CN105552448A - Preparation method for lithium-sulfur battery - Google Patents

Preparation method for lithium-sulfur battery Download PDF

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Publication number
CN105552448A
CN105552448A CN201610075890.1A CN201610075890A CN105552448A CN 105552448 A CN105552448 A CN 105552448A CN 201610075890 A CN201610075890 A CN 201610075890A CN 105552448 A CN105552448 A CN 105552448A
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lithium
solvent
binding agent
sulfur
preparation
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CN105552448B (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
Priority to CN201610961096.7A priority patent/CN106356567B/en
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Abstract

The invention relates to a preparation method for a lithium-sulfur battery. A negative electrode material comprises the following compositions based on mass: 5-10 parts of steady-state lithium powder, 3-7 parts of carbon material, 1 part of binding agent and a solvent. According to the preparation method, a mixture mixed by the steady-state lithium powder, carbon nanosphere/carbon nanotube and mesoporous carbon according to mass ratios of 5:2:1 is particularly selected as the carbon material in a negative electrode to prepare a negative electrode mixed paste, so that the negative electrode material of the lithium-sulfur battery has more excellent performance; the prepared battery according to the method is endowed with relatively small impedance, a shuttle effect and dendrite growth during the continuous charging/discharging process can be effectively reduced, and the battery shows batter cycle performance and rate performance than those of a conventional metal lithium foil.

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 material to prepare the method for lithium-sulfur cell.
Background technology
Lithium ion battery (Lithium-ionbattery, LIB), is also called lithium secondary battery, is a kind of portable power source equipment of charging capable of circulation.LIB has high-energy-density, high power density, has extended cycle life, cleans the plurality of advantages such as nontoxic and memory-less effect, and since the nineties in last century, Sony was by LIB commercialization, LIB obtains and develops rapidly and widely.Current LIB is own through becoming the power supply of most of mobile electronic device.In recent years, people had carried out going deep into and studying widely to LIB.In LIB, the performance of negative material on battery has very large impact, and the negative material of development excellence is also one of key factor improving LIB performance.Material with carbon element is topmost a kind of LIB negative material, and oneself is through there being hundreds of material with carbon element having different structure to be used as lithium ion battery negative at present, and these materials comprise native graphite, electrographite, coke, carbon fiber, carbonaceous mesophase spherules, carbon black etc.
Nontoxic, the global rich reserves of elemental sulfur, and have higher theoretical specific capacity (1675mAh/g).Lithium metal has low-density (0.534g/cm3), low potential (-3.045v) and height ratio capacity (3861mAh/g), and therefore lithium-sulfur cell can reach higher energy density, thus can play a significant role in stored energy, utilization of regenerative energy etc.But, there are problems in lithium-sulfur cell commercialization process, as lithium metal unstable chemcial property, during use, there is potential danger; When negative pole adopts metallic lithium foil, battery is after repeatedly discharge and recharge, and metallic lithium foil surface easily forms dendrite.The continuous growth of dendrite causes battery capacity to decline, and dendritic growth may pierce through barrier film, causes battery short circuit, causes safety problem.
Hard carbon is the RESEARCH OF PYROCARBON of high molecular polymer, even if be at high temperature also difficult to graphitization.The reversible capacity of hard carbon can be higher, and cycle performance is also fine.The shortcoming such as but hard carbon also exists, and electrode potential is too high, current potential is delayed (namely intercalation potential is less than de-lithium current potential) and circulation irreversible capacity is large first.
At present, most of lithium-sulfur cell all adopts lithium metal as negative pole.Lithium can cause being formed of a product by ten current densities inequalities as negative pole in repeatedly charge and discharge process.Branch product can cause barrier film to penetrate, and then battery is short-circuited, and are main potential safety hazard sources.If add Graphene in negative pole, the specific area of negative pole becomes large, and surface current density reduces, and meanwhile, loose Graphene provides the space of lithium deposition, thus makes the growth of lithium branch product more and more difficult.For cathode of lithium Problems existing, the improvement that researcher carries out and study less.Sum up and get up mainly to comprise two aspects: one is carry out modification from electrolysis additive, by adding different additives, as LiNO 3with PEO etc., impel cathode of lithium surface to form more stable SEI film fast in charge and discharge process, it is desirable to suppress Li dendrite and improve cycle performance.But additive is consumed gradually in charge and discharge process, affect stability and the continuity of battery.Two is start with from the preparation technology of lithium electrode, and by using the coated lithium powder of lithium compound 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 also comparatively complicated.
