CN107546357A - 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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- CN107546357A CN107546357A CN201710656252.3A CN201710656252A CN107546357A CN 107546357 A CN107546357 A CN 107546357A CN 201710656252 A CN201710656252 A CN 201710656252A CN 107546357 A CN107546357 A CN 107546357A
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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
- H01M50/443—Particulate material
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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
- 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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- 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, the barrier film being arranged 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 includes the Li H M O system compounds with Li, H, M and O element, and wherein M is transition metal.The present invention also provides a kind of application of composite diaphragm, lithium sulphur battery electrode component, compound 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 the rapid development of new-energy automobile industry, develop the energy storage device of 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 due to the problem of lithium-sulfur cell presently, there are low cycle life and security and stability difference, make it in practical road
Obstruction is still faced on road.How efficiently to suppress the shuttle effect of more lithium sulfides is lifting lithium-sulfur cell chemical property and security
The key factor of energy, and the focus of international research in recent years.
The shuttle effect of more lithium sulfides is mainly caused by two aspects, first, thermodynamically inevitably spreading, two
It is that slower kinetics causes the accumulation of more lithium sulfides in the electrolytic solution.At present, the main of the shuttle of more lithium sulfides is suppressed
Method is physical barrier, polarity absorption and storage, promotes more lithium sulfides to convert, by coating sulphur positive pole or sulphur being bound by into nanometer
Suppress the shuttle of more lithium sulfides in duct.Although formation protective layer or protection network can obstruct more to a certain extent on sulphur surface
Lithium sulfide, but still the long-life circulation of battery difficult to realize.
Existing numerous studies are golden by some transition metal oxides (M-O), transient metal sulfide (M-S) and lithium transition
Category oxide (Li-M-O) is coated on barrier film and improves the capacity of lithium-sulfur cell and cycle performance as functional material layer.Its
In some transistion metal compounds Co3O4、Ti4O7、NiO、V2O3、Li4Ti5O12Etc. surface polarity or acidic site can be passed through
Carry out the more lithium sulfides of absorbing and storing；Other transistion metal compound, such as TiO2、MnO2、VO2Also have catalysis to vulcanize simultaneously
The effect of lithium.Further, since nano material can be filled in the hole of barrier film, in guarantee lithium ion normal through premise
Under, the more lithium sulfides of physical barrier can also be played a part of to a certain extent.However, be frequently found in practical application, even if
Using above-mentioned transistion metal compound, it is still undesirable in terms of more lithium sulfide shuttles are prevented to reach effect.
The content of the invention
Be more effectively to prevent the shuttles of more lithium sulfides based on this, it is necessary to provide a kind of lithium-sulfur cell, composite diaphragm,
The application of lithium sulphur battery electrode component, compound 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；
The barrier film being arranged between the sulfur-based positive electrode and the lithium base negative pole；And
The functional material layer being arranged between the sulfur-based positive electrode and the lithium base negative pole, the functional material layer
Material includes the Li-H-M-O system compounds with Li, H, M and O element, and wherein M is transition metal.
In an embodiment wherein, H exists in the form of the crystallization water or constitution water in the Li-H-M-O systems compound.
In an embodiment wherein, the transition metal M in titanium, manganese, vanadium, tungsten, molybdenum, nickel and cobalt at least
It is a kind of.
In an embodiment wherein, the formula of the Li-H-M-O systems compound is Li(0.01~4)H(0.01~8)
MO(1- σ~6- σ), and 0≤σ≤1, wherein σ are the amount of Lacking oxygen.
In an embodiment wherein, the grain size of the primary particle of the Li-H-M-O systems compound is 1 nanometer
To 800 nanometers.
In an embodiment wherein, the specific surface area of the Li-H-M-O systems compound is 1m2/ g to 600m2/g。
In an embodiment wherein, the Li-H-M-O systems compound has layered crystal structure.
In an embodiment wherein, the thickness of the functional material layer is 10nm~200 μm, surface density is 0.1~
30mg/cm2。
In an embodiment wherein, the material of the functional material layer also includes electronic conductive material and binding agent,
The electronic conductive material and binding agent uniformly mix with the Li-H-M-O systems compound.
In an embodiment wherein, the functional material layer is arranged on the sulfur-based positive electrode towards the lithium base negative pole
Surface, at least one surface of the barrier film, or the lithium base negative pole is towards the surface of the sulfur-based positive electrode.
