CN113258076B - Metal lithium cathode, preparation method thereof and lithium ion battery - Google Patents
Metal lithium cathode, preparation method thereof and lithium ion battery Download PDFInfo
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- 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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/74—Meshes or woven material; Expanded metal
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- 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
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Abstract
The invention belongs to the technical field of batteries, and particularly relates to a metal lithium cathode and a preparation method thereof, and a lithium ion battery. Wherein, the lithium metal negative pole includes the lithium metal composite piece that a plurality of stromatolites laminating set up, the lithium metal composite piece includes: the lithium battery comprises a metal current collector mesh, a conductive carbon material layer combined on at least one surface of the metal current collector mesh, and a lithium metal layer deposited on the surface of the conductive carbon material layer. The lithium metal negative electrode can effectively reduce the influence of current density on the working surface of the negative electrode, inhibit the growth of lithium dendrites and has positive effects on the application of a high-rate lithium metal battery. When the metal lithium cathode is applied to a battery, the multiplying power performance of the battery material can be effectively improved, and the cycle life of the battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a metal lithium cathode and a preparation method thereof, and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, long cycle life, no memory effect and the like, and is widely applied to the fields of mobile phones, computers, cameras, electric vehicles and the like. With the continuous development of scientific technology, various application fields put higher demands on the performance of the lithium ion battery, wherein the most urgent is to improve the energy density of the lithium ion battery on the premise of ensuring safety. At present, the industry is pursuing higher energy density of lithium batteries, which is also an important index reflecting battery technology. For this reason, a higher gram capacity of the positive and negative electrode materials is required.
The lithium metal negative electrode is used as an ideal electrode material of a next-generation lithium battery and has ultrahigh theoretical specific capacity (3860mAh g)-1) And is extremely lowElectrochemical potential (-3.04V vs standard hydrogen electrode). At present, extensive research on lithium metal materials has been conducted all over the world, and lithium metal batteries have also been advanced to some extent on the way to applications. However, lithium metal is very reactive with other materials due to its chemical and electrochemical activity, and produces by-products. In addition, during the deposition of lithium ions on the working surface of the negative electrode, the deposition process of lithium ions is complicated due to the slight difference of potential at each point on the surface of the lithium metal electrode. Because the deposition speed of each point is different, the final deposition state of lithium ions also changes, lithium dendrite growth is finally caused, safety problems such as battery thermal runaway and the like are caused by puncturing a diaphragm, and the lithium dendrite growth caused by the potential difference is further aggravated by a larger current density. In the prior art, in the technology of improving the stability of lithium metal by compounding a carbon material and lithium metal, the carbon material is easy to fall off from a lithium metal negative electrode in the process of battery cyclic charge and discharge, so that the problems of uneven subsequent lithium ion deposition and the like are caused, and the cycle life of the battery is influenced.
Disclosure of Invention
The invention aims to provide a metallic lithium cathode, a preparation method thereof and a lithium ion battery, and aims to solve the problems that the conventional lithium metallic cathode is easy to grow lithium dendrites and the cycle stability and safety of the lithium ion battery are reduced to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a lithium metal negative electrode including a plurality of laminated lithium metal composite sheets, wherein the lithium metal composite sheets include: the lithium battery comprises a metal current collector mesh, a conductive carbon material layer combined on at least one surface of the metal current collector mesh, and a lithium metal layer deposited on the surface of the conductive carbon material layer.
In the lithium metal cathode provided by the first aspect of the invention, the conductive carbon material layer has excellent conductivity, and the electron transfer efficiency of the cathode can be improved; and the lithium ion conductive lithium ion battery has strong lithium affinity, can guide lithium ions into the metal lithium negative electrode, reduces the current density on the surface of the lithium metal layer, and simultaneously can reduce the safety risk that the lithium dendrite grows to pierce the diaphragm by depositing the lithium ions in the internal conductive carbon material layer. The lithium metal negative electrode can effectively reduce the influence of current density on the working surface of the negative electrode, inhibit the growth of lithium dendrites and has positive effects on the application of a high-rate lithium metal battery. When the metal lithium cathode is applied to a battery, the multiplying power performance of the battery material can be effectively improved, and the cycle life of the battery is prolonged.
Further, the metal lithium cathode comprises 3-25 layers/mm of lithium metal composite sheets laminated and attached; the metal lithium cathode made of the lithium metal composite sheets with the laminated number not only ensures the energy density of the cathode, but also has the lithium releasing and embedding effect; but also ensures the stability of the lithium metal cathode structure.
Further, the side surface formed by the lithium metal composite sheet which is formed by laminating the plurality of layers is used as a negative working surface, so that the current density of the negative working surface under the condition of high-rate current test can be greatly reduced, and the high-rate cycle life of the battery cell can be obviously prolonged. The current density of the working surface of the negative electrode is reduced, the speed of lithium ions depositing on the working surface of the negative electrode to form lithium dendrites is reduced, and the safety risk that the lithium dendrites grow and pierce through the diaphragm is reduced.
