CN109309195A - Containing lithium electrode, preparation method and contain the lithium ion battery of the electrode - Google Patents
Containing lithium electrode, preparation method and contain the lithium ion battery of the electrode Download PDFInfo
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- CN109309195A CN109309195A CN201710618561.1A CN201710618561A CN109309195A CN 109309195 A CN109309195 A CN 109309195A CN 201710618561 A CN201710618561 A CN 201710618561A CN 109309195 A CN109309195 A CN 109309195A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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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- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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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
- H01M4/38—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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
It discloses a kind of containing lithium electrode, preparation method and containing the lithium ion battery of the electrode.Containing lithium electrode 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.This, which contains lithium electrode, can inhibit lithium dendrite growth.
Description
Technical field
The present invention relates to battery technology fields, in particular to a kind of to contain lithium electrode, preparation method and application.
Background technique
Lithium ion battery is answered extensively because of the advantages that its specific energy is high, cell voltage is high, working range is wide, storage life is long
For communicating, electric car, the fields such as energy storage.Cathode is four big component part (anode, cathode, diaphragm and electricity of lithium ion battery
One of solve liquid), most of used negative electrode material is graphite type material currently on the market, such material price is cheap, safety.
But the specific capacity of its material is lower (372mAh/g), cycle life is general, the poor battery that limits of high rate performance is to higher property
The direction of energy is developed.Lithium anode has most negative electrode potential (- 3.04vs standard hydrogen electrode), high specific discharge capacity
(3860mAh/g), low density (most light metal) and be widely noticed.During lithium metal deposition, due to lithium metal table
Face it is uneven, cause lithium metal preferentially in certain site depositions, formed ingotism (Li dendrite), one side Li dendrite meeting
It pierces through the solid-state electrolyte layer (SEI) of metallic lithium surface and is reacted with electrolyte, consumption electrolyte leads to battery failure, another party
Face can consume lithium metal and cause coulombic efficiency low.In addition, Li dendrite is possible to pierce through diaphragm, lead to battery short circuit, causes peace
Full problem.
Summary of the invention
One of main object of the present invention is to provide one kind containing lithium electrode, preparation method and application, can be used for inhibiting
Lithium dendrite growth extends battery cycle life.
Present invention employs following technical solutions:
One kind is provided in some embodiments containing lithium electrode, wherein the electrode 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.
It provides in some embodiments and a kind of prepares the above-mentioned method containing lithium electrode, which comprises pass through and apply pressure
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.
A kind of lithium ion battery is provided in some embodiments, and the lithium ion battery includes the above-mentioned lithium electrode that contains as electricity
Pond 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 reduces cathode of lithium surface current density, can effectively inhibit lithium dendrite growth, extend the circulation longevity of lithium ion battery
Life, improves the coulombic efficiency of battery.
(2) in the preparation process containing lithium electrode, lithium carbon composite (powder material on unit area can be adjusted flexibly
Material) quality, and then adjust cathode unit area on capacity.It avoids holding because of positive and negative anodes high caused by being difficult to prepare thin lithium metal
Amount proportion, causes capacity of negative plates to waste.
(3) preparation process is simple, can be mass.
(4) different lithium ion anode materials can be suitable for.
Detailed description of the invention
Fig. 1 is that the charge and discharge cycles capacity of battery in embodiment 1 keeps figure and coulombic efficiency figure；
Fig. 2 is that the charge and discharge cycles capacity of battery in embodiment 2 keeps figure and coulombic efficiency figure；
Fig. 3 is that the charge and discharge cycles capacity of battery in embodiment 3 keeps figure and coulombic efficiency figure；
Fig. 4 is that the charge and discharge cycles capacity of battery in embodiment 4 keeps figure and coulombic efficiency figure；
Fig. 5 is that the charge and discharge cycles capacity of battery in embodiment 5 keeps figure and coulombic efficiency figure；
Fig. 6 is that the charge and discharge cycles capacity of battery in embodiment 6 keeps figure and coulombic efficiency figure；
Fig. 7 is that the charge and discharge cycles capacity of battery in embodiment 7 keeps figure and coulombic efficiency figure.
