CN107895767A - A kind of lithium-sulfur cell high-performance composite diaphragm and preparation method thereof - Google Patents
A kind of lithium-sulfur cell high-performance composite diaphragm and preparation method thereof Download PDFInfo
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- CN107895767A CN107895767A CN201711102332.0A CN201711102332A CN107895767A CN 107895767 A CN107895767 A CN 107895767A CN 201711102332 A CN201711102332 A CN 201711102332A CN 107895767 A CN107895767 A CN 107895767A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
The invention discloses a kind of lithium-sulfur cell high-performance composite diaphragm and preparation method thereof, the High-performance diaphragm is for electron conduction, ionic conductivity, the problems such as cyclical stability, technology depositing carbon material and zirconic acid lanthanum lithium on business barrier film are splashed altogether with the double targets of magnetron sputtering, this method effectively prevent the problems such as blocking barrier film hole that directly painting method is brought, so as to improve lithium ion conductivity.Wherein, the introducing of conductive carbon improves the insulation defect of sulphur positive pole, and provides possibility for physical absorption polysulfide；The distinctive structures of LLZO also improve lithium ion conductivity, and more reliable chemisorbed is provided for polysulfide.By the synergy of Van der Waals force and chemical bond, the high-capacity battery design of stable circulation is realized.The invention solves the problems, such as that polysulfide obstruction rate present in lithium-sulfur cell diagram modification and lithium ion diffusivity are difficult to balance to a certain extent.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, more particularly to a kind of high-performance lithium-sulfur cell composite diaphragm and its system
Preparation Method.
Background technology
Sulphur simple substance as positive electrode there is highest theoretical specific capacity (1675 m Ah/g) and theory to compare energy
（2600 Wh/kg）, it is the LiCoO in conventional lithium ion battery2（274mAh/g）Deng 6 times of positive electrode.In addition, sulphur is certainly
The reserves on right boundary are huge, and toxicity is low, and environmental pollution is small.Thus, lithium-sulfur cell has turned into the focus of current international research, is
The ideal chose of Future New Energy Source electrokinetic cell.
But the real commercialization of lithium-sulfur rechargeable battery still faces lot of challenges, the diffusion of polysulfide and the insulation sheet of sulphur
Matter is to limit the key factor of lithium-sulfur cell development.For lithium-sulfur cell first in charge and discharge process, generation dissolves in electrolyte
The polysulfide ion of higher valence state can be diffused into cathode of lithium, side reaction directly occurs with lithium metal, generates more vulcanizations of lower valency
Lithium, more lithium sulfides of these lower valencies spread back sulphur positive pole, generate more lithium sulfides of high-valence state, so as to produce shuttle effect.Fly
The generation of shuttle effect, the reduction of utilization efficiency and the corrosion of cathode of lithium are directly results in, make battery capacity decay rapid, coulomb
Efficiency reduces.In addition, S electrical conductivity is extremely low（At 25 DEG C, Ω=5 × 10-30S/cm）, insoluble Li in charge and discharge process2S
Negative pole is deposited on, cathode of lithium has dendrite generation, and volumetric expansion can occur for S positive poles and fragmentation（76%）, these can all cause lithium sulphur electric
Pond cyclical stability is deteriorated.
In order to solve lithium-sulfur cell above mentioned problem, researcher respectively from positive electrode modification, diagram modification, electrolyte,
Conduct a research work in terms of negative pole protection technique, battery structure design 5.Wherein, lithium-sulfur cell is due to discharge and recharge reaction process
Complexity and electrolyte diversity, traditional polyalkene diaphragm can not suppress lithium-sulfur cell intermediate product polysulfide well
The diffusion of thing.Therefore, developing higher performance diaphragm material also turns into one of improvement lithium-sulfur cell overall performance important directions.
