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CN115088106A - Metal anode for lithium ion battery - Google Patents

Metal anode for lithium ion battery Download PDF

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Publication number
CN115088106A
CN115088106A CN202180014416.7A CN202180014416A CN115088106A CN 115088106 A CN115088106 A CN 115088106A CN 202180014416 A CN202180014416 A CN 202180014416A CN 115088106 A CN115088106 A CN 115088106A
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Prior art keywords
metal
anode
composite coating
lithium
present disclosure
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CN202180014416.7A
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Chinese (zh)
Inventor
G·艾斯厄驰
P·R·尼莱什瓦
S·J·丹纳戈
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TVS Motor Co Ltd
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TVS Motor Co Ltd
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    • H01M4/64—Carriers or collectors
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    • H01M4/661—Metal or alloys, e.g. alloy coatings
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    • H01M4/04—Processes of manufacture in general
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    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
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Abstract

The present disclosure provides a metal anode comprising (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the copper current collector (106); (c) a composite coating (102) disposed on the lithium metal layer (104). The present disclosure discloses a composite coating comprising a porous mixed metal oxide and carbon nanotubes. The disclosure also discloses convenient methods of making the metal anodes.

Description

Metal anode for lithium ion battery
Technical Field
The present disclosure relates generally to the field of lithium ion batteries, and more particularly to an anode for a lithium ion battery.
Background
Lithium ion batteries are very popular in power technology because of their unique advantages over other technologies. Lithium ion rechargeable batteries have high energy density and are also lightweight. In addition, lithium ion rechargeable batteries can provide a large amount of current for high power applications, which is approximately three times the current provided by other types of batteries. Lithium ion batteries have found widespread use in many fields, such as portable electronic devices, electric vehicles, and aerospace power applications. However, in order to overcome some of the disadvantages of the lithium ion battery, the lithium ion battery needs various technical improvements. They have a tendency to overheat, thermal runaway, capacity loss and high manufacturing costs. Current research efforts are focused on electrode modification, electrolyte use, separator structures, etc. of lithium ion batteries in an effort to achieve improved performance.
While various methods are available for forming lithium anodes, there is still a need for improved methods of forming lithium anodes that will allow lithium ion batteries with high energy density, enhanced conductivity, and enhanced electrochemical performance to be more easily manufactured.
Disclosure of Invention
In one aspect of the present disclosure, there is provided a metal anode comprising: (a) a copper current collector (106); (b) a layer of lithium metal (104) disposed over a copper current collector (106); and (c) a composite coating (102) disposed on the lithium metal layer (104), wherein the composite coating (102) comprises a porous mixed metal oxide and carbon nanotubes.
In another aspect of the present invention, there is provided a method of manufacturing a metal anode, the method comprising: a) obtaining a metal precursor; b) milling the metal precursor to obtain a porous mixed metal oxide; c) bonding carbon nanotubes to a porous mixed metal oxide in the presence of a binder to obtain a composite coating; and d) encapsulating the lithium metal-copper-lithium metal with the composite coating.
In another aspect of the present invention, there is also provided a battery including: (a) a cathode, (b) a metal anode comprising: (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the copper current collector (106); and (iii) a composite coating (102) disposed on the lithium metal layer (104); and (c) an electrolyte.
These and other features, aspects, and advantages of the present subject matter will become better understood with reference to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.
Drawings
Specific embodiments are described with reference to the accompanying drawings. In the figures, the left-most digit(s) of a reference number identifies the figure in which the reference number first appears. The same numbers are used throughout the drawings to reference like features and components.
Figure 1 depicts a schematic representation of a metal anode fabricated according to an embodiment of the present subject matter.
Fig. 2 depicts a schematic representation of a lithium battery structure including a fabricated metal anode according to an embodiment of the present subject matter.
Fig. 3 depicts a schematic representation of a lithium pouch cell structure including a fabricated metal anode according to an embodiment of the present subject matter.