In an embodiment wherein, the functional material layer is arranged on two surfaces of the barrier film.
In an embodiment wherein, quality hundred of the Li-H-M-O systems compound in the functional material layer
It is 5%~99% to divide content.
A kind of composite diaphragm, the composite diaphragm are used for lithium-sulfur cell, and the composite diaphragm includes barrier film and is arranged on institute
The functional material layer at least one surface of barrier film is stated, the material of the functional material layer includes having Li, H, M and O element
Li-H-M-O system compounds, wherein M is transition metal.
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 Li-H-M-O system compounds of Li, H, M and O element, wherein M are transition metal.
A kind of lithium sulphur battery electrode component, including it is layered on top of each other lithium base negative pole, barrier film and the functional material layer of setting, institute
Stating the material of functional material layer includes the Li-H-M-O system compounds with Li, H, M and O element, and wherein M is transition metal
Element.
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 are arranged between the functional material layer and the plus plate current-collecting body, the functional material layer
Material include with Li, H, M and O element Li-H-M-O system compounds, wherein M is transition metal.
A kind of compound lithium base negative pole, including the lithium metal and functional material layer of setting are layered on top of each other, the feature material
The material of the bed of material includes the Li-H-M-O system compounds with Li, H, M and O element, and wherein M is transition metal.
A kind of application of functional material layer in lithium-sulfur cell, including：
The solidliquid mixture of Li-H-M-O system compounds with Li, H, M and O element is being coated on the sulfenyl just
The surface of at least one of pole, lithium base negative pole and barrier film, so as to form institute between the sulfur-based positive electrode and the lithium base negative pole
State functional material layer.
In an embodiment wherein, further comprise：
The solvent removed in the coating that the solidliquid mixture is formed is dried at being 30~120 DEG C in temperature.
A kind of Li-H-M-O system materials are introduced into lithium-sulfur cell by the present invention, and dehydrogenation group is gone compared to by high-temperature calcination
The Li-M-O system materials divided, Li-H-M-O system materials have bigger specific surface area, so as to provide more avtive spots,
Preferably play a part of absorbing and storing and/or the more lithium sulfides of catalysis, so as to efficiently play the effect for suppressing more lithium sulfides and shuttling,
Lift 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 is the SEM figures of functional material layer in PP@C＆LHTO-1 in embodiment 1；
Fig. 4 is to be existed in embodiment 1 using in PP@C＆LHTO-1 lithium-sulfur cell and comparative example using PP lithium-sulfur cell
Cycle performance comparison diagram under 0.2C；
Fig. 5 is the cycle performance and coulombic efficiency for use PP@C＆LHTO-1 lithium-sulfur cell under 1C in embodiment 1
Figure；
Fig. 6 is to use the forthright again of PP C＆LTO-1 lithium-sulfur cell using PP C＆LHTO-1 and comparative example in embodiment 1
Can comparison diagram.
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
Put the barrier film 30 between sulfur-based positive electrode 10 and lithium base negative pole 20.The lithium-sulfur cell also includes being arranged on sulfur-based positive electrode 10 and lithium
Functional material layer 32 between base negative pole 20.The material of the functional material layer 32 includes Li-H-M-O system compounds.
The Li-H-M-O systems compound has Li, H, M and O element, and wherein M is one or more transition metals.
The Li-H-M-O systems compound can be suppressed more lithium sulfides and shuttled with absorbing and storing and/or the more lithium sulfides of catalysis.
Further, since having hydrogen component in compound, it there may be a certain degree of reaction with lithium ion or adjusted by surface polarity
Lithium ion is uniformly distributed, so as to play a part of suppressing lithium dendrite growth.
Preferably, the Li-H-M-O systems compound has layered crystal structure, is suppressing the same of more lithium sulfides shuttles
When do not influence the transmission of lithium ion, provide quick conduction pathway for lithium ion.It is appreciated that " stratiform " crystal structure herein with
The nanometer plate shape of compound primary particle apparent form distinguishes, and layered crystal structure herein is row of the atom in structure cell
Row mode.
The transition metal can be selected from titanium (Ti), molybdenum (Mo), vanadium (V), tungsten (W), manganese (Mn), nickel (Ni) and cobalt (Co)
At least one.
