CN106356567B - A kind of lithium-sulfur cell - Google Patents

A kind of lithium-sulfur cell Download PDF

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CN106356567B
CN106356567B CN201610961096.7A CN201610961096A CN106356567B CN 106356567 B CN106356567 B CN 106356567B CN 201610961096 A CN201610961096 A CN 201610961096A CN 106356567 B CN106356567 B CN 106356567B
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lithium
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宗铭
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Lianyungang Dingzhicai Energy Technology Co ltd
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Ningbo Science And Technology Co Ltd
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Abstract

The present invention relates to a kind of preparation method of lithium-sulfur cell, wherein negative 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 especially selected stable state lithium powder and carbon nanospheres, carbon nanotube and mesoporous carbon according to mass ratio be 5:2：1 mixture mixed prepares cathode mixed slurry as the carbon material in cathode, so that the lithium-sulfur cell negative material has superior performance, battery shows smaller impedance made from the preparation method of the present invention, shuttle effect and the dendritic growth in continuous charge and discharge process can effectively be weakened, better cycle performance and high rate performance are shown than common metal lithium foil.

Description

A kind of lithium-sulfur cell
Technical field
The present patent application is February 03 2016 applying date, application No. is：201610075890.1 entitled " a kind of The divisional application of the application for a patent for invention of the preparation method of lithium-sulfur cell ".The invention belongs to electrode material preparation fields, especially relate to And a kind of lithium sulphur battery electrode material and the method for preparing lithium-sulfur cell using this kind of electrode material.
Background technology
Lithium ion battery (Lithium-ion battery, LIB), also known as lithium secondary battery are that a kind of be recycled is filled The mobile power equipment of electricity.LIB has high-energy density, high power density, has extended cycle life, cleans nontoxic and memory-less effect Many advantages, such as, since the nineties in last century, LIB was commercialized by Sony, LIB has been obtained rapid and has widely been developed. Oneself warps of LIB become the power supply of most of mobile electronic devices at present.In recent years, people to LIB deeply and widely grind Study carefully.In LIB, negative material has prodigious influence to the performance of battery, and it is also to improve LIB to develop excellent negative material One of the key factor of energy.Carbon material is a kind of most important LIB negative materials, oneself is through there is hundreds of to possess different structure at present Carbon material be used as negative electrode of lithium ion battery, these materials include natural graphite, electrographite, coke, carbon fiber, interphase Carbosphere, 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 play a significant role in energy stores, utilization of regenerative energy etc..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 declines, and dendritic growth may pierce through diaphragm, causes battery short circuit, causes 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. it is electric to be less than de- lithium to current potential lag for intercalation potential for hard carbon Position) and for the first time cycle irreversible capacity it is big the shortcomings 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 can cause diaphragm to 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.Existing for cathode of lithium Problem, the improvement and research that researcher carries out are less.It includes two aspects to sum up main：First, being 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 films, 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.
Invention content
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 that is prepared by the slurry, which solve in the prior art Using the material strips such as hard carbon come technological deficiency 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 preparation method of lithium-sulfur cell, includes the following steps：
The preparation of step 1, positive plate：It is positive active material, Nano carbon fibers peacekeeping expanded graphite according to matter using sublimed sulfur Amount is than being 1:It according to volume ratio is 2 that 1 mixture that is composed, which is conductive agent, polyvinylpyrrolidone and polyethyleneimine,:1 is mixed 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 1 according to mass ratio:The mass ratio of 1 conductive agent being composed and the binder is 9:7:1；Mixture binder is dissolved in Propene carbonate（PC）, methyl ethyl carbonate（EMC）And polyether sulfone（PES）It is 3 according to volume ratio:2:1 mixing that mixes is molten Solution is made in agent, wherein according to Mass Calculation, the ratio for being 30% according to solid content weighs solvent, solid be sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite；It is again 1 according to mass ratio by sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite:1 is composed 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 drying in vacuum drying chamber again, removes molten Agent and moisture, the temperature in vacuum drying chamber 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 vacuum drying chamber and is dried again；
It is prepared by step 2, negative plate：Stable state lithium powder, carbon material and polyvinylpyrrolidone and polyethyleneimine according to body Product is than being 2:The 1 mixed system binder mixed is weighed according to mass ratio, with propene carbonate（PC）, methyl ethyl carbonate （EMC）And polyether sulfone（PES）It is 3 according to volume ratio:2:1 mixture mixed is solvent, wherein according to quality meter It calculates, the ratio for being 30% according to solid content weighs solvent, and 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 to after mixing in foamed nickel current collector to Obtain negative plate；Negative plate is placed on heating plate and is heated so that solvent volatilization, then flattens negative plate；Wherein, stable state lithium The mass ratio of powder, carbon material and binder is 5-10：3-7：1；The temperature heated on heating plate is 70 DEG C, heating time 8- 15h；
Step 3, battery assembling：It is assembled into lithium sulphur electricity using negative plate made from positive plate made from step 1 and step 2 Pond.
A kind of lithium-sulfur cell negative material, it is characterised in that including：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 by dropping liquid emulsifying technology（DET）It is made, a diameter of 60 μm -90 μm of lithium powder.
Further, it according to mass ratio is 5 that the carbon material, which is carbon nanospheres, carbon nanotube and mesoporous carbon,：2：1 mixing and At mixture.
Further, it according to volume ratio is 2 that the binder, which is polyvinylpyrrolidone and polyethyleneimine,:1 mixes Binder；The solvent is propene carbonate（PC）, methyl ethyl carbonate（EMC）And polyether sulfone（PES）It is 3 according to volume ratio: 2:1 mixed solvent mixed.
A kind of preparation method of lithium-sulfur cell, using above-mentioned negative material as cathode, it is characterised in that including walking as follows Suddenly：
（1）The anode sizing agent of sulfur-bearing is coated in collector, 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）It is 3 according to volume ratio:2:1 mixture mixed is solvent；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 obtain negative plate；Negative plate is placed on heating plate and is heated so that solvent volatilizees；Then negative plate is flattened for use；
