CN109309202A - Lithium-oxygen battery cathode, preparation method and lithium-oxygen battery - Google Patents
Lithium-oxygen battery cathode, preparation method and lithium-oxygen battery Download PDFInfo
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- CN109309202A CN109309202A CN201710617327.7A CN201710617327A CN109309202A CN 109309202 A CN109309202 A CN 109309202A CN 201710617327 A CN201710617327 A CN 201710617327A CN 109309202 A CN109309202 A CN 109309202A
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Disclose a kind of lithium-oxygen battery cathode, preparation method and lithium-oxygen battery.Lithium-oxygen battery cathode include collector and be attached on collection liquid surface using lithium carbon composite as the electrode material layer of active material, the electrode material layer is made of lithium metal-skeleton carbon composite of micro/nano level or the electrode material layer includes lithium alloy-skeleton carbon composite of micro/nano level.The lithium-oxygen battery cathode can reduce the current density on cathode of lithium surface, to inhibit the growth of Li dendrite, improves the safety of lithium-oxygen battery, extends the cycle life of lithium-oxygen battery.
Description
Technical field
The present invention relates to battery technology fields, in particular to lithium-oxygen battery cathode, preparation method and lithium-oxygen battery.
Background technique
With the development of economy, traditional fossil fuel is largely using causing global warming and haze harsh weather increasingly tight
Weight, taps a new source of energy as the task of top priority.And electrochmical power source is concerned with its cleaning, efficient, safety.In various chemical-electricals
In source, metal-air battery is shown one's talent because of light, cheap, nontoxic and efficient, wherein the quality specific volume of lithium-oxygen (air)
Amount may be up to 5210Wh/Kg (oxygenous quality), be highest in metal-oxygen (air).
The etching problem of lithium anode is always the critical issue for restricting its development in lithium-oxygen (air) battery.One side
Face lithium-oxygen (air) battery is a unlimited system, and water, carbon dioxide, the nitrogen etc. in air diffuse to lithium anode table
Irreversible reaction occurs for face, leads to battery deterioration.On the other hand, Li dendrite is formed during metallic lithium surface charging (plating lithium) to ask
Topic also seriously affects the safety of battery.
For the Li dendrite for solving the problems, such as lithium-oxygen (air) battery, researcher proposes many methods, such as adds in the electrolytic solution
Enter additive to form stable, solid electrolyte layer (SEI) in metallic lithium surface, or lithium metal is pre-processed in lithium metal
Surface is pre-formed stable artificial SEI layers, or is coated on metallic lithium surface as protective layer using the substance of high-modulus.But
During being circulating battery, artificial SEI layers or protective layer are repeatedly subjected to Li dendrite impact, are eventually destroyed and lose protection
The function of cathode of lithium.
Summary of the invention
One of main object of the present invention is to provide a kind of lithium-oxygen battery cathode, preparation method and lithium-oxygen battery,
The current density on cathode of lithium surface can be reduced, to inhibit the growth of Li dendrite, the safety of lithium-oxygen battery is improved, extends lithium
The cycle life of oxygen cell.
Present invention employs following technical solutions:
A kind of lithium-oxygen battery cathode is provided in some embodiments, and the cathode includes collector and is attached to afflux body surface
On face using lithium carbon composite as the electrode material layer of active material, the electrode material layer by micro/nano level lithium metal-
Skeleton carbon composite composition or the electrode material layer include lithium alloy-skeleton carbon composite of micro/nano level.
A kind of method for preparing above-mentioned lithium-oxygen battery cathode is provided in some embodiments, which comprises by applying
Plus-pressure makes to be dispersed in the lithium carbon composite on collection liquid surface and is attached to formation lithium carbon composite layer on collection liquid surface
As electrode material layer；
Or the slurry containing lithium carbon composite is coated on collection liquid surface, it then dries to be formed containing described
The electrode material layer of lithium carbon composite.
A kind of lithium-oxygen battery is provided in some embodiments, and the lithium-oxygen battery includes above-mentioned cathode.
The present invention can have at least one of following beneficial effect:
(1) lithium carbon composite is made of micro/nano level particle, and the big specific surface of particle effectively increases the ratio of cathode of lithium
Surface area can effectively inhibit lithium dendrite growth, extend the cycle life of lithium-oxygen battery, improve the coulombic efficiency of battery.
(2) quality of lithium carbon composite on unit area can be adjusted flexibly in lithium-oxygen battery cathode preparation method, in turn
Adjust capacity on cathode unit area.It avoids leading to cathode because of capacity of negative plates proportion high caused by being difficult to prepare thin lithium metal
Waste of capacity.
(3) preparation process is simple, can be mass.
Detailed description of the invention
Fig. 1 is battery the 1st time and the 6th cycle charge-discharge curve in embodiment 1.