Yao et al. reports coats one layer of different types of conductive carbon to improve following for lithium-sulfur cell on membrane for polymer
Ring performance.Result of study shows that conductive carbon layer has preferable barrier effect to polysulfide.Fine and close conductive carbon layer can hinder more
The diffusion of sulfide, while conductive layer can also reuse the polysulfide held onto as secondary collector, so as to
The utilization rate of active material is improved, avoids the loss of battery capacity.In addition to carbon material, Zhang et al. reports gold
Belong to oxide Al2O3To the study on the modification of membrane for polymer, chemical phase that the metal oxygen key in oxide is formed with polysulfide
Interaction, it can effectively stop that polysulfide spreads.
Though it is coated modification using organic carbon material and inorganic, metal oxide to be diffused with various degree polysulfide
Inhibitory action, however, carbon material surface is nonpolar, it is impossible to form stable chemical bond with the polysulfide of polarity.It is more
Sulfide is easily deviate from from the hole of carbon material, it is difficult to effectively suppresses shuttle effect for a long time.Metal oxide such as TiO2,
Al2O3, MnO2Deng can carry out more structurally sound chemisorbed to polysulfide, be expected to further suppress the shuttle of polysulfide
Effect.Regrettably the oxide to insulate can hinder the transmission of electronics and lithium ion, reduce the utilization rate and high rate performance of sulphur.It is good
Good electric conductivity is difficult to satisfactory to both parties with reliable chemisorbed.Therefore, how the two is uniformly mixed, learnt from other's strong points to offset one's weaknesses, obtain high quality
Lithium-sulfur cell barrier film is a problem.
Although in addition, barrier film, which is modified, using directly painting method to hinder polysulfide by physics to a certain extent
Spread, but will also result in coating simultaneously to block membrane thicknesses increase, aperture sections, influence migration of lithium ion etc., i.e., it is more
The obstruction rate of sulphion and the percent of pass of lithium ion are difficult to reach a balance well；And using the painting of directly painting method barrier film
It is higher to cover irregularity, lithium ion skewness, aggravation lithium dendrite growth can be caused, cyclical stability is reduced, influence battery performance.
Therefore polysulfide diffusion can efficiently be suppressed, and can ensures that lithium ion conductivity is one of lithium-sulfur cell barrier film urgent need to resolve
Problem.
The content of the invention
It is existing to solve present invention aims at a kind of lithium-sulfur cell high-performance composite diaphragm and preparation method thereof of proposition
Above mentioned problem present in lithium-sulfur cell, the battery diaphragm prepared using this method have lithium ion selective penetrated property function, high
While effect hinders the diffusion of more sulphions, it is allowed to which lithium ion is quickly through while improving the insulation defect of sulphur positive pole, so as to effectively
Improve the cycle performance and high rate performance of lithium-sulfur cell.
The present invention to achieve the above object, adopts the following technical scheme that：
A kind of lithium-sulfur cell high-performance composite diaphragm, it is characterised in that：The composite diaphragm using polypropylene diaphragm as basilar memebrane,
Surface construction doping type LLZO/C nano-deposits.
It is further characterized by：The doping type LLZO/C nano-deposits are only oriented to the placement of anode side.
A kind of preparation method of above-mentioned lithium-sulfur cell high-performance composite diaphragm, it is characterised in that：Using magnetron sputtering
Double targets splash technology altogether, the pure carbon material of d.c. sputtering and radio-frequency sputtering zirconic acid lanthanum lithium on polypropylene diaphragm surface.
The preparation method comprises the following steps：
（1）Carbon target and zirconic acid lanthanum lithium target and polypropylene diaphragm are put into magnetron sputtering vacuum chamber, vacuumized to reach background
Magnetron sputtering is carried out after vacuum；
（2）Composite diaphragm after having sputtered is dried in vacuo at 60 DEG C, to remove moisture removal；
（3）Modified diaphragm is pressed into a diameter of 18 mm disk using manual sheet-punching machine, obtains lithium-sulfur cell with multi-functional compound
Barrier film.
Preferably：The direct current source power of the d.c. sputtering is 80W, and the RF source power of radio-frequency sputtering is 30W.
