CN105552448B - A kind of preparation method of lithium-sulfur cell - Google Patents

A kind of preparation method of lithium-sulfur cell Download PDF

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CN105552448B
CN105552448B CN201610075890.1A CN201610075890A CN105552448B CN 105552448 B CN105552448 B CN 105552448B CN 201610075890 A CN201610075890 A CN 201610075890A CN 105552448 B CN105552448 B CN 105552448B
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lithium
solvent
binding agent
mass ratio
carbon
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CN105552448A (en
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宗铭
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Zhong Neng Guo Sheng Battery Technology Beijing Co ltd
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Ningbo Liangneng New Material Co Ltd
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Priority to CN201610953313.8A priority patent/CN106410283B/en
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Abstract

The present invention relates to the preparation method of a kind of lithium-sulfur cell, wherein negative material is in terms of mass fraction, is made up of following feedstock composition: 5 10 parts of stable state lithium powder, 37 parts of material with carbon elements, 1 part of binding agent and solvent.The present invention has selected stable state lithium powder and carbon nanospheres, CNT and mesoporous carbon to be that the mixture that 5:2:1 mixes prepares negative pole mixed slurry as the material with carbon element in negative pole according to mass ratio especially, this lithium-sulfur cell negative material is made to have more excellent performance, the battery table that the preparation method of the present invention prepares reveals less impedance, shuttle back and forth effect and the dendritic growth in continuous charge and discharge process be can effectively weaken, more preferable cycle performance and high rate performance shown than common metal lithium paper tinsel.

Description

A kind of preparation method of lithium-sulfur cell
Technical field
The invention belongs to electrode material preparation field, particularly relate to a kind of lithium sulphur battery electrode material and utilize this kind of electrode The method of lithium-sulfur cell prepared by material.
Background technology
Lithium ion battery (Lithium-ion battery, LIB), is also called lithium secondary battery, and being that one is capable of circulation fills The portable power source equipment of electricity.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, Sony was by LIB commercialization, LIB has obtained developing rapidly and widely. LIB is own through becoming the power supply of most of mobile electronic device at present.In recent years, LIB had been carried out deeply and had ground widely by people Study carefully.In LIB, the performance of battery is had the biggest impact, the negative material of development excellence to be also to improve LIB by negative material One of key factor of energy.Material with carbon element is topmost a kind of LIB negative material, and oneself is through there being hundreds of to have different structure at present Material with carbon element be used as lithium ion battery negative, these materials include native graphite, electrographite, coke, carbon fiber, mesophase Carbosphere, carbon black etc..
Elemental sulfur rich reserves nontoxic, global, and have higher theoretical specific capacity (1675mAh/g).Lithium metal has Low-density (0.534g/cm), low potential (-3.045v) and height ratio capacity (3861mAh/g), therefore lithium-sulfur cell can reach To higher energy density, thus can store at energy, the aspect such as utilization of regenerative energy plays a significant role.But, lithium sulfur electricity There are problems in pond commercialization process, such as lithium metal unstable chemcial property, during use, there is potential danger；Work as negative pole When using metallic lithium foil, battery is after repeatedly discharge and recharge, and metallic lithium foil surface is easily formed dendrite.The constantly growth of dendrite causes Battery capacity declines, and dendritic growth may pierce through barrier film, causes battery short circuit, causes safety problem.
Hard carbon is the pyrolytic carbon of high molecular polymer, even if being the most also difficult to graphitization.The reversible capacity energy of hard carbon Higher, cycle performance is the most fine.But hard carbon there is also, and electrode potential is too high, current potential is delayed, and (i.e. intercalation potential is less than de-lithium electricity Position) and circulate the shortcomings such as irreversible capacity is big first.