H can exist in the form of the crystallization water in the Li-H-M-O systems compound, or with compound molecule
The form of constitution water is present.In addition, the Li-H-M-O systems compound can also have Lacking oxygen.The Li-H-M-O systems
The preferable formula of compound can be Li(0.01~4)H(0.01~8)MO(1- σ~6- σ), 0≤σ≤1, wherein σ are the amount of Lacking oxygen.It is described
Li-H-M-O system compounds are preferably nanometer materials, and the particle diameter of primary particle is preferably 1 nanometer to 800 nanometers, more preferably
For 1 nanometer to 100 nanometers.When the particle size of material is nanoscale, effectively can be filled in the hole of barrier film, certain
The more lithium sulfides of physical barrier can also be played a part of in degree to shuttle.
The Li-H-M-O systems compound is compared with the Li-M-O system materials for going after dehydrogenation component to obtain with bigger
Specific surface area, the specific surface area value of Li-H-M-O system compounds is preferably 1m2/ g to 600m2/ g, more preferably 100m2/g
To 600m2/g。
M is preferably Ti in the Li-H-M-O systems compound.In Li-H-Ti-O compounds, Li mass fraction is excellent
The mass fraction that the mass fraction for electing 3%~10%, H as is preferably 0.3%~8%, Ti is preferably 46%~53%, O matter
It is preferably 30%~50% to measure fraction.The formula of Li-H-Ti-O compounds can be Li(0.43~1.44)H(0.29~7.93)
Ti(0.96~1.11)O(1.88- σ~3.13- σ), wherein 0≤σ≤1.81.Exist in the Li-H-Ti-O compounds enough crystallizations water and/or
Constitution water, Li-H-Ti-O compounds are made to be able to maintain that layered crystal structure.
In more preferred embodiment, in Li-H-Ti-O compounds, Li mass fraction is preferably 4%~12%, H
Mass fraction be preferably that 0.1%~5%, Ti mass fraction is preferably that 48%~56%, O mass fraction is preferably 28%
~47%.The formula of Li-H-Ti-O compounds can be Li(0.58~1.73)H(0.10~4.96)Ti(1.00~1.17)O(1.75- σ~2.93- σ), its
In 0≤σ≤1.73.In this embodiment, a part of Li, Ti and O element can be with the Li of nanostructured4Ti5O12And TiO2Shape
Formula is present, and these nanostructureds are dispersed in Li-H-Ti-O layered crystal structures.
In one embodiment, the Li-H-M-O systems compound can be by by Li-M-O nano materials and acidic aqueous solution
Reacted to obtain.The Li-M-O nano materials for example can be Li4Ti5O12、LiMn2O4、LiMnO2、LiCoO2、LiNiO2、
Li2MoO4And Li3VO4At least one of.The Li-M-O nano materials can be carried out with the sour aqueous solution at normal temperatures and pressures
Reaction, hydro-thermal reaction can also be carried out in 80~200 DEG C and acid.Acid can be nitric acid, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, oxalic acid
And at least one of hydrofluoric acid, concentration can be 0.1~0.8mol/L.Powder is obtained after reaction to be carried further across separation
It is pure, Li-H-M-O nano material powders are dried to obtain, drying temperature is preferably less than 120 DEG C.The functional material layer 32
Thickness is preferably 10nm~200 μm, and surface density is preferably 0.1~30mg/cm2。
Preferably, the material of the functional material layer 32 further comprises electronic conductive material and binding agent, the electricity
Subconductivity material and binding agent uniformly mix with the Li-H-M-O systems compound.The Li-H-M-O systems compound is in institute
It is preferably 5%~99% to state the weight/mass percentage composition in functional material layer 32.The matter of the electronic conductive material and binding agent
Measure ratio preferably 1:9~9:1.
Preferably, the electronic conductive material is selected from activated carbon, graphene, CNT, Ketjen black, Super P, acetylene
At least one of black and graphite.
