior performance, battery made from preparation method of the invention shows lesser impedance, shuttle effect and the dendritic growth in continuous charge and discharge process can effectively be weakened, show better cycle performance and high rate performance than common metal lithium foil.

Description

Lithium sulphur battery electrode material and lithium-sulfur cell is prepared using this kind of electrode material
Technical field
The invention belongs to electrode material preparation field more particularly to a kind of lithium sulphur battery electrode material and utilize this kind of electrode The method that material prepares lithium-sulfur cell.
Background technique
Lithium ion battery (Lithium-ionbattery, LIB), also known as lithium secondary battery are a kind of recyclable chargings Mobile power source equipment.LIB has high-energy density, high power density, has extended cycle life, cleans nontoxic and memory-less effect etc. Plurality of advantages, since the nineties in last century, LIB was commercialized by Sony, LIB has obtained widely developing rapidly.Mesh Oneself warp of preceding LIB becomes the power supply of most of mobile electronic devices.In recent years, people deeply and widely study to LIB. In LIB, negative electrode material has very big influence to the performance of battery, and developing excellent negative electrode material is also to improve LIB performance One of key factor.Carbon material is a kind of most important LIB negative electrode material, oneself is through there is hundreds of to possess different structure at present Carbon material is used as negative electrode of lithium ion battery, these materials include natural graphite, electrographite, coke, carbon fiber, mesocarbon Microballoon, carbon black etc..
Elemental sulfur is nontoxic, global rich reserves, and has higher theoretical specific capacity (1675mAh/g).Lithium metal has Low-density (0.534g/cm3), low potential (- 3.045v) and height ratio capacity (3861mAh/g), therefore lithium-sulfur cell can reach To higher energy density, so as to energy stores, in terms of play a significant role.However, lithium sulphur electricity There are problems in the commercialization process of pond, such as lithium metal unstable chemcial property, when use, exists potential dangerous；Work as cathode When using metallic lithium foil, for battery after multiple charge and discharge, metallic lithium foil surface easily forms dendrite.The continuous growth of dendrite causes Battery capacity decline, and dendritic growth may pierce through diaphragm, cause battery short circuit, cause safety problem.
Hard carbon is the pyrolytic carbon of high molecular polymer, is difficult to be graphitized at high temperature.The reversible capacity energy of hard carbon Higher, cycle performance is also fine.But that there is also electrode potentials is excessively high, (i.e. intercalation potential is less than de- lithium electricity to current potential lag for hard carbon Position) and for the first time circulation irreversible capacity it is big the disadvantages of.
Currently, most of lithium-sulfur cell all uses lithium metal as cathode.Lithium is as cathode in multiple charge and discharge process It can lead to the formation of a product by ten current density unevenness.Branch product will lead to diaphragm and penetrate, and then make battery that short circuit occur, and be main Security risk source.If adding graphene in cathode, the specific surface area of cathode becomes larger, and surface current density reduces, meanwhile, Loose graphene provides the space of lithium deposition, to keep the growth of lithium branch product more and more difficult.For existing for cathode of lithium Problem, the improvement and research that researcher carries out are less.Sum up main include two aspect: one is to added from electrolyte Agent is modified, by the way that different additives, such as LiNO is added3With PEO etc., promote cathode of lithium surface fast in charge and discharge process Speed forms more stable SEI film, it would be desirable to inhibit Li dendrite and improve cycle performance.However additive is in charge and discharge process It is gradually consumed, influences the stability and continuity of battery.Second is that starting with from the preparation process of lithium electrode, closed by using lithiumation Object coats lithium powder or electrodeposit metals lithium, and lithium foil surface increases the methods of protective layer, improves cycle efficieny and cycle life, But operating process is also complex.
Summary of the invention
In order to solve the problems in the existing technology, the object of the present invention is to provide one kind by stable state lithium powder and special to match Than the negative electrode slurry that carbon material is prepared, and the lithium-sulfur cell being prepared by the slurry, which solve in the prior art Using the materials bring technological deficiency such as hard carbon and solve cathode of lithium battery it is improved present in stability and continuity The technical problems such as poor and complicated for operation.