At present, major part lithium-sulfur cell all uses lithium metal as negative pole.Lithium as negative pole in repeatedly charge and discharge process Being formed of a product can be caused by ten electric current density inequalities.Branch product can cause barrier film to penetrate, and then makes battery be short-circuited, and is main Potential safety hazard source.If adding Graphene in negative pole, the specific surface area of negative pole becomes big, and surface current density reduces, meanwhile, Loose Graphene provides the space of lithium deposition, so that the growth of lithium branch product is more and more difficult.Exist for cathode of lithium Problem, improvement that researcher is carried out and study less.Sum up to get up mainly to include two aspects: one is to add from electrolyte Agent is modified, by adding different additives, such as LiNO3With PEO etc., promote cathode of lithium surface fast in charge and discharge process Speed forms more stable SEI film, it would be desirable to suppression Li dendrite and raising cycle performance.But additive is in charge and discharge process Gradually it is consumed, affects stability and the seriality of battery.Two is that the preparation technology from lithium electrode starts with, by using lithiumation to close Thing cladding lithium powder or electrodeposit metals lithium, lithium paper tinsel surface increases the methods such as protective layer, improves cycle efficieny and cycle life, But operating process is the most complex.
Summary of the invention
In order to solve problems of the prior art, it is an object of the invention to provide a kind of by stable state lithium powder with special join The cathode size being prepared from than material with carbon element, and the lithium-sulfur cell being prepared from by this slurry, which solve in prior art Use technological deficiency that the material such as hard carbon brings and solve cathode of lithium battery improve present in stability and seriality The technical problems such as difference and operation complexity.
The preparation method of a kind of lithium-sulfur cell, comprises the following steps:
Step 1, the preparation of positive plate: with Sublimed Sulfur as positive active material, Nano carbon fibers peacekeeping expanded graphite is according to matter Amount than the mixture combined for 1:1 be conductive agent, polyvinylpyrrolidone and polymine be that 2:1 mixes according to volume ratio The mixed system closed is mixture binding agent；Sublimed Sulfur in the anode sizing agent of sulfur-bearing, Nano carbon fibers peacekeeping expanded graphite According to mass ratio be the conductive agent that combines of 1:1 and the mass ratio of described binding agent is 9:7:1；Mixture binding agent is dissolved in Allyl carbonate (PC), Ethyl methyl carbonate (EMC) and polyether sulfone (PES) are that the mixing that 3:2:1 mixes is molten according to volume ratio Agent is made solution, wherein, according to Mass Calculation, weighs solvent according to the ratio that solids content is 30%, solid be Sublimed Sulfur, Nano carbon fibers peacekeeping expanded graphite；It is that 1:1 combine with Nano carbon fibers peacekeeping expanded graphite according to mass ratio by Sublimed Sulfur again Conductive agent mix homogeneously in mass ratio after, pour in the solvent of solubilized solution binding agent, be fabricated to anode sizing agent；
Then the slurry obtained is uniformly coated on nickel foam collector；It is placed in again in vacuum drying oven and is dried, remove molten Agent and moisture, the temperature in vacuum drying oven is 50 DEG C, and drying time is 10-15h；With blade, the slurry on nickel foam surface is scraped Except clean, positive plate flattened, then positive plate is placed in after drying in vacuum drying oven；
Prepared by step 2, negative plate: stable state lithium powder, material with carbon element and polyvinylpyrrolidone and polymine according to body The mixed system binding agent that long-pending ratio mixes for 2:1 weighs according to mass ratio, with Allyl carbonate (PC), Ethyl methyl carbonate And polyether sulfone (PES) is solvent according to the mixture mixed that volume ratio is 3:2:1, wherein, according to quality meter (EMC) Calculating, weigh solvent according to the ratio that solids content is 30%, solid is stable state lithium powder and material with carbon element；First binding agent is dissolved in molten In agent, then stable state lithium powder and material with carbon element are poured in above-mentioned solution, be applied in after mix homogeneously in nickel foam collector thus Obtain negative plate；Negative plate is placed on heating plate heating so that solvent volatilization, then negative plate is flattened；Wherein, stable state lithium The mass ratio of powder, material with carbon element and binding agent is 5-10:3-7:1；On heating plate, the temperature of heating is 70 DEG C, and heat time heating time is 8- 15h；
Step 3, battery assemble: use step 1 prepare positive plate and step 2 prepare negative plate be assembled into lithium sulfur electricity 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 Become: 5-10 part stable state lithium powder, 3-7 part material with carbon element, 1 part of binding agent and solvent.
