CN107579204A - Lithium anode piece and preparation method thereof and lithium metal secondary battery - Google Patents
Lithium anode piece and preparation method thereof and lithium metal secondary battery Download PDFInfo
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- CN107579204A CN107579204A CN201710752590.7A CN201710752590A CN107579204A CN 107579204 A CN107579204 A CN 107579204A CN 201710752590 A CN201710752590 A CN 201710752590A CN 107579204 A CN107579204 A CN 107579204A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Lithium anode piece and preparation method thereof and lithium metal secondary battery, the lithium anode piece include：Collector, formed with metallic lithium layer on collector, formed with composite conductive film on metallic lithium layer.The preparation method of lithium anode piece is：Metallic lithium foil and collector are pressed together, or lithium metal is plated in collection liquid surface；Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added in polyelectrolyte solution and stirred, then mixed solution is coated on metallic lithium layer, after solvent evaporated, composite conductive film is formed on metallic lithium layer surface, obtains lithium anode piece；Or mixed solution is coated on base material, composite conductive film is obtained after solvent evaporated；Composite conductive film is pressed together on metallic lithium layer surface and forms composite conductive film, obtains lithium anode piece.The present invention can suppress Li dendrite, prevent battery short circuit, improve the security performance and cycle performance of lithium battery.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium anode piece and preparation method thereof, and
Use the lithium metal secondary battery of the lithium anode piece.
Background technology
The rechargeable battery that lithium ion battery is made up of positive plate, negative plate, barrier film and electrolyte or electrolyte, its
Because there is energy density height, have extended cycle life and environment-friendly is widely used in mobile communication equipment, notebook
In the electronic products such as computer, digital camera, and gradually played a role in electric vehicle and energy storage field.Lithium ion at present
The negative material of battery uses graphite more, because the theoretical specific capacity of graphite is limited, as market is wanted to battery energy density
More and more higher is sought, a kind of lithium anode negative pole high as theoretical specific capacity is widely studied.
Although lithium anode has very high theoretical specific capacity (3861mAh/g), being used as cathode of lithium battery can improve
Battery energy density, but process that is embedded and deviating from occurs in graphite flake layer not with lithium ion during graphite cathode discharge and recharge
Together, lithium anode happens is that the process of chemical deposition and the dissolving of lithium, this deposition and course of dissolution meeting in discharge and recharge
Sizable Volume Changes are brought, and nonuniform deposition can occur, Li dendrite is produced and punctures barrier film, cause the safe thing of short circuit
Therefore.Therefore, although lithium anode has been widely studied, it yet there are no its commercial applications.
In order to solve the problems, such as lithium anode application in Li dendrite, there is a kind of resolving ideas to be widely used, be exactly
Metallic lithium surface covers layer protecting film.Publication No. CN104966814A Chinese invention patent application discloses a kind of Gao An
Lithium anode of full property and preparation method thereof, this method uses thickness to be vaporized on lithium for 0.02~0.2 μm of silicon substrate protective layer
On powder porous electrode, the security of lithium anode is improved with this.Publication No. CN106159200A Chinese invention patent
Application disclose a kind of lithium anode with protective coating and its preparation and application, using assemble molecular layer and it is inorganic soon from
Sub- conductor layer reaches the mesh for suppressing Li dendrite with this in lithium anode active material layer surface construction solid electrolyte interface film
's.Publication No. CN105489944A Chinese invention patent application discloses the all-solid-state battery system that negative pole is done using lithium metal
Preparation Method, negative material thin layer is coated in metallic lithium surface to suppress Li dendrite.Publication No. CN105489845A middle promulgated by the State Council
Bright patent application discloses a kind of method that all-solid lithium-ion battery sheet metal lithium base negative pole is prepared based on PVD, thin
Layer metallic lithium base negative material surface stringer coat of metal, so as to suppress Li dendrite.Publication No. CN105280886A
Chinese invention patent application disclose lithium anode surface in situ processing method and application, pass through a small amount of phosphorous acid
Treatment fluid and lithium metal and its surface interface protective layer of the passivation layer reaction generation based on lithium phosphate, lithium branch is suppressed with this
It is brilliant.Publication No. CN105845891A Chinese invention patent application discloses a kind of lithium anode with double-decker,
The lithium anode is made up of the metallic lithium layer of bottom and the surface coating on upper strata, and the surface coating is carbon material, gathered
One or more in compound material and glass fibre.The preparation method of several lithium anodes can be to a certain extent above
Suppress Li dendrite, but the influence of lithium dendrite growth can not be completely eliminated, the security performance and cycle performance of lithium metal secondary battery
Remain to be further improved.
