CN112366322B - Current collector for improving structural stability and cycle performance of silicon-carbon negative electrode, preparation method of current collector and battery comprising current collector - Google Patents

Current collector for improving structural stability and cycle performance of silicon-carbon negative electrode, preparation method of current collector and battery comprising current collector Download PDF

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CN112366322B
CN112366322B CN202010005415.3A CN202010005415A CN112366322B CN 112366322 B CN112366322 B CN 112366322B CN 202010005415 A CN202010005415 A CN 202010005415A CN 112366322 B CN112366322 B CN 112366322B
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current collector
negative electrode
copper foil
battery
manganese
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CN112366322A (en
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郭彬林
彭波
许梦清
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Wanxiang A123 Systems Asia Co Ltd
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the field of lithium batteries, in particular to a current collector for improving the structural stability and the cycle performance of a silicon-carbon negative electrode. The invention overcomes the defects that the silicon-carbon negative electrode in the prior art has poor structural stability, so that the capacity and the energy density of the lithium battery are limited, has the advantage of inhibiting the destructive property of silicon volume expansion and further enhancing the binding force between the active material layer and the current collector layer, prolongs the cycle life of the battery, and provides possibility for large-current charging of the silicon-carbon negative electrode.

Description

Current collector for improving structural stability and cycle performance of silicon-carbon negative electrode, preparation method of current collector and battery comprising current collector
Technical Field
The invention relates to the field of lithium batteries, in particular to a current collector for improving the structural stability and the cycle performance of a silicon-carbon negative electrode, a preparation method of the current collector and a battery comprising the current collector.
Background
The rapid development of diversified portable electronic devices and new energy vehicles continues to advance the technological innovation of the lithium ion battery industry. The development of new lithium ion batteries with high capacity, high stability and low price has become a primary task in the front of researchers and practitioners in the battery industry. Si is taken as a negative electrode material which has the advantages of ultrahigh theoretical specific capacity, abundant reserve capacity, environmental friendliness, low voltage platform and the like, and is always taken as a good substitute of the conventional graphite negative electrode material. However, when silicon is used as a negative electrode of a lithium ion battery, severe volume expansion and shrinkage exist, and the silicon particles are gradually pulverized and peeled off along with the charging and discharging, so that the internal resistance of the battery is sharply increased; meanwhile, the SEI film on the silicon surface is continuously damaged and generated, so that active lithium is greatly lost, and the capacity of the battery is rapidly attenuated.
At present, the lithium ion battery industry mainly has the following solutions for the capacity attenuation of the silicon cathode: (1) compounding nano-sized silicon particles accounting for about 5-35% of the total weight of the graphite and performing carbon coating treatment; (2) the development of polyacrylic acid (PAA) type binders for silicon negative electrodes, which contain more carboxyl groups capable of forming hydrogen bonds with silicon surface groups with stronger bonding force (3) the development of electrolyte film-forming additives for silicon negative electrodes, such as FEC, has been shown to be advantageous for forming more stable SEI films on silicon material surfaces. (4) And a lithium supplement technology is developed to make up for the loss of active lithium of the silicon-carbon negative electrode.
The three solutions mentioned above all have their own drawbacks, namely: (1) although silicon-carbon compounding is the most feasible scheme for applying silicon materials to practical battery products at the present stage, the silicon proportion in the composite material is severely limited due to the volume expansion effect of silicon, which seriously hinders the further improvement of the capacity and the energy density of the lithium ion battery; (2) although the novel PAA binder can effectively enhance the binding property of the silicon-carbon negative electrode, the novel PAA binder is easy to generate carboxyl polymerization reaction at high temperature, so that not only is the binding power reduced, but also partial moisture is released; (3) the new electrolyte film-forming additive is difficult to give consideration to battery performances such as SEI film, internal resistance and the like; (4) the existing lithium supplement technology is slow in progress, and the lithium supplement method mainly based on lithium powder addition and lithium belt calendering has the problems of high environmental requirements, harsh safety conditions and difficulty in controlling the lithium supplement precision.
