CN107275551A - Lithium-sulfur cell and its component, and application of the functional material layer in lithium-sulfur cell - Google Patents
Lithium-sulfur cell and its component, and application of the functional material layer in lithium-sulfur cell Download PDFInfo
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- CN107275551A CN107275551A CN201710342173.5A CN201710342173A CN107275551A CN 107275551 A CN107275551 A CN 107275551A CN 201710342173 A CN201710342173 A CN 201710342173A CN 107275551 A CN107275551 A CN 107275551A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of lithium-sulfur cell, including sulfur-based positive electrode；Lithium base negative pole；It is arranged on the barrier film between the sulfur-based positive electrode and the lithium base negative pole；And the functional material layer between the sulfur-based positive electrode and the lithium base negative pole is arranged on, the material of the functional material layer includes the transition metal oxide with the crystallization water.The present invention also provides a kind of composite diaphragm, lithium sulphur battery electrode component, the compound application of sulfur-based positive electrode, compound lithium base negative pole and functional material layer in lithium-sulfur cell.
Description
Technical field
The present invention relates to field of lithium, more particularly to lithium-sulfur cell, composite diaphragm, lithium sulphur battery electrode component, compound
The application of sulfur-based positive electrode, compound lithium base negative pole and functional material layer in lithium-sulfur cell.
Background technology
With developing rapidly for new-energy automobile industry, the energy storage device of exploitation high-energy-density become research at present and
The important directions of development.Lithium-sulfur cell with its 1675mAh/g theoretical specific capacity and~2500Wh/kg theoretical energy density,
As replacement conventional lithium ion battery, the long-range continuation of the journey target of realization (>Power electric pond body most with prospects 500Wh/kg)
One of system.But, the problem of presently, there are low cycle life and poor security and stability due to lithium-sulfur cell makes it in practical road
Obstruction is still faced on road.The shuttle effect for how efficiently suppressing many lithium sulfides is lifting lithium-sulfur cell chemical property and security
The key factor of energy, is also the focus of international research in recent years.
The shuttle effect of many lithium sulfides is mainly caused by two aspects, and one is thermodynamically inevitably to spread, and two
It is that slower kinetics causes the accumulation of many lithium sulfides in the electrolytic solution.At present, the shuttle of many lithium sulfides of suppression is main
Method is physical barrier, polarity absorption and storage, promotes many lithium sulfides to convert, by coating sulphur positive pole or sulphur being bound by into nanometer
Suppress the shuttle of many lithium sulfides in duct.Although formation protective layer or protection network can obstruct many to a certain extent on sulphur surface
Lithium sulfide, but still the long-life circulation of battery difficult to realize.
Some transition metal oxides or sulfide are coated on barrier film by existing numerous studies is used as functional material layer
To improve the capacity and cycle performance of lithium-sulfur cell.The transition metal oxide or sulfide-oxidation thing of some of polarity, such as
Fe2O3、Co3O4、Ti4O7、NiO、ZnO、V2O3、Cu2O etc. can be by surface polarity or acidic site come many sulphur of absorbing and storing
Change lithium；Other transition metal oxide, such as TiO2、MnO2、CuO、VO2Also there is the effect for being catalyzed many lithium sulfides simultaneously.This
Outside,, can also be from one in guarantee lithium ion under the premise of because nano material can be filled in the hole of barrier film
Determine to play a part of many lithium sulfides of physical barrier in degree.However, being frequently found in practical application, even if using above-mentioned transition gold
Belong to oxide, reach that effect is still undesirable in terms of many lithium sulfide shuttles are prevented.
The content of the invention
Be more effectively to prevent the shuttle of many lithium sulfides based on this, it is necessary to provide a kind of lithium-sulfur cell, composite diaphragm,
Lithium sulphur battery electrode component, the compound application of sulfur-based positive electrode, compound lithium base negative pole and functional material layer in lithium-sulfur cell.
A kind of lithium-sulfur cell, including sulfur-based positive electrode；Lithium base negative pole；Be arranged on the sulfur-based positive electrode and the lithium base negative pole it
Between barrier film；And it is arranged on the functional material layer between the sulfur-based positive electrode and the lithium base negative pole, the feature material
The material of the bed of material includes the transition metal oxide with the crystallization water.
A kind of composite diaphragm, the composite diaphragm is used for lithium-sulfur cell, it is characterised in that the composite diaphragm includes barrier film
And the functional material layer at least one surface of barrier film is arranged on, the material of the functional material layer includes having crystallization
The transition metal oxide of water.
A kind of lithium sulphur battery electrode component, including it is layered on top of each other the sulfur-based positive electrode, barrier film and functional material layer of setting, institute
State functional material layer to be arranged between the sulfur-based positive electrode and the barrier film, the material of the functional material layer includes having
The transition metal oxide of the crystallization water.
A kind of lithium sulphur battery electrode component, it is characterised in that lithium base negative pole, barrier film and function including being layered on top of each other setting
Property material layer, the functional material layer is arranged between the lithium base negative pole and the barrier film, the functional material layer
Material includes the transition metal oxide with the crystallization water.