The content of the invention
It is an object of the invention to provide a kind of lithium anode piece, Li dendrite can be suppressed, prevent battery short circuit, improved
The security performance and cycle performance of lithium metal secondary battery.
Another object of the present invention is to provide a kind of preparation method of lithium anode piece.
A further object of the present invention is to provide a kind of lithium metal secondary battery with lithium anode piece.
In order to realize above-mentioned first purpose, the present invention takes following technical solution：
Lithium anode piece, including：Collector, formed with metallic lithium layer on the collector, shape on the metallic lithium layer
Into there is composite conductive film.
Optionally, the metallic lithium layer is that metallic lithium foil is pressed on the metallic lithium layer formed on collector；Or metallic lithium layer
It is the metallic lithium layer that lithium metal is plated in collection liquid surface formation.
Optionally, the collector is copper foil or porous copper foil or etching copper foil or copper mesh or nickel screen or foam copper or foam
Nickel.
Optionally, when the collector is copper foil or porous copper foil or etching copper foil, the thickness of collector is less than 20 μm；Institute
When to state collector be copper mesh or nickel screen, the thickness of collector is less than 200 μm；When the collector is foam copper or nickel foam, collection
The thickness of fluid is less than 1000 μm.
Optionally, the thickness of the metallic lithium layer is 1 μm~500 μm.
Optionally, the composite conductive film is to be formed at by conductive agent and the mixed solution that polymer dielectric is mixed
Film on the metallic lithium layer, thickness are 0.1~100 μm.
Optionally, the conductive agent is the one or more in conductive black or CNT or graphene or carbon fiber.
Optionally, polymer dielectric is polyethylene glycol oxide or Kynoar-hexafluoropropene or polyacrylate or gathered
One or more in carbonic ester or polyacrylonitrile.
In order to realize above-mentioned second purpose, the present invention takes following technical solution：
The method for preparing aforementioned metal lithium cathode sheet, step are as follows：
Metallic lithium foil and collector are pressed together, or lithium metal is plated in collection liquid surface, so as in collector
Surface forms metallic lithium layer；
Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added into polymer dielectric
After being stirred in solution, blended solution coating obtains composite conductive film on base material after solvent evaporated；
Composite conductive film is pressed together on metallic lithium layer surface and forms composite conductive film, obtains lithium anode piece.
The method for preparing aforementioned metal lithium cathode sheet, step are as follows：
Metallic lithium foil and collector are pressed together, or lithium metal is plated in collection liquid surface, so as in collector
Surface forms metallic lithium layer；
Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added into polymer dielectric
Stir, be then coated on mixed solution on the metallic lithium layer that previous step obtains, after solvent evaporated, in metal in solution
Lithium layer surface forms composite conductive film, obtains lithium anode piece.
Optionally, the concentration of the polyelectrolyte solution is 1~50%.
In order to realize above-mentioned 3rd purpose, the present invention takes following technical solution：
Lithium metal secondary battery, including：Positive plate, negative plate and barrier film, the negative plate are aforementioned metal lithium cathode sheet.
Optionally, the positive active material that the positive plate uses is LiFePO4 or cobalt acid lithium or ternary material or mangaic acid
Lithium or lithium nickelate or nickel ion doped or lithium-rich manganese base material or sulphur carbon composite anode material.
From above technical scheme, conductive agent and polymer dielectric are mixed and made into composite conductive film by the present invention, will
Composite conductive film is covered on metallic lithium layer, and composite conductive thin film layer can both conduct electronics, can be increased again with conducting lithium ions
The actual surface area of negative pole, so as to reducing the actual current density of negative pole, reach the purpose for suppressing lithium dendrite growth, even if
There is a small amount of lithium dendrite growth, can also be limited in composite conductive film growth inside, will not be grown to positive plate, so as to reduce lithium
Dendrite causes the risk of internal short-circuit of battery, prevents the generation of short-circuit security incident.Using the lithium metal of the lithium anode piece
Secondary cell, arrange in pairs or groups LiFePO4 or cobalt acid lithium or ternary material or LiMn2O4 or lithium nickelate or nickel ion doped or lithium-rich manganese-based material
The positive plate made of positive electrode active materials such as material or sulphur carbon composite anode material, and liquid electrolyte, gel electrolyte or solid
State electrolyte, lithium metal secondary battery is prepared into using lamination process or winding process, compared with common lithium secondary battery, can shown
Write and improve security performance and cycle performance.