A kind of lithium-sulfur cell, including anode and cathode, it is characterised in that: in terms of mass fraction, cathode is by following raw material Composition composition: 5-10 parts of stable state lithium powder, 3-7 parts of carbon materials, 1 part of binder and solvent；The binder is by polyvinyl pyrrole Alkanone and polyethyleneimine are mixed according to volume ratio for 2:1；The solvent is with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio is that 3:2:1 being mixed；Its anode is made of following material: anode sizing agent packet Contain: 9 parts of sublimed sulfurs, 7 parts of conductive agents, 1 part of binder and solvent；The conductive agent by Nano carbon fibers peacekeeping expanded graphite according to Mass ratio is composed for 1:1, and the polyvinylpyrrolidone and polyethyleneimine in the binder are mixed for 2:1 according to volume ratio It closes；The solvent is 3:2:1 according to volume ratio by propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) It mixes；
A kind of preparation method of lithium-sulfur cell, comprising the following steps:
The preparation of step 1, positive plate: being positive active material, Nano carbon fibers peacekeeping expanded graphite according to matter using sublimed sulfur Amount be conductive agent, polyvinylpyrrolidone and polyethyleneimine according to volume ratio is that 2:1 is mixed than be mixture that 1:1 is composed Mixed system made of conjunction is mixture binder；Sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite in the anode sizing agent of sulfur-bearing It is 9:7:1 according to the mass ratio that mass ratio is conductive agent and the binder that 1:1 is composed；Mixture binder is dissolved in Propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) are that the mixing that 3:2:1 is mixed is molten according to volume ratio Solution is made in agent, wherein according to Mass Calculation, weigh solvent according to the ratio that solid content is 30%, solid be sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite；Sublimed sulfur is composed with Nano carbon fibers peacekeeping expanded graphite according to mass ratio for 1:1 again Conductive agent in mass ratio after mixing, pour into the solvent for having dissolved binder, be fabricated to anode sizing agent；
Then obtained slurry is uniformly coated on foamed nickel current collector；It is placed in a vacuum drying oven drying again, removes molten Agent and moisture, the temperature in vacuum oven are 50 DEG C, drying time 10-15h；The slurry of foam nickel surface is scraped with blade Except clean, positive plate is flattened, then positive plate is placed in a vacuum drying oven and is dried again；
Step 2, negative electrode tab preparation: stable state lithium powder, carbon material and polyvinylpyrrolidone and polyethyleneimine according to body Product is than being that the mixed system binder that 2:1 is mixed is weighed according to mass ratio, with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to the mixture mixed that volume ratio is 3:2:1 is solvent, wherein according to quality meter It calculates, weighs solvent according to the ratio that solid content is 30%, solid is stable state lithium powder and carbon material；First binder is dissolved in molten In agent, then stable state lithium powder and carbon material are poured into above-mentioned solution, be applied in foamed nickel current collector after mixing to Obtain negative electrode tab；Negative electrode tab is placed on heating sheet and is heated so that solvent volatilization, then flattens negative electrode tab；Wherein, stable state lithium The mass ratio of powder, carbon material and binder is 5-10:3-7:1；The temperature heated on heating sheet is 70 DEG C, heating time 8- 15h；
Step 3, battery assembly: lithium sulphur electricity is assembled into using negative electrode tab made from positive plate made from step 1 and step 2 Pond.
A kind of lithium-sulfur cell negative electrode material, characterized by comprising: in terms of mass fraction, by following feedstock composition group At: 5-10 parts of stable state lithium powder, 3-7 parts of carbon materials, 1 part of binder and solvent.
Further, the stable state lithium powder is made of dropping liquid emulsifying technology (DET), and lithium powder diameter is 60 μm -90 μm.
Further, the carbon material to be carbon nanospheres, carbon nanotube and mesoporous carbon according to mass ratio be 5:2:1 mixing and At mixture.