Preferably, 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 select
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 mix 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 realizes at least one of above-mentioned function (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 completely cut off electronics and make lithium ion by, can be any one in organic polymer barrier film or anodic aluminium oxide membrane, such as
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 includes 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, such as 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 on 30 at least one surface of barrier film.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 Li-H-M-O system compounds is coated in the sulfur-based positive electrode 10, lithium base negative pole 20 and barrier film 30 at least
The surface of one, 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 Li-H-M-O systems compound in the solidliquid mixture, and can further comprise the electricity
Subconductivity material and the binding agent.Solid phase liquid phase is preferably solvent in the solidliquid mixture, the Li-H-M-O architectures
Compound, electronic conductive material, binding agent and solvent uniformly mix.The solvent functions as the Li-H-M-O architectures
The carrier of compound, it is therefore desirable to selection can not dissolve the Li-H-M-O systems compound, not with the Li-H-M-O architectures
Compound chemically reacts, and the solvent that can be removed completely under lower temperature (such as 30~120 DEG C), such as water or low molecule
Measure volatile organic solvent, can adjoin selected from N- methyl pyrrolidone, water, methanol, ethanol, propyl alcohol, isopropanol, second eyeball, acetone and
One or more in 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 slurry and mixed liquor, and the ratio of solid-liquid two
The selection of example can be carried out according to being actually needed, such as be determined according to the mode of coating.Certainly, to make coating easily carry out, slurry
It is preferred that there is suitable mobility；And be to make coating more efficiently, solid phase preferably has suitable ratio in mixed liquor.The painting
The mode covered for example can be 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 solidliquid mixture is formed into coating by the step of coating
Afterwards, it is only necessary to remove the solvent in coating, you can obtain the functional material layer 32.Therefore, the solid-liquid can be mixed
Thing is coated in the element surface needed.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
Single or double coated on the barrier film 30.
, can after by surface of the solidliquid mixture coated 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 Li-H-M-O system compounds in the functional material layer 32
Still there is hydrogen component.
On the surface of needs, such as the surface of positive electrode material layer 12 of sulfur-based positive electrode 10 and/or an at least surface for barrier film 30
After forming 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, described the step of being stacked, makes the functional material layer 32 be layered in the sulfur-based positive electrode
Between 10 and the barrier film 30.For example, form 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 at least table in the barrier film 30
After face forms 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, described the step of being stacked, makes the functional material layer 32 be layered in the barrier film 30
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.
Functional material layer 32 based on the system compound by Li-H-M-O is deposited in lithium-sulfur cell with absorption
The effect of more lithium sulfides is stored up and/or be catalyzed, and by the introducing of hydrogen component, improves Li-H-M-O bodies in functional material layer 32
The crystal structure of based compound and the diversity of nanometer dimension, improve the ionic conductivity of functional material layer 32.Pass through hydrogen
The introducing of component can improve the specific surface area of material, and bigger specific surface area can provide more avtive spots, Jin Ergao
Effect, which plays, suppresses the effect that more lithium sulfides shuttle, and lifts the chemical property and security performance of lithium-sulfur cell.
The technical scheme of the application, which has been broken, thinks that water can produce to the chemical property and security of lithium-sulfur cell in tradition
The idea of raw harm, find and be experimentally confirmed to introduce hydrogen component 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
The energy storage fields such as lithium-sulfur cell of the lithium-sulfur cell of property material layer 32 in electric automobile, energy-accumulating power station and Large Copacity electronic product
Have broad application prospects.
In addition, the most methods for preparing Li-H-M-O system compounds be wet chemistry method (such as hydrothermal synthesis method or
Sol-gal process), the product that these methods obtain is often hydrate, and the high temperature heat treatment that will pass through in tradition removes production
Hydrogen component in thing.And Li-H-M-O systems compound is directly eliminated into the heat treatment for functional material layer 32 and removed water
The step of, effectively reduce conventional method in energy consumption and pollution, material preparation process is gently controllable, new energy, new material with
And energy-conserving and environment-protective industrial field is respectively provided with important influence and meaning.
Embodiment 1
1) preparation of Li-H-M-O systems compound base functional material layer：By Li1.81H0.19Ti2O5-σ(σ represents that oxygen is empty
Position), Super P and PVDF be according to 8:1:1 mass ratio, which is added to N- methyl and adjoined, is mixed into slurry in pyrrolidone, then use
The tape casting one side on polypropylene diaphragm coats above-mentioned slurry, then slurry is dried in vacuo 10 hours at 60 DEG C, that is, is had
There is the composite diaphragm (hereinafter referred to as PP C＆LHTO-1) of Li-H-Ti-O system compound base functional material layers.PP@C&LHTO-
SEM (SEM) figure of functional material layer is as shown in Figure 3 in 1.
2) assembling of lithium-sulfur cell：Sulphur positive pole is prepared with sublimed sulfur, metal lithium sheet is negative pole, and PP@C＆LHTO-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＆LHTO-1 in embodiment 1 are only being replaced with commercialization lithium battery with poly- by difference
Propylene barrier film (hereinafter referred to as PP), assembles 2032 type button cells same as Example 1, and difference is only by PP@C＆LHTO-1
Replace with PP.