Brief description of the drawings
Fig. 1 is the structural representation of lithium anode piece of the present invention.
The embodiment of the present invention is described in more detail below in conjunction with accompanying drawing
Embodiment
In order to which above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention cited below particularly,
It is described below in detail.
As shown in figure 1, the lithium anode piece of the present invention includes collector 1, metallic lithium layer 2 and composite conductive film 3.Afflux
Body 1 can be the conventional current collector materials such as copper foil, porous copper foil, etching copper foil, copper mesh, nickel screen, foam copper or nickel foam.Metal
Lithium layer 2 can be that metallic lithium foil presses together to be formed by way of roll-in or concora crush with collector, or lithium metal is led to
Cross the techniques such as vacuum evaporation and be plated in collection liquid surface and formed.Composite conductive film 3 is a film layer, is being charged for reducing lithium battery
During growth Li dendrite cause the risk of battery short circuit.
The afflux body thickness of the present invention is general thickness, but based on the consideration for improving energy density, more specifically, works as afflux
When body is copper foil, porous copper foil, etching copper foil, thickness is less than 20 μm, and when collector is copper mesh or nickel screen, thickness is less than 200 μ
M, when collector is foam copper or nickel foam, thickness is less than 1000 μm.
The thickness of the metallic lithium layer of the present invention is 1 μm~500 μm.When metallic lithium layer is formed at copper foil, porous copper foil or quarter
When losing on the collectors of type such as copper foil, metallic lithium layer will cover the upper and lower both side surface of foil；When metallic lithium layer is formed at copper
When on the collector of the types such as net, nickel screen, foam copper or nickel foam, upper and lower both sides table of the metallic lithium layer except covering collector
Face, it can also fill to its internal surface.
The laminated film that the composite conductive film of the present invention is mixed for conductive agent with polymer dielectric, thickness 0.1
~100 μm.Conductive agent is that conductive black (including Super P, acetylene black, Ketjen black etc.), CNT, graphene and carbon are fine
One or more in dimension.Polymer dielectric be polyethylene glycol oxide (PEO), Kynoar-hexafluoropropene (PVDF-HFP),
One or more in polyacrylate, makrolon or polyacrylonitrile.
The present invention can form composite conductive film on a current collector using different methods：
Method one：
By metallic lithium foil, by roll-in, either concora crush presses together with collector or lithium metal is passed through into vacuum evaporation
Method is plated in collection liquid surface, so as to form metallic lithium layer in collection liquid surface；
Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added into polymer dielectric
After being stirred in solution, mixed solution is coated on the smooth base material in surface, composite conductive film is obtained after solvent evaporated；
Composite conductive film is pressed together on metallic lithium layer surface by roll-in or concora crush and forms composite conductive film, is produced required
Lithium anode piece.
Method two：
By metallic lithium foil, by roll-in, either concora crush presses together with collector or lithium metal is passed through into vacuum evaporation
Method is plated in collection liquid surface, so as to form metallic lithium layer in collection liquid surface；
Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added into polymer dielectric
Stir, be then coated on mixed solution on the metallic lithium layer that previous step obtains, after solvent evaporated, in metal in solution
Lithium layer surface forms one layer of composite conductive film, you can obtains required lithium anode piece.
The solvent species that the present invention is used to dissolve polymer dielectric is unlimited, can use Conventional solvents, only needs to dissolve and gathers
Polymer electrolyte.The concentration of manufactured polyelectrolyte solution does not have particular/special requirement, generally in the range of 1~50%.
The dosage of conductive agent and polymer dielectric is empirical value, is set according to used material and battery capacity requirement.
The lithium anode piece of the present invention, coordinate conventional cathode piece, barrier film and electrolyte (can if with solid electrolyte
Without barrier film) it can be made into lithium battery.Positive active material can be LiFePO4 or cobalt acid lithium or ternary used by positive plate
Material or LiMn2O4 or lithium nickelate or nickel ion doped or lithium-rich manganese base material or sulphur carbon composite anode material.
Below by specific embodiment and comparative example, the present invention is further illustrated.Arrived used in the description below
Reagent, material and instrument are commercially available as without special explanation, being conventional reagent, conventional material and conventional instrument
Obtain, involved reagent can also be synthesized by conventional synthesis process and obtained.