Detailed Description
Those skilled in the art will appreciate that variations and modifications of the present disclosure other than those specifically described may be made. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such steps, features, compositions and compounds referred to or indicated in the specification, individually or collectively, and any and all combinations of any or more of such steps or features.
Defining:
for convenience, certain terms and examples used in the specification are collated here before further description of the present disclosure. These definitions should be read and understood by those skilled in the art in light of the remainder of this disclosure. Terms used herein have meanings that are recognized and known by those skilled in the art, however, specific terms and their meanings are described below for convenience and complete understanding.
The terms "a", "an" and "the" are used to denote one or more (i.e., at least one) object in a grammatical sense.
The use of the word "comprising" and variations thereof to "comprising" is inclusive or open-ended and means that additional elements may be included. It should not be interpreted as "consisting of … … only".
In this specification, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated element or step or group of elements or steps but not the exclusion of any other element or step.
The term "including" is used to mean "including but not limited to", "including" and "including but not limited to" which are used interchangeably.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference.
Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a temperature range of about 20 ℃ to 70 ℃ should be interpreted to include not only the explicitly recited limits of about 20 ℃ to about 70 ℃, but also to include sub-ranges, such as 22 ℃ to 45 ℃ to 70 ℃, and the like, as well as individual amounts within the recited ranges, including fractions, such as 20.5 ℃, 41.1 ℃, and 59.9 ℃.
The term "current collector" refers to the metal used in the manufacture of the electrode. In the present invention, copper is the current collector at the anode end and aluminum is the current collector at the cathode end. The movement of the lithium ions generates free electrons in the anode, thereby generating a charge at the positive (anode) current collector. The current then flows from the current collector to the current collector through the means of supplying power to the negative (cathodic) current collector, thus the current collector improves the electrochemical performance.
In the present disclosure, the expression "disposed above" refers to a package. In the present disclosure, lithium metal is disposed over the copper current collector, which means that the lithium metal encapsulates the copper current collector and forms the Li-Cu-Li layer of the metal anode. In the present disclosure, the expression "disposed thereon" means coated on one side. In the present invention, the composite coating layer is provided on the lithium metal, which means that the composite coating layer is coated on one side (outer side) of the lithium metal.
The expression "spray layer formation" refers to a process of coating a material on a substrate by spraying the coating material on the surface of the substrate and further drying. In the present disclosure, the composite coating is layered on the metal surface by forming a sprayed layer.
The expression "blade coating" refers to a technique of coating a thin layer of coating material on a surface using an instrument blade. In the present disclosure, this technique is used for composite coatings on metal surfaces.
The term "separator" refers to a polymeric material that blocks the flow of electrons within the cell. The polymer separator acts as an electrical insulator.
The term "electrolyte" refers to a substance that conducts electricity when in contact with a solvent. The term "nonaqueous electrolyte solution" refers to an electrolyte salt solution dissolved in an organic solvent capable of conducting ions. The term "solid electrolyte" refers to a solid electrolytic material having high ionic conductivity. The term "inorganic solid electrolyte" refers to an inorganic material that can be used as an electrolyte. In the present disclosure, the terms "nonaqueous electrolytic solution", "solid electrolyte", "inorganic solid electrolyte" refer to all electrolytic materials commonly used in lithium ion batteries.
The scope of the present disclosure is not to be limited by the specific embodiments described herein, which are intended as illustrations only. Functionally equivalent products, compositions and methods are clearly within the scope of the present disclosure, as described herein.
