CN105261721A - Asymmetric diaphragm and application thereof in lithium-sulfur rechargeable battery - Google Patents
Asymmetric diaphragm and application thereof in lithium-sulfur rechargeable battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to an asymmetric diaphragm and an application thereof in a lithium-sulfur rechargeable battery. The asymmetric diaphragm comprises a polymer matrix layer and a conductive carbon layer, wherein the conductive carbon layer is adhered to the polymer matrix layer; and a main body of the conductive carbon layer is a carbon material, and is adhered through a binder or self-adhered through the carbon material. The conductive carbon layer contacts a composite sulfur anode when applied to the lithium-sulfur rechargeable battery; and the polymer matrix layer faces a cathode and contacts lithium metal. The asymmetric diaphragm is formed by the electrical conductivity and high specific surface area characteristics of the carbon material and the adhesive property of macromolecules; the utilization rate of a positive active material can be effectively improved under the condition of relatively low conductive layer additive amount; and polysulfide migration can be inhibited, so that the anode capacity and the cycling stability of the battery are improved.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of asymmetric barrier film and the application in lithium-sulfur rechargeable battery.
Background technology
Along with the continuous progress of modern science and technology, the especially development of electronics industry, modern society is increasing for the demand of electron stored energy equipment.On the other hand, along with emerging in large numbers of the aspect problems such as environmental pollution and traditional fossil energy exhaustion, energy storage technology is subject to people gradually and pays close attention to more and more widely.
The use of Ni-MH battery and lithium ion battery has successfully promoted to comprise mobile phone, a series of of electric automobile have the electronics of social change, the development of electric equipment and use.But owing to there being larger limitation in energy density, they can not meet the demand of social technology development completely.And lithium-sulfur cell is as a kind of model electrochemical system, because its high theoretical energy density and lower cost to receive the extensive concern of educational circles and industrial circle in recent years, and be expected to alternative existing lithium ion battery.
In the middle of lithium-sulfur cell, sulphur is a kind of positive electrode with high theoretical specific capacity, and its theoretical capacity can reach 1672mAh/g, and the theoretical energy density of the battery system formed with cathode of lithium can reach 2600Wh/kg.In addition, sulphur positive pole also has the plurality of advantages such as inexpensive, nontoxic.But the intermediate product (polysulfide) that lithium-sulfur cell produces in the middle of charge and discharge process easily dissolves in the electrolytic solution, spreads, and then active material is caused to depart from positive conductive network; In addition, due to polysulfide and the reaction of negative pole and the disproportionated reaction in the middle of electrolyte, active material can deposit at negative pole, barrier film and positive electrode surface, forms active material inert layer.This greatly reduces the utilance of active material on the one hand, not only reduces positive electrode capacity, also accelerates lithium-sulfur cell performance degradation, limits the raising of positive pole sulphur load capacity; On the other hand also because inert layer is formed, ion transfer channel jam, the internal resistance of cell increases, and causes the series of problems such as battery failure, heating.How to solve this long-term " migration effect " and " inert layer effect " existed in lithium-sulfur cell, promote positive electrode capacity and the cyclical stability of lithium-sulfur cell further, to its practicalization of promotion, there is great value.
At present, large quantity research based on lithium-sulfur cell concentrates on positive electrode side, main means comprise the structural design and preparation of carrying out positive pole sulphur/carbon composite, improve the utilance of positive pole sulfur materials by improving conductivity and pore-size distribution, and attempt to spread to the dissolving of polysulfide the suppression carried out to a certain degree.Such as: Nazar etc., by the compound of sulphur and ordered mesopore carbon, utilize ordered mesoporous pore canals to limit the migration of polysulfide, obtain electrode material (JiXL, the etal.Nat.Mater.2009 of superior performance; 8 (6): 500-6.); Wang Jiulin etc. are partially cured by what sulphur and polyacrylonitrile compound are achieved sulphur, thus improve performance (WangJL, the etal.Adv.Mater.2002 such as the cyclical stability of electrode; 14 (13-14): 963-5.; Wang Jiulin, Yang Jun, separate sparkling and crystal-clear, wait publication number: CN1384556).Although can improve element sulphur utilance by modes such as cathode material structure design, macromolecule compounds, part suppresses generation and the diffusion of polysulfide, and its concrete cycle performance and energy density still greatly differ from each other apart from practical.