Disclosure of Invention
The invention provides a current collector capable of effectively improving the structural stability and the cycle performance of a silicon-carbon negative electrode, a preparation method thereof and a battery comprising the current collector, aiming at overcoming the defects that the structural stability of the silicon-carbon negative electrode is poor and the capacity and the energy density of a lithium battery are limited in the prior art.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the utility model provides a promote mass flow body of silicon carbon negative pole structural stability and circulation performance which characterized in that, the mass flow body includes one deck copper foil, copper foil top deposit has the metal titanium layer of one deck doping manganese, and the metal titanium layer surface is provided with highly even orderly titanium dioxide nanotube array structure.
According to the invention, a stable structure is formed between the titanium dioxide nanotube array directly grown on the metal titanium substrate and the copper foil, and the highly ordered and hollow nanotubes provide a buffer space for the expansion of silicon, so that part of active materials are filled in the nanotubes, the bonding force between the active material layer and the current collector layer is further enhanced while the destructive property of the silicon volume expansion is inhibited, and the material pulverization and falling caused by the silicon carbon negative electrode volume expansion in the long-term circulation process are inhibited, thereby prolonging the cycle life of the battery. Meanwhile, the titanium dioxide nanotube array has lithium intercalation capacity and good rate performance, and the possibility of large-current charging of a silicon-carbon cathode is provided. Meanwhile, the titanium dioxide resists electrochemical corrosion, and the over-discharge performance of the battery can be effectively improved. And the titanium dioxide has strong chemical stability, and can prevent the current collector from being oxidized in the long-term storage process.
In addition, the metal titanium layer is doped with certain content of manganese which can form structural defects with titanium and copper elements in the thermal oxidation diffusion process and defective oxides which can provide expansion allowance for volume expansion of the negative electrode silicon material, so that the problem of component separation and final pulverization caused by different expansion effects among components of the positive electrode material after a large number of charge-discharge cycles is solved, meanwhile, the formed structural defects and defective oxides cannot generate obvious adverse effects on the structural stability of the negative electrode material, but can form cavities beneficial to the work of the electrode material, so that the capacitance of the electrode material can be better reserved in the cycle process, and the cycle performance is improved.
Preferably, the thickness of the metal titanium layer doped with the manganese metal is 1-2 μm, the length of the titanium dioxide nanotube is 0.5-1 μm, the pipe diameter is more than 150nm, and the pipe wall thickness is less than 50 nm.
A preparation method of a current collector for improving the structural stability and the cycle performance of a silicon-carbon negative electrode comprises the following steps:
(1) depositing a layer of ordered metal manganese array on the surface of the copper foil by using a physical vapor deposition method, and oxidizing the metal manganese array to obtain a manganese dioxide array;
(2) continuously utilizing a physical vapor deposition method to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and keeping the extreme ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and electrifying direct current in electrolyte to react to obtain the titanium-plated copper foil with a grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure to obtain the current collector.
The method comprises the following steps of firstly depositing a layer of ordered manganese dioxide array on the surface of a copper foil, then depositing a layer of pure metal titanium layer covering the manganese dioxide array on the surface of the copper foil, oxidizing the upper layer of the pure metal titanium layer through an anodic oxidation reaction to obtain a titanium dioxide layer, etching the titanium dioxide through electrochemical etching to obtain a titanium dioxide nanotube array, and finally annealing the copper foil, wherein the two effects are as follows: the titanium dioxide nanotube array obtained by the first etching is of an amorphous structure, has poor mechanical property, cannot be used for supporting a negative electrode material, and can convert amorphous titanium dioxide into crystalline anatase after being annealed, so that the mechanical property of the titanium dioxide nanotube array is greatly improved. Secondly, after annealing, manganese dioxide can form a defect structure with complex solid solution doping and excellent cycle performance of a counter electrode with copper foil and metal titanium, so that structural defects and defect oxides are formed, volume expansion allowance of the negative electrode material can be provided, and the problem that components are separated and finally pulverized due to different expansion effects among the components of the negative electrode material after a large number of charge and discharge cycles is avoided. Meanwhile, the formed structural defects and defective oxides do not have obvious adverse effects on the structural stability of the cathode material, but form cavities beneficial to the working of the electrode material, so that the capacitance is better reserved in the circulating process, and the circulating performance is improved.