Comparative example 2
Same as Example 1, difference is only by the Li in embodiment 11.81H0.19Ti2O5-σAfter 350 DEG C of thermal dehydrations
Obtain Li4Ti5O12-TiO2(hereinafter referred to as LTO-1) material, and by functional material layer preparation process in embodiment 1
Li1.81H0.19Ti2O5-σLTO-1 is substituted for, obtains composite diaphragm (the hereinafter referred to as PP@C＆ with Li-Ti-O system material coatings
LTO-1), 2032 type button cells same as Example 1 are assembled, PP@C＆LHTO-1 are only being replaced with PP@C＆LTO- by difference
1。
The test of battery performance
In discharge and recharge blanking voltage it is respectively to be carried out in 2.7V and 1.8V voltage range using LAND battery test systems
Constant current charge-discharge circulates, the electrochemistry cycle characteristics of testing example 1 and comparative example 1-2 button cell, the test number of battery
According to as shown in Table 1 and Table 2.Fig. 4 is to use PP lithium-sulfur cell in 0.2C using PP@C＆LHTO-1 and comparative example 1 in embodiment 1
Under cycle performance comparison diagram.Fig. 5 is cycle performance and storehouse of the embodiment 1 using PP@C＆LHTO-1 lithium-sulfur cell under 1C
Human relations efficiency chart.Fig. 6 is the multiplying power for the lithium-sulfur cell for using PP@C＆LTO-1 in embodiment 1 using PP@C＆LHTO-1 and comparative example 2
Performance comparison figure.
Table 1
| Current ratio | First discharge specific capacity | A specific capacity is put in n-th circulation | |
| Embodiment 1 | 0.2C | 1714mAh/g | 823mAh/g, N=200 |
| Embodiment 1 | 1C | 765mAh/g | 300mAh/g, N=2400 |
| Comparative example 1 | 0.2C | 979mAh/g | 285mAh/g, N=200 |
Table 2
| Current ratio | The specific discharge capacity of embodiment 1 | The specific discharge capacity of comparative example 2 |
| 0.1C | 1212mAh/g | 1062mAh/g |
| 0.2C | 1066mAh/g | 886mAh/g |
| 0.5C | 786mAh/g | 593mAh/g |
| 1C | 646mAh/g | 454mAh/g |
| 2C | 527mAh/g | 333mAh/g |
| 5C | 358mAh/g | 202mAh/g |
Contrasted by Fig. 4 cycle performance and can be seen that the lithium-sulfur cell for using PP@C＆LHTO-1 discharge capacity height first
Up to 1714mAh/g, and discharge capacity is only 979mAh/g first using PP control Battery pack.After 200 circulations, use
PP C＆LHTO-1 lithium-sulfur cell remains to keep 823mAh/g stable specific capacity, is the control Battery pack specific capacity using PP
2.9 times.As seen in Figure 5, under 1C big multiplying power, using PP@C＆LHTO-1 lithium-sulfur cell up to 2400 times
Circulation after still have 300mAh/g reversible specific capacity, close to 100%, " the shuttle effect " of more lithium sulfides substantially subtracts coulombic efficiency
Weak, battery shows very excellent big rate capability and cyclical stability.
Advantage of the hydrogeneous component in lithium-sulfur cell is investigated with PP@C＆LTO-1 and PP@C＆LHTO-1 contrasts.Can by Fig. 6
To find out, compared to PP@C＆LTO-1, PP@C＆LHTO-1 battery specific capacity can be made to lift 14.1% (0.1C), 20.3% respectively
(0.2C), 32.5% (0.5C), 42.3% (1C), 58.3% (2C), especially still maintain 358mAh g under 5C big multiplying power-1
Specific capacity, be nearly 2 times of PP@C＆LTO-1.This is due to a nanometer Li1.81H0.19Ti2O5-σMistake of the crystal structure in high temperature dehydration
Journey often will be roughened and reunite, and material granule becomes large-sized, and specific surface area is greatly reduced, and then reduce living in material
The absorbing and storing of the point-to-points lithium sulfide in property position and catalytic action；In addition, Li1.81H0.19Ti2O5-σTwo-dimensional layered structure also at any time
Disappear, be changed into three-dimensional structure, the Ion transfer ability of material reduces, and it is unsatisfactory to ultimately result in chemical property.
