CN109309205A - Lithium-sulfur cell cathode, preparation method and lithium-sulfur cell - Google Patents

Lithium-sulfur cell cathode, preparation method and lithium-sulfur cell Download PDF

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Publication number
CN109309205A
CN109309205A CN201710617871.1A CN201710617871A CN109309205A CN 109309205 A CN109309205 A CN 109309205A CN 201710617871 A CN201710617871 A CN 201710617871A CN 109309205 A CN109309205 A CN 109309205A
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lithium
sulfur cell
carbon
carbon composite
metal
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陈鹏
陈立桅
卢威
郇庆娜
沈炎宾
王亚龙
康拓
郭峰
张海洋
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China Amperex Technology Ltd (tianjin)
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China Amperex Technology Ltd (tianjin)
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Priority to CN201710617871.1A priority Critical patent/CN109309205A/en
Priority to PCT/CN2017/105654 priority patent/WO2019019407A1/en
Publication of CN109309205A publication Critical patent/CN109309205A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

Disclose a kind of lithium-sulfur cell cathode, preparation method and lithium-sulfur cell.Lithium-sulfur cell 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 cathode can reduce the current density on cathode of lithium surface, to inhibit the growth of Li dendrite, improve the safety of lithium-sulfur cell, extend the cycle life of lithium-sulfur cell.