Preferably, the preparation method of the ordered manganese dioxide array in the step (1) is as follows: uniformly covering a layer of mask plate with uniform holes on the surface of the copper foil, then depositing a layer of metal manganese on the surface of the copper foil, removing the mask plate after deposition is finished, wherein the metal manganese deposited in the holes is an ordered metal manganese array, and reacting the ordered metal manganese array with oxygen to obtain a manganese dioxide array.
The preparation method of the manganese metal array is characterized in that the manganese metal array is prepared through a mask, the mask contains a plurality of holes, so that manganese metal in the deposited holes can directly grow on a copper foil, and after the mask is removed, the manganese metal remaining on the copper foil can form a manganese metal array which is oxidized to finally obtain the manganese dioxide array.
Preferably, the mask can be polystyrene microspheres, and after the polystyrene microspheres are uniformly spread on the copper foil, gaps between the microspheres can become holes for depositing manganese metal, and after the manganese metal is deposited, the polystyrene can be washed away by cleaning with an organic solvent, so that the copper foil only containing the manganese metal array is obtained.
Preferably, the physical vapor deposition method in step (1) and step (2) includes magnetron sputtering, vacuum ion plating, electric spark deposition technology or multilayer spray deposition technology.
Preferably, the electrolyte in the step (3) is ethylene glycol: and (3) a solution in which 0.1-0.5 wt% of ammonium fluoride is fully dissolved in water in a mass ratio of (6-10), wherein the direct current voltage is 40-80V, and the reaction time is 0.5-2 h.
Preferably, in the step (4), the annealing temperature is 480-600 ℃, the annealing time is 20-45 min, and the annealing atmosphere is argon.
A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm and are wound or laminated to form a battery core, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell and is sealed to obtain the battery, a negative current collector in the negative electrode is a current collector prepared by the method, and a negative active substance in the negative electrode is a silicon-based material.
Preferably, the positive electrode current collector of the positive electrode is a rolled metal aluminum foil, and the positive electrode active material is one or more of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel-cobalt-aluminum and a lithium-rich manganese-based material.
Preferably, the separator is a polyethylene, polypropylene or polyimide film with a porous structure;
the electrolyte is an organic solution, ionic liquid or solid electrolyte dissolved with lithium salt;
the anode is provided with an aluminum-based material tab, and the cathode is provided with a copper nickel-plated tab.
Therefore, the invention has the following beneficial effects:
(1) the bonding force between the active material layer and the current collector layer is further enhanced while the destructiveness of silicon volume expansion is inhibited;
(2) the cycle life of the battery is prolonged;
(3) the silicon-carbon negative electrode is charged with large current.
Drawings
Fig. 1 is a schematic structural view of the current collector of the present invention.
Wherein: the structure comprises a copper foil 1, a metal titanium layer 2, a titanium dioxide nanotube array structure 3 and a manganese dioxide array 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
As shown in fig. 1, the current collector for improving the stability and the cycle performance of the silicon-carbon negative electrode structure comprises a copper foil 1, a titanium layer 2 doped with manganese dioxide array 4 and having a thickness of 1 μm is deposited on the copper foil, and a titanium dioxide nanotube array structure 3 having a height of 0.5 μm, a tube diameter of 200nm and a tube wall thickness of 40nm is arranged on the surface of the titanium layer 2.
The preparation method comprises the following steps:
(1) uniformly covering a layer of mask plate with uniform holes on the surface of the copper foil, depositing a layer of metal manganese on the surface of the copper foil through magnetron sputtering, removing the mask plate after deposition is finished, wherein the metal manganese deposited in the holes is an ordered metal manganese array, and reacting the ordered metal manganese array with oxygen to obtain a manganese dioxide array;
(2) continuously using a magnetron sputtering deposition method to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and keeping the polar ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and applying direct current to electrolyte, wherein the electrolyte is ethylene glycol: fully dissolving 0.1 wt% of ammonium fluoride solution with the water mass ratio of 6:1, wherein the direct current voltage is 40V, the reaction time is 2h, and reacting to obtain the titanium-plated copper foil with the grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure at 480 ℃ for 45min in an argon atmosphere to obtain the current collector.
A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm, a battery core is formed by winding or laminating, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell, and the battery is obtained by sealing.