Further, it according to volume ratio is that 2:1 is mixed that the binder, which is polyvinylpyrrolidone and polyethyleneimine, Binder；It is 3 that the solvent, which is propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio: The mixed solvent that 2:1 is mixed.
A kind of preparation method of lithium-sulfur cell, using above-mentioned negative electrode material as cathode, it is characterised in that including walking as follows It is rapid:
(1) anode sizing agent of sulfur-bearing is coated in collector and positive plate is made；
(2) stable state lithium powder, carbon material and binder are weighed according to mass ratio, with propene carbonate (PC), methyl ethyl carbonate Ester (EMC) and polyether sulfone (PES) are solvent according to the mixture mixed that volume ratio is 3:2:1；First the binder It is dissolved in the solvent, then stable state lithium powder and carbon material is poured into above-mentioned solution, are applied to nickel foam after mixing In to obtaining negative electrode tab；Negative electrode tab is placed on heating sheet and is heated so that solvent volatilizees；Then negative electrode tab is flattened stand-by；
(3) anode, cathode, diaphragm are assembled into button cell.
Further, the anode sizing agent of sulfur-bearing as described in step (1) includes: sublimed sulfur, conductive agent, binder and solvent； The conductive agent is composed of Nano carbon fibers peacekeeping expanded graphite according to mass ratio for 1:1, the poly- second in the binder Alkene pyrrolidone and polyethyleneimine are mixed according to volume ratio for 2:1；The solvent is by propene carbonate (PC), carbonic acid first Ethyl ester (EMC) and polyether sulfone (PES) are mixed according to volume ratio for 3:2:1；The in the mixed solvent that first binder is dissolved in, Again in mass ratio after mixing by sublimed sulfur and conductive agent, it pours into the solvent for having dissolved binder, is fabricated to anode sizing agent, Then anode sizing agent is uniformly applied to collector, positive plate is made.
Further, the positive plate need to heat moisture removal and solvent in a vacuum drying oven, then strike off its surface And pressing；Temperature in the vacuum oven is 50 DEG C, drying time 10h.
Further, the mass ratio of the sublimed sulfur in the anode sizing agent of the sulfur-bearing, conductive agent and binder is 9:7:1.
Further, negative electrode tab described in step (2) need to then be flattened in 40 DEG C of -70 DEG C of heating 8h-11h to remove solvent For use.
Further, the operation in step (2) and (3) is completed in the vacuum glove box full of argon gas.
The lithium-sulfur cell negative electrode material and lithium-sulfur cell that the present invention is prepared have the following beneficial effects:
(1) the lithium-sulfur cell negative electrode material that the present invention is prepared is made by stable state lithium powder and the carbon material of specific proportion Cathode is compared with common lithium foil electrode, and specific surface area is bigger, and porosity is higher, more complete with electrolyte contacts, to effectively put Electric area is bigger, and impedance is smaller, and can effectively inhibit the growth of Li dendrite, can express preferable cycle performance and forthright again Energy.
(2) using Nano carbon balls material in the lithium-sulfur cell negative electrode material that the present invention is prepared, Nano carbon balls have only Special appearance structure, have unique advantage in electrochemical performance: a, spherical shape may be implemented most closely to accumulate, and make lithium Ion battery has higher volume energy density；B, spherical graphite platelet structure makes Li+Can from all directions of ball into Row insertion and deintercalation, overcome graphite due to anisotropy is excessively high and causes graphite flake layer swelling, collapse and cannot quickly fill The problem of electric discharge；C, the shape of spherical particle is more convenient for the processing of electrode.It sufficiently combines carbon nanotube and mesoporous carbon again Structural advantage, highly ordered mesosize pores carbon have large specific surface area, uniform pore diameter, pore volume is very high, it is porous to be mutually related The features such as structure and high conductivity；And carbon nanotube has good orientation, and good contact and shape can be formed with collector At efficiently and directionally conducting matrix grain, lithium sulphur battery electrode material middle skeleton electric conductivity is effectively improved, and its internal regular pore canal The storage of advantageous ten polysulfide.The present invention makes full use of the advantage of this three's structure, can effectively weaken continuous charge and discharge process In shuttle effect and dendritic growth, show better cycle performance and high rate performance than conventional electrodes.