Embodiment 1
Together with 500 μm of metallic lithium foil is pressed to copper mesh collector；
PEO is dissolved in the polyelectrolyte solution for being made that concentration is 1% in acetonitrile, by Super P (Super P and PEO
Mass ratio be 1:99) add in polyelectrolyte solution and stir, mixed solution is coated on to the lithium metal of collector
On layer, solvent evaporated, the composite conductive film that a layer thickness is 0.1 μm is formed on metallic lithium layer surface, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is LiFePO4, by lithium anode
Piece, iron phosphate lithium positive pole piece, barrier film use winding process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 1
The material and preparation technology of comparative example 1 are same as Example 1, simply no composite conductive film.
Embodiment 2
One layer 1 μm of metallic lithium layer is plated in copper foil surface using vacuum vapour deposition；
PVDF-HFP is dissolved in be made in N,N-dimethylformamide (DMF) concentration be 10% polymer dielectric it is molten
Liquid, by CNT, (CNT and PVDF-HFP mass ratio are 99:1) add in polyelectrolyte solution and stir
It is even, mixed solution is coated on the metallic lithium layer of collector, solvent evaporated, a layer thickness is formed as 1 μm in metallic lithium surface
Composite conductive film, obtain lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is LiFePO4, by lithium anode
Piece, iron phosphate lithium positive pole piece, barrier film use lamination process, and lithium battery is made in collocation gel electrolyte.
Comparative example 2
The material and preparation technology of comparative example 2 are same as Example 2, simply no composite conductive film.
Embodiment 3
The metallic lithium layer of 5 μm of last layer is plated in etching copper foil surface using vacuum vapour deposition；
Carbonate polymer is dissolved in the polyelectrolyte solution that concentration 50% is made in acetone, by acetylene black (second
The mass ratio of acetylene black and carbonate polymer is 50:50) add in polyelectrolyte solution and stir, by mixed solution
It is coated on the smooth base material in a surface, the laminated film that thickness is 100 μm is obtained after solvent evaporated, laminated film is passed through into roller
Metallic lithium layer surface is pressed together on, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is LiFePO4, by lithium anode
Piece, iron phosphate lithium positive pole piece use lamination process, and lithium battery is made in collocation solid electrolyte.
Comparative example 3
The material and preparation technology of comparative example 3 are same as Example 3, simply no composite conductive film.
Embodiment 4
One layer 2 μm of metallic lithium layer is plated on porous copper foil surface using vacuum vapour deposition；
Carbonate polymer is dissolved in the polyelectrolyte solution for being made that concentration is 20% in acetonitrile, by Ketjen black
(mass ratio of Ketjen black and carbonate polymer is 40:60) add in polyelectrolyte solution and stir, will mix
Solution coating is 50 μm of laminated film in obtaining thick on the smooth base material in a surface, after solvent evaporated to degree, and laminated film is led to
Cross roll-in and be pressed together on metallic lithium layer surface, obtain lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is sulphur carbon composite anode material, by gold
Category lithium cathode sheet, sulphur carbon composite anode piece, barrier film use winding process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 4
The material and preparation technology of comparative example 4 are same as Example 4, simply no composite conductive film.
Embodiment 5
One layer 4 μm of metallic lithium layer is plated on foam copper surface using vacuum vapour deposition；
PEO is dissolved in the polyelectrolyte solution for being made that concentration is 2% in acetonitrile, by carbon fiber (carbon fiber and PEO's
Mass ratio is 15:85) add in polyelectrolyte solution and stir, mixed solution is coated on the smooth base material in a surface
On, the laminated film that thickness is 45 μm is obtained after solvent evaporated, laminated film is pressed together on metallic lithium layer surface by roll-in, obtained
To lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is sulphur carbon composite anode material, by gold
Category lithium cathode sheet, sulphur carbon composite anode piece, barrier film use lamination process, and lithium battery is made in collocation gel electrolyte.
Comparative example 5
The material and preparation technology of comparative example 5 are same as Example 5, simply no composite conductive film.
Embodiment 6
Together with 200 μm of metallic lithium foil is pressed to nickel screen collector；
Polyacrylonitrile polymer is dissolved in the polyelectrolyte solution for being made that concentration is 20% in DMF, by graphene (stone
The mass ratio of black alkene and polyacrylonitrile polymer is 70:30) add in polyelectrolyte solution and stir, by mixed solution
It is coated on the metallic lithium layer of collector, solvent evaporated, the composite conducting that a layer thickness is 25 μm is formed on metallic lithium layer surface
Film, obtain lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium nickelate positive electrode, by metal
Lithium cathode sheet, lithium nickelate positive plate, barrier film use winding process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 6
The material and preparation technology of comparative example 6 are same as Example 6, simply no composite conductive film.