Preparing a positive plate: selecting a nickel-cobalt-manganese ternary material as a positive electrode material, mixing positive electrode slurry according to the weight ratio of a positive electrode active material, a conductive agent and a binder of 96:2:2, and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece.
Preparing a negative plate: selecting a silicon-carbon material as a negative active material, and preparing the following raw materials in percentage by weight: conductive agent: and mixing the binder with solvent water in a ratio of 94:2:4 to obtain negative electrode slurry, and uniformly coating the negative electrode slurry on a copper foil with a titanium dioxide nanotube array structure growing on a negative electrode current collector. And (4) after drying, rolling by using a rolling machine, and then slitting to prepare the negative pole piece.
Preparing a diaphragm: a commercial PE separator was selected.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a tab: selecting a lithium ion battery positive lug, wherein the lug is made of aluminum; selecting a lithium ion battery cathode lug, wherein the lug is made of nickel-copper alloy.
Preparing a battery: the positive and negative pole pieces and the diaphragm are laminated to prepare a battery core, the lugs are welded, then the battery core is packaged in an aluminum plastic film, electrolyte is injected, and the battery is sealed and formed to obtain the battery.
Example 2
The utility model provides a promote mass flow body of silicon carbon negative pole structural stability and circulation performance, the mass flow body includes one deck copper foil, the deposit has the metal titanium layer that one deck thickness is 2 mu m doping manganese above the copper foil, and the metal titanium layer surface is provided with highly is 1 mu m, and pipe diameter 250nm, the titanium dioxide nanotube array structure of pipe wall thickness 30 nm.
The preparation method comprises the following steps:
(1) uniformly covering a layer of microspheres with polystyrene on the surface of the copper foil, then carrying out vacuum ion plating and deposition on the surface of the copper foil to form a layer of manganese metal, wherein gaps among the microspheres can be holes for depositing the manganese metal, the polystyrene can be washed away by washing with toluene after the deposition is finished, the manganese metal deposited in the holes is an ordered manganese metal array, and the ordered manganese metal array is reacted with oxygen to obtain a manganese dioxide array;
(2) continuously using a vacuum ion plating deposition method to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and keeping the extreme ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and applying direct current to electrolyte, wherein the electrolyte is ethylene glycol: fully dissolving 0.5 wt% of ammonium fluoride solution with the water mass ratio of 10:1, wherein the direct current voltage is 80V, the reaction time is 0.5h, and reacting to obtain the titanium-plated copper foil with the grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure at 600 ℃ for 20min in an argon atmosphere to obtain the current collector.
A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm, a battery core is formed by winding or laminating, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell, and the battery is obtained by sealing.
Preparing a positive plate: selecting a nickel-cobalt-manganese ternary material as a positive electrode material, mixing positive electrode slurry according to the weight ratio of a positive electrode active material, a conductive agent and a binder of 96:2:2, and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece.
Preparing a negative plate: selecting a silicon-carbon material as a negative active material, and preparing the following raw materials in percentage by weight: conductive agent: and mixing the binder with solvent water in a ratio of 94:2:4 to obtain negative electrode slurry, and uniformly coating the negative electrode slurry on a copper foil with a titanium dioxide nanotube array structure growing on a negative electrode current collector. And (4) after drying, rolling by using a rolling machine, and then slitting to prepare the negative pole piece.
Preparing a diaphragm: a commercial PP separator was selected.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a tab: selecting a lithium ion battery positive lug, wherein the lug is made of aluminum; selecting a lithium ion battery cathode lug, wherein the lug is made of nickel-copper alloy.
Preparing a battery: the positive and negative pole pieces and the diaphragm are laminated to prepare a battery core, the lugs are welded, then the battery core is packaged in an aluminum plastic film, electrolyte is injected, and the battery is sealed and formed to obtain the battery.
Example 3
The utility model provides a promote mass flow body of silicon carbon negative pole structural stability and circulation performance, the mass flow body includes a layer copper foil, the deposit has the metal titanium layer that a layer thickness is 1.5 mu m doping manganese above the copper foil, and the metal titanium layer surface is provided with highly is 0.8 mu m, and pipe diameter 180nm, the titanium dioxide nanotube array structure of 20nm of pipe wall thickness.