Summary of the invention
In order to solve problems of the prior art, the object of this invention is to provide a kind of cathode size be prepared from by stable state lithium powder and special proportioning material with carbon element, and the lithium-sulfur cell to be prepared from by this slurry, which solve in prior art the technological deficiency that adopts the materials such as hard carbon to bring and solve stability and the technical problem such as poor continuity and complicated operation of the middle existence that cathode of lithium battery improves.
A preparation method for lithium-sulfur cell, comprises the following steps:
The preparation of step 1, positive plate: take sublimed sulfur as positive active material, the mixture that combines for 1:1 according to mass ratio of Nano carbon fibers peacekeeping expanded graphite be conductive agent, polyvinylpyrrolidone and polymine according to volume ratio for the mixed system that 2:1 mixes is mixture binding agent; The mass ratio that sublimed sulfur in the anode sizing agent of sulfur-bearing, Nano carbon fibers peacekeeping expanded graphite are the conductive agent that combines of 1:1 and described binding agent according to mass ratio is 9:7:1; It is make solution in the mixed solvent that mixes of 3:2:1 that mixture binding agent is dissolved in propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio, wherein, according to Mass Calculation, the ratio being 30% according to solids content takes solvent, and solid is sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite; Be, after conductive agent that 1:1 combines mixes in mass ratio, pour into sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite and dissolve in the solvent of binding agent, be made into anode sizing agent according to mass ratio again;
Then the slurry obtained is uniformly coated on nickel foam collector; Be placed in vacuum drying chamber drier, except desolventizing and moisture, the temperature in vacuum drying chamber is 50 DEG C, and drying time is 10-15h; By the slurry scraped clean of blade by nickel foam surface, positive plate is flattened, then positive plate is placed in vacuum drying chamber again dry;
Prepared by step 2, negative plate: be that the mixed system binding agent that 2:1 mixes weighs according to mass ratio, is that the mixture mixed of 3:2:1 is for solvent with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio stable state lithium powder, material with carbon element and polyvinylpyrrolidone and polymine according to volume ratio, wherein, according to Mass Calculation, the ratio being 30% according to solids content takes solvent, and 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 is poured in above-mentioned solution, to be applied in after mixing in nickel foam collector thus to obtain negative plate; Negative plate is placed on heating plate and heats to make solvent evaporates, then negative plate is flattened; Wherein, the mass ratio of stable state lithium powder, material with carbon element and binding agent is 5-10:3-7:1; The temperature that heating plate heats is 70 DEG C, and heating time is 8-15h;
Step 3, battery are assembled: what use the obtained positive plate of step 1 and the obtained negative plate of step 2 is assembled into lithium-sulfur cell.
A kind of lithium-sulfur cell negative material, is characterized in that comprising: in mass fraction, is made up of following feedstock composition: 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), and lithium powder diameter is 60 μm-90 μm.
Further, described material with carbon element is carbon nanospheres, carbon nano-tube and mesoporous carbon is the mixture that 5:2:1 mixes according to mass ratio.
Further, described binding agent is polyvinylpyrrolidone and polymine is the binding agent that 2:1 mixes according to volume ratio; Described solvent is propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) are the mixed solvent that 3:2:1 mixes according to volume ratio.
A preparation method for lithium-sulfur cell, adopts above-mentioned negative material as negative pole, it is characterized in that comprising the steps:
(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 being weighed according to mass ratio, is that the mixture mixed of 3:2:1 is for solvent with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio; First described binding agent is dissolved in described solvent, then stable state lithium powder and material with carbon element is poured in above-mentioned solution, to be applied in after mixing in nickel foam thus to obtain negative plate; Negative plate is placed on heating plate and heats to make solvent evaporates; 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, and the polyvinylpyrrolidone in described binding agent and polymine are that 2:1 mixes according to volume ratio; Described solvent is that 3:2:1 mixes by propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio; In the mixed solvent first binding agent is dissolved in, then after sublimed sulfur is mixed in mass ratio with conductive agent, pour into and dissolve in the solvent of binding agent, be made into anode sizing agent, then by anode sizing agent uniform application at collector, make positive plate.