In the recent period, other researchers are had to be conceived to the assembly such as negative pole and barrier film in lithium-sulfur rechargeable battery, wish the stability by suppressing " migration effect " to improve battery system, such as: Zhang etc. form inertia protective layer (ZhangSS.Electro.Acta.2012 by adding lithium nitrate additive in the electrolytic solution in negative terminal surface; 70:344-8.), Huang etc. prepare ion selective separator (HuangJQ, etal.EnergyEnviron.Sci.2014 by applying Nafion on barrier film; 7 (1): 347-53.).These attempt the diffusion that inhibit polysulfide to a certain extent, but its capacity characteristic is still not fully up to expectations.If the design of the system component of lithium-sulfur cell own can be utilized, develop a kind of asymmetric barrier film for the recyclable active material of lithium-sulfur rechargeable battery, be then expected to the capacity and the cyclical stability that significantly improve battery, and then promote the development of lithium-sulfur rechargeable battery.
Summary of the invention
The object of this invention is to provide a kind of asymmetric barrier film and the application in lithium-sulfur rechargeable battery, concrete technical scheme is as follows:
A kind of asymmetric barrier film, described asymmetric barrier film is made up of macromolecule matrix layer and conductive carbon layer, make use of the adhesive of the conductivity of conductive carbon layer, high-specific surface area speciality and macromolecule matrix layer; Described conductive carbon layer is bonded on macromolecule matrix layer; Described conductive carbon layer main body is material with carbon element, by binding agent adhesion or material with carbon element from adhesion.
Preferably, described material with carbon element is one or more in carbon black, micro-pore carbon material, meso-porous carbon material, macropore material with carbon element, multi-stage porous carbon material, carbonaceous mesophase spherules, fullerene, carbon nano-fiber, carbon nano-tube, Graphene, carbon aerogels, and above-mentioned oxygen, nitrogen, boron, sulphur, phosphorus or transition metal atoms doped forms.
Preferably, described binding agent is one or more in Kynoar, polytetrafluoroethylene, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, butadiene-styrene rubber, sodium carboxymethylcellulose, shitosan, poly-dopamine, sodium alginate, cyclodextrin.
Preferably, described macromolecule matrix layer is polypropylene diaphragm, polypropylene-polyethylene-polypropylene diaphragm, polyimide diaphragm, Kynoar, polysulfones barrier film, poly-perfluoro sulfonic acid membrane, polybenzimidazole membrane or porous cellulose film.
Preferably, the thickness of described asymmetric barrier film is 1-1000 μm, and the thickness of conductive carbon layer is 0.0001-1000 μm.
Preferably, described binding agent is 0-60% at the mass fraction of conductive carbon layer.
The application of asymmetric barrier film as above in lithium-sulfur rechargeable battery: described conductive carbon layer and composite sulfur positive contact; Macromolecule matrix aspect, to negative pole, contacts with lithium metal.
Described asymmetric barrier film is for promoting the utilance of the polysulfide produced in lithium-sulfur rechargeable battery charge and discharge process and suppressing it to spread.
Beneficial effect of the present invention is:
The present invention is directed to polysulfide migration in lithium-sulfur cell and cause the defect that active material effective rate of utilization is low, cyclical stability is poor, propose a kind of asymmetric barrier film for the recyclable active material of lithium-sulfur rechargeable battery.
(1) micropore/meso/macroporous structure utilizing material with carbon element to be formed and larger specific area thereof, achieve the physical barriers for polysulfide and absorption, positive pole and dispersed and be fixed on asymmetric barrier film from the shuttle back and forth polysulfide of returning of negative side will be diffused out, the concentration gradient of polysulfide between mild side of the positive electrode and negative side, thus the migration effect reduced between polysulfide both positive and negative polarity, improve the cyclical stability of lithium-sulfur cell.
(2) utilize the conductivity of material with carbon element, by introducing conducting matrix grain, improving active material utilization, eliminating inert layer, thus greatly promoting the positive electrode capacity of lithium-sulfur cell, reduce the internal resistance of battery.
(3) applied widely for material with carbon element of the present invention, preparation method is simple, huge to lithium-sulfur cell performance boost, and collaboration high power capacity positive electrode, can obtain the lithium-sulfur cell of high-energy-density.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but the present invention is not only confined to following examples.