Fig. 2 is that battery capacity keeps curve graph in embodiment 1.
Fig. 3 is battery the 1st time and the 5th cycle charge-discharge curve in embodiment 2
Fig. 4 is that battery capacity keeps curve graph in embodiment 2.
Fig. 5 is battery the 1st time and the 7th cycle charge-discharge curve in embodiment 3.
Fig. 6 is that battery capacity keeps curve in embodiment 3.
Specific embodiment
One aspect of the present invention provides a kind of lithium-oxygen battery cathode comprising collector and is attached on collection liquid surface
Using lithium carbon composite as the electrode material layer of active material, the electrode material layer by micro/nano level lithium metal-skeleton
Carbon composite composition or the electrode material layer include lithium alloy-skeleton carbon composite of micro/nano level.The present invention
In, lithium-oxygen battery is synonymous with lithia (air) battery, indicates by the oxygen in cathode of lithium and oxygen or surrounding air to constituting
Battery system.In the present invention, lithium metal-skeleton carbon composite and lithium alloy-skeleton carbon composite are referred to as lithium carbon and answer
Condensation material.
In some embodiments, collector is made of metal foil, and metal foil may include copper foil and nickel foil etc..Metal foil
Thickness can be in 6-20 micron range, and surface roughness can be Ra 0.2-0.38.
In some embodiments, negative current collector is made of porous metal material.Porous metal material may include foam
Metal, punch metal and metal mesh etc..
In some embodiments, foam metal may include foam copper, nickel foam, foamed iron and foamed alloy, such as steep
Foam iron nickel and foam cupro-nickel etc..The thickness of foam metal can be within the scope of 10-300mm, and porosity can be in 30-85% range
Interior, pore-size distribution can be 10-150PPI, different according to different foam metal materials.
In some embodiments, collector can be formed using punch metal.Punch metal may include punching copper foil etc.,
Its pore diameter range can be 0.8-25mm, and thickness range can be 0.04-3mm.
In some embodiments, negative current collector can be the form of metal mesh.For example, collector can be copper mesh, mesh
Number range: 100-400 mesh.
In some embodiments, in lithium-oxygen battery cathode the surface density of lithium carbon composite (in collection liquid surface unit plane
Quality in product) it can be 5-30mg/cm2, preferably 15-25mg/cm2。
In some embodiments, lithium carbon composite is the micro/nano level particle or powder that partial size is 20 nanometers -100 microns
End, it includes porous carbon materials carriers and the lithium metal or lithium alloy that are present in porous carbon materials carrier hole and surface.
In some embodiments, the content of lithium metal or lithium alloy can be by percentage to the quality in lithium carbon composite
10%-95%, such as 20-70%, 30-60% etc..
In some embodiments, porous carbon materials carrier may include carbon fiber microballoon, porous carbon nanotube microballoon and second
Acetylene black is at least one.
In some embodiments, porous carbon materials carrier is porous carbon nanotube microballoon, is mutually handed over by carbon nanotube
Twine reunite and formed, on internal and surface with the microballoon of nanoscale hole, microspherulite diameter is 1-100 microns.It is such
Microballoon has approximate solid structure (similar ball of yarn structure), i.e., carbon nanotube or carbon nano-fiber are full of inside microballoon, but
Be entwine reunion carbon nanotube or carbon nano-fiber between there are nanoscale hole, these holes can be used for accommodating metal
Lithium particle.
In some embodiments, it can be 1 μm~100 μ that carbon nanotube microballoon, which is spherical or near-spherical particle, average diameter,
M, preferably 1 μm~25 μm；Specific surface area can be 100~1500m2/ g, preferably 150~500m2/g；Contained hole in microballoon
The pore-size distribution of gap can be 1~200nm, preferably 1~50nm.
In some embodiments, carbon nanotube microballoon at least have tiny spherical solid aggregated structure, spherical aggregated structure,
Any one in spherical aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure.
In some embodiments, carbon nanotube includes in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
Any one or two or more combinations, the carbon nanotube optionally pass through surface-functionalized processing.It modifies in carbon nanotube
The group on surface may be selected from but not limited to-COOH ,-OH ,-NH2Equal groups.
In some embodiments, carbon nanotube microballoon can form dispersion liquid by dispersing carbon nanotube in solvent,
Then it is spray-dried and prepares.For example, preparation method may comprise steps of:
A, carbon nanotube is distributed in dispersion solvent (without surfactant) by ultrasonic treatment, obtains dispersion liquid；
B, the dispersion liquid obtained in step A is sprayed by the nozzle of spray dryer, presetting inlet air temperature and outlet air
Temperature, it is stirring that solution is kept in spray process；
C, cooling, i.e. acquisition carbon nanotube microballoon.