Further, described stable state lithium powder is made up of dropping liquid emulsifying technology (DET), a diameter of 60 μm-90 μm of lithium powder.
Further, described material with carbon element is carbon nanospheres, CNT and mesoporous carbon according to mass ratio be 5:2:1 mixing and The mixture become.
Further, described binding agent is polyvinylpyrrolidone and polymine is that 2:1 mixes according to volume ratio Binding agent；Described solvent be Allyl carbonate (PC), Ethyl methyl carbonate (EMC) and polyether sulfone (PES) be 3 according to volume ratio: The mixed solvent that 2:1 mixes.
The preparation method of a kind of lithium-sulfur cell, uses above-mentioned negative material as negative pole, it is characterised in that include walking as follows Rapid:
(1) anode sizing agent of sulfur-bearing is coated in collector and makes positive plate；
(2) stable state lithium powder, material with carbon element and binding agent are weighed according to mass ratio, with Allyl 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 described binding agent It is dissolved in described solvent, then stable state lithium powder and material with carbon element is poured in above-mentioned solution, after mix homogeneously, be applied in nickel foam In thus obtain negative plate；Negative plate is placed on heating plate heating so that solvent volatilizees；Then negative plate is flattened stand-by；
(3) positive pole, negative pole, barrier film are assembled into button cell.
Further, the anode sizing agent of the sulfur-bearing described in step (1) comprises: Sublimed Sulfur, conductive agent, binding agent and solvent； Described conductive agent is that 1:1 combines by Nano carbon fibers peacekeeping expanded graphite according to mass ratio, the poly-second in described binding agent Alkene pyrrolidone and polymine are that 2:1 mixes according to volume ratio；Described solvent is by Allyl carbonate (PC), carbonic acid first Ethyl ester (EMC) and polyether sulfone (PES) are that 3:2:1 mixes according to volume ratio；In the mixed solvent first binding agent being dissolved in, After again Sublimed Sulfur being mixed homogeneously in mass ratio with conductive agent, pour in the solvent of solubilized solution binding agent, be fabricated to anode sizing agent, Then by anode sizing agent uniform application at collector, positive plate is made.
Further, described positive plate need to add heat abstraction moisture and solvent in vacuum drying oven, is then struck off on its surface And pressing；The described temperature in vacuum drying oven is 50 DEG C, and drying time is 10h.
Further, Sublimed Sulfur, conductive agent in the anode sizing agent of described sulfur-bearing are 9:7:1 with the mass ratio of binding agent.
Further, negative plate described in step (2) then need to flatten at 40 DEG C-70 DEG C heating 8h-11h to remove solvent Stand-by.
Further, the operation in step (2) and (3) all completes in the vacuum glove box of full argon.
Lithium-sulfur cell negative material and lithium-sulfur cell that the present invention prepares have the advantages that
(1) the lithium-sulfur cell negative material that the present invention prepares is made by the material with carbon element of stable state lithium powder and specific proportioning Negative pole is compared with common lithium foil electrode, and specific surface area is bigger, and porosity is higher, more complete with electrolyte contacts, thus effectively puts Electricity area is bigger, and impedance is less, and can effectively suppress the growth of Li dendrite, can show preferable cycle performance and the most forthright Energy.
(2) using Nano carbon balls material in the lithium-sulfur cell negative material that the present invention prepares, Nano carbon balls has solely Special appearance structure, has the advantage of uniqueness: a, spherical profile can realize piling up the most closely, make lithium in electrochemistry performance Ion battery has higher volume energy density；B, spherical graphite platelet structure make Li+Can enter from all directions of ball Row embed and deintercalation, overcome graphite too high due to anisotropy and cause graphite flake layer swelling, subside and can not quickly fill The problem of electric discharge；C, the profile of spherical particle are more convenient for the processing of electrode.It the most fully combines CNT and mesoporous carbon Structural advantage, highly ordered mesosize pores carbon has that specific surface area is big, uniform pore diameter, pore volume are the highest, be mutually related porous The feature such as structure and high conductivity；And CNT has good orientation, good contacting and shape can be formed with collector Become efficiently and directionally conducting matrix grain, be effectively improved skeleton electric conductivity in lithium sulphur battery electrode material, and its internal regular pore canal is also The storage of favourable ten polysulfides.The present invention makes full use of the advantage of this three's structure, can effectively weaken continuous charge and discharge process In shuttle back and forth effect and dendritic growth, show more preferable cycle performance and high rate performance than conventional electrodes.