Embodiment 7
One layer 10 μm of metallic lithium layer is plated on porous copper foil surface using vacuum vapour deposition；
Polyacrylate polymers are dissolved in the polymer electrolytic for being made that concentration is 10% in 1-METHYLPYRROLIDONE (NMP)
Matter solution, by Super P, (mass ratio of Super P and polyacrylate polymers is 40:60) it is molten to add polymer dielectric
Stirred in liquid, mixed solution is coated on the smooth base material in a surface, thickness is obtained after solvent evaporated be 60 μm answering
Film is closed, laminated film is pressed together on metallic lithium layer surface by concora crush, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium nickelate positive electrode, by metal
Lithium cathode sheet, lithium nickelate positive plate, barrier film use lamination process, and lithium battery is made in collocation gel electrolyte.
Comparative example 7
The material and preparation technology of comparative example 7 are same as Example 7, simply no composite conductive film.
Embodiment 8
Together with 90 μm of metallic lithium foil is pressed to foamed nickel current collector；
PEO is dissolved in be made in acetonitrile concentration be 3% polyelectrolyte solution, by CNT (CNT with
PEO mass ratio is 2:98) add in polyelectrolyte solution and stir, mixed solution is coated on to the metal of collector
In lithium layer, solvent evaporated, the composite conductive film that a layer thickness is 0.5 μm is formed on metallic lithium layer surface, obtains lithium anode
Piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium-rich manganese base material positive electrode,
Lithium anode piece, lithium-rich manganese base material positive plate, barrier film are used into winding process, lithium battery is made in collocation liquid electrolyte.
Comparative example 8
The material and preparation technology of comparative example 8 are same as Example 8, simply no composite conductive film.
Embodiment 9
Together with 50 μm of metallic lithium foil is pressed to foam copper current collector；
By PEO and carbonate polymer according to 1:After 1 mass ratio mixing, it is dissolved in acetonitrile and concentration is made as 5%
Polyelectrolyte solution, by graphene, (mass ratio of graphene and aforementioned polymer electrolyte mixture is 5:95) add
Stirred in polyelectrolyte solution, mixed solution is coated on the metallic lithium layer of collector, solvent evaporated, in metal
Lithium layer surface forms the composite conductive film that a layer thickness is 2 μm, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium-rich manganese base material positive electrode,
Lithium anode piece, lithium-rich manganese base material positive plate, barrier film are used into lamination process, lithium battery is made in collocation gel electrolyte.
Comparative example 9
The material and preparation technology of comparative example 9 are same as Example 9, simply no composite conductive film.
Embodiment 10
The metallic lithium layer of one layer 8 μm of copper foil surface plating is being etched using vacuum vapour deposition；
By carbonate polymer and PVDF-HFP according to 2:After 1 mass ratio mixing, it is dissolved in NMP and concentration is made is
10% polyelectrolyte solution, by carbon fiber, (mass ratio of carbon fiber and aforementioned polymer electrolyte mixture is 3:97)
Add in polyelectrolyte solution and stir, mixed solution is coated on the metallic lithium layer of collector, solvent evaporated,
Metallic lithium layer surface forms the composite conductive film that a layer thickness is 5 μm, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium-rich manganese base material positive electrode,
Lithium anode piece, lithium-rich manganese base material positive plate are used into lamination process, lithium battery is made in collocation solid electrolyte.
Comparative example 10
The material and preparation technology of comparative example 10 are same as in Example 10, simply no composite conductive film.
Embodiment 11
One layer 5 μm of metallic lithium layer is plated in copper mesh using vacuum vapour deposition；
By PVDF-HFP and polyacrylate polymers according to 1:3 mass ratio mixing after, be dissolved in acetonitrile be made it is dense
The polyelectrolyte solution for 6% is spent, (Super P and aforementioned polymer electrolyte mixture mass ratio is by Super P
1:99) add in polyelectrolyte solution and stir, mixed solution is coated on the smooth base material in a surface, is evaporated molten
The laminated film that thickness is 65 μm is obtained after agent, laminated film is pressed together on metallic lithium layer surface by concora crush, obtains lithium metal
Negative plate.
Positive plate is prepared using conventional method, the positive active material on positive plate is tertiary cathode material, by lithium metal
Negative plate, tertiary cathode piece use lamination process, and lithium battery is made in collocation solid electrolyte.
Comparative example 11
The material and preparation technology of comparative example 11 are identical with embodiment 11, simply no composite conductive film.