Fig. 8 is that the charge and discharge cycles capacity of battery in embodiment 8 keeps figure and coulombic efficiency figure.
Fig. 9 is that the charge and discharge cycles capacity of battery in embodiment 9 keeps figure and coulombic efficiency figure.
Figure 10 is that the charge and discharge cycles capacity of battery in embodiment 10 keeps figure and coulombic efficiency figure.
Specific embodiment
One aspect of the present invention provides one kind containing lithium electrode, and the electrode 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.Herein
In, 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 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, 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, be become according to different foam metal materials.
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, mesh number model
It encloses: 100-400 mesh.
In some embodiments, the surface density containing lithium carbon composite in lithium electrode is (on collection liquid surface unit area
Quality) 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%, 60%-65% 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, which provides, a kind of prepares the above-mentioned method containing lithium electrode, comprising: by applying pressure, makes
The lithium carbon composite being dispersed on collection liquid surface, which is attached on collection liquid surface, forms lithium carbon composite layer 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.When using pressure bonding method, lithium carbon composite pressure bonding need to only collected
It, can step acquisition electrode plates on fluid.
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.
The present invention also provides the above-mentioned applications containing lithium electrode.As a typical application, it can be used as lithium containing lithium electrode
The cathode of ion battery.Lithium ion battery refers to the battery constituted to store up lithium compound as positive and negative pole material, circulating battery process
Middle lithium ion is swapped in positive and negative interpolar.Therefore, another aspect of the present invention provides a kind of lithium ion battery, the lithium from
Sub- battery include it is above-mentioned containing lithium electrode as battery cathode.
In some embodiments, the anode of lithium ion battery may include cobalt acid lithium, LiFePO4, LiMn2O4, lithium titanate,
Ni-Co-Mn or Ni-Co-Al ternary material etc. is used as positive electrode active materials.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific embodiment 1 is a kind of containing lithium electrode, and the electrode includes 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 material composition or the electrode material layer include lithium alloy-skeleton carbon composite of micro/nano level.
Specific embodiment 2 is the electrode according to specific embodiment 1, wherein the collector is by porous metals material
Material or metal foil are constituted.
Specific embodiment 3 is the electrode according to specific embodiment 2, wherein the porous metal material includes bubble
Foam metal, punch metal and metal mesh；And/or the metal foil includes copper foil and nickel foil.
Specific embodiment 4 is the electrode according to specific embodiment 3, wherein the foam metal includes foam
Copper, nickel foam, foamed iron, foam iron-nickel and foam cupro-nickel.
Specific embodiment 5 is the electrode according to any one of specific embodiment 1-4, wherein the lithium carbon is compound
Quality of the material on the collection liquid surface unit area is 5-30mg/cm2, preferably 15-25mg/cm2。
Specific embodiment 6 is the electrode according to any one of specific embodiment 1-5, wherein the lithium carbon is compound
Material includes that porous carbon materials carrier and the lithium metal being present in the porous carbon materials carrier hole and surface or lithium close
Gold.
Specific embodiment 7 is the electrode according to any one of specific embodiment 1-6, wherein the lithium carbon is compound
The content of lithium metal or lithium alloy is 10%-95% by percentage to the quality in material.
Specific embodiment 8 is the electrode according to specific embodiment 6, wherein the porous carbon materials include carbon fiber
Tie up at least one of microballoon, porous carbon nanotube microballoon and acetylene black.
Specific embodiment 9 is the electrode according to specific embodiment 8, wherein the porous carbon nanotube microballoon is
It is mutually entwined and is reunited and microballoon being formed, having nanoscale hole on internal and surface, microspherulite diameter are by carbon nanotube
1-100 microns.
Specific embodiment 10 is the electrode according to specific embodiment 9, wherein the ratio of the carbon nanotube microballoon
Surface area 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 specific embodiment 8, wherein the acetylene black is the second of purification
Alkynes gas high temperature completely cuts off air cracking gained.