(3) in terms of the conductive additive of positive pole, the present invention adds Nano carbon fibers peacekeeping expanded graphite, and the former can form three Dimension conductive network, can increase the remote conductive ability in pole piece, is difficult to again be permitted the product formed in discharge process to cover completely Lid, thus improve the surface texture of pole piece;The latter utilizes abundant network gap structure and the good adsorption properties of expanded graphite, Also utilization rate and the cycle performance of elemental sulfur can be improved.
(4) present invention has selected the mixed system using polyvinylpyrrolidone and polymine as bonding the most especially Agent, thus it is followed by the holding sulfur positive pole loose structure in cyclic process of power.
(5) present invention has selected the mixed system of three kinds of materials as solvent, and through experiment, this solvent can preferably keep The raw-material architectural feature of various pole pieces and advantage so that the product finally prepared has more preferable stability and more High quality.
Detailed description of the invention
Embodiment one:
A kind of lithium-sulfur cell and preparation method thereof is as follows:
1, the preparation of positive plate: with Sublimed Sulfur as positive active material, Nano carbon fibers peacekeeping expanded graphite is according to mass ratio The mixture combined for 1:1 is conductive agent, polyvinylpyrrolidone and polymine according to volume ratio be 2:1 mixing and The mixed system become is binding agent.
Sublimed Sulfur, Nano carbon fibers peacekeeping expanded graphite in the anode sizing agent of sulfur-bearing are that 1:1 combines according to mass ratio The mass ratio of conductive agent and binding agent be 9:7:1.Mixture binding agent is dissolved in Allyl carbonate (PC), Ethyl methyl carbonate And polyether sulfone (PES) is to make solution, wherein, according to quality in the mixed solvent that mixes of 3:2:1 according to volume ratio (EMC) Calculate, weigh solvent according to the ratio that solids content is 30%.Again by Sublimed Sulfur and Nano carbon fibers peacekeeping expanded graphite according to quality After the conductive agent mix homogeneously in mass ratio combined for 1:1, pour in the solvent of solubilized solution binding agent, be fabricated to positive pole Slurry.
Then the slurry obtained is uniformly coated on nickel foam collector.It is placed in again in vacuum drying oven and is dried, remove molten Agent and moisture, the temperature in vacuum drying oven is 50 DEG C, and drying time is 10h, is struck off by the slurry on nickel foam surface with blade Totally, then with certain pressure positive plate is flattened.Then positive plate is placed in after drying in vacuum drying oven.More than operation is all Vacuum glove box completes.
2, prepared by negative plate: stable state lithium powder, material with carbon element and polyvinylpyrrolidone and polymine according to volume ratio The mixed system binding agent mixed for 2:1 weighs according to mass ratio, with Allyl carbonate (PC), Ethyl methyl carbonate (EMC) It is solvent with polyether sulfone (PES) according to the mixture mixed that volume ratio is 3:2:1, wherein, according to Mass Calculation, according to Solids content be 30% ratio weigh solvent.
First binding agent is dissolved in solvent, then stable state lithium powder and material with carbon element is poured in above-mentioned solution, mix homogeneously After be applied in nickel foam collector thus obtain negative plate；Negative plate is placed on heating plate heating so that solvent volatilizees；And Afterwards negative plate is flattened stand-by；Wherein, the mass ratio of stable state lithium powder, material with carbon element and binding agent is 10:7:1；Heat on heating plate Temperature be 70 DEG C, heat time heating time is 8h.More than operation all completes in vacuum glove box.
3, battery assembles: use above-mentioned positive plate and above-mentioned negative plate is assembled into battery.