（3）Anode, cathode, diaphragm are assembled into button cell.
Further, step（1）Described in the anode sizing agent of sulfur-bearing include：Sublimed sulfur, conductive agent, binder and solvent； The conductive agent is 1 according to mass ratio by Nano carbon fibers peacekeeping expanded graphite:1 is composed, the poly- second in the binder Alkene pyrrolidone and polyethyleneimine are 2 according to volume ratio:1 mixes；The solvent is by propene carbonate（PC）, carbonic acid first Ethyl ester（EMC）And polyether sulfone（PES）It is 3 according to volume ratio:2:1 mixes；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 in vacuum drying chamber and remove moisture removal and solvent, then strike off its surface And pressing；Temperature in the vacuum drying chamber 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, step（2）Described in negative plate need to 40 DEG C -70 DEG C heating 8h-11h to remove solvent, then flatten For use.
Further, step（2）With（3）In operation completed in the vacuum glove box full of argon gas.
The lithium-sulfur cell negative material and lithium-sulfur cell that the present invention is prepared have the advantages that：
（1）The lithium-sulfur cell negative material that the present invention is prepared is made by stable state lithium powder and the carbon material of specific proportioning Cathode is compared with common lithium foil electrode, specific surface area bigger, and porosity higher is more complete with electrolyte contacts, to effectively put Electric area bigger, impedance smaller, and can effectively inhibit the growth of Li dendrite can express out preferable cycle performance and forthright again Energy.
（2）Nano carbon balls material, Nano carbon balls is used to have only in the lithium-sulfur cell negative material that the present invention is prepared Special appearance structure, there is 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 fully 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 have good orientation, can be formed with collector it is good contact simultaneously shape 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, the remote conductive ability in pole piece can be increased and 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）The present invention has also especially been selected using the mixed system of polyvinylpyrrolidone and polyethyleneimine as bonding Agent, to the porous structure with strong holding sulphur anode in cyclic process.
（5）The present invention has selected the mixed system of three kinds of substances as solvent, and by experiment, which can preferably keep 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 implementation mode
Embodiment one：
A kind of lithium-sulfur cell and preparation method thereof is as follows：
1, the preparation of positive plate：It is positive active material, Nano carbon fibers peacekeeping expanded graphite according to mass ratio using sublimed sulfur It is 1:It according to volume ratio is 2 that 1 mixture being composed, which is conductive agent, polyvinylpyrrolidone and polyethyleneimine,:1 mixing and At mixed system be binder.
Sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite in the anode sizing agent of sulfur-bearing are 1 according to mass ratio:1 is composed 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）It is 3 according to volume ratio:2:Solution is made in 1 in the mixed solvent mixed, wherein according to quality It calculates, the ratio for being 30% according to solid content weighs solvent.Again by sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite according to quality Than being 1:1 conductive agent being composed in mass ratio after mixing, pours into the solvent for having dissolved binder, is fabricated to anode Slurry.
Then obtained slurry is uniformly coated on foamed nickel current collector.It is placed in drying in vacuum drying chamber again, removes molten Agent and moisture, the temperature in vacuum drying chamber is 50 DEG C, drying time 10h, is struck off the slurry of foam nickel surface with blade Totally, then with certain pressure positive plate is flattened.Then positive plate is placed in vacuum drying chamber and is dried again.The above operation is equal It is completed in vacuum glove box.
2, prepared by negative plate：Stable state lithium powder, carbon material and polyvinylpyrrolidone and polyethyleneimine according to volume ratio It is 2:The 1 mixed system binder mixed is weighed according to mass ratio, with propene carbonate（PC）, methyl ethyl carbonate（EMC） And polyether sulfone（PES）It is 3 according to volume ratio:2:1 mixture mixed is solvent, 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 obtain negative plate；Negative plate is placed on heating plate and is heated so that solvent volatilizees；And Negative plate is flattened afterwards for use；Wherein, the mass ratio of stable state lithium powder, carbon material and binder is 10: 7:1；It is heated on heating plate Temperature be 70 DEG C, heating time 8h.The above operation is completed in vacuum glove box.
3, battery assembles：It is assembled into battery using above-mentioned positive plate and above-mentioned negative plate.
Battery assembles and test：Button battery assembles in the glove box full of argon gas.Using above-mentioned negative plate as cathode, Using Celgard2400 diaphragms and 2025 type button batteries.Electrolyte is 1M LiClO4、0.15M LiNO3It is dissolved in DOL：DME （Volume ratio 1：1）.Battery is placed in blue electrical measurement test system（CT2001A）Carry out constant current test.Charging/discharging voltage ranging from 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 plate preparation process Mass ratio be 7：4：1, the temperature heated on heating plate 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 plate preparation process Mass ratio be 5：5：1, the temperature heated on heating plate 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, The lithium-sulfur cell of the present invention can express out better first charge-discharge specific capacity, while capacity retention ratio exists after 100 cycles 95.2% or more.
The button cell of each embodiment is AC impedance contrast experiment 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, complete with electrolyte contacts of stable state lithium powder, can express out faster electronics biography It passs and shifts.
Meanwhile Nano carbon balls material is used in the lithium-sulfur cell negative material that is prepared of the present invention, Nano carbon balls have Unique appearance structure, there is unique advantage in electrochemical performance：（a）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 sides of the Li+ from ball To embedded 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）The shape of spherical particle is more convenient for the processing of electrode.
In turn, the present invention fully 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.
As the progress charge and discharge contrast experiment under different multiplying using the electrode of each embodiment and common lithium foil electrode.It is real It tests the results show that when electrode using the present invention, lithium-sulfur cell can express out higher specific capacity under different multiplying.Especially Under high current density, the common lithium foil electrode battery of lithium-sulfur cell ratio prepared using stable state lithium powder and mixing carbon material is shown 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 can increase the remote conductive ability in pole piece and 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, also may be used 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 final The product being prepared has better stability and higher quality.
The basic principles and main features and advantages of the present invention of the present invention have been shown and described in above example.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 (1)