Embodiment 1
Method of swimming is grown the double-walled carbon nano-tube obtained and polytetrafluoroethylene according to after the abundant combination drying of mass ratio 1:1, make the conductive carbon layer that thickness is about 100 μm.By the polypropylene diaphragm compound of rolling by this conductive carbon layer and 25 μm, form the asymmetric barrier film of recyclable active material, thickness is 125 μm.Simultaneously with sulphur/multi-wall carbon nano-tube composite material for positive pole, metal lithium sheet is negative pole, and the ethylene glycol dimethyl ether solution of lithium perchlorate is as electrolyte, and the polypropylene matrix aspect of asymmetric barrier film is to metal lithium sheet.Under the charge-discharge velocity of 2C, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 982mAh/g, front 200 circle circulation individual pen attenuation rates about 0.03%, far below the lithium-sulfur cell (about 0.29%) adopting common diaphragm.
Embodiment 2
To take magnesium oxide as template, chemical vapour deposition technique grows the meso-porous carbon material obtained, and to be distributed to mass fraction be in the aqueous povidone solution of 1%, and suction filtration, to polypropylene diaphragm surface, forms the asymmetric barrier film that thickness is 26 μm.Wherein conductive carbon layer contains the meso-porous carbon material of mass fraction 90% and the polyvinylpyrrolidone of 10%, and thickness is 1 μm, and polypropylene diaphragm is 25 μm.By the polypropylene side of this asymmetric barrier film in the face of lithium anode, with sulphur/absorbent charcoal composite material for positive pole, 1,3-dioxolane of methyl triethyl group LiBF4,1,2-dimethoxyethane solution, as electrolyte, are assembled into lithium-sulfur cell.Under the discharge rate of 0.01C, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 1589mAh/g, front 200 circle circulation individual pen attenuation rates are about 0.04%, far below the lithium-sulfur cell (about 0.5%) adopting common diaphragm.
Embodiment 3
After the nitrating carbon nano-fiber carbonization of electrospinning polyacrylonitrile fibre obtained mixes with the mass ratio of 8:2 with polyvinyl alcohol, blade coating is on 50 μm of polypropylene-polyethylene-polypropylene diaphragms, forms asymmetric barrier film.Conductive carbon layer thickness is 200 μm, and asymmetric membrane thicknesses is 250 μm.By sulphur/carbon black composite material positive pole load in the conductive carbon layer of this asymmetric barrier film, take lithium metal as the polypropylene-polyethylene-polypropylene side of negative pole in the face of this barrier film, use 1 of trifluoromethyl sulfonic acid lithium, lithium nitrate, many lithium sulfides, 3-dioxolane, 1,2-dimethoxyethane solution, as electrolyte, makes lithium-sulfur cell.Under 0.2C charge-discharge velocity, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 1053mAh/g, front 200 circle circulation individual pen number cases are 0.06%, far below common lithium-sulfur cell (about 0.45%).
Embodiment 4
Mixed with 7:3 mass ratio with the methylpyrrolidone solution of 2% Kynoar by conductive black, after being uniformly dispersed, spin coating loads to 10 μm of thick polypropylene diaphragm surfaces, and form the asymmetric barrier film that conductive layer thickness is about 1 μm, membrane thicknesses is 11 μm.By this asymmetric diaphragm application in lithium-sulfur cell, positive pole faced by conductive carbon layer, with sulphur/graphene composite material for positive pole, lithium metal is negative pole, 1, the 3-dioxolane of two (trimethyl fluoride sulfonyl) imine lithium, 1,2-dimethoxyethane solution are as electrolyte.Under the discharge rate of 0.5C, adopt the lithium-sulfur cell initial capacity of asymmetric barrier film to reach 1011mAh/g, front 400 circle circulation individual pen attenuation rates are about 0.07%, far below the lithium-sulfur cell (about 0.5%) adopting common diaphragm.
Embodiment 5
Phosphorus doping carbonaceous mesophase spherules and carbon nano pipe array are made conductive carbon layer according to mass ratio 1:3 compound, thickness is about 800 μm, utilize carbon nano pipe array from blocking characteristics, sticked on 200 μm of polybenzimidazoles matrixes by rolling and form asymmetric barrier film, thickness is 1000 μm.Be used in lithium-sulfur cell by this asymmetric barrier film, positive pole faced by conductive carbon layer, with sulphur/mesoporous carbon complex for positive pole, lithium metal is negative pole, 1,3-dioxolane, 1, the 2-dimethoxyethane solution of tetraethyl LiBF4, lithium nitrate make lithium-sulfur cell as electrolyte.Under 5C current density, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 734mAh/g, front 200 circle circulation individual pen rates of decay are 0.03%, far below the lithium-sulfur cell (about 0.33%) adopting common diaphragm.