Battery assembles with test: button battery assembles in the glove box of full argon.With above-mentioned negative plate as negative pole, Use Celgard2400 barrier film 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 testing system (CT2001A) and carries out constant current test.Charging/discharging voltage scope is 1.5- 3.0V, test temperature is room temperature.
Embodiment two:
Compared with embodiment one, embodiment two, in negative plate preparation process, changes stable state lithium powder, material with carbon element and binding agent Mass ratio be 7:4:1, on heating plate heating temperature be 40 DEG C, heat time heating time is 11h.Remaining operates and same embodiment is described One.
Embodiment three:
Compared with embodiment one, embodiment two, in negative plate preparation process, changes stable state lithium powder, material with carbon element and binding agent Mass ratio be 5:5:1, on heating plate heating temperature be 60 DEG C, heat time heating time is 9h.Remaining operates and same embodiment is described One.
Phase comparison common lithium foil electrode, when the negative pole of embodiment one, two and three uses stable state lithium powder and mixing material with carbon element, The lithium-sulfur cell of the present invention can show more preferable first charge-discharge specific capacity, and after 100 circulations, capability retention all exists simultaneously More than 95.2%.
The button cell of each embodiment is AC impedance contrast experiment after standing 24 hours.Experimental result shows, works as enforcement After example one, two and three uses stable state lithium powder and mixing material with carbon element, phase comparison common lithium foil electrode, the resistance of the lithium-sulfur cell of the present invention Resisting and be greatly reduced, reason is that the specific surface area of stable state lithium powder is big and electrolyte contacts is complete, can show faster electronics and pass Pass and shift.
Meanwhile, using Nano carbon balls material in the lithium-sulfur cell negative material that the present invention prepares, Nano carbon balls has Unique appearance structure, has the advantage of uniqueness in electrochemistry performance: (a) spherical profile can realize piling up the most closely, Lithium ion battery is made to have higher volume energy density；B graphite platelet structure that () is spherical makes the Li+ can be from each side of ball Embed and deintercalation to carrying out, overcome graphite too high due to anisotropy and cause graphite flake layer swelling, subside and can not be fast The problem of speed discharge and recharge；C the profile of () spherical particle is more convenient for the processing of electrode.
And then, the present invention the most fully combines the structural advantage of CNT and mesoporous carbon, and highly ordered mesosize pores carbon has Specific surface is big, uniform pore diameter, pore volume are the highest, loose structure and the high conductivity etc. of being mutually related feature；And carbon nanometer Pipe has again good orientation, can be formed with collector and good contact and formed efficiently and directionally conducting matrix grain, be effectively improved lithium Skeleton electric conductivity in sulfur battery electrode material, and the storage of its internal the most favourable ten polysulfides of regular pore canal.The present invention fills Divide the advantage utilizing this three's structure, can effectively weaken shuttle back and forth effect and the dendritic growth in continuous charge and discharge process, than routine Electrode shows more preferable cycle performance and high rate performance.
When utilize the electrode of each embodiment and common lithium foil electrode in different multiplying under carry out discharge and recharge contrast experiment.Real Testing result to show, when using the electrode of the present invention, lithium-sulfur cell can show higher specific capacity under different multiplying.Especially Under high current density, the lithium-sulfur cell using stable state lithium powder and mixing material with carbon element to prepare reveals than common lithium foil electrode battery table Significantly specific capacity promotes.
In terms of the conductive additive of positive pole, we add Nano carbon fibers peacekeeping expanded graphite, and the former can form three-dimensional and lead Electric network, can increase the remote conductive ability in pole piece, is difficult to again be permitted the product formed in discharge process to be completely covered, from And improve the surface texture of pole piece;The latter utilizes abundant network gap structure and the good adsorption properties of expanded graphite, it is possible to Improve utilization rate and the cycle performance of elemental sulfur.
The present invention selected the most especially the mixed system using polyvinylpyrrolidone and polymine as binding agent, Thus it is followed by the holding sulfur positive pole loose structure in cyclic process of power.The present invention has selected the mixed system of three kinds of materials For solvent, through experiment, this solvent can preferably keep raw-material architectural feature and the advantage of various pole piece so that final The product prepared has more preferable stability and higher quality.