(3) in terms of the conductive additive of anode, the present invention adds Nano carbon fibers peacekeeping expanded graphite, the former can form three Conductive network is tieed up, not only can increase the remote conductive ability in pole piece, but also be not easy that the product formed in discharge process is permitted to cover completely Lid, so as to improve the surface texture of pole piece;The latter utilizes the abundant network gap structure and good adsorption properties of expanded graphite, Also the utilization rate and cycle performance of elemental sulfur can be improved.
(4) present invention has also especially been selected using the mixed system of polyvinylpyrrolidone and polyethyleneimine as bonding Agent, thus the porous structure with strong holding sulphur anode in cyclic process.
(5) present invention has selected the mixed system of three kinds of substances as solvent, and by experiment, which can preferably be kept The structure feature and advantage of the raw material of various pole pieces, so that the product being finally prepared is with better stability and more High quality.
Specific embodiment
Embodiment one:
A kind of lithium-sulfur cell and preparation method thereof is as follows:
1, the preparation of positive plate: being positive active material, Nano carbon fibers peacekeeping expanded graphite according to mass ratio using sublimed sulfur To be conductive agent, polyvinylpyrrolidone and polyethyleneimine according to volume ratio be 2:1 mixing for the mixture that 1:1 is composed and At mixed system be binder.
Sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite in the anode sizing agent of sulfur-bearing are composed according to mass ratio for 1:1 Conductive agent and binder mass ratio be 9:7:1.Mixture binder is dissolved in propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio is that solution is made in the in the mixed solvent that mixes of 3:2:1, wherein according to quality It calculates, weighs solvent according to the ratio that solid content is 30%.Again by sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite according to quality Conductive agent than being composed for 1:1 pours into the solvent for having dissolved binder in mass ratio after mixing, is fabricated to anode Slurry.
Then obtained slurry is uniformly coated on foamed nickel current collector.It is placed in a vacuum drying oven drying again, removes molten Agent and moisture, the temperature in vacuum oven are 50 DEG C, drying time 10h, are struck off the slurry of foam nickel surface with blade Completely, then with certain pressure positive plate is flattened.Then positive plate is placed in a vacuum drying oven and is dried again.The above operation is equal It is completed in vacuum glove box.
2, prepared by negative electrode tab: stable state lithium powder, carbon material and polyvinylpyrrolidone and polyethyleneimine according to volume ratio It is weighed for the mixed system binder that 2:1 is mixed according to mass ratio, with propene carbonate (PC), methyl ethyl carbonate (EMC) It according to the mixture mixed that volume ratio is 3:2:1 is solvent with polyether sulfone (PES), wherein according to Mass Calculation, according to The ratio that solid content is 30% weighs solvent.
First binder is dissolved in solvent, then stable state lithium powder and carbon material are poured into above-mentioned solution, is uniformly mixed After be applied in foamed nickel current collector to obtaining negative electrode tab；Negative electrode tab is placed on heating sheet and is heated so that solvent volatilizees；And Negative electrode tab is flattened afterwards stand-by；Wherein, the mass ratio of stable state lithium powder, carbon material and binder is 10:7:1；It is heated on heating sheet Temperature be 70 DEG C, heating time 8h.The above operation is completed in vacuum glove box.
3, battery assembly: battery is assembled into using above-mentioned positive plate and above-mentioned negative electrode tab.
Battery assembly and test: button battery assembles in the glove box full of argon gas.Using above-mentioned negative electrode tab as cathode, Using Celgard2400 diaphragm and 2025 type button batteries.Electrolyte is 1MLiClO4、0.15MLiNO3It is dissolved in DOL:DME (volume ratio 1:1).Battery is placed in blue electrical measurement test system (CT2001A) and carries out constant current test.Charging/discharging voltage range is 1.5- 3.0V, test temperature are room temperature.
Embodiment two:
Compared with embodiment one, embodiment two changes stable state lithium powder, carbon material and binder in negative electrode tab preparation process Mass ratio be 7:4:1, the temperature heated on heating sheet is 40 DEG C, heating time 11h.Remaining operates and illustrates same embodiment One.