Description

Lithium-sulfur cell cathode, preparation method and lithium-sulfur cell
Technical field
The present invention relates to battery technology fields, in particular to lithium-sulfur cell cathode, preparation method and lithium-sulfur cell.
Background technique
Lithium battery has the features such as high-energy density, good cyclical stability, safety, currently used lithium battery master If lithium ion battery, since its operating voltage is high, energy density is big, memory-less effect, has extended cycle life and pollution-free etc. Advantage is widely used in mancarried electronic aid, electric car and power grid energy storage.Commercial lithium ion battery It is the compound to contain elemental lithium as anode, graphite is as cathode, and the specific capacity limit of graphite negative electrodes material is about 370mAh/g, LiFePO4The specific capacity limit of class positive electrode is about 170mAh/g, but is come with mobile internet era Face, electronics miniaturization and electric bicycle, electric car, large-scale energy-accumulating power station enter the rank of extensive development and application Section, has been difficult to further increase the energy density of lithium battery based on this positive and negative pole material, it is difficult to adapt to market to more high energy The demand of metric density lithium battery.Therefore, develop a kind of specific capacity is high, have extended cycle life, battery material that security performance is high especially It is important.
It is ten times of graphite specific capacity, while lithium metal is with most negative since lithium metal has the specific capacity of 3860mAh/g Current potential and most light density, then using lithium metal for cathode, the energy density of lithium battery will be greatly improved.Another party Face, lithium metal are capable of providing sufficient lithium ion as battery cathode, then anode can be higher without lithium member using capacity The material, such as sulphur, air etc. of element.As positive electrode, elemental sulfur has highest theoretical specific capacity (1675mAh/g), with The theoretical specific energy for the lithium-sulfur cell that lithium metal is cathode, elemental sulfur is anode is 2600Wh/kg, in addition, elemental sulfur also has The advantages such as hypotoxicity, amount of storage be big and cheap.Therefore, lithium/sulphur battery system with development potential, becomes high energy in recent years One of research hotspot and emphasis in metric density secondary cell field.
Unfortunately the cycle life of lithium-sulfur cell is limited to lithium anode.Lithium anode is in cyclic process In, it will form dendrite in metallic lithium surface, one side dendrite, which can consume electrolyte with electrolyte contacts, leads to battery failure, another The consumption of aspect lithium metal causes the coulombic efficiency of cathode low.Cause inside battery short in addition, Li dendrite may pierce through diaphragm Cell safety problem is caused on road.
Summary of the invention
One of main object of the present invention is to provide a kind of lithium-sulfur cell cathode, preparation method and lithium-sulfur cell, The current density on cathode of lithium surface can be reduced, to inhibit the growth of Li dendrite, the safety of lithium-sulfur cell is improved, extends lithium The cycle life of sulphur battery.
Present invention employs following technical solutions:
A kind of lithium-sulfur cell 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-sulfur cell 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-sulfur cell is provided in some embodiments, and the lithium-sulfur cell 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 lowers the ratio of cathode of lithium Surface area can effectively inhibit lithium dendrite growth, extend the cycle life of lithium-sulfur cell, improve the coulombic efficiency of battery.
(2) quality of lithium carbon composite on unit area can be adjusted flexibly in the preparation process of lithium-sulfur cell cathode, And then adjust capacity on cathode unit area.It avoids leading because of positive and negative anodes capacity ratio high caused by being difficult to prepare thin lithium metal Cause capacity of negative plates waste.
(3) preparation process is simple, can be mass.
(4) different lithium sulfur battery anode materials can be suitable for.
Detailed description of the invention
Fig. 1 is that the capacity of battery in embodiment 1 keeps curve graph.
Fig. 2 is that the capacity of battery in embodiment 2 keeps curve graph.
Fig. 3 is that the capacity of battery in embodiment 3 keeps curve graph.
Fig. 4 is that the capacity of battery in embodiment 4 keeps curve graph.
Fig. 5 is that the capacity of battery in embodiment 5 keeps curve graph.
Fig. 6 is that the capacity of battery in embodiment 6 keeps curve graph.
Specific embodiment
One aspect of the present invention provides a kind of lithium-sulfur cell 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.Herein, Lithium metal-skeleton carbon composite and lithium alloy-skeleton carbon composite are referred to as lithium carbon composite.
In some embodiments, collector is made of copper foil, nickel foil or other metal foils；Collector can also be by porous Metal material is constituted, including foam metal, punch metal and metal mesh.In some embodiments, the thickness of metal foil can be In 6-20 micron range, surface roughness can be Ra 0.2-0.38.In some embodiments, foam metal may include bubble Foam copper, nickel foam, foamed iron and foamed alloy, such as foam iron-nickel and foam cupro-nickel.The thickness of foam metal can be in 10- Within the scope of 300um, porosity can be within the scope of 30-85%, and pore-size distribution can be 10~150PPI according to different foams Metal material and it is different.
In some embodiments, collector can be formed using punch metal.Punch metal may include punching copper foil etc..
In some embodiments, collector can be the form of metal mesh.For example, collector can be copper mesh.
In some embodiments, in lithium-sulfur cell 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 10-80%, 20-70%, 50%-60% etc..
In some embodiments, porous carbon materials carrier may include carbon fiber microballoon, porous carbon nanotube microballoon and second At least one of acetylene black.
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-sulfur cell 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 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.
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-sulfur cell, and the lithium-sulfur cell includes above-mentioned cathode.
In some embodiments, the anode of lithium-sulfur cell may include elemental sulfur and elemental sulfur and inorganic carbon material or organic The composite material of material is as active electrode material.
In some embodiments, inorganic carbon material used in lithium-sulphur cell positive electrode includes carbon aerogels, graphene and activity At least one of charcoal；Organic material used includes polyacrylonitrile (PAN).
In some embodiments, using the composite material of elemental sulfur and inorganic carbon material or organic material, wherein elemental sulfur Content be in mass 50-85%.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific embodiment 1 is a kind of lithium-sulfur cell 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-sulfur cell 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-sulfur cell 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-sulfur cell 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-sulfur cell 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-sulfur cell 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-sulfur cell 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-sulfur cell cathode according to any one of above-mentioned specific embodiment 1-7, wherein The porous carbon materials include at least one of carbon fiber microballoon, porous carbon nanotube microballoon and acetylene black.
Specific embodiment 9 is the lithium-sulfur cell 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-sulfur cell 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 lithium sulphur battery electrode according to any one of specific embodiment 1-10, wherein institute Lithium alloy is stated to be 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 the electrode according to specific embodiment 11 or 12, wherein the lithium alloy is lithium magnesium Alloy, Li-Si alloy, lithium-aluminium alloy or lithium boron alloy.
Specific embodiment 14 is that a kind of to prepare the lithium-sulfur cell according to any one of specific embodiment 1-13 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 15 is the method according to specific embodiment 14, 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 16 is the method according to specific embodiment 14 or 15, wherein the pressure is 30KPa- 30MPa。