Specific embodiment 12 is the electrode according to specific embodiment 11, wherein the specific surface area of the acetylene black
For 120-200m2/g；
And/or the partial size of the acetylene black is 20-100nm；
And/or the acetylene black is spherical or subsphaeroidal.
Specific embodiment 13 is the electrode according to any one of specific embodiment 1-12, 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 14 is the electrode according to specific embodiment 13, wherein in lithium alloy lithium weight percent
Than being 70%~99.9%.
Specific embodiment 15 is the electrode according to specific embodiment 13 or 14, wherein the lithium alloy is lithium magnesium
Alloy, Li-Si alloy, lithium-aluminium alloy or lithium boron alloy.
Specific embodiment 16 is a kind of method for preparing the electrode according to any one of specific embodiment 1-15,
The described method includes: making to be dispersed in the lithium carbon composite on collection liquid surface by applying pressure and being attached to collection liquid surface
Upper formation lithium carbon composite layer is 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 17 is the method according to specific embodiment 16, 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 18 is the method according to specific embodiment 16 or 17, wherein the pressure is 30KPa-
30MPa。
Specific embodiment 19 is a kind of lithium ion battery, and the lithium ion battery includes according to specific embodiment 1-15
Any one of described in electrode as battery cathode.
Specific embodiment 20 is the lithium ion battery according to specific embodiment 19, wherein the lithium ion battery
Anode include that cobalt acid lithium, LiFePO4, LiMn2O4, lithium titanate, Ni-Co-Mn or Ni-Co-Al ternary material are living as anode
Property 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≤10ppm, oxygen≤10ppm), by 10 grams of Battery grade lithium metals
(Tianjin China Energy Lithium Co., Ltd.) and 5 grams of carbon nanotube microballoons are added in the heater with stainless steel cauldron, are heated to
It 200 degrees Celsius, stirs 1 minute, 100 revs/min of mixing speed, is then heated to 230 DEG C, stirs 20 minutes, stir data 500
Rev/min, it is cooled to room temperature, products obtained therefrom is lithium carbon composite.Lithium content is about 50% in gained lithium carbon composite.
About 25 milligrams of lithium carbon composite is dispersed in diameter as (foam metal founds in Suzhou Thailand on 15 millimeters of foam copper
Factory, thickness 1.6mm, similarly hereinafter), apply pressure manually and lithium carbon composite is firmly pressed on foam copper, directly as button
Formula battery (non-specified otherwise is 2025 type button cells, and Shenzhen is than source battery Co., Ltd, similarly hereinafter) cathode pole piece.
(take in the fresh 15 millimeters of diameter of iron phosphate lithium positive pole piece Energy Science Co., Ltd in Suzhou, 6.7 milligrams of surface density/flat
Square centimetre, LiFePO4 content is 90%, similarly hereinafter) as anode, electrolyte is 1mol/L LiPF6EC/DMC/EMC
(vol 1/1/1, Dongguan Shan Shan battery material Co., Ltd, similarly hereinafter), diaphragm is that (section of Shenzhen crystalline substance intelligence is limited up to science and technology for PP diaphragm
Company Celgard 2400, similarly hereinafter).Battery testing condition is that 0.25C is recycled 130 times, voltage range 4.1V-2.8V, test
The capacity of battery is kept and coulombic efficiency.
(3 times cyclic activation is electric in figure with coulombic efficiency figure for 140 charge and discharge cycles capacity holding figures of the battery by Fig. 1
Pole).The battery recycles the battery at 140 times still and can keep 70% capacity, and coulombic efficiency is protected in cyclic process
It holds 95%.
Embodiment 2
Lithium carbon composite preparation process is as described in example 1 above.
Preparing for cathode pole piece is as described in example 1 above.
15 millimeters of lithium cobaltate cathode pieces of diameter (section of Shenzhen crystalline substance intelligence reach Science and Technology Ltd., 15 microns of aluminum foil thickness, single side
128 grams/m of active material surface density, activity substance content 95.7%) it is used as anode, electrolyte 1mol/L
LiPF6EC/DMC/EMC (vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.1C recycles 3 times with active cell,
1C is recycled 300 times, and charging/discharging voltage range is 4.2-3V, and the capacity for testing battery is kept and coulombic efficiency.