Further, described positive plate need add heat abstraction moisture and solvent in vacuum drying chamber, then its surface is struck off and is flattened; Temperature in described vacuum drying chamber is 50 DEG C, and drying time is 10h.
Further, the mass ratio of the sublimed sulfur in the anode sizing agent of described sulfur-bearing, conductive agent and binding agent is 9:7:1.
Further, negative plate described in step (2) need, at 40 DEG C-70 DEG C heating 8h-11h to remove solvent, then flatten stand-by.
Further, the operation in step (2) and (3) all completes in the vacuum glove box being full of argon gas.
The lithium-sulfur cell negative material that the present invention prepares and lithium-sulfur cell have following beneficial effect:
(1) negative pole that the lithium-sulfur cell negative material that the present invention prepares is made by stable state lithium powder and the material with carbon element of specific proportioning is compared with common lithium foil electrode, specific area is larger, porosity is higher, more complete with electrolyte contacts, thus effectively machining area is larger, impedance is less, and effectively can suppress the growth of Li dendrite, can show good cycle performance and high rate performance.
(2) Nano carbon balls material is adopted in the lithium-sulfur cell negative material that the present invention prepares, Nano carbon balls has unique appearance structure, electrochemistry performance there is unique advantage: a, spherical profile can realize piling up the most closely, make lithium ion battery have higher volume energy density; B, spherical graphite platelet structure make Li +can carry out embedding and deintercalation from all directions of ball, overcome graphite too high due to anisotropy and cause graphite flake layer swelling, to subside and can not the problem of fast charging and discharging; The profile of c, spherical particle is more convenient for the processing of electrode.It fully combines again the structural advantage of carbon nano-tube and mesoporous carbon, and highly ordered mesosize pores carbon has that specific area is large, uniform pore diameter, pore volume are very high, loose structure and the high conductivity etc. of being mutually related feature; And carbon nano-tube has good orientation, can good contact be formed with collector and form efficiently and directionally conducting matrix grain, effectively improve skeleton conductivity in lithium sulphur battery electrode material, and the storage of the regular pore canal of its inside also favourable ten polysulfides.The present invention makes full use of the advantage of this three's structure, effectively can weaken shuttle back and forth effect and dendritic growth in continuous charge and discharge process, show better cycle performance and high rate performance than conventional electrodes.
(3) in the conductive additive of positive pole; the present invention adds Nano carbon fibers peacekeeping expanded graphite, and the former can form three-dimensional conductive network, can increase the remote conductive ability in pole piece; not easily covered completely by the product formed in fair discharge process again, thus improve the surface texture of pole piece; What the latter utilized expanded graphite enriches network gap structure and good adsorption properties, also can improve utilance and the cycle performance of elemental sulfur.
(4) the present invention has also selected especially and has adopted the mixed system of polyvinylpyrrolidone and polymine as binding agent, thus with the strong loose structure of maintenance sulphur positive pole in cyclic process.
(5) the present invention has selected the mixed system of three kinds of materials as solvent, and through experiment, this solvent can better keep raw-material architectural feature and the advantage of various pole piece, makes the product finally prepared have the quality of better stability and Geng Gao.
Embodiment
Embodiment one:
A kind of lithium-sulfur cell and preparation method thereof is as follows:
1, the preparation of positive plate: take sublimed sulfur as positive active material, Nano carbon fibers peacekeeping expanded graphite according to mass ratio for the mixture that 1:1 combines is conductive agent, polyvinylpyrrolidone and polymine are the mixed system that 2:1 mixes according to volume ratio is binding agent.
The mass ratio that sublimed sulfur in the anode sizing agent of sulfur-bearing, Nano carbon fibers peacekeeping expanded graphite are the conductive agent that combines of 1:1 and binding agent according to mass ratio is 9:7:1.It is make solution in the mixed solvent that mixes of 3:2:1 that mixture binding agent is dissolved in propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio, wherein, according to Mass Calculation, the ratio being 30% according to solids content takes solvent.Be, after conductive agent that 1:1 combines mixes in mass ratio, pour into sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite and dissolve in the solvent of binding agent, be made into anode sizing agent according to mass ratio again.