Further, the thickness of the conductive carbon material layer is 0.3-3 μm; the conductive carbon material layer with the thickness not only ensures the covering effect of the conductive carbon material on the metal current collector net, but also ensures the lithium ion guiding effect of the conductive carbon material on the lithium metal layer and the working surface of the negative electrode.
Further, the surface capacity of the lithium metal layer is 0.2-10 mAh/cm2(ii) a Sufficient active lithium is provided for carrying out lithium ion deposition and peeling behaviors, and the influence of electrochemical potential difference of each point on the surface of the metal lithium on stability is reduced.
Further, in the lithium metal composite sheet, the mass ratio of the conductive carbon material layer to the metal current collector net is 1: (5-15); the conductive carbon material prepared according to the proportion can form a complete conductive carbon material layer with uniform thickness on the surface of the metal current collector net.
Further, the conductive carbon material layer includes: an electrically conductive carbon material and a binder, wherein the electrically conductive carbon material is selected from the group consisting of: at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene, wherein the carbon material has excellent conductivity; the binder is selected from: the binding agent is at least one of polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene butadiene rubber, polyvinylidene fluoride and epoxy resin, has strong cohesiveness, can improve the combination stability of the conductive carbon material and the metal current collector net, and has a certain inhibiting effect on the volume expansion between the middle layers of the negative electrode.
Further, the metallic current collector mesh comprises: at least one metal selected from copper, nickel and titanium; the current collector nets made of the materials have high conductivity, and can collect the current generated by the battery so as to form large current to be output outwards.
Further, the mesh length and the mesh width of the metal current collector net are respectively and independently 0.5-2 mm. Further, the surface density of the metal current collector net is 150-500 g/m2(ii) a If the meshes of the metal current collector net are too large, current conduction is affected, the temperature rises too fast under a large multiplying power, and the safety performance of the battery is reduced; if the mesh of the metal current collector net is too small, the difficulty of the preparation process is high, and meanwhile, the coating effect of the conductive agent and the lithium metal deposition effect are reduced.
Further, the thickness of the metal current collector net is 15-45 μm; if the thickness of the metal current collector mesh is too high, the mass energy density of the battery is reduced, and if the thickness of the metal current collector mesh is too low, the Direct Current Resistance (DCR) is excessively large.
Furthermore, in the conductive carbon material layer, the mass ratio of the conductive carbon material to the binder is (1-2): (0.4-3.5), the conductive carbon material is favorably coated and deposited on the surface of the metal current collector net, a conductive carbon material layer which is uniform and stable in combination is formed on the surface of the metal current collector net, and meanwhile, the cohesiveness among the conductive carbon materials and between the carbon materials and the copper net is ensured.
In a second aspect, the present invention provides a method for preparing a lithium metal anode, comprising the steps of:
obtaining a metal current collector net, and combining a conductive carbon material on at least one surface of the metal current collector net to form a conductive carbon material layer;
depositing metal lithium on the surface of the conductive carbon material layer to form a lithium metal layer, so as to obtain a lithium metal composite sheet;
and laminating and attaching a plurality of lithium metal composite sheets to obtain the metal lithium cathode.
The preparation method of the lithium metal cathode provided by the second aspect of the invention has a simple process and is suitable for industrial large-scale production and application. The prepared metal lithium cathode can guide lithium ions into the metal lithium cathode through the lithium affinity performance of the conductive carbon material layer in the lamination, effectively reduces the influence of current density on the working surface of the cathode, inhibits the growth of lithium dendrites, and has positive effects on the application of a high-rate lithium metal battery.
Further, the step of bonding the conductive carbon material to the surface of the metallic current collector mesh comprises: after the metal current collector net is subjected to chemical modification treatment, the mixed slurry of the conductive carbon material and the binder is deposited on at least one surface of the metal current collector net, and the conductive carbon material layer is formed through drying. The metal current collector net is subjected to chemical modification treatment, so that the bonding performance of the conductive carbon material on the current collector net can be improved, and the using amount of a binder is reduced. The binder can further improve the combination stability of the conductive carbon material and the metal current collector mesh, can inhibit the expansion problem between layers of the metal current collector mesh in the lithium deposition process to a certain extent, and reduces the aging and separation risks between the layers of the metal lithium negative electrode.
Further, in the mixed slurry of the conductive carbon material and the binder, the mass ratio of the conductive carbon material to the binder to the solvent is (1-2): (0.4-3.5): (0.3-3), the proportion can make conductive carbon material and binder form the suitable thick liquids of viscosity, is favorable to thick liquids coating deposit at the metal mass flow body net surface, forms comparatively even and combines stable conductive carbon material layer at the metal mass flow body net surface, has guaranteed the cohesiveness between the conductive carbon material and between carbon material and the copper mesh simultaneously.