The preparation method comprises the following steps:
(1) uniformly covering a layer of mask plate with uniform holes on the surface of the copper foil, then depositing a layer of metal manganese on the surface of the copper foil through electric spark, removing the mask plate after deposition is finished, wherein the metal manganese deposited in the holes is an ordered metal manganese array, and reacting the ordered metal manganese array with oxygen to obtain a manganese dioxide array;
(2) continuing the electric spark deposition method to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and keeping the polar ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and applying direct current to electrolyte, wherein the electrolyte is ethylene glycol: fully dissolving 0.3 wt% of ammonium fluoride solution with the water mass ratio of 8:1, wherein the direct current voltage is 60V, the reaction time is 1h, and reacting to obtain the titanium-plated copper foil with the grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure at 550 ℃ for 30min in an argon atmosphere to obtain the current collector.
A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm, a battery core is formed by winding or laminating, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell, and the battery is obtained by sealing.
Preparing a positive plate: selecting a nickel-cobalt-manganese ternary material as a positive electrode material, mixing positive electrode slurry according to the weight ratio of a positive electrode active material, a conductive agent and a binder of 96:2:2, and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece.
Preparing a negative plate: selecting a silicon-carbon material as a negative active material, and preparing the following raw materials in percentage by weight: conductive agent: and mixing the binder with solvent water in a ratio of 94:2:4 to obtain negative electrode slurry, and uniformly coating the negative electrode slurry on a copper foil with a titanium dioxide nanotube array structure growing on a negative electrode current collector. And (4) after drying, rolling by using a rolling machine, and then slitting to prepare the negative pole piece.
Preparing a diaphragm: a commercial polyimide film separator was selected.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a tab: selecting a lithium ion battery positive lug, wherein the lug is made of aluminum; selecting a lithium ion battery cathode lug, wherein the lug is made of nickel-copper alloy.
Preparing a battery: the positive and negative pole pieces and the diaphragm are laminated to prepare a battery core, the lugs are welded, then the battery core is packaged in an aluminum plastic film, electrolyte is injected, and the battery is sealed and formed to obtain the battery.
Example 4
The utility model provides a promote mass flow body of silicon carbon negative pole structural stability and circulation performance, the mass flow body includes one deck copper foil, the deposit has the metal titanium layer that one deck thickness is 1.8 mu m doping manganese above the copper foil, and the metal titanium layer surface is provided with highly is 0.8 mu m, and pipe diameter 200nm, the titanium dioxide nanotube array structure of pipe wall thickness 40 nm.
The preparation method comprises the following steps:
(1) uniformly covering a layer of mask plate with uniform holes on the surface of the copper foil, then depositing a layer of metal manganese on the surface of the copper foil (magnetron sputtering, vacuum ion plating and electric spark), removing the mask plate after deposition is finished, wherein the metal manganese deposited in the holes is an ordered metal manganese array, and reacting the ordered metal manganese array with oxygen to obtain a manganese dioxide array;
(2) continuing (magnetron sputtering, vacuum ion plating and electric spark) deposition methods to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and reserving the extreme ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and applying direct current to electrolyte, wherein the electrolyte is ethylene glycol: fully dissolving 0.4 wt% of ammonium fluoride solution with the water mass ratio of 9:1, wherein the direct current voltage is 75V, the reaction time is 1.5h, and reacting to obtain the titanium-plated copper foil with the grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure at 580 ℃ for 40min in an argon atmosphere to obtain the current collector.
A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm, a battery core is formed by winding or laminating, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell, and the battery is obtained by sealing.
Preparing a positive plate: selecting a nickel-cobalt-manganese ternary material as a positive electrode material, mixing positive electrode slurry according to the weight ratio of a positive electrode active material, a conductive agent and a binder of 96:2:2, and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece.
Preparing a negative plate: selecting a silicon-carbon material as a negative active material, and preparing the following raw materials in percentage by weight: conductive agent: and mixing the binder with solvent water in a ratio of 94:2:4 to obtain negative electrode slurry, and uniformly coating the negative electrode slurry on a copper foil with a titanium dioxide nanotube array structure growing on a negative electrode current collector. And (4) after drying, rolling by using a rolling machine, and then slitting to prepare the negative pole piece.