Embodiment 2
1) preparation of the functional material layer with Li-H-M-O system compounds：By Li0.71H0.49Mn1.73O3.88, section's qin
Black and PVDF is according to 7:2:1 mass ratio, which is added in alcohol solvent, is mixed into slurry, then using rotary coating in poly- second
The above-mentioned slurry of dual coating on alkene barrier film, then slurry is dried in vacuo 10 hours at 80 DEG C, that is, obtain with Li-H-Mn-O bodies
The composite diaphragm (hereinafter referred to as PE@C＆LHMO-2) of based compound base functional material layer.
2) assembling of lithium-sulfur cell：Same as Example 1, PP@C＆LHTO-1 are only being replaced with PE@C＆LHMO- by difference
2。
Embodiment 3
1) preparation of the functional material layer with Li-H-M-O system compounds：By 7Li2WO4·4H2O, 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＆LHWO-3) with Li-H-W-O system compound base functional material layers.
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＆LHTO-1 replace with PE/PP@C＆LHWO-3.
Embodiment 4
1) preparation of the functional material layer with Li-H-M-O system compounds：By LiVO3·0.5H2O, CNT
And PTFE is according to 6:3:1 mass ratio, which is added in methanol, is mixed into slurry, then using the tape casting made of 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 with Li-H-V-O
The compound sulfur-based positive electrode (hereinafter referred to as S C＆LHVO-4) of system compound base functional material layer.
2) assembling of lithium-sulfur cell：Using S@C＆LHVO-4 as positive pole, metal lithium sheet is negative pole, and barrier film is the lithium of commercialization
Battery polypropylene-polyethylene-polypropylene diaphragm, electrolyte are the solution that LiTFSI is formed in DME and DOL in the mixed solvent
(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 5
1) preparation of the functional material layer with Li-H-M-O system compounds：By LiMoO3·H2O, graphene and
Kynoar is according to 70:15:15 mass ratio, which is added in ethanol, is mixed into slurry, then porous in PAN using doctor blade method
Film one side coats above-mentioned slurry, then slurry is dried in vacuo 10 hours at 60 DEG C, that is, obtains with Li-H-Mo-O system chemical combination
The composite diaphragm (hereinafter referred to as PAN@C＆LHMO-5) of thing 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＆LHTO-1 replace with PAN@C＆LHMO-5.
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) presoma that is prepared often has hydrogen component (crystallization water or constitution water).And traditionally carry
The compound of the crystallization water need by high-temperature calcination water removal could be used for high voltage organic electrolyte system lithium ion battery or
Lithium-sulfur cell.But present inventor has found, the material after high temperature water removal is for the functional material layer for lithium-sulfur cell
For be and nonideal state.In this application, present inventor is by avoiding high-temperature calcination, the hydrogen group in reserved materials
Point, roughening and reunion of the nanocrystalline structure during high temperature dehydration are avoided, there is Li-H-M-O system compounds
Substantial amounts of avtive spot, by a large amount of avtive spots come absorbing and storing and (or) the more lithium sulfides of catalysis, the suppression more sulphur of lithium-sulfur cell
Change lithium to shuttle.The introducing of protium can not only promote diversity (such as the 2D nanometer sheets, 1D nanotubes/line of material microscopic appearance
With 0D nano particles), the crystal structure (crystal of its more " loose " can also be kept during the quick intercalation/deintercalation of ion
The close heap degree of structure intermediate ion is low, is advantageous to ion diffusion), the diversity (such as two of Li-H-M-O system compound microscopic appearances
Dimension stratiform) ionic conductance of material can be greatly improved, and then it is effectively improved the chemical property of lithium-sulfur cell.In addition, when change
When compound has less crystallite dimension, the more lithium sulfides of physical barrier can be come with the easier organic barrier film hole that is filled in, reached
To the more preferable effect for suppressing the more lithium sulfides of lithium-sulfur cell and shuttling.
Embodiment described above only expresses the several embodiments of the present invention, and its description is 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 (19)
1. a kind of lithium-sulfur cell, including：
Sulfur-based positive electrode；
Lithium base negative pole；
The barrier film being arranged between the sulfur-based positive electrode and the lithium base negative pole；And
The functional material layer being arranged between the sulfur-based positive electrode and the lithium base negative pole, the material of the functional material layer
Including the Li-H-M-O system compounds with Li, H, M and O element, wherein M is transition metal.