A kind of compound sulfur-based positive electrode, including it is layered on top of each other the positive electrode material layer, plus plate current-collecting body and functional material of setting
Layer, the positive electrode material layer is arranged between the functional material layer and the plus plate current-collecting body, the functional material layer
Material include with the crystallization water transition metal oxide.
A kind of compound lithium base negative pole, including it is layered on top of each other the lithium metal and functional material layer of setting, the feature material
The material of the bed of material includes the transition metal oxide with the crystallization water.
A kind of application of functional material layer in lithium-sulfur cell, including the transition metal with the crystallization water will be contained
The solidliquid mixture of oxide is coated on the surface of at least one of the sulfur-based positive electrode, lithium base negative pole and barrier film, so that in institute
State and form the functional material layer between sulfur-based positive electrode and the lithium base negative pole.
Transition metal oxide with the crystallization water is introduced into lithium-sulfur cell by the present invention, compared to the mistake for removing the crystallization water
Metal oxide is crossed, the bigger specific surface area that the transition metal oxide with the crystallization water can have, so as to provide more
Avtive spot, preferably plays a part of absorbing and storing and/or is catalyzed many lithium sulfides, is worn so as to efficiently play and suppress many lithium sulfides
The effect of shuttle, lifts the chemical property of lithium-sulfur cell.
Brief description of the drawings
Fig. 1 is the structural representation of lithium-sulfur cell of the embodiment of the present invention；
Fig. 2 is the structural representation of lithium sulphur battery electrode component of the embodiment of the present invention；
Fig. 3 schemes for the SEM of functional material layer in PP@C＆HTO-1 in embodiment 1；
Fig. 4 is existed in the lithium-sulfur cell and comparative example to use PP@C＆HTO-1 in embodiment 1 using PP lithium-sulfur cell
Cycle performance comparison diagram under 0.2C；
Fig. 5 is cycle performance and coulombic efficiency of the lithium-sulfur cell under 1C to use PP@C＆HTO-1 in embodiment 1
Figure；
Fig. 6 is cycle performance and coulombic efficiency of the comparative example using PP@C＆TO-1 lithium-sulfur cell under 1C in embodiment 1
Figure；
Fig. 7 is the SEM figures of PP@C＆HTO-2 functional material layers in embodiment 2；
Fig. 8 is the cycle performance comparison diagram in embodiment 2 using PP@C＆HTO-2 and PP lithium-sulfur cell under 0.2C；
Fig. 9 is the cyclicity for being the lithium-sulfur cell that is prepared into using PP@C＆HTO-2 coatings under 0.5C in embodiment 2
Can be with coulombic efficiency figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with drawings and Examples pair
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
Fig. 1 and Fig. 2, offer lithium-sulfur cell of the embodiment of the present invention, including sulfur-based positive electrode 10, lithium base negative pole 20 are provided and set
The barrier film 30 between sulfur-based positive electrode 10 and lithium base negative pole 20 is put, the lithium-sulfur cell further comprises being arranged on sulfur-based positive electrode 10
With the functional material layer 32 between lithium base negative pole 20.The material of the functional material layer 32 includes the transition with the crystallization water
Metal oxide.The transition metal oxide can be suppressed many lithium sulfides and shuttled with absorbing and storing and/or many lithium sulfides of catalysis.
Further, since having the crystallization water in material, it there may be a certain degree of reaction with lithium ion or lithium adjusted by surface polarity
Uniform ion is distributed, so as to play a part of suppressing lithium dendrite growth.
The metallic element of the transition metal oxide can selected from titanium (Ti), ruthenium (Ru), molybdenum (Mo), vanadium (V), tungsten (W),
At least one of iron (Fe) and cobalt (Co).
The transition metal oxide with the crystallization water includes but is not limited to TiO2·xH2O、H2TinO2n+1·H2O、
RuO2·xH2O、MoO3·xH2O、(H3O)xMoO3·xH2O、HyV4O10·xH2O、HzV2O5·xH2O、V2O5·xH2O、V2O4·
xH2O、WO3·xH2O、Fe2O3·xH2O and Co2O3·xH2At least one of O, 2≤n≤9,0.5≤x≤10,0<Y≤1,0<
z≤1。
The transition metal oxide with the crystallization water is preferably nanometer materials, the oxo transition metal with the crystallization water
The primary particle size of compound is preferably 1 nanometer to 100 nanometers, more elects 1 nanometer to 10 nanometers as.When the particle size of material is to receive
It during meter level, can effectively be filled in the hole of barrier film, many lithium sulfides of physical barrier can also be played to a certain extent and are shuttled
Effect.
The transition metal oxide with the crystallization water is compared with the transition metal oxide obtained after the removal crystallization water
With bigger specific surface area, the specific surface area value of the transition metal oxide with the crystallization water is preferably 100m2/ g to 600m2/
g。
The thickness of the functional material layer 32 is preferably 10nm~200 μm, and surface density is preferably 0.1~10mg/cm.