Embodiment 12
Together with 100 μm of metallic lithium foil is pressed to nickel screen collector；
By polyacrylate, PVDF-HFP and makrolon according to 1:1:After 1 mass ratio mixing, it is dissolved in DMF and makes
Into the polyelectrolyte solution that concentration is 7%, by acetylene black and graphene (acetylene black, graphene and aforementioned polymer electrolysis
The mass ratio of matter mixture is 10:5:85) add in polyelectrolyte solution and stir, mixed solution is coated on a table
On the smooth base material in face, the laminated film that thickness is 20 μm is obtained after solvent evaporated, laminated film is pressed together on gold by concora crush
Belong to lithium layer surface, obtain lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is tertiary cathode material, by lithium metal
Negative plate, tertiary cathode piece and barrier film use winding process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 12
The material and preparation technology of comparative example 11 are identical with embodiment 11, simply no composite conductive film.
Embodiment 13
Together with 50 μm of metallic lithium foil is pressed to foamed nickel current collector；
By PEO and polyacrylonitrile according to 1:After 1 mass ratio mixing, it is dissolved in and concentration is made in tetrahydrofuran as 5%
Polyelectrolyte solution, by graphene, (mass ratio of graphene and aforementioned polymer electrolyte mixture is 1:99) add poly-
Stirred in polymer electrolyte solution, mixed solution is coated on the metallic lithium layer of collector, solvent evaporated, in lithium metal
Layer surface forms the composite conductive film that a layer thickness is 15 μm, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is tertiary cathode material, by lithium metal
Negative plate, tertiary cathode piece and barrier film use winding process, and lithium battery is made in collocation gel electrolyte.
Comparative example 13
The material and preparation technology of comparative example 13 are identical with embodiment 13, simply no composite conductive film.
Embodiment 14
One layer 3 μm of metallic lithium layer is plated on copper foil using vacuum vapour deposition；
Polyacrylonitrile polymer is dissolved in the polyelectrolyte solution for being made that concentration is 30% in DMF, by CNT
(mass ratio of CNT and polyacrylonitrile polymer is 40:60) add in polyelectrolyte solution and stir, will be mixed
Solution coating is closed on the metallic lithium layer of collector, solvent evaporated, a layer thickness is formed on metallic lithium layer surface be 16 μm and answer
Conducting film is closed, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium cobaltate cathode material, by metal
Lithium cathode sheet, lithium cobaltate cathode piece, barrier film use lamination process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 14
The material and preparation technology of comparative example 14 are identical with embodiment 14, simply no composite conductive film.
Embodiment 15
Together with 200 μm of metallic lithium foil is pressed to copper mesh collector；
PEO is dissolved in the polyelectrolyte solution for being made that concentration is 5% in tetrahydrofuran, by Super P (Super P
Mass ratio with PEO is 1:99) add in polyelectrolyte solution and stir, mixed solution is coated on to the gold of collector
Belong in lithium layer, solvent evaporated, the composite conductive film that a layer thickness is 70 μm is formed on metallic lithium layer surface, obtains lithium anode
Piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium cobaltate cathode material, by metal
Lithium cathode sheet, lithium cobaltate cathode piece, barrier film use winding process, and lithium battery is made in collocation gel electrolyte.
Comparative example 15
The material and preparation technology of comparative example 15 are identical with embodiment 15, simply no composite conductive film.
Embodiment 16
Using the metallic lithium layer of vacuum vapour deposition one layer 20 μm of plating on etching copper foil；
Polyacrylate is dissolved in the polyelectrolyte solution for being made that concentration is 3% in NMP, by Super P (Super
The mass ratio of P and polyacrylate is 60:40) add in polyelectrolyte solution and stir, mixed solution is coated on
On the metallic lithium layer of collector, solvent evaporated, the composite conductive film that a layer thickness is 5 μm is formed on metallic lithium layer surface, is obtained
Lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is lithium cobaltate cathode material, by metal
Lithium cathode sheet, lithium cobaltate cathode piece use lamination process, and lithium battery is made in collocation solid electrolyte.
Comparative example 16
The material and preparation technology of comparative example 16 are identical with embodiment 16, simply no composite conductive film.