Conventional lithium ion batteries have graphite as the anode, lithium metal oxide as the cathode, lithium salt containing an organic solvent as the electrolyte, and a polymer separator. The conventional graphite electrode is replaced with lithium metal as an anode to achieve high energy density. But electrochemical cycling with lithium metal as the anode is challenging due to its large volume change and unstable interface. When lithium metal is used as the anode, lithium ions can be deposited anywhere at the interface of the battery device and tend to be highly dendritic. This leads to solid electrolyte interface cracking, which in turn leads to electrochemical hot spots and triggers filament growth. This sustained reaction between lithium metal and the electrolyte results in severe capacity fade. Therefore, there is a need for a suitable anode which in a first stage can suppress dendrite formation and subsequently avoid capacity fade. To inhibit dendrite formation and enhance lithium ion mobility, the present disclosure provides a metal anode comprising a copper current collector (106); a lithium metal layer (104) disposed over the current collector; and a composite coating (102) disposed on the lithium metal layer, wherein the composite coating includes a porous mixed metal oxide (binary mixture of mixed metal oxides) and conductive carbon nanotubes.
In one embodiment of the present disclosure, there is provided a metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the current collector; and (c) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating includes a porous mixed metal oxide and carbon nanotubes.
In one embodiment of the present disclosure, there is provided a metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the current collector; and (c) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating comprises a porous mixed metal oxide and carbon nanotubes, and wherein the lithium metal layer has a thickness in a range of 40 μm to 50 μm.
In one embodiment of the present disclosure, there is provided a metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the copper current collector (106); and (c) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating comprises a porous mixed metal oxide and carbon nanotubes, and wherein the lithium metal layer has a thickness in a range of 45 μm to 50 μm. In another embodiment of the present disclosure, there is provided a metal anode as described herein, wherein the lithium metal layer has a thickness of 50 μm.
In one embodiment of the present disclosure, there is provided a metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the current collector; and (c) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating comprises a porous mixed metal oxide and carbon nanotubes, and wherein the composite coating has a thickness in a range of 5 μm to 20 μm. In another embodiment of the present disclosure, wherein the composite coating has a thickness in a range of 10 μm to 20 μm. In another embodiment of the present disclosure, wherein the composite coating has a thickness of 20 μm.
In one embodiment of the present disclosure, there is provided a metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the current collector; and (c) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating comprises a porous mixed metal oxide and carbon nanotubes, and wherein the composite coating comprises at least one binder.
In one embodiment of the present disclosure, there is provided a metal anode as described herein, wherein the composite coating comprises at least one binder and is selected from the group consisting of: polyvinylidene fluoride, carboxymethylcellulose (CMC), polyacrylic acid (PAA), and combinations thereof. In another embodiment of the present disclosure, there is provided a metal anode as described herein, wherein the binder is polyvinylidene fluoride.
In one embodiment of the present disclosure, there is provided a metal anode as described herein, wherein the composite coating has a porosity in the range of 30 to 40 vol% relative to the composite coating.
In one embodiment of the present disclosure, there is provided a metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) having a thickness in the range of 40 μm to 50 μm; and (c) a composite coating having a thickness in the range of 5 μm to 20 μm, the composite coating comprising a porous mixed metal oxide and carbon nanotubes disposed on the lithium metal layer, wherein the composite coating comprises at least one binder selected from the group consisting of: polyvinylidene fluoride, carboxymethylcellulose (CMC), polyacrylic acid (PAA), and combinations thereof, and wherein the composite coating has a porosity in a range of 30 to 40 vol% relative to the composite coating.
In one embodiment of the present disclosure, there is provided a method of manufacturing a metal anode, the metal anode including: (a) a copper current collector (106); (b) a lithium metal layer (104) disposed over the current collector; and (c) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating comprises a porous mixed metal oxide and carbon nanotubes, the method comprising (i) obtaining a metal precursor; (ii) milling the metal precursor to obtain a porous mixed metal oxide; (iii) bonding carbon nanotubes to a porous mixed metal oxide in the presence of a binder to obtain a composite coating; and (iv) encapsulating the lithium metal-copper-lithium metal with the composite coating.
In one embodiment of the present disclosure, there is provided a method of making a metal anode described herein, wherein the metal precursor is selected from the group consisting of: SiO 2 2 、SnF 2 And combinations thereof.