Further, the step of chemically modifying treatment comprises: treating the metal current collector net by using an alkaline solution; the etching effect of the alkaline solution on the smooth surface of the metal current collector net enables the current collector net to form a rough and irregular surface, and simultaneously forms chemical active groups such as alkaline hydroxyl groups and the like, so that the conductive carbon material is more firmly combined.
Further, the alkaline solution includes: the alkaline solution can chemically modify the metal current collector net to form a rough and irregular surface containing active groups, which is favorable for the combination of conductive carbon materials.
Further, the concentration of the alkaline solution is 0.5-3 mol/L; the alkaline solution with the concentration range has the best chemical modification effect on the metal current collector net.
Further, the step of depositing metallic lithium on the surface of the conductive carbon material layer comprises: under the inert atmosphere with the water oxygen content of less than 0.5ppm, assembling a composite layer of a conductive carbon material layer and a metal current collector net and metal lithium into a half cell, and depositing the metal lithium on the surface of the conductive carbon material layer under the drive of current to form a lithium metal layer; the composite layer and the lithium metal are assembled into the half-cell, and the metal lithium is deposited in an electrochemical mode, so that the formed lithium metal layer is compact and stable, and the surface capacity of the lithium metal layer can be flexibly regulated and controlled.
Further, the step of laminating and arranging the plurality of lithium metal composite sheets comprises: and (3) laminating the plurality of lithium metal composite sheets, and then performing rolling treatment to fix the plurality of lithium metal composite sheets to form the lithium metal cathode. The stability of the binding capacity between layers in the lithium metal cathode is improved, and the lithium metal cathode is ensured not to fall off among lithium metal composite sheets in the subsequent cycle process; the stability and the safety of the metal lithium cathode and the battery are improved.
Further, the metal lithium cathode comprises 3-25 layers/mm of lithium metal composite sheets laminated and attached; the metal lithium cathode made of the lithium metal composite sheets with the laminated number not only ensures the energy density of the cathode, but also has the lithium releasing and embedding effect; but also ensures the stability of the lithium metal cathode structure.
Further, a lamination side surface of a side surface formed by laminating and attaching a plurality of lithium metal composite sheets is used as a working surface of the negative electrode; the current density of the working surface of the negative electrode can be greatly reduced under the condition of high-rate current test, and the high-rate cycle life of the battery cell can be obviously prolonged. The current density of the working surface of the negative electrode is reduced, the speed of lithium ions depositing on the working surface of the negative electrode to form lithium dendrites is reduced, and the safety risk that the lithium dendrites grow to pierce through the diaphragm is reduced.
Further, the thickness of the conductive carbon material layer is 0.3-3 μm; the conductive carbon material layer with the thickness not only ensures the covering effect of the conductive carbon material on the metal current collector net, but also ensures the lithium ion guiding effect of the conductive carbon material on the lithium metal layer and the working surface of the negative electrode.
Further, the surface capacity of the lithium metal layer is 0.2-10 mAh/cm2(ii) a And enough active lithium is provided for carrying out lithium ion deposition and exfoliation, and the influence of electrochemical potential difference of each point on the surface of the metal lithium on stability is reduced.
Further, in the lithium metal composite sheet, the mass ratio of the conductive carbon material layer to the metal current collector net is 1: (5-15); the conductive carbon material with the proportion can form a complete conductive carbon material layer with uniform thickness on the surface of the metal current collector net.
Further, the conductive carbon material layer includes: an electrically conductive carbon material and a binder, wherein the electrically conductive carbon material is selected from the group consisting of: at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene; the binder is selected from: at least one of polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene butadiene rubber, polyvinylidene fluoride and epoxy resin.
Further, the metallic current collector mesh comprises: at least one metal selected from copper, nickel and titanium; the current collector nets made of the materials have high conductivity, and can collect the current generated by the battery so as to form large current to be output.
Further, the mesh length and the mesh width of the metal current collector net are respectively and independently 0.5-2 mm; the surface density of the metal current collector net is 150-500 g/m2(ii) a If the meshes of the metal current collector net are too large, current conduction is affected, the temperature rises too fast under a large multiplying power, and the safety performance of the battery is reduced; if the meshes of the metal current collector net are too small, the preparation process difficulty is high, and meanwhile, the conductive agent coating and lithium metal deposition effects are reducedLow.
Furthermore, the thickness of the metal current collector net is 15-45 μm. If the thickness of the metal current collector mesh is too high, the mass energy density of the battery is reduced, and if the thickness of the metal current collector mesh is too low, the Direct Current Resistance (DCR) is excessively large.
In a third aspect, the present invention provides a lithium ion battery comprising the above-described metallic lithium negative electrode, or comprising the metallic lithium negative electrode prepared by the above-described method.