It is preferred that, the material of the functional material layer 32 further comprises electronic conductive material and binding agent, the electricity
Subconductivity material and binding agent are uniformly mixed with the transition metal oxide with the crystallization water.The mistake with the crystallization water
It is preferably 5%~99% to cross weight/mass percentage composition of the metal oxide in the functional material layer 32.The electronic conduction
The mass ratio of material and binding agent is preferably 1:9~9:1.
It is preferred that, the electronic conductive material is selected from activated carbon, graphene, CNT, Ketjen black, Super P, acetylene
At least one of black and graphite.
It is preferred that, the binding agent is selected from polyvinylidene fluoride (PVDF), polyethylene glycol oxide (PEO), vinylidene-hexafluoro
Propylene copolymer (PVDF-HFP), laurate acrylate (LA), polytetrafluoroethylene (PTFE) (PTFE), polyvinyl alcohol (PVA), asphalt mixtures modified by epoxy resin
At least one of fat, polyacrylic acid (PAA) and sodium carboxymethylcellulose (CMC).
The functional material layer 32 can be arranged on the sulfur-based positive electrode 10 towards lithium base negative pole 20 (namely towards every
Film 30) surface, at least one surface of the barrier film 30, or the lithium base negative pole 20 towards the sulfur-based positive electrode 10 (
Be exactly towards barrier film 30) surface.In a preferred embodiment, the functional material layer 32 is arranged at the barrier film 30
Towards the surface of the sulfur-based positive electrode 10.In one embodiment, the functional material layer 32 is arranged on the two of the barrier film 30
Individual surface.
The sulfur-based positive electrode 10 includes positive electrode material layer 12 and plus plate current-collecting body 14, and the plus plate current-collecting body 14 is used to support
The positive electrode material layer 12 simultaneously conducts electric current, and shape can be paillon foil or netted.The material of the plus plate current-collecting body 14 can be selected
From aluminium, titanium or stainless steel.The positive electrode material layer 12 is arranged on a plus plate current-collecting body 14 at least surface.The positive electrode
The material of layer 12 includes sulfur-bearing positive electrode active materials, further selectable including conductive agent and binding agent.The conductive agent
And binding agent can uniformly be mixed with the sulfur-bearing positive electrode active materials.The sulfur-bearing positive electrode active materials are with electrochemistry
Store up the sulfenyl material of lithium ability, such as at least one of sulphur simple substance, sulfenyl composite and vulcanized conducting polymer.The sulphur
Based composites for example can be by composite material of core-shell structure obtained from sulphur simple substance particle surface coated with conductive carbon-coating, or
It is composite porous obtained from sulphur simple substance particle is arranged in porous carbon materials.The sulfenyl conducting polymer for example can be with
Selected from vulcanization polypyrrole pyridine, vulcanization polystyrene, vulcanization polyethylene glycol oxide, vulcanized polyethylene alcohol, vulcanization polyvinylidene chloride, sulphur
Change polyvinylidene fluoride, vulcanized polyvinyl chloride, vulcanization polyvinyl fluoride, the poly- 1,2-dichloroethene of vulcanization, poly- 1, the 2- difluoros second of vulcanization
One or more in alkene, vulcanization polymethyl methacrylate and vulcanization phenolic resin.
The functional material layer 32 can be arranged on the positive electrode material layer 12 towards the lithium base negative pole 20 (namely
Towards the barrier film 30) surface.The positive electrode material layer 12 is arranged on the functional material layer 32 and the anode collection
Between body 14.
The functional material layer 32 preferably directly contacted with the positive electrode material layer 12, or directly with the barrier film
30 contacts.Two surfaces of more preferably described functional material layer 32 respectively with the positive electrode material layer 12 and the barrier film 30
Directly contact is set.But in certain embodiments, between the functional material layer 32 and the positive electrode material layer 12, Huo Zhesuo
State and other materials layer is may be inserted between functional material layer 32 and the barrier film 30, such as tack coat, conductive layer or diversion
Layer, as long as not influenceing functional material layer 32 to realize at least one of above-mentioned functions (1) to (3).
The lithium base negative pole 20 may include negative electrode active layer 22, such as metallic lithium layer or lithium alloy layer, such as lithium-tin alloy layer
Or lithium-aluminium alloy layer, and negative current collector 24 can be further comprised.The negative current collector 24 is used to support the negative electrode active
Layer 22 simultaneously conducts electric current, and shape can be paillon foil or netted.The material of the negative current collector 24 can be selected from copper, nickel or stainless
Steel.
The barrier film 30 can be traditional lithium battery diaphragm, can be in the sulfur-based positive electrode 10 and the lithium base negative pole 20
Between isolation electronics and pass through lithium ion, can be any one in organic polymer barrier film or anodic aluminium oxide membrane, for example
The double-layer porous film of polyethylene porous membrane, polypropylene porous film, polyethylene-polypropylene, polypropylene-poly- second can be selected from, but not limited to,
Three layers of perforated membrane of alkene-polypropylene, glass fibre perforated membrane, non-woven fabrics perforated membrane, Electrospun perforated membrane, PVDF-HFP perforated membranes and
Any one in polyacrylonitrile porous membrane.The nonwoven cloth diaphragm can enumerate such as polyimide nano-fiber non-woven fabrics, gather
PETP (PET) nano fiber non-woven fabric, cellulose nano-fibrous non-woven fabrics, aramid nano-fiber non-woven fabrics,
Nylon nano fiber non-woven fabrics and Kynoar (PVDF) nano fiber non-woven fabric.The Electrospun perforated membrane can enumerate as
Polyimides electrospun membrane, PET electrospun membrane and Kynoar electrospun membrane.