In one embodiment of the present disclosure, a method of manufacturing a metal anode as described herein is provided, wherein milling a metal precursor is accomplished at a temperature in the range of 20 ℃ to 70 ℃ to obtain a porous mixed metal oxide. In another embodiment of the present disclosure, wherein milling the metal precursor is done at a temperature in the range of 20 ℃ to 60 ℃ to obtain the porous mixed metal oxide. In another embodiment of the present disclosure, wherein milling the metal precursor is done at an initial temperature in the range of 20 ℃ to 30 ℃ and at a final temperature in the range of 50 ℃ to 60 ℃ to obtain the porous mixed metal oxide.
In one embodiment of the present disclosure, a method of making a metal anode described herein is provided, wherein lithium metal-copper-lithium metal is encapsulated with a composite coating by a process selected from spray layer formation or doctor blade coating.
In one embodiment of the present disclosure, there is provided a method of manufacturing a metal anode, the method comprising: (a) obtaining a metal precursor, the metal precursor selected from the group consisting of: SiO 2 2 、SnF 2 And combinations thereof; (b) milling the metal precursor at a temperature in the range of 20 ℃ to 30 ℃ to obtain a porous mixed metal oxide; (c) combining carbon nanotubes into a porous mixed metal oxide in the presence of a binder to obtain a composite(ii) co-coating, the binder being selected from the group consisting of: polyvinylidene fluoride, carboxymethylcellulose (CMC), polyacrylic acid (PAA), and combinations thereof; and (d) encapsulating the lithium metal-copper-lithium metal with the composite coating by a process selected from the group consisting of spray layer formation or blade coating.
In one embodiment of the present disclosure, there is provided a method of manufacturing a metal anode, the method comprising: (a) obtaining a metal precursor, the metal precursor selected from the group consisting of: SiO 2 2 、SnF 2 And combinations thereof; (b) milling the metal precursor at a temperature in the range of 20 ℃ to 30 ℃ to obtain a porous mixed metal oxide; (c) bonding carbon nanotubes to a porous mixed metal oxide in the presence of a binder, polyvinylidene fluoride, to obtain a composite coating; and (d) encapsulating the lithium metal-copper-lithium metal with the composite coating by a process selected from the group consisting of spray layer formation or blade coating.
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating comprises a porous mixed metal oxide and carbon nanotubes; and (c) an electrolyte.
In one embodiment of the present disclosure, there is provided a battery as described herein, wherein the cathode and the metal anode are held apart by a porous separator.
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer, wherein the cathode and the metal anode are held apart by a porous separator.
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer, wherein the separator prevents electrical contact between the cathode and the anode while allowing ionic conduction between the cathode and the anode.
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer, wherein the separator comprises a material selected from polyethylene, polypropylene, or a ceramic coated polymer film.
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer, wherein the cathode and the metal anode are held apart by a porous separator selected from polyethylene or polypropylene, and wherein the separator prevents electrical contact between the cathode and the anode while allowing ionic conduction between the cathode and the anode.
In one embodiment of the present disclosure, there is provided a battery as described herein, wherein the electrolyte is selected from the group consisting of: nonaqueous electrolytic solutions, solid electrolytes, and inorganic solid electrolytes.