The condition of the magnetron sputtering is that background vacuum is 6.6 × 10-4, sputtering pressure 0.9Pa, sputtering time is
20-40min。
The present invention has technique effect：
（1）Polypropylene diaphragm surface, build doping type LLZO/C nano-deposits.Polysulfide shuttle phenomenon can efficiently be suppressed, and
Lithium ion conductivity and electronic conductivity can be improved.
（2）Doping type LLZO/C nano-deposits, the high-specific surface area of carbon make its physical absorption polysulfide, in zirconic acid lanthanum lithium
Metal oxygen key and polysulfide there is higher combination energy, provide possibility for more reliable chemisorbed.Porous-Organic material
Expect with the synergy of inorganic, metal oxide efficient absorption polysulfide to be achieved.
（3）The electric conductivity of carbon compensate for the insulating properties defect of positive active material sulphur, and the distinctive structure of zirconic acid lanthanum lithium is lithium
Ion provides express passway.The synergy of electronic conductive material and fast ion conducting material causes with the lithium ion improved
The lithium-sulfur cell barrier film of electrical conductivity and electronic conductivity is achieved.
（4）It is high compared with directly painting method thickness of thin, porosity that the double targets of magnetron sputtering splash technology composite diaphragm altogether.
（5）Magnetron sputtering technique is easy to operate, smaller on the characteristic influence of barrier film in itself, can be mass-produced.
Brief description of the drawings
Fig. 1 is C/LLZO/PP composite separator structure schematic diagrames in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of C/LLZO/PP composite diaphragms in the embodiment of the present invention 1.
Fig. 3 is using the lithium-sulfur cell of polypropylene business barrier film and the embodiment of the present invention 1, comparative example 1, the institute of comparative example 2
The interface impedance comparison diagram of the lithium-sulfur cell of preparation.
Fig. 4 is using the lithium-sulfur cell of polypropylene business barrier film and the embodiment of the present invention 1, comparative example 1, the institute of comparative example 2
The lithium ion conductivity comparison diagram of the lithium-sulfur cell of preparation.
Fig. 5 is using modified diaphragm prepared by polypropylene business barrier film and the embodiment of the present invention 1, comparative example 1, comparative example 2
Cycle performance correlation curve of the lithium-sulfur cell under 0.2C multiplying powers.
Fig. 6 is using modified diaphragm prepared by polypropylene business barrier film and the embodiment of the present invention 1, comparative example 1, comparative example 2
Lithium-sulfur cell exist（0.2C、0.5C、1C、2C、3C、0.5C）High rate performance comparison diagram under multiplying power.
Embodiment
Embodiment 1：
A kind of lithium-sulfur cell high-performance composite diaphragm, including polypropylene business barrier film and the C and LLZO that are sputtered in membrane surface
Nano particle.The corresponding carbon target in DC source and the zirconic acid lanthanum lithium target corresponding to radio frequency source are installed, using polypropylene business
Industry barrier film is base material, and vacuum chamber atmosphere is high-purity argon in Sample Preparation Procedure, background vacuum 6.6 × 10 -4Pa, sputtering pressure
It is 30 W in room temperature, sputtering power 80W, radio-frequency sputtering power to control as 0.9 Pa, substrate temperature control, and sample deposits
Time is 40min.
Embodiment 2：
A kind of lithium-sulfur cell high-performance composite diaphragm, including polypropylene business barrier film and the C and LLZO that are sputtered in membrane surface
Nano particle.The corresponding carbon target in DC source and the zirconic acid lanthanum lithium target corresponding to radio frequency source are installed, using polypropylene business
Industry barrier film is base material, and vacuum chamber atmosphere is high-purity argon in Sample Preparation Procedure, the Pa of background vacuum 6.6 × 10-4, sputters gas
Voltage-controlled to be made as 0.9 Pa, substrate temperature control is 30 W in room temperature, sputtering power 80W, radio-frequency sputtering power, and sample sinks
The product time is 30min.