Then the slurry obtained is uniformly coated on nickel foam collector.Be placed in vacuum drying chamber drier, except desolventizing and moisture, the temperature in vacuum drying chamber is 50 DEG C, and drying time is 10h, by the slurry scraped clean of blade by nickel foam surface, then with certain pressure, positive plate is flattened.Then positive plate is placed in vacuum drying chamber again dry.More than operation all completes in vacuum glove box.
2, negative plate preparation: be that the mixed system binding agent that 2:1 mixes weighs according to mass ratio according to volume ratio stable state lithium powder, material with carbon element and polyvinylpyrrolidone and polymine, be that the mixture mixed of 3:2:1 is for solvent with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio, wherein, according to Mass Calculation, the ratio being 30% according to solids content takes solvent.
First binding agent is dissolved in solvent, then stable state lithium powder and material with carbon element is poured in above-mentioned solution, to be applied in after mixing in nickel foam collector thus to obtain negative plate; Negative plate is placed on heating plate and heats to make solvent evaporates; Then 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; The temperature that heating plate heats is 70 DEG C, and heating time is 8h.More than operation all completes in vacuum glove box.
3, battery assembling: what use above-mentioned positive plate and above-mentioned negative plate is assembled into battery.
Battery assembling and test: button battery assembles in the glove box being full of argon gas.With above-mentioned negative plate for negative pole, adopt Celgard2400 barrier film and 2025 type button batteries.Electrolyte is 1MLiClO 4, 0.15MLiNO 3be 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, and probe temperature is room temperature.
Embodiment two:
Compared with embodiment one, embodiment two is in negative plate preparation process, and the mass ratio changing stable state lithium powder, material with carbon element and binding agent is 7:4:1, and the temperature that heating plate heats is 40 DEG C, and heating time is 11h.All the other operations and explanation are with embodiment one.
Embodiment three:
Compared with embodiment one, embodiment two is in negative plate preparation process, and the mass ratio changing stable state lithium powder, material with carbon element and binding agent is 5:5:1, and the temperature that heating plate heats is 60 DEG C, and heating time is 9h.All the other operations and explanation are with embodiment one.
Compare common lithium foil electrode, when the negative pole of embodiment one, two and three uses stable state lithium powder and mixes material with carbon element, lithium-sulfur cell of the present invention can show better first charge-discharge specific capacity, and the rear capability retention of 100 circulations is all more than 95.2% simultaneously.
The button cell of each embodiment leaves standstill and is AC impedance contrast experiment after 24 hours.Experimental result shows, after embodiment one, two and three uses stable state lithium powder and mixing material with carbon element, compare common lithium foil electrode, the impedance of lithium-sulfur cell of the present invention reduces greatly, reason is that the specific area of stable state lithium powder is large, complete with electrolyte contacts, can show electron transmission and transfer faster.
Simultaneously, Nano carbon balls material is adopted in the lithium-sulfur cell negative material that the present invention prepares, Nano carbon balls has unique appearance structure, electrochemistry performance there is unique advantage: (a) spherical profile can realize piling up the most closely, makes lithium ion battery have higher volume energy density; B graphite platelet structure that () is spherical makes Li+ can carry out embedding and deintercalation from all directions of ball, overcome graphite too high due to anisotropy and cause graphite flake layer swelling, to subside and can not the problem of fast charging and discharging; C the profile of () spherical particle is more convenient for the processing of electrode.
And then the present invention fully combines again the structural advantage of carbon nano-tube and mesoporous carbon, highly ordered mesosize pores carbon has that specific surface is large, uniform pore diameter, pore volume are very high, loose structure and the high conductivity etc. of being mutually related feature; And carbon nano-tube has good orientation, can good contact be formed with collector and form efficiently and directionally conducting matrix grain, effectively improve skeleton conductivity in lithium sulphur battery electrode material, and the storage of the regular pore canal of its inside also favourable ten polysulfides.The present invention makes full use of the advantage of this three's structure, effectively can weaken shuttle back and forth effect and dendritic growth in continuous charge and discharge process, show better cycle performance and high rate performance than conventional electrodes.
Under different multiplying, discharge and recharge contrast experiment is carried out when what utilize the electrode of each embodiment and common lithium foil electrode.Experimental result shows, and when adopting 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 adopting stable state lithium powder and mixing material with carbon element to prepare reveals obvious specific capacity than common lithium foil electrode battery table and promotes.