Fig. 2 is that 300 charge and discharge cycles capacity of the battery keep figure and coulombic efficiency figure.The battery maintains higher library
Human relations efficiency.
Embodiment 3
Lithium carbon composite preparation process is as described in example 1 above.
Preparing for cathode pole piece is as described in example 1 above.
15 millimeters of lithium manganate anode slices of diameter (section of Shenzhen crystalline substance intelligence reach Science and Technology Ltd., 15 microns of aluminum foil thickness, single side
166 grams/m of active material surface density, activity substance content 94.2%) it is used as anode, electrolyte 1mol/L
LiPF6EC/DMC/EMC (vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.1C recycles 3 times with activated electrode,
1C is recycled 300 times, voltage range 4.5V-3.3V, and the capacity for testing battery is kept and coulombic efficiency.
Fig. 3 is that the capacity of the battery keeps curve and coulombic efficiency curve.It can be seen that the battery is in 300 cyclic processes
Middle held stationary, 300 times circulation after can still keep 88% capacity.
Embodiment 4
Lithium carbon composite preparation process is as described in example 1 above.
Preparing for cathode pole piece is as described in example 1 above.
(section of Shenzhen crystalline substance intelligence reaches Science and Technology Ltd. to 15 millimeters of ternary material positive plates of diameter, and Ni:Co:Mn=5:2:3 divides
Minor atomicity ratio, 15 microns of aluminum foil thickness, 121 grams/m of single side active material surface density, activity substance content is
94.2%) it is used as anode, electrolyte is 1mol/L LiPF6EC/DMC/EMC (vol 1/1/1), diaphragm are PP diaphragm.Electricity
Pond test condition is that 0.2C is recycled 200 times, voltage range 4.2V-3V, and the capacity for testing battery is kept and coulombic efficiency.
Fig. 4 is that the capacity of the battery keeps curve and coulombic efficiency curve.It can be seen that battery library in cyclic process
Human relations efficiency is maintained at 95% or more.
Embodiment 5
Lithium carbon composite preparation process is as described in example 1 above.
Preparing for cathode pole piece is as described in example 1 above.
Anode pole piece preparation: N-Methyl pyrrolidone is solvent, and (LTO, section of Shenzhen crystalline substance intelligence reach the limited public affairs of science and technology to lithium titanate
Department, D50:0.5-1.0 microns, specific surface area: 2.0-6.0m2/ g, discharge gram volume >=165mAh/g for the first time, voltage range:
0.8-2.7V, 0.1C, similarly hereinafter) it is positive active material, acetylene black (AB, Alfa Aesar, similarly hereinafter) is conductive agent, polyvinylidene fluoride
Alkene (PVDF, section of Shenzhen crystalline substance intelligence reach Science and Technology Ltd., similarly hereinafter) is binder, mass ratio LTO:AB:PVDF=8:1:1 preparation
Slurry, the solid-to-liquid ratio of slurry are 0.2 gram: 1 milliliter, blade coating (blade thickness is 150 microns), 100 C overnights on aluminium foil
(being greater than 10 hours) drying, is washed into 15 millimeters of diameter of anode pole piece, as anode, electrolyte 1mol/L
LiPF6EC/DMC/EMC (vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.1C recycles 3 times with active cell,
1C is recycled 300 times, voltage range 2.7V-0.8V, and the capacity for testing battery is kept and coulombic efficiency.
Fig. 5 is that the capacity of the battery keeps curve and coulombic efficiency curve.It can be seen that in the process recycling of the battery
Capacity keeps preferably, maintaining essentially in 95%, and coulombic efficiency also may remain in 97% or more substantially.
Embodiment 6
Lithium carbon composite preparation process is as described in example 1 above.