In some embodiments, the solvent use can make carbon nano-tube/carbon nano fabric and nano carbon particle uniform
Dispersion organic and/or inorganic liquid, for example, water, ammonium hydroxide, hydrochloric acid solution, ethyl alcohol, acetone, isopropanol any one or it is more
The combination of kind.
In some embodiments, the solvent can be the mixture of ethyl alcohol and water that volume ratio is 1:10.
In some embodiments, it is 150~250 DEG C that the condition of spray drying, which may include: inlet air temperature, and leaving air temp is
75 DEG C or more, such as 75~150 DEG C, or be 90 DEG C or more；One preferred spray drying condition includes: that inlet air temperature is 190
~210 DEG C, leaving air temp is 90~110 DEG C.
In some embodiments, spray velocity when spray drying can be 1 ml/min to 100 liters/min.
In some embodiments, porous carbon materials carrier is carbon fiber microballoon, the pattern and structure of the carbon fiber microballoon
It is similar with carbon nanotube microballoon, and can be prepared by similar spray drying process.
In some embodiments, porous carbon materials carrier is acetylene black, and acetylene black used is purified acetylene gas in height
The lower isolation air of temperature carries out obtained by thermal cracking, and partial size is 20~100nm, preferred value 70-80nm；Specific surface be 120~
200m2/ g, preferred value are 140~160m2/g。
In some embodiments, lithium carbon composite can by the way that molten metal lithium is mixed with porous carbon skeleton material,
It is obtained after cooling.The mixing may include stirring lithium metal and porous carbon skeleton material under heating (for example, about 200 DEG C)
Mixing immerses porous carbon skeleton material in molten metal lithium.The preparation of lithium carbon composite carries out in an inert atmosphere,
Such as in the glove box of argon atmosphere (water content < 10ppm, oxygen content < 10ppm).
In some embodiments, lithium carbon composite is also passing through screening step using preceding.For example, in the hand of argon gas protection
50-100 the polished standard screen is crossed in casing, collects the lithium carbon composite for passing through sieve pore.
In some embodiments, lithium carbon composite is lithium alloy-skeleton carbon composite, and the lithium alloy is by lithium metal
Formed with selected from one of the following or multiple element: magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc,
Gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium, platinum, gold, mercury, thallium, lead, bismuth and polonium.
In some embodiments, the weight percent of lithium is 70%~99.9% in lithium alloy.
In some embodiments, lithium alloy may be used also in addition to the bianry alloy (such as lithium magnesium alloy, Li-Si alloy etc.) of lithium
To include ternary alloy three-partalloy such as the lithium magnalium, lithium gold and silver ternary alloy three-partalloy of lithium, the quaternary alloy of lithium such as lithium magnalium tin, lithium Au-Ag-Pt
Quaternary alloy, etc..When the lithium alloy is formed by lithium metal and other multiple element, in the lithium alloy, it is based on institute
State the total weight of lithium alloy, the weight percent of the other multiple element is 0.1-30 weight %, preferably 1-25 weight %, simultaneously
And more preferably 10-15 weight %.
In some embodiments, lithium alloy is lithium magnesium alloy, Li-Si alloy, lithium-aluminium alloy, lithium boron alloy and other are more
First derivative.
In some embodiments, lithium alloy-skeleton carbon composite can be prepared by the following method:
(1) by heating lithium metal to 180-220 DEG C of temperature, to obtain molten lithium；
(2) under the stirring of 500-800 revolutions per seconds of revolving speed, molten lithium obtained in step (1) is warming up to 220~
1000 DEG C, one or more element meltings are added and obtain the lithium alloy of molten condition, the element of addition include magnesium, silicon, boron, carbon,
Nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium,
Platinum, gold, mercury, thallium, lead, bismuth and polonium etc.；
(3) molten is in in described obtained in the step (2) under the stirring of 500-800 revolutions per seconds of revolving speed
Porous carbon materials carrier is added in the lithium alloy of state, continues stirring 20-40 minutes, to obtain lithium alloy-skeleton carbon composite.
Another aspect of the present invention provides a kind of method for preparing above-mentioned lithium-oxygen battery cathode, comprising: is pressed by applying
Power makes to be dispersed in the lithium carbon composite on collection liquid surface and is attached to formation lithium carbon composite layer conduct on collection liquid surface
Electrode material layer, or by the slurry containing lithium carbon composite be coated in collection liquid surface on, then dry with formed containing
The electrode material layer of the lithium carbon composite.It, only need to be by lithium carbon composite pressure bonding when using pressure bonding method
It on a current collector, can step acquisition cathode pole piece.
About " collector " and " lithium carbon composite ", referring to the associated description of preceding sections.