In one embodiment of the present disclosure, there is provided a battery as described herein, wherein the cathode is selected from the group consisting of: LiCoO 2 、LiCo 0.99 Al 0.01 O 2 、LiNiO 2 、LiMnO 2 、LiCo 0.5 Ni 0.5 O 2 、LiCo 0.7 Ni 0.3 O 2 、LiCO 0.8 Ni 0.2 O 2 、LiCoO 0.82 Ni 0.18 O 2 、LiC0 0.8 Ni 0.15 Al 0.05 O 2 、LiN 0.4 Co 0.3 Mn 0.3 O 2 And LiNi 0.33 Co 0.33 Mn 0.34 O 2 。
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer; and (c) an electrolyte, wherein the cathode and the metal anode are passed through a porous separatorHeld apart, and wherein the separator prevents electrical contact between the cathode and the anode while allowing ionic conduction between the cathode and the anode, and wherein the separator comprises a material selected from polyethylene, polypropylene or ceramic coated polymeric membranes, and wherein the electrolyte is selected from the group consisting of: a non-aqueous electrolyte solution, a solid electrolyte, and an inorganic solid electrolyte, and wherein the cathode is selected from the group consisting of: LiCoO 2 、LiCo 0.99 Al 0.01 O 2 、LiNiO 2 、LiMnO 2 、LiCo 0 . 5 Ni 0.5 O 2 、LiCo 0.7 Ni 0.3 O 2 、LiCO 0.8 Ni 0.2 O 2 、LiCoO 0.82 Ni 0.18 O 2 ，LiC0 0.8 Ni 0.15 Al 0.05 O 2 、LiN 0.4 Co 0.3 Mn 0.3 O 2 And LiNi 0.33 Co 0.33 Mn 0.34 O 2 。
In one embodiment of the present disclosure, there is provided a battery comprising (a) a cathode; (b) the metal anode includes (i) a copper current collector (106); (ii) a lithium metal layer (104) disposed over the current collector; and (iii) a composite coating (102) disposed on the lithium metal layer, wherein the composite coating includes a porous mixed metal oxide and carbon nanotubes for electric vehicle and storage grid applications.
Although the present subject matter has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible.
Examples of the invention
The present disclosure will now be explained in terms of working examples, which are intended to illustrate the working principle of the present disclosure, without implying any limitation to the scope of the present disclosure in a limiting way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, exemplary methods, devices, and materials are described herein. It is to be understood that this disclosure is not limited to the methods and experimental conditions described, as such methods and conditions are applicable.
The present disclosure relates to a metal anode for a lithium metal battery based on a non-aqueous electrolyte or a polymer gel electrolyte. The shape of the lithium ion battery can be cylindrical, square, button-shaped, and the like. The metal anode of the present disclosure includes a copper current collector (106), a lithium metal layer (104) disposed over the current collector, and a composite coating (102) disposed on the lithium metal layer, wherein the composite coating includes a porous mixed metal oxide (binary mixture of mixed metal oxides) and conductive carbon nanotubes. The composite coating may include at least one binder selected from polyvinylidene fluoride, carboxymethylcellulose (CMC), or polyacrylic acid (PAA). The present disclosure addresses the problem of dendrite formation and regulates lithium deposition by employing a stable composite coating that encapsulates lithium metal and prevents dendrite formation. The fabricated metal anode is used in a lithium ion battery structure that further includes a lithium metal oxide as a cathode and an electrolyte.
Example 1
Preparation of composite coatings
The composite coating of the present disclosure is prepared by the following process. The metal precursor used for the preparation is SiO 2 And SnF 2 。SiO 2 Are commercially available. SnF obtained by evaporation of a solution of SnO in 40% hydrogen fluoride 2 . SiO metal precursor 2 And SnF 2 Grinding at a weight ratio of 3: 1 to obtain the mixed metal oxide. The precursor is continuously milled at an initial temperature in the range of 20 ℃ to 30 ℃ and at a final temperature in the range of 50 ℃ to 60 ℃ to obtain a porous mixed metal oxide having a particle size of less than 1 micron. The porosity of the mixed metal oxide is in the range of 30 to 45 volume% of the mixed metal oxide.
Carbon nanotubes are added to the porous mixed metal oxide in a weight range of 2 to 3% carbon nanotubes relative to the mixed metal oxide. The mixture containing the mixed metal oxide and carbon nanotubes was milled and then 5% of the binder polyvinylidene fluoride (PVDF) was added. This results in a homogeneous mixture comprising the binder, the mixed metal oxide and the carbon nanotubes. To the homogeneous mixture, NMP (N-methyl-2-pyrrolidone) as a solvent was added in an amount of 50 to 60 wt% to obtain a composite coating slurry. The presence of the carbon nanotubes enhances the surface area and also helps to increase the electrical conductivity. Therefore, such commercially available carbon nanotubes are used in the present disclosure.