About 25 milligrams of lithium carbon composites are dispersed on the foam copper that diameter is 15 millimeters, apply pressure manually and make lithium
Carbon composite is firmly pressed on foam copper, the negative electrode material as battery.Prepared by anode pole piece: N-Methyl pyrrolidone is
Solvent, lithium titanate (LTO) are positive active material, and acetylene black (AB) is conductive agent, and Kynoar (PVDF) is binder, matter
Amount prepares slurry than LTO:AB:PVDF=8:1:1, and the solid-to-liquid ratio of slurry is 0.2 gram: 1 milliliter, and (scraper is thick on aluminium foil for blade coating
Degree is 150 microns), 100 degrees Celsius of drying are washed into 15 millimeters of diameter of anode pole piece, capacity per unit area: 1.86mAh/cm2
(0.2C), as anode, electrolyte is that 1mol/L LiTFSI DOL/DME (vol 1/1) contains 2%LiNO3Additive (Soviet Union
Zhou Ganmin chemical reagent Co., Ltd), diaphragm is PP diaphragm.Battery testing condition is that 0.1C recycles 3 times with active cell, and 1C is followed
Ring 300 times, voltage range 2.7V-0.8V, the capacity for testing battery is kept and coulombic efficiency.
Fig. 6 is that the capacity of the battery is kept and coulombic efficiency curve.It can be seen that capacity in the process recycling of the battery
96% is substantially remained in, and coulombic efficiency also may remain in 97% or more.
Embodiment 7
Another lithium carbon composite-is prepared using step in the same manner as in Example 1Lithium acetylene black-materials, detailed process
It is as follows:
2g acetylene black (AlfaAesar (Alfa Aesar)) is added in 200 ml deionized waters and 20 milliliters of ethyl alcohol,
130W ultrasonic probe is handled 5 hours, so that acetylene black is uniformly dispersed in a solvent.Later, sample is added in spray dryer,
Setup parameter are as follows: inlet air temperature is 200 DEG C, and leaving air temp is 150 DEG C, atomisation pressure 40MPa, sample volume 500mL/h, spray
The dry gained of mist is spraying acetylene black (partial size 70-80nm).Repeat the above process, with prepare use enough it is spraying
Acetylene black.
In the glove box full of argon gas (moisture content≤1ppm, oxygen≤10ppm), by 5 grams of Battery grade lithium metals and 5
Gram spraying acetylene black is added in the heater with stainless steel cauldron, is heated to 200 degrees Celsius, stirs 1 minute, stirring speed
100 revs/min of degree is then heated to 230 DEG C, stirs 20 minutes, stirs 500 revs/min of data, is cooled to room temperature, and gained produces
Product are lithium acetylene black composite material.The specific capacity of gained lithium acetylene black-materials is 1500mAh/g.
About 20 milligrams of lithium acetylene black composite materials are dispersed on the foam copper that diameter is 15 millimeters, applying pressure manually makes
It obtains lithium carbon composite to be firmly pressed on foam copper, the negative electrode material as battery.
For 15 millimeters of diameter of iron phosphate lithium positive pole piece as anode, electrolyte is 1mol/L LiPF6EC/DMC/EMC
(vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.1C recycles 4 times with activated electrode, and 1C is recycled 300 times, voltage
Range is 4.1V-2.5V, and the capacity for testing battery is kept and coulombic efficiency.Fig. 7 is that the battery capacity keeps curve and coulomb effect
Rate curve.It can be seen that battery capacity can still be maintained 80%, and cycle efficieny is kept at 98% or more after 300 times are followed.
Embodiment 8
Lithium carbon composite preparation process is as described in example 1 above.
According to butadiene-styrene rubber: polystyrene: acetylene black: lithium 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 China, molecular weight 2,000,000, similarly hereinafter) and polystyrene (Sigma-Aldrich is Chinese, and melt index can be 6g/
Min (200 DEG C/5kg), similarly hereinafter) it is 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 is 250 micro-
Rice, copper thickness are 10 microns.The above process is in the glove box full of argon gas (moisture content≤10ppm, oxygen≤10ppm)
It carries out.
For 15 millimeters of diameter of iron phosphate lithium positive pole piece as anode, electrolyte is 1mol/L LiPF6EC/DMC/EMC
(vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.5C is recycled 90 times, voltage range 4.1V-2.5V, test
The capacity of battery is kept and coulombic efficiency.