Embodiment 6
By the boron-doping carbon nano-tube of chemical vapor deposition growth and graphene oxide and poly-dopamine according to the ratio composite coating of mass ratio 1:1:1 at 10 μm of polyimide diaphragms, the conductive carbon layer thickness formed is 5 μm, obtains the asymmetric barrier film of conductive carbon layer/polyimides that thickness is 15 μm.Be used in lithium-sulfur cell by this asymmetric barrier film, positive pole faced by conductive carbon layer, with sulphur/mesoporous carbon composite material for positive pole, lithium metal is negative pole, 1, the 3-dioxolane, 1 of trifluoromethyl sulfonic acid lithium, lithium nitrate, many lithium sulfides, 2-dimethoxyethane solution is electrolyte, prepares lithium-sulfur cell.Under 1C current density, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 1082mAh/g, front 150 circle circulation individual pen rates of decay are 0.04%, far below the lithium-sulfur cell (about 0.3%) adopting common diaphragm.
Embodiment 7
Be that 1:1 is spin-coated on 1 μm of Kynoar barrier film by porous nitrogen, sulphur codope Graphene and sodium alginate soln according to mass ratio, obtain the conductive carbon layer that 10nm is thick, form the asymmetric barrier film that thickness is 1.01 μm.This asymmetric barrier film is used for lithium-sulfur cell, conductive carbon layer is in the face of positive pole, and with sulphur/microporous carbon compound for positive pole, lithium metal is negative pole, using four (glycol dimethyl ether) solution of two (trimethyl fluoride sulfonyl) imine lithium, lithium nitrate as electrolyte, make lithium-sulfur cell.Under 0.05C current density, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 1432mAh/g, front 200 circle circulation individual pen rates of decay are 0.04%, far below the lithium-sulfur cell (about 0.25%) adopting common diaphragm.
Embodiment 8
The carbon nano-tube prepared by template pyrolysismethod, mix cobalt multi-stage porous carbon material and the polyethylene glycol material ratio according to mass ratio 6:3:1, by the surface of knife coating load at 5 μm of polysulfones barrier films, repressed rear conductive carbon layer thickness is about 500nm, and asymmetric membrane thicknesses is 5.5 μm.This asymmetric barrier film is used as lithium-sulfur cell barrier film, conductive carbon layer is between polysulfones barrier film and positive pole, and simultaneously using sulphur/acrylonitrile composite material as positive pole, metal lithium sheet is as negative pole, the dimethyl carbonate of lithium hexafluoro phosphate, diethyl carbonate solution, as electrolyte, make lithium-sulfur cell.Under the charge-discharge velocity of 0.8C, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 946mAh/g, front 200 circle circulation individual pen attenuation rates about 0.01%, far below the lithium-sulfur cell (about 0.19%) adopting common diaphragm.
Embodiment 9
Fullerene, sulfur doping carbon aerogels and polyacrylic acid are mixed according to mass ratio 1:2:3 and disperse in aqueous, by after suction filtration at the polyvinylidene fluoride surface of 5 μm, making thickness is 10 μm of conductive carbon layer, and the thickness of the asymmetric barrier film obtained is 15 μm.Simultaneously with sulphur/ordered mesopore carbon for positive pole, lithium metal is negative pole, and the Kynoar of asymmetric barrier film is in the face of cathode of lithium, and the ethylene glycol dimethyl ether solution of methyl triethyl group LiBF4, as electrolyte, makes lithium-sulfur cell.Under 10C charge-discharge velocity, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 632mAh/g, front 100 circle circulation individual pen number cases are 0.02%, far below the lithium-sulfur cell (about 0.3%) adopting common diaphragm.
Embodiment 10
By the microporous carbon that obtains after sucrose carbonization and shitosan according to mass ratio 3:1 solid phase mixing, rolling, on porous cellulose film surface, forms asymmetric barrier film, conductive carbon layer thickness 200 μm, asymmetric membrane thicknesses 500 μm.This asymmetric barrier film is used for lithium-sulfur cell, and conductive carbon layer, in the face of positive pole, adopts sulphur/carbon nano-tube/poly dopamine as positive pole, take lithium metal as 1, the 3-dioxolane, 1 of negative pole, many lithium sulfides, 2-dimethoxyethane solution, as electrolyte, makes lithium-sulfur cell.Under 1C charge-discharge velocity, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 1231mAh/g, front 300 circle circulation individual pen number cases are 0.02%, far below the lithium-sulfur cell (about 0.35%) adopting common diaphragm.