In some embodiments, collection liquid surface can will be evenly distributed on by way of manual pressure or mechanical pressurization
On lithium carbon composite pressure bonding in collector.Mechanical pressurization may include using roll squeezer or static pressure machine etc..
In some embodiments, pressure when pressure bonding can be 30KPa-30MPa.
In some embodiments, the electrode material layer for containing the lithium carbon composite, packet are formed using coating method
It includes:
(1) electrode material layer, binder and optional conductive agent containing the lithium carbon composite are dispersed in anhydrous
In solvent (herein, " anhydrous " refers to water content < 50ppm), it is uniform to form the electrode material layer containing the lithium carbon composite
Slurry dispersed therein；
(2) slurry obtained in step (1) is coated on collection liquid surface, is then dried to be formed containing the lithium carbon
The coating of composite material.
Step (1) and (2) carry out in an inert atmosphere, for example, argon gas protection glove box (water content <
10ppm, oxygen content < 10ppm) in or carry out in drying room (dew point be lower than -40 DEG C).
In some embodiments, binder can be the mixture of butadiene-styrene rubber and polystyrene (mass ratio of the two can
Think 1:1), Kynoar (PVDF) or other oil-based solvents etc., make between lithium carbon composite particle, lithium carbon is compound
It is sticked together between material and collector.The molecular weight of butadiene-styrene rubber can be 2,000,000, and the melt index of polystyrene can be with
For 6g/min (200 DEG C/5kg).The mass ratio of binder (butadiene-styrene rubber and polystyrene) and lithium carbon composite can for 5~
10:95~90.
In some embodiments, solvent can be for paraxylene etc., for dissolving binder, while by binder and lithium carbon
Composite material is uniformly mixed.In some cases, the mass ratio of solvent and binder dispersed therein and lithium carbon composite
It can be 10~15:1.
In some embodiments, the slurry containing lithium carbon composite can be coated in afflux body surface by the following method
On face: electrostatic spraying scratches, painting, spin coating and drop-coating.
Another aspect of the present invention provides a kind of lithium-oxygen battery, and the lithium-oxygen battery includes above-mentioned cathode.
In some embodiments, the anode of lithium-oxygen battery includes collector and the porous carbon for being attached to collection liquid surface
Material.Porous carbon materials are at least one of carbon fiber, carbon nanotube, acetylene black, active carbon or mesoporous carbon.
In some embodiments, first anode sizing agent coating is coated in after being dried on substrate (such as glass plate) and activity is made
Substance film, active matter plasma membrane with a thickness of 100-150 microns.Then active material membrane pressure is made to positive pole on a current collector
Piece, pressure applied 10-15MPa.
Anode sizing agent can be by the way that porous carbon materials, binder and solvent to be mixed in some embodiments.Bonding
Agent can be Kynoar, aqueous binders LA132, aqueous binders LA133, solvent can for N-Methyl pyrrolidone,
At least one of tetrahydrofuran, water.
In some embodiments, the mass ratio of porous carbon materials and binder can be 1:1-1.5 in anode sizing agent.
In some embodiments, plus plate current-collecting body can be made of aluminium foil, porous metal material or carbon paper.Porous metals
Material is identical as the porous metal material of negative current collector, may include foam metal, metal mesh and punch metal, preferably steeps
Foam nickel or foamed iron.
In some embodiments, lithium-oxygen battery is obtained and arranging each component part according to following sequence: positive pole
Piece/diaphragm/electrolyte/cathode pole piece.
In some embodiments, diaphragm can be glass fibre membrane, porous polypropylene (PP) film or porous polyethylene
(PE) film.
In some embodiments, each composition of lithium-oxygen battery is partially disposed in shell, and shell is open system, can be with
Oxygen is absorbed from external environment.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific embodiment 1 is a kind of lithium-oxygen battery cathode, and the cathode includes collector and is attached to collection liquid surface
On using lithium carbon composite as the electrode material layer of active material, the electrode material layer by micro/nano level lithium metal-bone
Frame carbon composite composition or the electrode material layer include lithium alloy-skeleton carbon composite of micro/nano level.
Specific embodiment 2 is the lithium-oxygen battery cathode according to above-mentioned specific embodiment 1, wherein the collector
It is made of porous metal material or metal foil.
Specific embodiment 3 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
Stating porous metal material includes foam metal, punch metal and metal mesh；And/or the metal foil includes copper foil and nickel foil.
Specific embodiment 4 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
Stating foam metal includes foam copper, nickel foam, foamed iron, foam iron-nickel and foam cupro-nickel.
Specific embodiment 5 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
Stating quality of the lithium carbon composite on the collection liquid surface unit area is 5-30mg/cm2, preferably 15-25mg/cm2。
Specific embodiment 6 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
State the gold that lithium carbon composite includes porous carbon materials carrier and is present in the porous carbon materials carrier hole and surface
Belong to lithium or lithium alloy.