The lithium-sulfur cell also include nonaqueous electrolytic solution 40, the nonaqueous electrolytic solution 40 be arranged on the sulfur-based positive electrode 10 with
Between the lithium base negative pole 20, for example, it can permeate in the barrier film 30.The nonaqueous electrolytic solution 40 includes solvent and is dissolved in institute
State the lithium salts solute of solvent, the solvent may be selected from but be not limited to cyclic carbonate, linear carbonate, ring-type ethers, chain ethers,
One or more in nitrile and amide-type, such as ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid
Methyl ethyl ester, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, diethyl ether, acetonitrile, propionitrile, methyl phenyl ethers anisole,
Butyrate, glutaronitrile, dintrile, gamma-butyrolacton, gamma-valerolactone, tetrahydrofuran, 1,2- dimethoxy-ethanes and acetonitrile and two
One or more in NMF.The lithium salts solute may be selected from but be not limited to lithium chloride (LiCl), lithium hexafluoro phosphate
(LiPF6), LiBF4 (LiBF4), methanesulfonic acid lithium (LiCH3SO3), trifluoromethanesulfonic acid lithium (LiCF3SO3), hexafluoroarsenate lithium
(LiAsF6), lithium perchlorate (LiClO4) and di-oxalate lithium borate (LiBOB) in one or more.
The lithium-sulfur cell also includes seal casinghousing 50, the sulfur-based positive electrode 10, lithium base negative pole 20, barrier film 30, feature
Material layer 32 and nonaqueous electrolytic solution 40 are arranged in the seal casinghousing 50.
The embodiment of the present invention also provides a composite diaphragm, and the composite diaphragm is used for the lithium-sulfur cell, it is described it is compound every
Film includes the barrier film 30 and is arranged on the functional material layer 32 at least one surface of barrier film 30.In preferred embodiment
In, functional material layer 32 is arranged on barrier film 30 towards the surface of the sulfur-based positive electrode 10 in lithium-sulfur cell.
The embodiment of the present invention also provides a lithium sulphur battery electrode component, including is layered on top of each other the sulfur-based positive electrode of setting
10th, barrier film 30 and the functional material layer 32, functional material layer 32 are arranged on the sulfur-based positive electrode 10 and the barrier film 30
Between.
The embodiment of the present invention also provides a lithium sulphur battery electrode component, including be layered on top of each other setting lithium base negative pole 20, every
Film 30 and functional material layer 32, functional material layer 32 are arranged between lithium base negative pole 20 and barrier film 30.
The embodiment of the present invention also provides a kind of compound sulfur-based positive electrode, including is layered on top of each other the positive electrode material layer 12, just of setting
Pole collector 14 and functional material layer 32, the positive electrode material layer 12 are arranged on the functional material layer 32 and the positive pole
Between collector 14.
The embodiment of the present invention also provides a kind of compound lithium base negative pole, including is layered on top of each other the lithium metal 22 and feature of setting
Material layer 32.
The embodiment of the present invention provides application of the functional material layer 32 in the lithium-sulfur cell, including will contain
The solidliquid mixture for stating the transition metal oxide with the crystallization water is coated at least one in the sulfur-based positive electrode 10 and barrier film 30
The surface of person, so as to form the functional material layer 32 between the sulfur-based positive electrode 10 and the lithium base negative pole 20.
Solid phase includes the transition metal oxide with the crystallization water in the solidliquid mixture, and can further wrap
Include the electronic conductive material and the binding agent；The liquid phase is preferably solvent.Have described in the solidliquid mixture
Transition metal oxide, electronic conductive material, binding agent and the solvent of the crystallization water are uniformly mixed.The solvent is functioned as
The carrier of the transition metal oxide with the crystallization water, it is therefore desirable to which selection can not dissolve the transition with the crystallization water
Metal oxide, does not chemically react with the transition metal oxide with the crystallization water, and can be in lower temperature (such as
30~120 DEG C) under the solvent that removes completely, such as low molecule amount volatile organic solvent, can adjoin selected from N- methyl pyrrolidone,
One or more in water, methanol, ethanol, propyl alcohol, isopropanol, second eyeball, acetone and ether.