Embodiment three:
Compared with embodiment one, embodiment two changes stable state lithium powder, carbon material and binder in negative electrode tab preparation process Mass ratio be 5:5:1, the temperature heated on heating sheet is 60 DEG C, heating time 9h.Remaining operates and illustrates same embodiment One.
Compared to common lithium foil electrode, when the cathode of embodiment one, two and three is using stable state lithium powder and mixing carbon material, Lithium-sulfur cell of the invention can express better first charge-discharge specific capacity, while capacity retention ratio exists after 100 circulations 95.2% or more.
The button cell of each embodiment does AC impedance comparative experiments after standing 24 hours.Experimental result is shown, works as implementation After example one, two and three is using stable state lithium powder and mixing carbon material, compared to common lithium foil electrode, the resistance of lithium-sulfur cell of the invention Anti- to greatly reduce, reason is the large specific surface area of stable state lithium powder, expressible out faster electronics biography complete with electrolyte contacts It passs and shifts.
Meanwhile using Nano carbon balls material in the lithium-sulfur cell negative electrode material that is prepared of the present invention, Nano carbon balls have Unique appearance structure, there is unique advantage in electrochemical performance :(a) and spherical shape may be implemented most closely to accumulate, Make lithium ion battery that there is higher volume energy density；(b) spherical graphite platelet structure allows each side of the Li+ from ball To insertion and deintercalation is carried out, overcome graphite due to anisotropy is excessively high and causes graphite flake layer swelling, collapse and cannot be fast The problem of fast charge and discharge；(c) shape of spherical particle is more convenient for the processing of electrode.
In turn, the present invention sufficiently combines the structural advantage of carbon nanotube and mesoporous carbon again, and highly ordered mesosize pores carbon has The features such as specific surface is big, uniform pore diameter, pore volume is very high, porous structure and the high conductivity of being mutually related；And carbon nanometer Pipe again have good orientation, can be formed with collector it is good contact and formed efficiently and directionally conducting matrix grain, effectively improve lithium Sulphur battery electrode material middle skeleton electric conductivity, and the storage of its internal regular pore canal also advantageous ten polysulfide.The present invention fills Divide the advantage using this three's structure, can effectively weaken shuttle effect and the dendritic growth in continuous charge and discharge process, than routine Electrode shows better cycle performance and high rate performance.
When the progress charge and discharge comparative experiments under different multiplying using the electrode of each embodiment and common lithium foil electrode.It is real It tests the results show that lithium-sulfur cell can express higher specific capacity under different multiplying when using electrode of the invention.Especially Under high current density, shown using the lithium-sulfur cell of stable state lithium powder and mixing carbon material preparation than common lithium foil electrode battery Apparent specific capacity is promoted.
In terms of the conductive additive of anode, we add Nano carbon fibers peacekeeping expanded graphite, the former can form three-dimensional and lead Electric network not only can increase the remote conductive ability in pole piece, but also be not easy that the product formed in discharge process is permitted to be completely covered, from And improve the surface texture of pole piece;The latter utilizes the abundant network gap structure and good adsorption properties of expanded graphite, can also Improve the utilization rate and cycle performance of elemental sulfur.
The present invention has also especially selected the mixed system using polyvinylpyrrolidone and polyethyleneimine as binder, To the porous structure with strong holding sulphur anode in cyclic process.The present invention has selected the mixed system of three kinds of substances most For solvent, by experiment, which can preferably keep the structure feature and advantage of the raw material of various pole pieces, so that finally The product being prepared has better stability and higher quality.
Basic principles and main features and advantages of the present invention of the invention have been shown and described in above embodiments.The industry Technical staff it should be appreciated that the present invention is not limited to the above embodiments, what is described in the above embodiment and the description is only Illustrate the principle of the present invention, rather than limits the scope of the invention in any way, without departing from the scope of the invention, Various changes and improvements may be made to the invention, these changes and improvements are both fallen in claimed range.