Embodiment 17
One layer 1 μm of metallic lithium layer is plated on nickel screen using vacuum vapour deposition；
By PEO and polyacrylate according to 1:After 4 mass ratio mixing, the polymerization for being made that concentration is 20% in NMP is dissolved in
Thing electrolyte solution, by Super P and CNT (Super P, CNT and aforementioned polymer electrolyte mixture matter
Amount is than being 1:1:98) add in polyelectrolyte solution and stir, mixed solution is coated on to the metallic lithium layer of collector
On, solvent evaporated, the composite conductive film that a layer thickness is 100 μm is formed on metallic lithium layer surface, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is manganate cathode material for lithium, by metal
Lithium cathode sheet, lithium manganate anode slice, barrier film use lamination process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 17
The material and preparation technology of comparative example 17 are identical with embodiment 17, simply no composite conductive film.
Embodiment 18
Together with 30 μm of metallic lithium foil is pressed to foamed nickel current collector；
PVDF-HFP and PEO is pressed 4:After 1 mass ratio mixing, be dissolved in be made in tetrahydrofuran concentration be 40% it is poly-
Polymer electrolyte solution, by Ketjen black, (Ketjen black, CNT mix my matter with aforementioned polymer electrolyte with CNT
Amount is than being 2.5:2.5:95) add in polyelectrolyte solution and stir, mixed solution is coated on to the metal of collector
In lithium layer, solvent evaporated, the composite conductive film that a layer thickness is 4 μm is formed on metallic lithium layer surface, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is manganate cathode material for lithium, by metal
Lithium cathode sheet, lithium manganate anode slice, barrier film use winding process, and lithium battery is made in collocation gel electrolyte.
Comparative example 18
The material and preparation technology of comparative example 18 are identical with embodiment 18, simply no composite conductive film.
Embodiment 19
Together with 50 μm of metallic lithium foil is pressed to copper foil；
PEO is dissolved in be made in acetonitrile concentration be 3% polyelectrolyte solution, by Super P, CNT and
(Super P, CNT, graphene and PEO mass ratio are 5 to graphene:2:3:90) add in polyelectrolyte solution
Stir, mixed solution is coated on the metallic lithium layer of collector, solvent evaporated, a thickness is formed on metallic lithium layer surface
The composite conductive film for 100 μm is spent, obtains lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is nickel lithium manganate cathode material, by gold
Category lithium cathode sheet, nickel ion doped positive plate, barrier film use winding process, and lithium battery is made in collocation liquid electrolyte.
Comparative example 19
The material and preparation technology of comparative example 19 are identical with embodiment 19, simply no composite conductive film.
Embodiment 20
One layer 1 μm of metallic lithium layer is plated on copper foil using vacuum vapour deposition；
PEO is dissolved in the polyelectrolyte solution for being made that concentration is 2% in acetonitrile, by CNT and graphene (carbon
The mass ratio of nanotube, graphene and PEO is 2:2:96) add in polyelectrolyte solution and stir, by mixed solution
It is coated on the metallic lithium layer of collector, solvent evaporated, the composite conductive film that a layer thickness is 20 μm is formed in metallic lithium surface,
Obtain lithium anode piece.
Positive plate is prepared using conventional method, the positive active material on positive plate is nickel lithium manganate cathode material, by gold
Category lithium cathode sheet, nickel ion doped positive plate use lamination process, and lithium battery is made in collocation solid electrolyte.
Comparative example 20
The material and preparation technology of comparative example 20 are identical with embodiment 20, simply no composite conductive film.
Lithium battery made from embodiment 1-20 and comparative example 1-20 is tested, carry out security test, 25 DEG C,
Battery lithium dendrite growth situation after cycle performance test and circulation under 1C/1C, test result are as shown in table 1.
Table 1
As can be known from the results of Table 1, the lithium anode piece with composite conductive film prepared using the inventive method is made
Lithium battery, increased substantially compared to lithium battery cycle performance made from common metal cathode of lithium, security performance has also obtained pole
Big lifting, significantly inhibiting Li dendrite and reducing lithium dendrite growth causes the risk of battery internal short-circuit.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
Embodiment illustrated herein is not intended to be limited to, and is to fit to consistent with principles disclosed herein and features of novelty
Widest range.
Claims (13)
1. lithium anode piece, it is characterised in that including：Collector, formed with metallic lithium layer, the metal on the collector
Formed with composite conductive film in lithium layer.
2. lithium anode piece as claimed in claim 1, it is characterised in that：The metallic lithium layer is that metallic lithium foil is pressed on collection
The metallic lithium layer formed on fluid；Or metallic lithium layer is the metallic lithium layer that lithium metal is plated in collection liquid surface formation.