The solidliquid mixture can be mixed liquor or slurry, and the difference of mixed liquor and slurry is only in the ratio of solid-liquid two-phase
Example, is slurry when solid phase is more, is mixed liquor when liquid phase is more.From the ratio of slurry and mixed liquor, and solid-liquid two
The selection of example can be carried out according to actual needs, and for example the mode according to coating is determined.Certainly, to make coating easily carry out, slurry
It is preferred that with suitable mobility；And be to make coating more efficiently, solid phase preferably has suitable ratio in mixed liquor.It is described to apply
The mode covered can be for example infusion process, spin coating method, scraper cladding process, curtain coating cladding process, suction filtration (filtering) cladding process, list
Any one into pulling method and biaxial tension method.The step of by the solidliquid mixture by the coating, forms coating
Afterwards, it is only necessary to remove the solvent in coating, you can obtain the functional material layer 32.It therefore, it can mix the solid-liquid
Thing is coated in the element surface of needs.When the solidliquid mixture is coated on into the sulfur-based positive electrode 10, institute can be coated on
Positive electrode material layer 12 is stated towards the surface of the barrier film 30., can be with when the solidliquid mixture is coated on into the barrier film 30
It is coated on the single or double of the barrier film 30.
, can after the solidliquid mixture to be coated on to the surface of at least one of the sulfur-based positive electrode 10 and barrier film 30
Further comprise drying the solvent removed in the coating.The drying means is, for example, in temperature is 30~120 DEG C of environment
Vacuum drying 4~24 hours.It is appreciated that the step of the drying is intended merely to remove the liquid phase solvent in the coating and suction
Attached water, the temperature of drying steps is relatively low, so as to keep after drying that transition metal oxide still has in the functional material layer 32
There is the crystallization water, hydrone in the form of the crystallization water still to be present in the functional material layer 32.
On the surface of needs, the surface of positive electrode material layer 12 of such as sulfur-based positive electrode 10 and/or an at least surface for barrier film 30
Formed after the functional material layer 32, further comprise the step for being stacked the sulfur-based positive electrode 10 and the barrier film 30
Suddenly.
In one embodiment, it is described the functional material layer 32 is layered in the sulfur-based positive electrode the step of be stacked
Between 10 and the barrier film 30.For example, forming the functional material on the surface of positive electrode material layer 12 of the sulfur-based positive electrode 10
After layer 32, the barrier film 30 can be laid on to the surface of functional material layer 32.Or in an at least table for the barrier film 30
Face is formed after the functional material layer 32, can by the barrier film 30 have the one side of functional material layer 32 towards it is described just
Pole material layer 12, and it is laid on the surface of positive electrode material layer 12.
In another embodiment, it is described the functional material layer 32 is layered in the barrier film 30 the step of be stacked
Surface away from the sulfur-based positive electrode 10.In this embodiment, by further with the functional material layer 32 every
The surface of film 30 stacking lithium base negative pole 20, the functional material layer 32 can be equally arranged on the sulfur-based positive electrode 10 with it is described
Between lithium base negative pole 20.
, can be according to biography after the sulfur-based positive electrode 10, functional material layer 32, barrier film 30 and lithium base negative pole 20 are layered on top of each other
The stepped construction is encapsulated in the seal casinghousing 50 by the lithium-sulfur cell preparation technology of system；And in the seal casinghousing 50
The middle injection electrolyte 40.
The functional material layer 32 based on the transition metal oxide with the crystallization water has in lithium-sulfur cell
There is absorbing and storing and/or be catalyzed many lithium sulfides, and pass through crystallization water H2O introducing, improves functional material layer 32
The crystal structure of middle transition metal oxide and the diversity of nanometer dimension, improve the ionic conductance of functional material layer 32
Rate.Pass through crystallization water H2O introducing can improve the specific surface area of material, and bigger specific surface area can provide more activity
Site, and then the effect for suppressing many lithium sulfides shuttles is efficiently played, lift the chemical property and security performance of lithium-sulfur cell.
The technical scheme of the application, which has been broken, thinks that water can be produced to the chemical property and security of lithium-sulfur cell in tradition
The idea of raw harm, finds and has been experimentally confirmed to introduce the crystallization water in functional material layer 32 and do not interfere with lithium sulphur not only
The performance of battery, while can also make lithium-sulfur cell that there is excellent rate capability and stable circulation performance.Using the function
Property material layer 32 the energy storage neck such as lithium ion battery of the lithium-sulfur cell in electric automobile, energy-accumulating power station and Large Copacity electronic product
Domain has broad application prospects.
In addition, the most methods for preparing transition metal oxide are wet chemistry method (such as hydrothermal synthesis methods or colloidal sol
Gel method), the product that these methods are obtained often hydrate, the high temperature heat treatment that will pass through in tradition is removed in product
The crystallization water.And the transition metal oxide with the crystallization water is directly eliminated into the heat treatment for functional material layer 32
The step of water removal, energy consumption and the pollution in conventional method are effectively reduced, material preparation process is gently controllable, in new energy, green wood
Material and energy-conserving and environment-protective industrial field are respectively provided with important influence and meaning.
Embodiment 1
1) preparation of the transition metal oxide base functional material layer with the crystallization water：By TiO2·xH2O、Super P
And PVDF is according to 8:1:1 mass ratio, which is added to N- methyl and adjoined, is mixed into slurry in pyrrolidone, then using the tape casting poly-
One side coats above-mentioned slurry on propylene barrier film, then slurry is dried in vacuo 10 hours at 60 DEG C, that is, obtains with the crystallization water
The composite diaphragm (hereinafter referred to as PP@C＆HTO-1) of transition metal oxide base functional material layer.Feature in PP@C＆HTO-1
SEM (SEM) figure of material layer is as shown in Figure 3.