Specific embodiment 7 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
State the content of lithium metal or lithium alloy in lithium carbon composite is 10%-95% by percentage to the quality.
Specific embodiment 8 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
Stating porous carbon materials includes at least one of carbon fiber microballoon, porous carbon nanotube microballoon and acetylene black.
Specific embodiment 9 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
Stating porous carbon nanotube microballoon is mutually to be entwined reunite and formed, have nanoscale pore on internal and surface by carbon nanotube
The microballoon of gap, microspherulite diameter are 1-100 microns.
Specific embodiment 10 is the lithium-oxygen battery cathode according to any one of above-mentioned specific embodiment, wherein institute
The specific surface area for stating carbon nanotube microballoon is 100~1500m2/g；
And/or the aperture of hole contained by the carbon nanotube microballoon is 1~200nm；
And/or the carbon nanotube microballoon at least has tiny spherical solid aggregated structure, spherical aggregated structure, class ball
Any one in shape aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure；
And/or the carbon nanotube includes any in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
A combination of one or more, the carbon nanotube optionally pass through surface-functionalized processing.
Specific embodiment 11 is the electrode according to any one of specific embodiment 1-10, wherein the lithium alloy
Formed by lithium metal and selected from one of the following or multiple element: magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur,
Chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium, platinum, gold, mercury, thallium, lead, bismuth and
Polonium.
Specific embodiment 12 is the electrode according to specific embodiment 11, wherein in lithium alloy lithium weight percent
Than being 70%~99.9%.
Specific embodiment 13 is that a kind of to prepare the lithium-oxygen battery according to any one of specific embodiment 1-12 negative
The method of pole, the method comprise the steps that making to be dispersed in the lithium carbon composite attachment on collection liquid surface by applying pressure
Lithium carbon composite layer is formed on collection liquid surface as electrode material layer；
Or the slurry containing lithium carbon composite is coated on collection liquid surface, it then dries to be formed containing described
The electrode material layer of lithium carbon composite.
Specific embodiment 14 is the method according to specific embodiment 13, wherein the application pressure is using manual
The mode of pressurization or mechanical pressurization (for example, by using roll squeezer or static pressure machine).
Specific embodiment 15 is the method according to specific embodiment 13 or 14, wherein the pressure is 30KPa-
30MPa。
Specific embodiment 16 is a kind of lithium-oxygen battery, wherein the lithium-oxygen battery includes according to specific embodiment 1-12
Any one of described in cathode.
Specific embodiment 17 is the lithium-oxygen battery according to specific embodiment 16, the anode of the lithium-oxygen battery by
Collector and the porous carbon materials being attached on collection liquid surface are constituted.
Specific embodiment 18 is the lithium-oxygen battery according to specific embodiment 17, wherein the porous carbon materials packet
Include at least one of carbon fiber, carbon nanotube, acetylene black, active carbon and mesoporous carbon.
Specific embodiment 19 is the lithium-oxygen battery according to any one of specific embodiment 16-18, wherein described
Lithium-oxygen battery anode by by anode sizing agent coated substrate and dry be made active matter plasma membrane, the anode sizing agent include it is more
Then hole carbon material, binder and solvent active material membrane pressure are made on a current collector by way of pressurization.
Specific embodiment 20 is the lithium-oxygen battery according to specific embodiment 19, wherein the binder is poly- inclined
Vinyl fluoride, aqueous binders LA132, aqueous binders LA133；The solvent is N-Methyl pyrrolidone, tetrahydrofuran and water
At least one of.
Specific embodiment 21 is the lithium-oxygen battery according to any one of specific embodiment 17-20, wherein described
Collector includes nickel foam and foamed iron.
Specific embodiment 22 is the lithium-oxygen battery according to any one of specific embodiment 16-21, wherein described
Lithium-oxygen battery is constituted and arranging each component part according to following sequence: anode pole piece/diaphragm/electrolyte/cathode pole piece.
Specific embodiment 23 is the lithium-oxygen battery according to specific embodiment 22, wherein the lithium-oxygen battery is each
Component part is placed in the housing, and shell is open system.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Postscript, used various products structural parameters, various reaction partners and technique item among following examples
Part is more typical example, but is verified by inventor's a large number of experiments, in the other different structures of those listed above
Parameter, other types of reaction partner and other process conditions are also applicable, and also equal attainable cost invention is claimed
Technical effect.