In the conductive additive of positive pole; we add Nano carbon fibers peacekeeping expanded graphite, and the former can form three-dimensional conductive network, can increase the remote conductive ability in pole piece; not easily covered completely by the product formed in fair discharge process again, thus improve the surface texture of pole piece; What the latter utilized expanded graphite enriches network gap structure and good adsorption properties, also can improve utilance and the cycle performance of elemental sulfur.
The present invention has also selected especially and has adopted the mixed system of polyvinylpyrrolidone and polymine as binding agent, thus with the strong loose structure of maintenance sulphur positive pole in cyclic process.The present invention has selected the mixed system solvent the most of three kinds of materials, and through experiment, this solvent can better keep raw-material architectural feature and the advantage of various pole piece, makes the product finally prepared have the quality of better stability and Geng Gao.
Above embodiment shows and describes general principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; instead of limit the scope of the 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 all fall in claimed scope.

Claims (4)

1. a preparation method for lithium-sulfur cell, comprises the following steps:
The preparation of step 1, positive plate: take sublimed sulfur as positive active material, the mixture that combines for 1:1 according to mass ratio of Nano carbon fibers peacekeeping expanded graphite be conductive agent, polyvinylpyrrolidone and polymine according to volume ratio for the mixed system that 2:1 mixes is mixture binding agent; The mass ratio that sublimed sulfur in the anode sizing agent of sulfur-bearing, Nano carbon fibers peacekeeping expanded graphite are the conductive agent that combines of 1:1 and described binding agent according to mass ratio is 9:7:1; It is make solution in the mixed solvent that mixes of 3:2:1 that mixture binding agent is dissolved in propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio, wherein, according to Mass Calculation, the ratio being 30% according to solids content takes solvent, and solid is sublimed sulfur, Nano carbon fibers peacekeeping expanded graphite; Be, after conductive agent that 1:1 combines mixes in mass ratio, pour into sublimed sulfur and Nano carbon fibers peacekeeping expanded graphite and dissolve in the solvent of binding agent, be made into anode sizing agent according to mass ratio again;
Then the slurry obtained is uniformly coated on nickel foam collector; Be placed in vacuum drying chamber drier, except desolventizing and moisture, the temperature in vacuum drying chamber is 50 DEG C, and drying time is 10-15h; By the slurry scraped clean of blade by nickel foam surface, positive plate is flattened, then positive plate is placed in vacuum drying chamber again dry;
Prepared by step 2, negative plate: be that the mixed system binding agent that 2:1 mixes weighs according to mass ratio, is that the mixture mixed of 3:2:1 is for solvent with propene carbonate (PC), methyl ethyl carbonate (EMC) and polyether sulfone (PES) according to volume ratio stable state lithium powder, material with carbon element and polyvinylpyrrolidone and polymine according to volume ratio, wherein, according to Mass Calculation, the ratio being 30% according to solids content takes solvent, and 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 is poured in above-mentioned solution, to be applied in after mixing in nickel foam collector thus to obtain negative plate; Negative plate is placed on heating plate and heats to make solvent evaporates, then negative plate is flattened; Wherein, the mass ratio of stable state lithium powder, material with carbon element and binding agent is 5-10:3-7:1; The temperature that heating plate heats is 70 DEG C, and heating time is 8-15h;
Step 3, battery are assembled: what use the obtained positive plate of step 1 and the obtained negative plate of step 2 is assembled into lithium-sulfur cell.
2. the preparation method of lithium-sulfur cell according to claim 1, is characterized in that: by the slurry scraped clean of blade by nickel foam surface described in step 1, and operating in vacuum glove box of flattening of positive plate is completed.
3. the preparation method of lithium-sulfur cell according to claim 1-2, is characterized in that: in step 2, negative plate is placed on heating plate and heats to make solvent evaporates, then negative plate being flattened stand-by operation is complete in vacuum glove box.
4. the preparation method of lithium-sulfur cell according to claim 1-3, is characterized in that: the stable state lithium powder described in step 2 is made up of dropping liquid emulsifying technology (DET), and lithium powder diameter is 60 μm-90 μm.
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