2) assembling of lithium-sulfur cell：Sulphur positive pole is prepared with sublimed sulfur, metal lithium sheet is negative pole, and PP@C＆HTO-1 are barrier film,
Electrolyte is LiTFSI and LiNO3(DME is 1 with DOL volume ratios to the mixed solution formed in DME and DOL in the mixed solvent:
1, LiTFSI concentration is 1mol/L, LiNO3Concentration be 0.2mol/L).1ppm high-purity argon is below in water and oxygen content
2032 type button cells are assembled in the glove box of gas atmosphere.
Comparative example 1
Same as Example 1, the PP@C＆HTO-1 in embodiment 1 are only being replaced with commercialization lithium battery with poly- third by difference
Alkene barrier film (hereinafter referred to as PP), assembles 2032 type button cells same as Example 1, and difference is only replaced by PP@C＆HTO-1
For PP.
Comparative example 2
Same as Example 1, difference is only by the TiO in embodiment 12·xH2O is obtained after 350 DEG C of thermal dehydrations
TiO2(hereinafter referred to as TO-1) material, and by the TiO in functional material layer preparation process in embodiment 12·xH2O is substituted for
TO-1, obtains the composite diaphragm (hereinafter referred to as PP@C＆TO-1) with transition metal oxide coating, assembling and the phase of embodiment 1
PP@C＆HTO-1 are only being replaced with PP@C＆TO-1 by 2032 same type button cells, difference.
Embodiment 2
Same as Example 1, difference is only by the TiO in embodiment 12·xH2O replaces with H2Ti3O7, and by the tape casting
Scraper cladding process is replaced with, the composite diaphragm (hereinafter referred to as PP@C＆HTO-2) with transition metal oxide coating, group is obtained
2032 type button cells same as Example 1 are filled, PP@C＆HTO-1 are only being replaced with PP@C＆HTO-2 by difference.
SEM (SEM) figure of functional material layer is as shown in Figure 7 in PP@C＆HTO-2.
The test of battery performance
Using LAND battery test systems discharge and recharge blanking voltage be respectively 2.7V and 1.8V voltage range in carry out
Constant current charge-discharge is circulated, the electrochemistry cycle characteristics of testing example 1-2 and comparative example 1-2 button cell, the test of battery
Data are as shown in table 1.Fig. 4 is cycle performance comparison diagram respectively using PP@C＆HTO-1 and PP lithium-sulfur cell under 0.2C.
Fig. 5 is the cycle performance and coulombic efficiency figure under 1C using PP@C＆HTO-1 lithium-sulfur cell.Fig. 6 is that comparative example 2 uses PP@
Cycle performance of the C＆TO-1 lithium-sulfur cell under 1C and coulombic efficiency figure.Fig. 8 is respectively using PP@C＆HTO-2 and PP lithium
Cycle performance comparison diagram of the sulphur battery under 0.2C.Fig. 9 is the cyclicity under 0.5C using PP@C＆HTO-2 lithium-sulfur cell
Can be with coulombic efficiency figure.
Contrasted by Fig. 4 cycle performance and can be seen that the lithium-sulfur cell for using PP@C＆HTO-1 discharge capacity height first
Up to 1735mAh/g, and discharge capacity is only 979mAh/g first using PP control Battery pack.After 400 cycles, use
PP C＆HTO-1 lithium-sulfur cell remains to keep 671mAh/g stable specific capacity, is the control Battery pack specific capacity using PP
2.5 again.As seen in Figure 5, under 1C big multiplying power, followed using PP@C＆HTO-1 lithium-sulfur cell up to 1400 times
Still there is 420mAh/g reversible specific capacity after ring, coulombic efficiency is close to 100%, and " the shuttle effect " of many lithium sulfides substantially weakens,
Battery shows very excellent big rate capability and cyclical stability.
The advantage for investigating material containing the crystallization water in lithium-sulfur cell is contrasted with PP@C＆TO-1 and PP@C＆HTO-1.Pass through Fig. 6
As can be seen that using PP@C＆TO-1 lithium-sulfur cell, discharge capacity is only 650mAh/g first.1400 circulations after
In, the specific capacity of battery is constantly reduced, and 420mAh/g is had already decreased to specific capacity during 250 circulations.And in Fig. 5, same
Under conditions of, it is still higher than 420mAh/g after PP@C＆HTO-1 1400 circulations of lithium-sulfur cell.After 1400 times circulate,
The specific capacity of PP@C＆TO-1 lithium-sulfur cell only residue 130mAh/g.This is due to nano-TiO2·xH2O crystal structures are in high temperature
The process of dehydration often will be roughened and reunite, and material granule becomes large-sized, and specific surface area is greatly reduced, and then reduce
The absorbing and storing of the point-to-points lithium sulfide of active sites and catalytic action, cause chemical property unsatisfactory in material.