Embodiment 1
2g multi-wall carbon tube (Shandong great Zhan nanometers of Co., Ltd) is added in 200 ml deionized waters and 20 milliliters of ethyl alcohol,
130W ultrasonic probe is handled 5 hours, so that carbon pipe is uniformly dispersed in a solvent.Later, spray dryer (Shanghai is added in sample
Refined journey experimental instruments and equipment limited, model YC-015) in, setup parameter are as follows: inlet air temperature is 200 DEG C, leaving air temp 150
DEG C, atomisation pressure 40MPa, sample volume 500mL/h, spray drying gained are carbon nanotube microballoon.
In the glove box full of argon gas (water and oxygen content are not higher than 10ppm), by 10 grams of Battery grade lithium metal (Tianjin
Zhong Nengli industry Co., Ltd) and 5 grams of carbon nanotube microballoons be added in the heater with stainless steel cauldron, be heated to 200 and take the photograph
Family name's degree stirs 1 minute, 100 revs/min of mixing speed, is then heated to 230 DEG C, stirs 20 minutes, 500 revs/min of mixing speed
Clock is cooled to room temperature, and products obtained therefrom is lithium carbon composite.
About 25 milligrams of lithium carbon composite is dispersed on the foam copper that diameter is 15 millimeters, applies pressure manually and make
Lithium carbon composite is firmly pressed in foam copper (Suzhou Tai Li foam metal factory, thickness 1.6mm), negative directly as battery
Pole material.
Weigh 30 milligrams of active carbons (section of Shenzhen crystalline substance intelligence reaches Science and Technology Ltd.) and 20 milligrams of polytetrafluoroethylene (PTFE) (Shenzhen
Section's crystalline substance intelligence reaches Science and Technology Ltd.) with agate mortar, 2ml N-Methyl pyrrolidone (Shanghai Aladdin biochemistry section is then added
Skill limited liability company) it is used as solvent, it grinds 30 minutes.Uniformly mixed sample is scratched by the way of blade coating in glass plate
On, blade thickness is 200 microns, and first natural air drying, then 100 C overnights are dried, and active matter plasma membrane is made, and be cut into
0.5cm*0.5cm square piece, square piece quality are 1.0 milligrams, square piece with a thickness of 150 microns, then with the pressure of 15MPa by pole piece
It is pressed into collector nickel foam, lithium-oxygen battery anode is made.
Used button cell shell is the CR2032 type battery case of repacking, wherein punching on anode shell, so that oxygen
Gas can enter in battery system (similarly hereinafter).Electrolyte is 1M LiPF6EC/DMC/EMC (vol 1/1/1, EC: ethylene carbonate
Ester, DMC: dimethyl carbonate, EMC: methyl ethyl carbonate, Dongguan Shan Shan battery material Co., Ltd, similarly hereinafter), diaphragm is glass fibers
It ties up film (Whatman, similarly hereinafter), by battery as in oxygen atmosphere.
Constant current charge-discharge is carried out under battery 0.025mA electric current, charging/discharging voltage section is 2.0-4.3V.Fig. 1 is simulation electricity
Pond charging and discharging curve, it is known that using lithium carbon composite as negative electrode material, formed using the cathode of lithium and anode of above-mentioned method preparation
Battery can work normally.Fig. 2 is that the button cell capacity keeps curve, it can be seen that the lithium-oxygen battery can recycle 6 times.
Embodiment 2
2g multi-wall carbon tube (Shandong great Zhan nanometers of Co., Ltd) is added in 200 ml deionized waters and 20 milliliters of ethyl alcohol,
130W ultrasonic probe is handled 5 hours, so that carbon pipe is uniformly dispersed in a solvent.Later, spray dryer (Shanghai is added in sample
Refined journey experimental instruments and equipment limited, model YC-015) in, setup parameter are as follows: inlet air temperature is 200 DEG C, leaving air temp 150
DEG C, atomisation pressure 40MPa, sample volume 500mL/h, spray drying gained are carbon nanotube microballoon.It repeats the above process,
To prepare the carbon nanotube microballoon used enough.
In the glove box full of argon gas (moisture content≤10ppm, oxygen≤10ppm), by 2 grams of Li-Si alloy (Tianjin
Zhong Nengli industry Co., Ltd, wherein the content (quality) of lithium is 44%) and 1 gram of carbon nanotube microballoon be added with stainless steel reaction
In the heater of kettle, 200 degrees Celsius are heated to stir 20 minutes, be cooled to room temperature, products obtained therefrom is up to alloy molten
Li-Si alloy carbon composite.