Embodiment 3：
One kind has a lithium-sulfur cell high-performance composite diaphragm, including polypropylene business barrier film and be sputtered in the C of membrane surface with
LLZO nano particles.The corresponding carbon target in DC source and the zirconic acid lanthanum lithium target corresponding to radio frequency source are installed, using poly- third
Alkene business barrier film is base material, and vacuum chamber atmosphere is high-purity argon in Sample Preparation Procedure, background vacuum 6.6 × 10 -4Pa, sputtering
Pressure control is 0.9 Pa, and substrate temperature control is in room temperature, sputtering power 80W, and radio-frequency sputtering power is 30 W, sample
Sedimentation time is 20min.
Comparative example 1：
It is a kind of that there is suppression polysulfide to spread and improve the lithium-sulfur cell composite diaphragm of positive electrode electric conductivity, including polypropylene
Business barrier film and the carbon nano-particle for being sputtered in membrane surface.Pure carbon target material is installed, uses polypropylene business barrier film as base
Material, vacuum chamber atmosphere is high-purity argon in Sample Preparation Procedure, background vacuum 6.6 × 10 -4 Pa, sputtering pressure control are
0.9Pa, substrate temperature are controlled in room temperature, sputtered using DC source, sputtering power 80W, and sample sedimentation time is 40
min。
Comparative example 2：
It is a kind of that there is the efficient polysulfide that suppresses to spread and improve the lithium-sulfur cell composite diaphragm of lithium ion conductivity, including poly- third
Alkene business barrier film and the zirconic acid lanthanum lithium nano particle for being sputtered in membrane surface.Zirconic acid lanthanum lithium target is installed, using polypropylene
Business barrier film is base material, and vacuum chamber atmosphere is high-purity argon in Sample Preparation Procedure, background vacuum 6.6 × 10 -4Pa, sputter gas
Voltage-controlled to be made as 0.9 Pa, substrate temperature is controlled in room temperature, sputtered using radio frequency, and sputtering power is made as 30W, when sample deposits
Between be 40 min.
Fig. 1 and Fig. 2 is respectively C/LLZO/PP composite separator structures schematic diagram and scanning electron microscope (SEM) photograph in the embodiment of the present invention 1.
As illustrated, the modified diaphragm splashed altogether using the double targets of C and LLZO still member-retaining portion pore structure, is hindering polysulfide diffusion
While, have no effect on lithium ion and pass through.
Fig. 3 is made using the lithium-sulfur cell and the embodiment of the present invention 1 of polypropylene business barrier film, comparative example 1, comparative example 2
The interface impedance comparison diagram of standby lithium-sulfur cell.As seen from the figure, the barrier film that carbon is modified has minimum interface impedance, double to splash modification
Barrier film there is the impedance value similar with its, and respectively less than business barrier film and LLZO is mono- splashes modified diaphragm, this is due to that carbon has
Electric conductivity, so as to substantially increase Charge-transfer resistance, be advantageous to improve the specific capacity of lithium-sulfur cell.
Fig. 4 is made using the lithium-sulfur cell and the embodiment of the present invention 1 of polypropylene business barrier film, comparative example 1, comparative example 2
The lithium ion conductivity comparison diagram of standby lithium-sulfur cell.As can be seen that the barrier film that LLZO is modified has highest lithium ion conductance
Rate, this is due to that the distinctive structure of zirconic acid lanthanum lithium is determined.But the mono- barrier film lithium ion conductivities that splash of C are even below common
Business barrier film.But it is double to splash modified barrier film there is higher lithium ion conductivity, be advantageous to lithium-sulfur cell chemical property
Improve.
Fig. 5 is using modified diaphragm prepared by polypropylene business barrier film and the embodiment of the present invention 1, comparative example 1, comparative example 2
Cycle performance correlation curve of the lithium-sulfur cell under 0.2C multiplying powers.As seen from the figure, splashed altogether using C and LLZO in embodiment 1
Modified diaphragm has highest initial specific capacities and most excellent cyclical stability.This is due to splash technology altogether using magnetron sputtering
LLZO and C uniform mixing is realized, is learnt from other's strong points to offset one's weaknesses, realizes high performance lithium-sulfur cell composite diaphragm.