The porosity of the composite coating was found to be 30 to 40 volume% of the composite coating. The thickness of the lithium metal is in the range of 40 to 50 microns, which is impregnated into the copper metal on both sides, forming lithium metal-copper-lithium metal (Li-Cu-Li). The Li-Cu-Li layer was then encapsulated with the composite coating of example 1. And completing the encapsulation of the composite coating on the Li-Cu-Li through spray coating formation or scraper coating. The composite coating has a thickness of 5 to 20 microns over Li-Cu-Li. The above metal anode was produced in a glove box under an inert atmosphere with an oxygen content of less than 1 ppm. Thus, as shown in fig. 1, a metal anode, a lithium metal-copper-lithium structure encapsulated by a composite coating and a metal anode of the present disclosure were obtained.
Fig. 1 shows a metal anode comprising a copper current collector 106, a lithium metal layer 104 disposed over the current collector, and a composite coating 102 disposed on the lithium metal layer.
Example 3
Lithium ion battery fabricated using metal anodes of the present disclosure
Fig. 2 depicts a lithium ion battery structure using a metal anode of the present disclosure. Fig. 2 shows a lithium battery comprised of a metal anode 208 of the present disclosure, as described in example 2, with an anode current collector 210 at one end and an electrolyte 206 at the other end. The cathode 204 is further attached to a cathode current collector 202 using lithium metal/lithium metal oxide as the cathode 204. Fig. 3 depicts a lithium pouch cell structure with a metal anode of the present disclosure, as described in example 2 above. For pouch cell configurations, a square or rectangular cathode and anode are sandwiched between separators. For cylindrical cells, the continuous winding of the electrode is sandwiched between separators (jelly rolls), while for button-type cells, the disk electrode is sandwiched between separators for cell assembly. The lithium battery is constructed of a three-layered structure. These three layers include cathode 304, separator 302, and metal anode 308 in example 2. Anode (copper) collectorThe fluid 310 is disposed between the metal anodes including the composite coating. The cathode 304 is constructed by coating lithium metal oxide on both sides of a cathode (aluminum) current collector 306. The lithium metal oxide used to make the cathode in the present disclosure is selected from the group consisting of: LiCoO 2 、LiCo 0.99 A10 .01 O 2 、LiNiO 2 、LiMnO 2 、LiCo 0.5 Ni 0.5 O 2 、LiCo 0.7 Ni 0.3 O 2 、LiCO 0.8 Ni 0.2 O 2 、LiCo 0.82 Ni 0.18 O 2 、LiCo 0.8 Ni 0.15 Al 0.05 O 2 、LiN 0.4 Co 0.3 Mn 0.3 O 2 And LiNi 0.33 Co 0.33 Mn 0.34 O 2 . The fabricated cathode was about 70 microns thick and was further used in battery construction. The separator 302 used is a polymeric material selected from polyethylene and polypropylene. Separator 302 is placed between the metal anode and the fabricated cathode of the present disclosure.
The composite coating of the present disclosure is a porous layer that improves conductivity by allowing movement of lithium ions in and out for intercalation, and also suppresses dendrites while reactions occur on the lithium metal electrode. And the separator serves to prevent electrical contact between the cathode and the anode while allowing ionic conduction between the cathode and the anode.
Three layers including an anode, a separator and a cathode were fixed into a case filled with an electrolyte to obtain a lithium battery of the present disclosure. The electrolyte is a solid or liquid electrolyte.
Lithium ion batteries including the metal anodes of the present disclosure provide an enhanced battery arrangement. Such a metal anode comprising a copper current collector, a composite coating and a lithium metal layer will have improved conductivity properties, thereby improving battery characteristics. And more particularly to improving overall battery performance and battery life by increasing the number of charge/discharge cycles.
Although the present subject matter has been described in considerable detail with reference to certain examples and embodiments, other embodiments are possible.