3. lithium anode piece as claimed in claim 1 or 2, it is characterised in that：The collector is copper foil or porous copper foil
Or etching copper foil or copper mesh or nickel screen or foam copper or nickel foam.
4. lithium anode piece as claimed in claim 3, it is characterised in that：The collector is copper foil or porous copper foil or quarter
When losing copper foil, the thickness of collector is less than 20 μm；When the collector is copper mesh or nickel screen, the thickness of collector is less than 200 μm；
When the collector is foam copper or nickel foam, the thickness of collector is less than 1000 μm.
5. lithium anode piece as claimed in claim 1 or 2, it is characterised in that：The thickness of the metallic lithium layer be 1 μm~
500μm。
6. lithium anode piece as claimed in claim 1 or 2, it is characterised in that：The composite conductive film be by conductive agent with
The mixed solution that polymer dielectric is mixed is formed at the film on the metallic lithium layer, and thickness is 0.1~100 μm.
7. lithium anode piece as claimed in claim 6, it is characterised in that：The conductive agent is conductive black or CNT
Or the one or more in graphene or carbon fiber.
8. lithium anode piece as claimed in claim 6, it is characterised in that：Polymer dielectric is polyethylene glycol oxide or gathered inclined
One or more in PVF-hexafluoropropene or polyacrylate or makrolon or polyacrylonitrile.
9. prepare the method for the lithium anode piece described in any one of claim 1 to 8, it is characterised in that step is as follows：
Metallic lithium foil and collector are pressed together, or lithium metal is plated in collection liquid surface, so as in collection liquid surface
Form metallic lithium layer；
Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added into polyelectrolyte solution
In stir after, mixed solution is coated on base material, composite conductive film is obtained after solvent evaporated；
Composite conductive film is pressed together on metallic lithium layer surface and forms composite conductive film, obtains lithium anode piece.
10. prepare the method for the lithium anode piece described in any one of claim 1 to 8, it is characterised in that step is as follows：
Metallic lithium foil and collector are pressed together, or lithium metal is plated in collection liquid surface, so as in collection liquid surface
Form metallic lithium layer；
Polymer dielectric is dissolved in solvent polyelectrolyte solution is made, conductive agent is added into polyelectrolyte solution
In stir, then mixed solution is coated on the metallic lithium layer that previous step obtains, after solvent evaporated, in metallic lithium layer
Surface forms composite conductive film, obtains lithium anode piece.
11. the preparation method of the lithium anode piece as described in claim 9 or 10, it is characterised in that：The polymer electrolytic
The concentration of matter solution is 1~50%.
12. lithium metal secondary battery, including：Positive plate, negative plate and barrier film, it is characterised in that：The negative plate will for right
Seek the lithium anode piece described in any one of 1-8.
13. lithium metal secondary battery as claimed in claim 12, it is characterised in that：The positive electrode active material that the positive plate uses
Matter is LiFePO4 or cobalt acid lithium or ternary material or LiMn2O4 or lithium nickelate or nickel ion doped or lithium-rich manganese base material or sulphur carbon
Composite positive pole.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985840A (en) * | 2014-06-04 | 2014-08-13 | 中国科学院上海硅酸盐研究所 | Lithium negative electrode with functional protective layer and lithium sulfur battery |
| CN104966814A (en) * | 2015-07-07 | 2015-10-07 | 李震祺 | High-security metallic lithium cathode and preparation method thereof |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN106159313A (en) * | 2015-05-15 | 2016-11-23 | 三星电子株式会社 | Lithium metal battery |
| CN206059514U (en) * | 2016-10-14 | 2017-03-29 | 四川赛尔雷新能源科技有限公司 | A kind of cuprio lithium piece negative pole poly-lithium battery |
-
2017
- 2017-08-28 CN CN201710752590.7A patent/CN107579204A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985840A (en) * | 2014-06-04 | 2014-08-13 | 中国科学院上海硅酸盐研究所 | Lithium negative electrode with functional protective layer and lithium sulfur battery |
| CN106159313A (en) * | 2015-05-15 | 2016-11-23 | 三星电子株式会社 | Lithium metal battery |
| CN104966814A (en) * | 2015-07-07 | 2015-10-07 | 李震祺 | High-security metallic lithium cathode and preparation method thereof |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN206059514U (en) * | 2016-10-14 | 2017-03-29 | 四川赛尔雷新能源科技有限公司 | A kind of cuprio lithium piece negative pole poly-lithium battery |
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| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Applicant after: Zhuhai Guanyu Battery Co.,Ltd. Address before: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address after: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Applicant after: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address before: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180112 |