By above-mentioned experiment it is known that in the preparation method of nano-oxide, wet chemistry method (such as hydro-thermal reaction or
Person's solgel reaction) hydrate of oxide for preparing, it has the crystallization water.And traditionally carry the water of the crystallization water
Compound needs to obtain final product by high-temperature calcination water removal.But present inventor has found, the material pair after high temperature water removal
It is and nonideal state for the functional material layer for lithium-sulfur cell.In this application, present inventor passes through
Avoid the crystallization water in high-temperature calcination, reserved materials, it is to avoid roughening of the nanocrystalline structure during high temperature dehydration and
Reunite, make transition metal oxide that there is substantial amounts of avtive spot, by a large amount of avtive spots come absorbing and storing and (or) catalysis
Many lithium sulfides.Also, when oxide has less crystallite dimension, thing can be come with the easier organic barrier film hole that is filled in
The many lithium sulfides of reason barrier, reach and preferably suppress the effect that many lithium sulfides of lithium-sulfur cell shuttle.
Contrasted by Fig. 8 cycle performance and can be seen that the lithium-sulfur cell for using PP@C＆HTO-2 discharge capacity height first
Up to 1536mAh/g, and discharge capacity is only 979mAh/g first using PP control Battery pack.After 400 cycles, use
PP C＆HTO-2 lithium-sulfur cell remains to keep 639mAh/g stable specific capacity, is the control Battery pack specific capacity using PP
2.5 again.Under 0.5C multiplying power (Fig. 9), still had after the circulation up to 1200 circles using PP@C＆HTO-2 lithium-sulfur cell
442mAh/g reversible specific capacity, coulombic efficiency is close to 100%, and " the shuttle effect " of many lithium sulfides substantially weakens, and battery shows
Go out very excellent big rate capability and cyclical stability.
Table 1
| Current ratio | First discharge specific capacity | What n-th was circulated puts a specific capacity | |
| Embodiment 1 | 0.2C | 1735mAh/g | 671mAh/g, N=400 |
| Embodiment 1 | 1C | 958mAh/g | 420mAh/g, N=1400 |
| Comparative example 1 | 0.2C | 979mAh/g | 263mAh/g, N=400 |
| Comparative example 2 | 1C | 650mAh/g | 130mAh/g, N=1400 |
| Embodiment 2 | 0.2C | 1536mAh/g | 639mAh/g, N=400 |
| Embodiment 2 | 0.5C | 694mAh/g | 442mAh/g, N=1200 |
Embodiment 3
1) preparation of the transition metal oxide base functional material layer with the crystallization water：By MoO3·xH2O, Ketjen black with
And PVDF is according to 7:2:1 mass ratio, which is added in alcohol solvent, is mixed into slurry, then using rotary coating polyethylene every
The above-mentioned slurry of dual coating on film, then slurry is dried in vacuo 10 hours at 80 DEG C, that is, obtain with the mistake with the crystallization water
Cross the composite diaphragm (hereinafter referred to as PE@C＆HMO-3) of metal oxide base functional material layer.
2) assembling of lithium-sulfur cell：Same as Example 1, PP@C＆HTO-1 are only being replaced with PE@C＆HMO-3 by difference.
Embodiment 4
1) preparation of the transition metal oxide base functional material layer with the crystallization water：By V2O5·xH2O, acetylene black with
And LA is according to 85:15:5 mass ratio, which is added in deionized water, is mixed into slurry, is then existed using suction filtration (filtering) cladding process
One side coats above-mentioned slurry on polyethylene-polypropylene two-layer separator, then slurry is dried in vacuo 10 hours at 80 DEG C, that is, obtains
Composite diaphragm (hereinafter referred to as PE/PP@C＆HVO- with the transition metal oxide base functional material layer with the crystallization water
4)。
2) assembling of lithium-sulfur cell：Same as Example 1, sublimed sulfur is only being replaced with sulphur carbon composite by difference, will
PP@C＆HTO-1 replace with PE/PP@C＆HVO-4.
Embodiment 5
1) preparation of the transition metal oxide base functional material layer with the crystallization water：By WO3·xH2O, CNT
And PTFE is according to 6:3:1 mass ratio, which is added in methanol, is mixed into slurry, is then made using the tape casting in sublimed sulfur
Positive electrode layer surface coats above-mentioned slurry, then slurry is dried in vacuo 10 hours at 80 DEG C, that is, obtains having crystallization
The sulfur-based positive electrode (hereinafter referred to as S@C＆HWO-5) of the transition metal oxide base functional material layer of water.
2) assembling of lithium-sulfur cell：Using S@C＆HWO-5 as positive pole, metal lithium sheet is negative pole, and barrier film is the lithium of commercialization
Battery polypropylene-polyethylene-polypropylene diaphragm, electrolyte is solution of the LiTFSI in DME and DOL in the mixed solvent formation
(DME is 1 with DOL volume ratios:1, LiTFSI concentration is 1mol/L).1ppm high-purity argon gas gas is below in water and oxygen content
2032 type button cells are assembled in the glove box of atmosphere.