The advantages of the present disclosure:
the present disclosure provides a metal anode comprising a copper current collector, lithium metal, and a composite coating. The composite coating is a binary mixture of a porous mixed metal oxide and conductive carbon nanotubes. The metal anode of the present disclosure inhibits dendritic growth of lithium ions at the metal anode and exhibits enhanced conductivity. The metal anode of the present disclosure helps to avoid short circuits. Metal anodes exhibit high energy densities and are useful in portable electronic devices and electric vehicles. In vehicles, lithium ion batteries including the metal anodes of the present disclosure exhibit enhanced performance, durability, usability, and ease of assembly. Such metal anodes reduce cell weight, reduce cost, and are easy to handle.

Claims (16)

1. A metal anode, comprising:
(a) a copper current collector (106);
(b) a lithium metal layer (104) disposed over the copper current collector (106); and
(c) a composite coating (102) disposed on the lithium metal layer (104),
wherein the composite coating (102) comprises a porous mixed metal oxide and carbon nanotubes.
2. The metal anode of claim 1, wherein the lithium metal layer (104) has a thickness in the range of 40 μ ι η to 50 μ ι η.
3. The metal anode of claim 1, wherein the composite coating (102) has a thickness in the range of 5 μ ι η to 20 μ ι η.
4. The metal anode of claim 1, wherein the composite coating (102) comprises at least one binder.
5. The metal anode of claim 4, wherein the at least one binder is selected from the group consisting of: polyvinylidene fluoride, carboxymethylcellulose (CMC), polyacrylic acid (PAA), and combinations thereof.
6. The metal anode of claim 1, wherein the composite coating (102) has a porosity in the range of 30 to 40 vol.% relative to the composite coating (102).
7. A method of making the metal anode of claim 1, the method comprising:
a) obtaining a metal precursor;
b) milling the metal precursor to obtain a porous mixed metal oxide;
c) bonding carbon nanotubes to the porous mixed metal oxide in the presence of a binder to obtain a composite coating; and
d) encapsulating lithium metal-copper-lithium metal (Li-Cu-Li) with the composite coating.
8. The method of making the metal anode of claim 7, wherein the metal precursor is selected from the group consisting of: SiO 2 2 、SnF 2 And combinations thereof.
9. The method of manufacturing the metal anode of claim 7, wherein milling the metal precursor is done at a temperature in the range of 20 ℃ to 70 ℃ to obtain a porous mixed metal oxide.
10. The method of making the metal anode of claim 7, wherein lithium metal-copper-lithium metal is encapsulated with the composite coating by a process selected from spray layer formation or doctor blade coating.
11. A battery, comprising:
(a) a cathode;
(b) the metal anode of any one of claims 1 to 6; and
(c) an electrolyte.
12. The battery of claim 11, wherein the cathode and the metal anode are held apart by a porous separator.
13. The battery of claim 11, wherein the separator prevents electrical contact between the cathode and the anode while allowing ionic conduction between the cathode and the anode.
14. The battery of claim 13, wherein the separator comprises a material selected from a polyethylene coated polymer film, a polypropylene coated polymer, or a ceramic coated polymer film.
15. The battery of claim 11, wherein the electrolyte is selected from the group consisting of: nonaqueous electrolytic solutions, solid electrolytes, and inorganic solid electrolytes.
16. The battery of claim 11, wherein the cathode is selected from the group consisting of: LiCoO 2 、LiCo 0.99 Al 0.01 O 2 、LiNiO 2 、LiMnO 2 、LiCo 0.5 Ni 0.5 O 2 、LiCo 0.7 Ni 0.3 O 2 、LiCO 0.8 Ni 0.2 O 2 、LiCoO 0.82 Ni 0.18 O 2 、LiC0 0.8 Ni 0.15 Al 0.05 O 2 、LiN 0.4 Co 0.3 Mn 0.3 O 2 And LiNi 0.33 Co 0.33 Mn 0.34 O 2 。
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