Specific embodiment 17 is a kind of lithium-sulfur cell, wherein the lithium-sulfur cell includes according to specific embodiment 1-13 Any one of described in cathode.
Specific embodiment 18 is the lithium-sulfur cell according to specific embodiment 17, wherein the lithium-sulfur cell is just Pole includes the composite material of elemental sulfur and elemental sulfur and inorganic carbon material or organic material as active electrode material.
Specific embodiment 19 is the lithium-sulfur cell according to specific embodiment 18, wherein the inorganic carbon material packet Include at least one of carbon aerogels, graphene and active carbon；The organic material includes polyacrylonitrile.
Specific embodiment 20 is the lithium-sulfur cell according to specific embodiment 18 or 19, wherein the elemental sulfur and Simple substance sulfur content is 50-85 mass % in the composite material of inorganic carbon material or organic material.
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.It repeats the above process, To prepare the carbon nanotube microballoon used enough.
In the glove box full of argon gas (moisture content and oxygen content are not higher than 10ppm), by 10 grams of LITHIUM BATTERY metals Lithium (Tianjin China Energy Lithium Co., Ltd.) and 5 grams of carbon nanotube microballoons are added in the heater with stainless steel cauldron, heating To 200 degrees Celsius, stirs 1 minute, 100 revs/min of mixing speed, be then heated to 230 DEG C, stir 20 minutes, stir data It 500 revs/min, is cooled to room temperature, 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 on foam copper, and directly as battery, (button cell, CR2025 type, Shenzhen has than source electronics Limit company, similarly hereinafter) cathode pole piece.
Elemental sulfur (Shanghai Aladdin biochemical technology limited liability company, similarly hereinafter) and active carbon are weighed according to the ratio of 2:1 (section of Shenzhen crystalline substance intelligence reaches Science and Technology Ltd.), (ratio of grinding media to material 1:1,500 revs/min of revolving speed, the time 12 hours, solvent was second to ball milling Alcohol), after sintering (argon atmosphere, 100 degrees Celsius, 6 hours), prepare sulphur carbon composite.According to sulphur carbon composite: acetylene Black (AlfaAesar (Alfa Aesar), similarly hereinafter): LA132 (aqueous binders, Chengdu Yindile Power Source Science and Technology Co., Ltd, under Together, mass fraction 5%)=8:1:1 ratio (mass ratio) mixing, be stirred overnight, be coated on a thickness of on 15 micron aluminum foils, Scratching blade thickness used is 200 microns, and 80 degrees Celsius of drying (are greater than 10 hours) overnight, and pole piece unit area sulphur contains after drying Amount is 1.5mg/cm2。
Sulphur carbon anode pole piece is washed into 15 millimeters of diameter of disk as anode, electrolyte is 1mol/L LiTFSI DOL/DME (vol 1/1/1, LiTFSI: bis trifluoromethyl sulfimide lithium or two (trifluoromethane sulfonic acid) imine lithiums, DOL: 1,3-dioxolane, DME: glycol dimethyl ether, similarly hereinafter, and Dongguan Shan Shan battery material Co., Ltd), diaphragm is that PP diaphragm is (deep Section of ditch between fields city crystalline substance intelligence reaches Science and Technology Ltd. Celgard 2400, similarly hereinafter).Test condition is 0.25C constant current charge-discharge, charge and discharge electricity Press range are as follows: 1.5V-2.8V.
Fig. 1 is that the capacity of the battery keeps curve.It can be seen that the negative electrode material can be used for lithium-sulfur cell, after 20 times recycle Its capacity may remain in 80% of initial capacity or more.
Embodiment 2
Lithium carbon composite and cathode pole piece the preparation method is the same as that of Example 1
According to PAN (molecular weight: 150,000, lark prestige Science and Technology Ltd.): elemental sulfur=4:6 ratio weighs each substance, It is roasted 3 hours in 350 degrees Celsius of argon atmospheres, gained is PAN/S composite material.According to PAN/S: acetylene black: LA132=8: 1:1 is stirred overnight, and is coated on 15 microns of aluminium foil, and scratching blade thickness used is 200 microns, the drying of 80 C overnights, Obtained pole piece mass area ratio is 1.77mg/cm2。
PAN/S anode is washed into 15 millimeters of positive plates of diameter as anode, and electrolyte is 1mol/LiTFSI DOL/DME 2% LiNO is added in=1/1 (v/v)3(lithium nitrate) be additive (Suzhou Gan Min chemical reagent Co., Ltd), diaphragm be PP every Film.Test condition is 0.25C constant current charge-discharge, charging/discharging voltage range are as follows: 1.5V-2.8V.
Fig. 2 is that the capacity of the battery keeps curve.It is recycled by 50 times, which keeps 95%.
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 Li-Si alloy (Tianjin Zhong Nengli industry Co., Ltd, lithium content (quality) they are 44%) and 1 gram of carbon nanotube microballoon addition adding with stainless steel cauldron In hot device, 200 degrees Celsius are heated to stir 20 minutes, be cooled to room temperature up to alloy molten, products obtained therefrom is that lithium silicon closes Golden 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 (- 0.1Mpa) dry pole piece overnight, then in a state of excitement by the pole piece of drying The disk that journey diameter is 15 microns, the cathode pole piece as battery.The above process (moisture content in the glove box full of argon gas ≤ 10ppm, oxygen≤10ppm) it carries out.
Elemental sulfur (Shanghai Aladdin biochemical technology limited liability company, similarly hereinafter) and active carbon are weighed according to the ratio of 5:1 (section of Shenzhen crystalline substance intelligence reaches Science and Technology Ltd.), (ratio of grinding media to material 1:1,500 revs/min of revolving speed, the time 12 hours, solvent was second to ball milling Alcohol), after sintering (argon atmosphere, 100 degrees Celsius, 6 hours), prepare sulphur carbon composite.
According to sulphur carbon composite: acetylene black (AlfaAesar (Alfa Aesar), similarly hereinafter): LA132 (aqueous binders, Chengdu Yindile Power Source Science and Technology Co., Ltd, similarly hereinafter, mass fraction 5%)=8:1:1 ratio (mass ratio) mixing, stirring Overnight, being coated on a thickness of blade thickness used on 15 micron aluminum foils, is scratched is 75 microns, first naturally dry, then 80 degrees Celsius Drying (is greater than 10 hours) overnight, and pole piece unit area sulfur content is 0.4mg/cm after drying2。
Battery assembly: electrolyte is 1mol/L LiTFSI DOL/DME, and diaphragm is PP diaphragm.Test condition is 0.25C permanent Flow charge and discharge, charging/discharging voltage range are as follows: 1.5V-2.8V.
Fig. 3 is that the capacity of the battery keeps curve.Battery capacity can still keep 80 or so after 40 circulations, performance compared with Good capacity retention energy.
Embodiment 4
The preparation method of carbon nanotube microballoon is as described in Example 1.
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, content of magnesium (quality) they are 10%) and 1 gram of carbon nanotube microballoon addition adding with stainless steel cauldron In hot device, 200 degrees Celsius are heated to stir 20 minutes, be cooled to room temperature up to alloy molten, products obtained therefrom is that lithium magnesium closes Golden carbon composite.
The preparation method of cathode pole piece is as shown in Example 3.
The preparation method of anode pole piece is as shown in Example 3.
It is as shown in Example 3 that method is put in battery assembly and test.
Fig. 4 is that the battery capacity keeps curve.The battery still is able to keep 75% capacity after 40 circulations.
Embodiment 5
It is as described in example 3 above containing Li-Si alloy carbon composite preparation method.
PAN/S anode pole piece preparation method is as described in Example 2.Wherein blade thickness used is 300 microns, pole after drying Piece unit area sulfur content is 2.3mg/cm2。
Battery assembly and test are as described in example 2 above.
Fig. 5 is that the capacity of the battery keeps curve.Battery can still keep 95% or more capacity after 100 circulations.
Embodiment 6
It is as described in example 4 above containing lithium magnesium alloy carbon composite preparation method.
PAN/S anode pole piece preparation method is as described in example 2 above.Wherein blade thickness used is 300 microns, after drying Pole piece unit area sulfur content is 2.3mg/cm2。
Battery assembly and test are as described in example 2 above.
Fig. 6 is that the capacity of the battery keeps curve.Battery can still keep 95% or more capacity after 100 circulations.
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 (9)