Preparing a diaphragm: a commercial PE separator was selected.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a tab: selecting a lithium ion battery positive lug, wherein the lug is made of aluminum; selecting a lithium ion battery cathode lug, wherein the lug is made of nickel-copper alloy.
Preparing a battery: the positive and negative pole pieces and the diaphragm are laminated to prepare a battery core, the lugs are welded, then the battery core is packaged in an aluminum plastic film, electrolyte is injected, and the battery is sealed and formed to obtain the battery.
Example 5
The utility model provides a promote mass flow body of silicon carbon negative pole structural stability and circulation performance, the mass flow body includes one deck copper foil, the deposit has the metal titanium layer that one deck thickness is 1.2 mu m doping manganese above the copper foil, and the metal titanium layer surface is provided with highly is 0.6 mu m, and pipe diameter 160nm, pipe wall thickness 40 nm's titanium dioxide nanotube array structure.
The preparation method comprises the following steps:
(1) uniformly covering a layer of mask plate with uniform holes on the surface of the copper foil, then depositing a layer of metal manganese on the surface of the copper foil (magnetron sputtering, vacuum ion plating and electric spark), removing the mask plate after deposition is finished, wherein the metal manganese deposited in the holes is an ordered metal manganese array, and reacting the ordered metal manganese array with oxygen to obtain a manganese dioxide array;
(2) continuing (magnetron sputtering, vacuum ion plating and electric spark) deposition methods to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and reserving the extreme ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and applying direct current to electrolyte, wherein the electrolyte is ethylene glycol: fully dissolving 0.2 wt% of ammonium fluoride solution with the water mass ratio of 7:1, wherein the direct current voltage is 45V, the reaction time is 1.5h, and reacting to obtain the titanium-plated copper foil with the grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure for 40min at 500 ℃ in an argon atmosphere to obtain the current collector.
A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm, a battery core is formed by winding or laminating, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell, and the battery is obtained by sealing.
Preparing a positive plate: selecting a nickel-cobalt-manganese ternary material as a positive electrode material, mixing positive electrode slurry according to the weight ratio of a positive electrode active material, a conductive agent and a binder of 96:2:2, and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil. After drying, rolling by a rolling machine, and then slitting to prepare the positive pole piece.
Preparing a negative plate: selecting a silicon-carbon material as a negative active material, and preparing the following raw materials in percentage by weight: conductive agent: and mixing the binder with solvent water in a ratio of 94:2:4 to obtain negative electrode slurry, and uniformly coating the negative electrode slurry on a copper foil with a titanium dioxide nanotube array structure growing on a negative electrode current collector. And (4) after drying, rolling by using a rolling machine, and then slitting to prepare the negative pole piece.
Preparing a diaphragm: a commercial PE separator was selected.
Preparing electrolyte: selecting commercial LiPF6An electrolyte dissolved in an organic solution.
Preparing a tab: selecting a lithium ion battery positive lug, wherein the lug is made of aluminum; selecting a lithium ion battery cathode lug, wherein the lug is made of nickel-copper alloy.
Preparing a battery: the positive and negative pole pieces and the diaphragm are laminated to prepare a battery core, the lugs are welded, then the battery core is packaged in an aluminum plastic film, electrolyte is injected, and the battery is sealed and formed to obtain the battery.
Comparative example 1
The battery used in comparative example 1 had the same composition as in example 1, except that: the current collector used was copper foil.
Comparative example 2
The battery used in comparative example 2 had the same composition as in example 1, except that: the used current collector is a metal titanium layer on which a titanium dioxide nanotube array grows.
And (3) carrying out cycle performance test on the prepared battery material. The test results are shown in table 1 below.
Table 1: and (5) testing the cycle performance.
Figure BDA0002355098550000091
Figure BDA0002355098550000101
As is obvious from the detection results in the table, the battery material prepared by the embodiment of the invention shows excellent cycle performance in the temperature ranges of normal temperature (20 +/-1 ℃) and medium temperature (45 +/-1 ℃) and under the working conditions of 0.1C/3.0V and 1.0C/3.0V.