Above example has been shown and described the ultimate principle of the present invention, principal character and advantages of the present invention.The industry Skilled person will appreciate that, the present invention is not restricted to the described embodiments, described in above-described embodiment and description simply The principle of the present invention is described rather than limits the scope of the present invention by any way, without departing from the scope of the invention, The present invention also has various changes and modifications, and these changes and improvements both fall within claimed scope.

Claims (4)

1. a preparation method for lithium-sulfur cell, comprises the following steps:
Step 1, the preparation of positive plate: with Sublimed Sulfur as positive active material, Nano carbon fibers peacekeeping expanded graphite is according to mass ratio The mixture combined for 1:1 is conductive agent, polyvinylpyrrolidone and polymine according to volume ratio be 2:1 mixing and The mixed system become is mixture binding agent；Sublimed Sulfur in the anode sizing agent of sulfur-bearing, Nano carbon fibers peacekeeping expanded graphite according to Mass ratio is the conductive agent that combines of 1:1 and the mass ratio of described binding agent is 9:7:1；Mixture binding agent is dissolved in carbonic acid Propylene (PC), Ethyl methyl carbonate (EMC) and polyether sulfone (PES) are in the mixed solvent that 3:2:1 mixes according to volume ratio Make solution；Wherein, calculated by mass, weigh solvent according to the ratio that solids content is 30%, solid is Sublimed Sulfur, nano-sized carbon Fiber and expanded graphite；It is conduction that 1:1 combine with Nano carbon fibers peacekeeping expanded graphite according to mass ratio by Sublimed Sulfur again After agent mix homogeneously in mass ratio, pour in the solvent of solubilized solution binding agent, be fabricated to anode sizing agent；
Then the slurry obtained is uniformly coated on nickel foam collector；Be placed in again in vacuum drying oven be dried, remove solvent and Moisture, the temperature in vacuum drying oven is 50 DEG C, and drying time is 10-15h；With blade, the slurry on nickel foam surface is struck off dry Only, positive plate is flattened, then positive plate is placed in after drying in vacuum drying oven；
Prepared by step 2, negative plate: stable state lithium powder, material with carbon element and polyvinylpyrrolidone and polymine according to volume ratio The mixed system binding agent mixed for 2:1 weighs according to mass ratio, with Allyl carbonate (PC), Ethyl methyl carbonate (EMC) It is solvent with polyether sulfone (PES) according to the mixture mixed that volume ratio is 3:2:1；Wherein, calculated by mass, according to solid Body burden be 30% ratio weigh solvent, solid is stable state lithium powder and material with carbon element；First binding agent is dissolved in solvent, then Stable state lithium powder and material with carbon element are poured in above-mentioned solution, is applied in after mix homogeneously in nickel foam collector thus obtains negative pole Sheet；Negative plate is placed on heating plate heating so that solvent volatilization, then negative plate is flattened；Wherein, stable state lithium powder, material with carbon element It is 5-10:3-7:1 with the mass ratio of binding agent；On heating plate, the temperature of heating is 70 DEG C, and heat time heating time is 8-15h；Described Material with carbon element is that carbon nanospheres, CNT and mesoporous carbon are according to the mixture that mass ratio is that 5:2:1 mixes；
Step 3, battery assemble: use step 1 prepare positive plate and step 2 prepare negative plate be assembled into lithium-sulfur cell.
The preparation method of lithium-sulfur cell the most according to claim 1, it is characterised in that: with blade by foam described in step 1 The slurry scraped clean of nickel surface, the operation that positive plate is flattened completes in vacuum glove box.
The preparation method of lithium-sulfur cell the most according to claim 1, it is characterised in that: step 2 is placed in heating negative plate Heating on sheet is so that solvent volatilization, and then negative plate being flattened stand-by operation is to complete in vacuum glove box.
The preparation method of lithium-sulfur cell the most according to claim 1, it is characterised in that: the stable state lithium powder described in step 2 by Dropping liquid emulsifying technology (DET) is made, a diameter of 60 μm-90 μm of lithium powder.
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