Fig. 8 is that the battery capacity keeps curve and coulombic efficiency curve.The battery still is able to keep after 90 circulations
70% or more capacity.
Embodiment 9
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 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 (- 0.1Mpa) dry pole piece overnight, then by the pole of drying
Piece is washed into the disk that diameter is 15 microns, the cathode pole piece as battery.The above process (moisture in the glove box full of argon gas
Content≤10ppm, oxygen≤10ppm) it carries out.
For 15 millimeters of diameter of iron phosphate lithium positive pole piece as anode, electrolyte is 1mol/L LiPF6EC/DMC/EMC
(vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.5C is recycled 90 times, voltage range 4.1V-2.5V, test
The capacity of battery is kept and coulombic efficiency.
Fig. 9 is that the battery capacity keeps curve and coulombic efficiency curve.Battery capacity can still be kept after 200 circulations
60% or more.
Embodiment 10
The preparation of carbon nanotube microballoon is as described in example 8 above.
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, stir 20 minutes, be cooled to room temperature, products obtained therefrom is lithium magnesium alloy carbon composite wood
Material.
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 (- 0.1Mpa) dry pole piece overnight, then by the pole of drying
Piece rushes the disk that stroke length is 15 microns, the cathode pole piece as battery.The above process (water in the glove box full of argon gas
Divide content≤10ppm, oxygen≤10ppm) it carries out.
For 15 millimeters of diameter of iron phosphate lithium positive pole piece as anode, electrolyte is 1mol/L LiPF6EC/DMC/EMC
(vol 1/1/1), diaphragm are PP diaphragm.Battery testing condition is that 0.5C is recycled 90 times, voltage range 4.1V-2.5V, test
The capacity of battery is kept and coulombic efficiency.Figure 10 is that the battery capacity keeps curve and coulombic efficiency curve, it can be seen that is passed through
Battery capacity can still keep 90% or more after 90 circulations, and the coulombic efficiency of battery maintains cyclic process to be above 95%, 200
The capacity of battery can still keep 60% or more after secondary circulation.
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. one kind contains lithium electrode, it is characterised in that the electrode includes collector and is attached to multiple with lithium carbon on collection liquid surface
Condensation material be active material electrode material layer, 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.
2. electrode according to claim 1, it is characterised in that the collector is made of porous metal material or metal foil.
3. electrode according to claim 2, it is characterised in that the porous metal material includes foam metal, punch metal
And metal mesh；And/or the metal foil includes copper foil and nickel foil.
4. electrode according to claim 1, it is characterised in that the lithium carbon composite is in the collection liquid surface unit
Quality on area is 5-30mg/cm2。
5. electrode according to claim 1, it is characterised in that the lithium carbon composite include porous carbon materials carrier and
The lithium metal or lithium alloy being present in the porous carbon materials carrier hole and surface.
6. electrode according to claim 1, it is characterised in that lithium metal or lithium alloy contains in the lithium carbon composite
Amount is 10%-95% by percentage to the quality.
7. electrode according to claim 5, it is characterised in that the porous carbon materials include that carbon fiber microballoon, porous carbon are received
At least one of mitron microballoon and acetylene black.
8. a kind of method for preparing electrode described in any one of -7 according to claim 1, it is characterised in that the described method includes:
By apply pressure, make to be dispersed in the lithium carbon composite on collection liquid surface be attached on collection liquid surface formed lithium carbon it is compound
Material layer is 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. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes according to claim 1 described in any one of -7
Electrode as battery cathode.
10. lithium ion battery according to claim 9, it is characterised in that the anode of the lithium ion battery includes cobalt acid
Lithium, LiFePO4, LiMn2O4, lithium titanate, Ni-Co-Mn or Ni-Co-Al ternary material are as positive electrode active materials.
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| CN114068871A (en) * | 2020-07-31 | 2022-02-18 | 天津中能锂业有限公司 | Composite belt with ultrathin lithium layers coated on two surfaces and preparation method thereof |
| CN115763795A (en) * | 2021-09-02 | 2023-03-07 | 天津中能锂业有限公司 | Secondary battery and method for manufacturing the same |
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