Claims (3)

1. a kind of lithium-sulfur cell, including anode and cathode, it is characterised in that: in terms of mass fraction, cathode is by following raw material group Close object composition: 5-10 parts of stable state lithium powder, 3-7 parts of carbon materials, 1 part of binder and solvent；The binder is by polyvinylpyrrolidine Ketone and polyethyleneimine are mixed according to volume ratio for 2:1；The solvent is with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio is that 3:2:1 being mixed；Its anode is made of following material: anode sizing agent packet Contain: 9 parts of sublimed sulfurs, 7 parts of conductive agents, 1 part of binder and solvent；The conductive agent by Nano carbon fibers peacekeeping expanded graphite according to Mass ratio is composed for 1:1, and the polyvinylpyrrolidone and polyethyleneimine in the binder are mixed for 2:1 according to volume ratio It closes；The solvent is 3:2:1 according to volume ratio by propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) It mixes；
The stable state lithium powder is made of dropping liquid emulsifying technology (DET), and lithium powder diameter is 60 μm -90 μm；
The preparation method of the lithium-sulfur cell, comprising the following steps:
Step 1: the preparation of positive plate: using sublimed sulfur as positive active material, Nano carbon fibers peacekeeping expanded graphite is according to mass ratio To be conductive agent, polyvinylpyrrolidone and polyethyleneimine according to volume ratio be 2:1 mixing for the mixture that 1:1 is composed and At mixed system be mixture binder；Sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite in the anode sizing agent of sulfur-bearing according to Mass ratio is that the mass ratio of conductive agent and the binder that 1:1 is composed is 9:7:1；Mixture binder is dissolved in carbonic acid Acrylic ester (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) are according to the in the mixed solvent that volume ratio is that 3:2:1 is mixed Solution is made, wherein according to Mass Calculation, weigh solvent according to the ratio that solid content is 30%, solid is sublimed sulfur, nanometer Carbon fiber and expanded graphite；Sublimed sulfur is led with Nano carbon fibers peacekeeping expanded graphite according to mass ratio for what 1:1 was composed again Electric agent in mass ratio after mixing, is poured into the solvent for having dissolved binder, and anode sizing agent is fabricated to；
Then obtained slurry is uniformly coated on foamed nickel current collector；Be placed in a vacuum drying oven drying again, remove solvent and Moisture, the temperature in vacuum oven are 50 DEG C, drying time 10-15h；The slurry of foam nickel surface struck off with blade dry Only, positive plate is flattened, then positive plate is placed in a vacuum drying oven and is dried again；
Step 2: negative electrode tab preparation: weighing stable state lithium powder, carbon material and binder according to mass ratio, and the binder is poly- second Alkene pyrrolidone and polyethyleneimine are according to the mixed system binder that volume ratio is that 2:1 is mixed, with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) are solvent according to the mixture mixed that volume ratio is 3:2:1, In, according to Mass Calculation, solvent is weighed according to the ratio that solid content is 30%, solid is stable state lithium powder and carbon material；First viscous Knot agent is dissolved in solvent, and then stable state lithium powder and carbon material are poured into above-mentioned solution, are applied to nickel foam after mixing To obtain negative electrode tab in collector；Negative electrode tab is placed on heating sheet and is heated so that solvent volatilization, then flattens negative electrode tab； Wherein, the mass ratio of stable state lithium powder, carbon material and binder is 5-10:3-7:1；The temperature heated on heating sheet is 70 DEG C, is added The hot time is 8-15h；
Step 3: battery assembly: being assembled into lithium-sulfur cell using negative electrode tab made from positive plate made from step 1 and step 2.
2. lithium-sulfur cell according to claim 1, it is characterised in that: with blade by the slurry of foam nickel surface described in step 1 Expect scraped clean, the operation that positive plate flattens is completed in vacuum glove box.
3. lithium-sulfur cell according to claim 1, it is characterised in that: in step 2 negative electrode tab be placed on heating sheet heat with Solvent is set to volatilize, negative electrode tab, which is then flattened stand-by operation, is completed in vacuum glove box.
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