2. lithium-sulfur cell according to claim 1, it is characterised in that H is to crystallize in the Li-H-M-O systems compound
Water or constitution water form are present.
3. lithium-sulfur cell according to claim 1, it is characterised in that the transition metal M be selected from titanium, manganese, vanadium,
At least one of tungsten, molybdenum, nickel and cobalt.
4. lithium-sulfur cell according to claim 1, it is characterised in that the formula of the Li-H-M-O systems compound is
Li(0.01~4)H(0.01~8)MO(1- σ~6- σ), and 0≤σ≤1, wherein σ are the amount of Lacking oxygen.
5. lithium-sulfur cell according to claim 1, it is characterised in that the primary particle of the Li-H-M-O systems compound
Grain size be 1 nanometer to 800 nanometers.
6. lithium-sulfur cell according to claim 1, it is characterised in that the specific surface area of the Li-H-M-O systems compound
For 1m2/ g to 600m2/g。
7. lithium-sulfur cell according to claim 1, it is characterised in that the Li-H-M-O systems compound has stratiform brilliant
Body structure.
8. 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 0.1~30mg/cm2。
9. lithium-sulfur cell according to claim 1, it is characterised in that the material of the functional material layer also includes electronics
Conductive material and binding agent, the electronic conductive material and binding agent uniformly mix with the Li-H-M-O systems compound.
10. lithium-sulfur cell according to claim 1, it is characterised in that the functional material layer is arranged on the sulfenyl
Positive pole is towards the surface of the lithium base negative pole, at least one surface of the barrier film, or the lithium base negative pole towards the sulphur
The surface of base positive pole.
11. lithium-sulfur cell according to claim 1, it is characterised in that the functional material layer is arranged on the barrier film
Two surfaces.
12. lithium-sulfur cell according to claim 1, it is characterised in that the Li-H-M-O systems compound is in the work(
Weight/mass percentage composition in energy property material layer is 5%~99%.
13. 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 be arranged on the functional material layer at least one surface of the barrier film, the material of the functional material layer include with Li,
H, the Li-H-M-O system compounds of M and O elements, wherein M are transition metal.
14. 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 are arranged between the sulfur-based positive electrode and the barrier film, the functional material layer
Material includes the Li-H-M-O system compounds with Li, H, M and O element, and wherein M is transition metal.
15. 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 material of the functional material layer includes the Li-H-M-O system compounds with Li, H, M and O element, wherein
M is transition metal.
A kind of 16. 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 are arranged between the functional material layer and the plus plate current-collecting body, the work(
The material of energy property material layer includes the Li-H-M-O system compounds with Li, H, M and O element, and wherein M is transition metal member
Element.
17. 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 Li-H-M-O system compounds with Li, H, M and O element, and wherein M is transition metal
Element.
A kind of 18. application of functional material layer in lithium-sulfur cell, it is characterised in that including：
By the solidliquid mixture of the Li-H-M-O system compounds with Li, H, M and O element coated on the sulfur-based positive electrode, lithium
The surface of at least one of base negative pole and barrier film, so as to form the function between the sulfur-based positive electrode and the lithium base negative pole
Property material layer.
19. application of the functional material layer according to claim 18 in lithium-sulfur cell, it is characterised in that further bag
Include：
The solvent removed in the coating that the solidliquid mixture is formed is dried at being 30~120 DEG C in temperature.
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| PCT/CN2017/110639 WO2019024313A1 (en) | 2017-08-03 | 2017-11-27 | Lithium sulfur battery and assembly thereof, and application of functional material layer in lithium sulfur battery |
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| CN111463414A (en) * | 2020-04-09 | 2020-07-28 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Interlayer material and preparation method and application thereof |
| CN113422153A (en) * | 2021-05-19 | 2021-09-21 | 大连理工大学 | Preparation method of positive electrode side interlayer material for lithium-sulfur battery |
| CN113471402A (en) * | 2021-07-03 | 2021-10-01 | 江西理工大学 | Preparation method of carbon nanotube/lithium vanadate composite membrane with multiple polarization centers and application of composite membrane in catalysis of lithium-sulfur battery reaction |
| CN115411262A (en) * | 2022-09-13 | 2022-11-29 | 江苏正力新能电池技术有限公司 | Preparation method of positive electrode material and battery |
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