Claims (9)

1. The preparation method of the current collector is characterized in that the current collector comprises a layer of copper foil, a manganese-doped metal titanium layer is deposited above the copper foil, and a titanium dioxide nanotube array structure with uniform and ordered height is arranged on the surface of the metal titanium layer, and comprises the following steps:
(1) depositing a layer of ordered metal manganese array on the surface of the copper foil by using a physical vapor deposition method, and oxidizing the metal manganese array to obtain a manganese dioxide array;
(2) continuously utilizing a physical vapor deposition method to uniformly deposit pure metal titanium on the surface of the copper foil and cover the manganese dioxide array, and keeping the extreme ear position of the copper foil;
(3) taking the obtained titanium-plated copper foil as an anode, taking a common copper electrode or an inert electrode as a counter electrode, and electrifying direct current in electrolyte to react to obtain the titanium-plated copper foil with a grown titanium dioxide nanotube array structure;
(4) and annealing the obtained titanium-plated copper foil with the grown titanium dioxide nanotube array structure to obtain the current collector.
2. The preparation method of the current collector for improving the structural stability and the cycle performance of the silicon-carbon negative electrode according to claim 1, wherein the thickness of the manganese-doped metal titanium layer is 1-2 μm, the length of the titanium dioxide nanotube is 0.5-1 μm, the outer diameter of the titanium dioxide nanotube is more than 150nm, and the thickness of the tube wall is less than 50 nm.
3. The method for preparing the current collector for improving the structural stability and the cycle performance of the silicon-carbon negative electrode according to claim 1, wherein the method for preparing the manganese dioxide array in the step (1) comprises the following steps: uniformly covering a layer of mask plate with uniform holes on the surface of the copper foil, then depositing a layer of metal manganese on the surface of the copper foil, removing the mask plate after deposition is finished, wherein the metal manganese deposited in the holes is an ordered metal manganese array, and reacting the ordered metal manganese array with oxygen to obtain a manganese dioxide array.
4. The method for preparing the current collector for improving the structural stability and the cycle performance of the silicon-carbon negative electrode according to claim 1 or 3, wherein the physical vapor deposition method in the step (1) and the step (2) comprises magnetron sputtering, vacuum ion plating, an electric spark deposition technique or a multilayer jet deposition technique.
5. The method for preparing the current collector for improving the structural stability and the cycle performance of the silicon-carbon negative electrode according to claim 1, wherein the electrolyte in the step (3) is ethylene glycol: and (3) the mass ratio of water is (6-10): 1, the ammonium fluoride is fully dissolved in the solution, the concentration of the ammonium fluoride in the electrolyte is (0.1-0.5) wt%, the direct current voltage is 40-80V, and the reaction time is 0.5-2 h.
6. The preparation method of the current collector for improving the structural stability and the cycle performance of the silicon-carbon negative electrode according to claim 1, wherein in the step (4), the annealing temperature is 480-600 ℃, the annealing time is 20-45 min, and the annealing atmosphere is argon.
7. A long-cycle high energy density lithium ion battery, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a tab and a shell, wherein the tab is welded on the positive electrode plate and the negative electrode plate respectively, the positive electrode and the negative electrode are separated by the diaphragm and are wound or laminated to form a battery core, the battery core is packaged into the battery shell, the electrolyte is injected into the battery shell and is sealed to obtain the battery, the negative electrode current collector in the negative electrode is the current collector prepared by the preparation method in any one of claims 1 to 6, and a negative electrode active substance in the negative electrode is a silicon-based material.
8. The long-cycle high energy density lithium ion battery of claim 7, wherein the positive current collector of the positive electrode is a rolled metal aluminum foil, and the positive active material in the positive electrode is one or more of lithium iron phosphate, lithium manganate, lithium cobaltate, nickel cobalt aluminum, and lithium-rich manganese-based materials.
9. The long-cycle high energy density lithium ion battery according to claim 7,
the diaphragm is a polyethylene, polypropylene or polyimide film with a porous structure;
the electrolyte is an organic solution, ionic liquid or solid electrolyte dissolved with lithium salt;
the anode is provided with an aluminum-based material tab, and the cathode is provided with a copper nickel-plated tab.
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