Fig. 6 is using modified diaphragm prepared by polypropylene business barrier film and the embodiment of the present invention 1, comparative example 1, comparative example 2
Lithium-sulfur cell exist（0.2C、0.5C、1C、2C、3C、0.5C）High rate performance comparison diagram under current density.As seen from the figure, not
With under current density, embodiment is respectively provided with highest specific capacity.
It should be added that sputtering carbon nano-particle on business barrier film in comparative example 1 significantly reduces electric charge turn
Impedance is moved, and physics hinders the diffusion of polysulfide to a certain extent.But nonpolar carbon and the more lithium sulfides of polarity is affine
Power is not strong, causes its absorption to polysulfide to be made not strong, is unfavorable for the raising of stable circulation performance.Zirconium is sputtered in comparative example 2
Though sour lanthanum lithium composite diaphragm improves lithium ion conductivity, and has strong chemisorption to polysulfide, insulation
Oxide can hinder the transmission of electronics, reduce the utilization rate of active material.Carbon and the double targets of zirconic acid lanthanum lithium in the embodiment of the present invention
The composite membrane splashed altogether, carbon advantage in comparative example 1 is combined, reduces Charge-transfer resistance, hinder vulcanize more to a certain extent
The diffusion of thing.The characteristic of the fast lithium ion conductor of zirconic acid lanthanum lithium in comparative example 2 is provided simultaneously with, is expanded in the polysulfide further hindered
While dissipating, lithium ion conductivity is significantly improved.What the double targets of carbon and zirconic acid lanthanum lithium used in the embodiment of the present invention splashed altogether answers
Synergy of the film by C and LLZO is closed, obtains the double conduction of electronic and ionic, the high-performance lithium-sulfur cell of stable circulation.
Claims (6)
- A kind of 1. lithium-sulfur cell high-performance composite diaphragm, it is characterised in that：The composite diaphragm is using polypropylene diaphragm as substrate Film, surface construction doping type LLZO/C nano-deposits.
- 2. lithium-sulfur cell according to claim 1 high-performance composite diaphragm, it is characterised in that：The doping type LLZO/C Nano-deposit is only oriented to the placement of anode side.
- A kind of 3. preparation method of the lithium-sulfur cell high-performance composite diaphragm described in claim 1 or 2, it is characterised in that：Adopt Technology is splashed altogether with the double targets of magnetron sputtering, the pure carbon material of d.c. sputtering and radio-frequency sputtering zirconic acid lanthanum lithium on polypropylene diaphragm surface.
- 4. the lithium-sulfur cell according to claim 3 preparation method of high-performance composite diaphragm, it is characterised in that including with Lower step：（1）Carbon target and zirconic acid lanthanum lithium target and polypropylene diaphragm are put into magnetron sputtering vacuum chamber, vacuumized to reach background Magnetron sputtering is carried out after vacuum；（2）Composite diaphragm after having sputtered is dried in vacuo at 60 DEG C, to remove moisture removal；（3）Modified diaphragm is pressed into a diameter of 18 mm disk using manual sheet-punching machine, obtains lithium-sulfur cell with multi-functional compound Barrier film.
- 5. the lithium-sulfur cell according to claim 4 preparation method of high-performance composite diaphragm, it is characterised in that：It is described straight The direct current source power of stream sputtering is 80W, and the RF source power of radio-frequency sputtering is 30W.
- 6. the lithium-sulfur cell according to claim 4 preparation method of high-performance composite diaphragm, it is characterised in that：The magnetic The condition of control sputtering is that background vacuum is 6.6 × 10-4, sputtering pressure 0.9Pa, sputtering time 20-40min.
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| CN112201904A (en) * | 2020-10-30 | 2021-01-08 | 天目湖先进储能技术研究院有限公司 | Diaphragm interlayer material of lithium-sulfur battery and preparation method and application thereof |
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| CN112201904A (en) * | 2020-10-30 | 2021-01-08 | 天目湖先进储能技术研究院有限公司 | Diaphragm interlayer material of lithium-sulfur battery and preparation method and application thereof |
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| CN107895767B (en) | 2020-08-04 |
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