According to butadiene-styrene rubber: polystyrene: acetylene black: Li-Si alloy carbon composite: paraxylene=20mg:20mg:
40mg:320mg:1.5ml weighs each substance, is placed in vial and is stirred overnight and (is greater than 10 hours).Wherein butadiene-styrene rubber
(Sigma-Aldrich is Chinese, and melt index can be with for (Sigma-Aldrich China, molecular weight 2,000,000, similarly hereinafter) and polystyrene
It is for 6g/min (200 DEG C/5kg), similarly hereinafter) binder, acetylene black is conductive agent, paraxylene (water content≤50ppm, Shanghai
Aladdin biochemical technology limited liability company, similarly hereinafter) it is solvent.The slurry stirred evenly is coated on copper foil, blade thickness
It is 250 microns, copper thickness is 10 microns.60 DEG C of vacuum dry (be greater than 10 hours, -0.1MPa) overnight.By the pole piece of drying
It is washed into the disk that diameter is 15 millimeters, the cathode as lithium-oxygen battery.(moisture contains the above process in the glove box full of argon gas
Amount≤10ppm, oxygen≤10ppm) it carries out.
The preparation process of the anode pole piece of lithium-oxygen battery is as described in example 1 above.
The Integration Assembly And Checkout of lithium-oxygen battery is as described in example 1 above.
Fig. 3 is the charging and discharging curve of the 1st time and the 6th time of lithium-oxygen battery circulation, use Li-Si alloy-carbon composite for
Active material prepares cathode pole piece by the method for coating, can lithium-oxygen battery be worked, and battery appearance with higher
Amount.Fig. 4 is that the capacity of the lithium-oxygen battery keeps curve, as can be seen that the battery can keep 5 circulations from curve.
Embodiment 3
2g multi-wall carbon tube (Shandong great Zhan nanometers of Co., Ltd) is added in 200 ml deionized waters and 20 milliliters of ethyl alcohol,
130W ultrasonic probe is handled 5 hours, so that carbon pipe is uniformly dispersed in a solvent.Later, spray dryer (Shanghai is added in sample
Refined journey experimental instruments and equipment limited, model YC-015) in, setup parameter are as follows: inlet air temperature is 200 DEG C, leaving air temp 150
DEG C, atomisation pressure 40MPa, sample volume 500mL/h, spray drying gained are carbon nanotube microballoon.It repeats the above process,
To prepare the carbon nanotube microballoon used enough.
In the glove box full of argon gas (moisture content≤10ppm, oxygen≤10ppm), by 2 grams of lithium magnesium alloy (Tianjin
Zhong Nengli industry Co., Ltd, wherein content of magnesium (quality) is 10%) and 1 gram of carbon nanotube microballoon be added with stainless steel cauldron
Heater in, be heated to 200 degrees Celsius to stir 20 minutes, be cooled to room temperature, products obtained therefrom is lithium up to alloy molten
Magnesium alloy carbon composite.
According to butadiene-styrene rubber: polystyrene: acetylene black: lithium magnesium alloy carbon composite: paraxylene=20mg:20mg:
40mg:320mg:1.5ml weighs each substance, is placed in vial and is stirred overnight and (is greater than 10 hours).Wherein butadiene-styrene rubber and poly-
Styrene is binder, and acetylene black is conductive agent, and paraxylene is solvent.The slurry stirred evenly is coated on copper foil, is scraped
For knife with a thickness of 250 microns, copper thickness is 10 microns.60 DEG C of vacuum dry (be greater than 10 hours, -0.1MPa) overnight.It will drying
Pole piece to be washed into diameter be 15 millimeters of disk, the cathode as lithium-oxygen battery.The above process is in the glove box full of argon gas
(moisture content≤10ppm, oxygen≤10ppm) carries out.
The preparation process of the anode pole piece of lithium-oxygen battery is as described in example 1 above.
The Integration Assembly And Checkout of lithium-oxygen battery is as described in example 1 above.
Fig. 5 is the charging and discharging curve of the 1st time and the 7th time circulation of lithium-oxygen battery, is prepared using above-mentioned material and method negative
Pole pole piece can make lithium-oxygen battery work.And battery capacity with higher.
Fig. 6 is that the capacity of the lithium-oxygen battery keeps curve, as can be seen that the battery can maintain 7 circulations from curve.
It should be appreciated that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the invention, it is all at this
Made any modifications, equivalent replacements, and improvements etc., should be included in protection model of the invention within the spirit and principle of invention
Within enclosing.
Claims (10)
1. a kind of lithium-oxygen battery cathode, it is characterised in that the cathode include collector and be attached on collection liquid surface with lithium
Carbon composite is the electrode material layer of active material, and the electrode material layer is compound by lithium metal-skeleton carbon of micro/nano level
Material composition or the electrode material layer include lithium alloy-skeleton carbon composite of micro/nano level.
2. lithium-oxygen battery cathode according to claim 1, it is characterised in that the collector is by porous metal material or gold
Belong to foil to constitute.
3. lithium-oxygen battery cathode according to claim 2, it is characterised in that the porous metal material include foam metal,
Punch metal and metal mesh；And/or the metal foil includes copper foil and nickel foil.