1. a kind of lithium-sulfur cell, it is characterised in that：Its making includes the following steps：
The preparation of step 1, positive plate：It is positive active material, Nano carbon fibers peacekeeping expanded graphite according to mass ratio using sublimed sulfur It is 1:It according to volume ratio is 2 that 1 mixture that is composed, which is conductive agent, polyvinylpyrrolidone and polyethyleneimine,:1 mixing 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 1:The mass ratio of 1 conductive agent being composed and the binder is 9:7:1；Mixture binder is dissolved in carbonic acid Acrylic ester（PC）, methyl ethyl carbonate（EMC）And polyether sulfone（PES）It is 3 according to volume ratio:2:1 in the mixed solvent mixed Solution is made；Wherein, calculated by mass, the ratio for being 30% according to solid content weighs solvent, and solid is sublimed sulfur, nano-sized carbon Fiber and expanded graphite；It is again 1 according to mass ratio by sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite:1 conduction being composed 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 again in vacuum drying chamber it is dry, remove solvent and Moisture, the temperature in vacuum drying chamber 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 vacuum drying chamber and is dried again；With blade by foam described in step 1 The slurry scraped clean of nickel surface is completed the operation that positive plate flattens in vacuum glove box；
It is prepared by step 2, negative plate：Stable state lithium powder, carbon material and polyvinylpyrrolidone and polyethyleneimine according to volume ratio It is 2:The 1 mixed system binder mixed is weighed according to mass ratio, with propene carbonate（PC）, methyl ethyl carbonate（EMC） And polyether sulfone（PES）It is 3 according to volume ratio:2:1 mixture mixed is solvent；Wherein, calculated by mass, according to solid The ratio that body content is 30% weighs solvent, and solid is stable state lithium powder and carbon material；First binder is dissolved in solvent, then Stable state lithium powder and carbon material are poured into above-mentioned solution, are applied in foamed nickel current collector to obtain cathode after mixing Piece；Negative plate is placed on heating plate and is heated so that solvent volatilization, then flattens negative plate；Wherein, stable state lithium powder, carbon material Mass ratio with binder is 5-10：3-7：1；The temperature heated on heating plate is 70 DEG C, heating time 8-15h；Described It according to mass ratio is 5 that carbon material, which is carbon nanospheres, carbon nanotube and mesoporous carbon,：2：1 mixture mixed；Handle in step 2 Negative plate negative plate, which is placed on heating plate, to be heated so that solvent volatilizees, and it is vacuum glove that negative plate, which is then flattened for use operation, It is completed in case；Stable state lithium powder described in step 2 is by dropping liquid emulsifying technology（DET）It is made, a diameter of 60 μm -90 μm of lithium powder；
Step 3, battery assembling：It is assembled into lithium-sulfur cell using negative plate made from positive plate made from step 1 and step 2.
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