Embodiment 11
Using the macropore carbon of conductive black, reversion opal structural as carbon-coating; butadiene-styrene rubber, sodium carboxymethylcellulose are as binding agent; make aqueous slurry according to mass ratio 2:6:1:1 mixing dispersion; be coated in the polypropylene screen surface of 25 μm; after drying, gained conductive carbon layer thickness is 105 μm, and the thickness of the asymmetric barrier film obtained is 130 μm.This asymmetric barrier film is used for lithium-sulfur cell, and conductive carbon layer is in the face of positive pole, and adopting sulphur/carbon nano-tube/graphene oxide as positive pole, take lithium metal as negative pole, and the ethylene glycol dimethyl ether solution of trifluoromethyl sulfonic acid lithium, as electrolyte, makes lithium-sulfur cell.Under 0.02C charge-discharge velocity, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 1408mAh/g, front 400 circle circulation individual pen number cases are 0.08%, far below the lithium-sulfur cell (about 0.5%) adopting common diaphragm.
Embodiment 12
Graphene, microporous activated carbon, cyclodextrin are made water system gel according to after mass ratio 2:3:1 compound, and immersion coating forms conductive carbon layer on the surface of poly-perfluoro sulfonic acid membrane, and carbon layers having thicknesses is about 1 μm, and asymmetric membrane thicknesses is 31 μm.Use this barrier film to assemble lithium-sulfur cell, make conductive carbon layer in the face of positive pole, simultaneously with sulphur/nitrating graphene complex for positive pole, lithium metal is negative pole, and the dimethyl sulfoxide solution of lithium perchlorate, lithium hexafluoro phosphate, as electrolyte, makes lithium-sulfur cell.Under the charge-discharge velocity of 3C, adopt the lithium-sulfur cell initial capacity of this asymmetric barrier film to reach 904mAh/g, front 2000 circle circulation individual pen attenuation rates about 0.005%, far below the lithium-sulfur cell (about 0.27%) adopting common diaphragm.
Claims (8)
1. an asymmetric barrier film, is characterized in that, described asymmetric barrier film is made up of macromolecule matrix layer and conductive carbon layer, make use of the adhesive of the conductivity of conductive carbon layer, high-specific surface area speciality and macromolecule matrix layer; Described conductive carbon layer is bonded on macromolecule matrix layer; Described conductive carbon layer main body is material with carbon element, by binding agent adhesion or material with carbon element from adhesion.
2. asymmetric barrier film according to claim 1, it is characterized in that, described material with carbon element is one or more in carbon black, micro-pore carbon material, meso-porous carbon material, macropore material with carbon element, multi-stage porous carbon material, carbonaceous mesophase spherules, fullerene, carbon nano-fiber, carbon nano-tube, Graphene, carbon aerogels, and above-mentioned oxygen, nitrogen, boron, sulphur, phosphorus or transition metal atoms doped forms.
3. asymmetric barrier film according to claim 1, it is characterized in that, described binding agent is one or more in Kynoar, polytetrafluoroethylene, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, butadiene-styrene rubber, sodium carboxymethylcellulose, shitosan, poly-dopamine, sodium alginate, cyclodextrin.
4. asymmetric barrier film according to claim 1, it is characterized in that, described macromolecule matrix layer is polypropylene diaphragm, polypropylene-polyethylene-polypropylene diaphragm, polyimide diaphragm, Kynoar, polysulfones barrier film, poly-perfluoro sulfonic acid membrane, polybenzimidazole membrane or porous cellulose film.
5. asymmetric barrier film according to claim 1, is characterized in that, the thickness of described asymmetric barrier film is 1-1000 μm, and the thickness of conductive carbon layer is 0.0001-1000 μm.
6. asymmetric barrier film according to claim 1, is characterized in that, described binding agent is 0-60% at the mass fraction of conductive carbon layer.
7. the application of asymmetric barrier film in lithium-sulfur rechargeable battery described in any one of claim 1 ~ 6, is characterized in that, described conductive carbon layer and composite sulfur positive contact; Macromolecule matrix aspect, to negative pole, contacts with lithium metal.
8. application according to claim 7, is characterized in that, described asymmetric barrier film is for promoting the utilance of the polysulfide produced in lithium-sulfur rechargeable battery charge and discharge process and suppressing it to spread.
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