1. a kind of lithium-sulfur cell 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-sulfur cell cathode according to claim 1, it is characterised in that the collector is by porous metal material or gold Belong to foil to constitute；It is preferred that the metal foil includes copper foil, nickel foil；The porous metal material include foam metal, punch metal and Metal mesh.
3. lithium-sulfur cell 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。
4. lithium-sulfur cell 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.
5. lithium-sulfur cell 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.
6. lithium-sulfur cell cathode according to claim 5, it is characterised in that the porous carbon materials include carbon fiber microballoon, At least one of porous carbon nanotube microballoon and acetylene black.
7. a kind of method for preparing lithium-sulfur cell 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.
8. 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.
9. a kind of lithium-sulfur cell, it is characterised in that the lithium-sulfur cell includes bearing described in any one of -7 according to claim 1 Pole.
CN201710617871.1A 2017-07-26 2017-07-26 Lithium-sulfur cell cathode, preparation method and lithium-sulfur cell Pending CN109309205A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112993244A (en) * 2021-02-07 2021-06-18 广东工业大学 Room-temperature full-liquid-state lithium-sulfur battery and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102354759A (en) * 2011-11-04 2012-02-15 上海空间电源研究所 Lithium negative pole, preparation method thereof and battery comprising lithium negative pole
CN103000934A (en) * 2011-09-16 2013-03-27 苏州宝时得电动工具有限公司 Lithium-sulfur battery
CN104659410A (en) * 2015-02-26 2015-05-27 广东烛光新能源科技有限公司 Lithium-sulfur battery 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
CN105529490A (en) * 2016-02-05 2016-04-27 宁波良能新材料有限公司 Preparation method for lithium-sulfur battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103000934A (en) * 2011-09-16 2013-03-27 苏州宝时得电动工具有限公司 Lithium-sulfur battery
CN102354759A (en) * 2011-11-04 2012-02-15 上海空间电源研究所 Lithium negative pole, preparation method thereof and battery comprising lithium negative pole
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
CN104659410A (en) * 2015-02-26 2015-05-27 广东烛光新能源科技有限公司 Lithium-sulfur battery and preparation method thereof
CN105529490A (en) * 2016-02-05 2016-04-27 宁波良能新材料有限公司 Preparation method for lithium-sulfur battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112993244A (en) * 2021-02-07 2021-06-18 广东工业大学 Room-temperature full-liquid-state lithium-sulfur battery and preparation method thereof

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Application publication date: 20190205