4. lithium-oxygen battery cathode according to claim 1, it is characterised in that the lithium carbon composite is in the collector
Quality on surface unit area is 5-30mg/cm2。
5. lithium-oxygen battery cathode according to claim 1, it is characterised in that the lithium carbon composite includes porous carbon
Material carrier and the lithium metal or lithium alloy being present in the porous carbon materials carrier hole and surface.
6. lithium-oxygen battery cathode according to claim 1, it is characterised in that lithium metal or lithium in the lithium carbon composite
The content of alloy is 10%-95% by percentage to the quality.
7. lithium-oxygen battery cathode according to claim 5, it is characterised in that the porous carbon materials include carbon fiber microballoon,
Porous carbon nanotube microballoon and acetylene black are at least one.
8. a kind of method for preparing lithium-oxygen battery cathode described in any one of -7 according to claim 1, it is characterised in that described
Method includes: to make to be dispersed in the lithium carbon composite on collection liquid surface by applying pressure and be attached to shape on collection liquid surface
At lithium carbon composite layer as electrode material layer；
Or the slurry containing lithium carbon composite is coated on collection liquid surface, then dry to be formed containing the lithium carbon
The electrode material layer of composite material.
9. according to the method described in claim 8, it is characterized in that the pressure that applies is using manual pressure or mechanical pressurization
Mode.
10. a kind of lithium-oxygen battery, it is characterised in that the lithium-oxygen battery includes bearing described in any one of -7 according to claim 1
Pole.
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| CN201710617327.7A CN109309202A (en) | 2017-07-26 | 2017-07-26 | Lithium-oxygen battery cathode, preparation method and lithium-oxygen battery |
| PCT/CN2017/105654 WO2019019407A1 (en) | 2017-07-26 | 2017-10-11 | Lithium-containing electrode, preparation method therefor and lithium battery containing same |
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| CN201710617327.7A CN109309202A (en) | 2017-07-26 | 2017-07-26 | Lithium-oxygen battery cathode, preparation method and lithium-oxygen battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916766A (en) * | 2020-06-24 | 2020-11-10 | 太原理工大学 | Mg-Bi-Ca-In alloy as negative electrode material of magnesium air battery and preparation method thereof |
| CN112670516A (en) * | 2019-11-15 | 2021-04-16 | 华中科技大学 | Three-dimensional composite current collector and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157763A (en) * | 2011-03-09 | 2011-08-17 | 哈尔滨工业大学 | Lithium/air battery |
| CN102468487A (en) * | 2010-11-09 | 2012-05-23 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN102948006A (en) * | 2010-04-27 | 2013-02-27 | 汉阳大学校产学协力团 | Lithium-air battery |
| CN104218275A (en) * | 2013-05-31 | 2014-12-17 | 华为技术有限公司 | Lithium air cell and preparation method thereof |
| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN106953101A (en) * | 2017-03-22 | 2017-07-14 | 中国科学院长春应用化学研究所 | A kind of lithia gas anode of secondary battery and preparation method thereof, lithia gas secondary cell |
| CN106960993A (en) * | 2017-03-09 | 2017-07-18 | 上海空间电源研究所 | Lithium-air battery and its test device |
-
2017
- 2017-07-26 CN CN201710617327.7A patent/CN109309202A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102948006A (en) * | 2010-04-27 | 2013-02-27 | 汉阳大学校产学协力团 | Lithium-air battery |
| CN102468487A (en) * | 2010-11-09 | 2012-05-23 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN102157763A (en) * | 2011-03-09 | 2011-08-17 | 哈尔滨工业大学 | Lithium/air battery |
| CN104218275A (en) * | 2013-05-31 | 2014-12-17 | 华为技术有限公司 | Lithium air cell and preparation method thereof |
| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN106960993A (en) * | 2017-03-09 | 2017-07-18 | 上海空间电源研究所 | Lithium-air battery and its test device |
| CN106953101A (en) * | 2017-03-22 | 2017-07-14 | 中国科学院长春应用化学研究所 | A kind of lithia gas anode of secondary battery and preparation method thereof, lithia gas secondary cell |
Non-Patent Citations (1)
| Title |
|---|
| 沈文忠: "《太阳能光伏技术与应用》", 31 October 2013 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670516A (en) * | 2019-11-15 | 2021-04-16 | 华中科技大学 | Three-dimensional composite current collector and preparation method thereof |
| CN112670516B (en) * | 2019-11-15 | 2023-11-14 | 华中科技大学 | Three-dimensional composite current collector and preparation method thereof |
| CN111916766A (en) * | 2020-06-24 | 2020-11-10 | 太原理工大学 | Mg-Bi-Ca-In alloy as negative electrode material of magnesium air battery and preparation method thereof |
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