Embodiment 6
1) preparation of the transition metal oxide base functional material layer with the crystallization water：By Fe2O3·xH2O, graphene
And Kynoar is according to 70:15:15 mass ratio, which is added in ethanol, is mixed into slurry, then using doctor blade method in PAN
Perforated membrane one side coats above-mentioned slurry, then slurry is dried in vacuo 10 hours at 60 DEG C, that is, obtains with the crystallization water
The composite diaphragm (hereinafter referred to as PAN@C＆HFO-6) of transition metal oxide base functional material layer.
2) assembling of lithium-sulfur cell:Same as Example 1, sublimed sulfur is only being replaced with sulphur carbon composite by difference, will
PP@C＆HTO-1 replace with PE/PP@C＆HVO-6.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (16)
1. a kind of lithium-sulfur cell, including：
Sulfur-based positive electrode；
Lithium base negative pole；
It is arranged on the barrier film between the sulfur-based positive electrode and the lithium base negative pole；And
It is arranged on the functional material layer between the sulfur-based positive electrode and the lithium base negative pole, the material of the functional material layer
Including the transition metal oxide with the crystallization water.
2. lithium-sulfur cell according to claim 1, it is characterised in that the metallic element choosing in the transition metal oxide
From at least one of titanium, ruthenium, molybdenum, vanadium, tungsten, iron and cobalt.
3. lithium-sulfur cell according to claim 1, it is characterised in that the transition metal oxide bag with the crystallization water
Include TiO2·xH2O、H2TinO2n+1·H2O、RuO2·xH2O、MoO3·xH2O、(H3O)xMoO3·xH2O、HyV4O10·xH2O、
HzV2O5·xH2O、V2O5·xH2O、V2O4·xH2O、WO3·xH2O、Fe2O3·xH2O and Co2O3·xH2At least one of O, 2
≤ n≤9,0.5≤x≤10,0<Y≤1,0<z≤1.
4. lithium-sulfur cell according to claim 1, it is characterised in that the transition metal oxide with the crystallization water
Primary particle size size is 1 nanometer to 100 nanometers.
5. lithium-sulfur cell according to claim 1, it is characterised in that the thickness of the functional material layer be 10nm~
200 μm, surface density is 0.1~10mg/cm.
6. lithium-sulfur cell according to claim 1, it is characterised in that the material of the functional material layer further comprises
Electronic conductive material and binding agent, the electronic conductive material and binding agent and the transition metal oxide with the crystallization water
Uniform mixing.
7. lithium-sulfur cell according to claim 1, it is characterised in that the functional material layer is being arranged on the sulfenyl just
Pole-face is to the surface of the lithium base negative pole, at least one surface of the barrier film, or the lithium base negative pole towards the sulfenyl
The surface of positive pole.
8. lithium-sulfur cell according to claim 1, it is characterised in that the functional material layer is arranged on the barrier film
Two surfaces.
9. lithium-sulfur cell according to claim 1, it is characterised in that the transition metal oxide with the crystallization water exists
Weight/mass percentage composition in the functional material layer is 5%~99%.
10. a kind of barrier film, the barrier film is used for lithium-sulfur cell, it is characterised in that the barrier film includes diaphragm matrix and is arranged on
The functional material layer at least one surface of diaphragm matrix, the material of the functional material layer is included with the crystallization water
Transition metal oxide.
11. a kind of lithium sulphur battery electrode component, it is characterised in that sulfur-based positive electrode, barrier film and function including being layered on top of each other setting
Property material layer, the functional material layer is arranged between the sulfur-based positive electrode and the barrier film, the functional material layer
Material includes the transition metal oxide with the crystallization water.
12. a kind of lithium sulphur battery electrode component, it is characterised in that lithium base negative pole, barrier film and function including being layered on top of each other setting
Property material layer, the functional material layer is arranged between the lithium base negative pole and the barrier film, the functional material layer
Material includes the transition metal oxide with the crystallization water.
13. a kind of compound sulfur-based positive electrode, it is characterised in that including be layered on top of each other the positive electrode material layer of setting, plus plate current-collecting body and
Functional material layer, the positive electrode material layer is arranged between the functional material layer and the plus plate current-collecting body, the work(
The material of energy property material layer includes the transition metal oxide with the crystallization water.
14. a kind of compound lithium base negative pole, it is characterised in that lithium metal and functional material layer including being layered on top of each other setting, institute
Stating the material of functional material layer includes the transition metal oxide with the crystallization water.
15. a kind of application of functional material layer, it is characterised in that including the oxo transition metal with the crystallization water will be contained
The solidliquid mixture of compound is coated on the surface of at least one of sulfur-based positive electrode, lithium base negative pole and barrier film, so that in the sulfenyl
The functional material layer is formed between positive pole and the lithium base negative pole, and then forms lithium-sulfur cell.
16. the application of functional material layer according to claim 15, it is characterised in that further comprise：
Solvent in the coating for removing the solidliquid mixture formation is dried at temperature is 30~120 DEG C.
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