According to the lithium ion battery provided by the third aspect of the invention, due to the fact that the lithium metal negative electrode with the characteristics of high energy density, low surface current density, slow growth of lithium dendrite and the like is included, the rate capability, the cyclic charge and discharge life and the safety performance of the battery material are effectively improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a lithium metal composite sheet according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a lithium metal negative electrode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In the present invention, the term "and/or" describes the association relationship of the associated objects, and means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present invention, the sequence numbers of the above-mentioned processes do not imply an order of execution, some or all steps may be executed in parallel or executed sequentially, and the order of execution of each process should be determined by its function and inherent logic, and should not limit the implementation process of the embodiments of the present invention in any way.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the mass in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1 to 2, in a first aspect, an embodiment of the present invention provides a lithium metal negative electrode, including a plurality of laminated lithium metal composite sheets, where the lithium metal composite sheets include: the lithium battery comprises a metal current collector mesh, a conductive carbon material layer combined on at least one surface of the metal current collector mesh, and a lithium metal layer deposited on the surface of the conductive carbon material layer.
The lithium metal negative electrode provided by the first aspect of the embodiment of the invention comprises a plurality of laminated lithium metal composite sheets, and each lithium metal composite sheet comprises a metal current collector net, a conductive carbon material layer and a lithium metal layer which are sequentially laminated and combined. The metal current collector adopts a net structure, so that materials such as a conductive carbon material layer and the like can be fixed, the using amount of a binder is reduced, and the energy density of the metal lithium cathode can be improved. The conductive carbon material layer has excellent conductivity, and can improve the electron transfer efficiency of the cathode; and the lithium ion conductive lithium ion battery has strong lithium affinity, can guide lithium ions into the metal lithium negative electrode, reduces the current density on the surface of the lithium metal layer, and simultaneously can reduce the safety risk that the lithium dendrite grows to pierce the diaphragm by depositing the lithium ions in the internal conductive carbon material layer. The lithium metal negative electrode provided by the embodiment of the invention can effectively reduce the influence of current density on the working surface of the negative electrode, inhibit the growth of lithium dendrites, and has a positive effect on the application of a high-rate lithium metal battery. When the metal lithium cathode is applied to a battery, the multiplying power performance of the battery material can be effectively improved, and the cycle life of the battery is prolonged.
As shown in fig. 2, in some embodiments, the side surface formed by several layers of the lithium metal composite sheets arranged in a lamination manner is used as the working surface of the negative electrode, i.e. the working surface of the negative electrode contacting with the separator. In some embodiments, the laminated side surface may be a cross section of a side surface formed by a plurality of lithium metal composite sheets laminated and arranged in the lithium metal negative electrode, and in an application, the lithium metal negative electrode is cut into a suitable size according to an actual application requirement, and the cut laminated section is used as a working surface of the negative electrode. In the embodiment of the present invention, a side surface formed by a plurality of laminated lithium metal composite sheets is used as a negative working surface, that is, the negative working surface is a laminated arrangement plane of the lithium metal composite sheets, for example: the negative electrode plane is formed by an alternate lamination structure of a metal current collector net, a conductive carbon material layer and a lithium metal layer, or the alternate lamination structure of the lithium metal layer, the conductive carbon material layer, the metal current collector net, the conductive carbon material layer and the lithium metal layer. On the one hand, the current density of the working surface of the negative electrode can be greatly reduced under the condition of high-rate current test, and the high-rate cycle life of the battery cell can be obviously prolonged. On the other hand, the normal lithium ion exfoliation deposition behavior occurs on the lithium metal surface, however, in the embodiment of the present invention, the laminated side surface is adopted as the negative working surface, since the metal current collector mesh has lithium-phobic property, and the conductive carbon material has lithium-philic property, the conductive carbon material can sufficiently guide the lithium ions on the negative working surface into and enrich in the conductive carbon material layer inside the negative electrode, thereby reducing the current density of the negative working surface, reducing the rate of lithium ions depositing on the negative working surface to form lithium dendrites, and reducing the safety risk of the lithium dendrites growing to pierce the diaphragm.
The number of the laminated layers of the lithium metal composite sheet in the metal lithium cathode can be flexibly selected according to application requirements of actual battery packaging form, battery system, energy density, volume and the like. In some embodiments, the metal lithium cathode comprises 3-25 layers/mm of laminated and laminated lithium metal composite sheets, and the metal lithium cathode made of the laminated lithium metal composite sheets not only ensures the energy density of the cathode, but also ensures the lithium releasing and embedding effects; but also ensures the stability of the lithium metal cathode structure. In the application process, reasonable selection and application can be carried out according to the actual battery system and the requirement. In some embodiments, the lithium metal negative electrode comprises 3-8 layers/mm, 8-12 layers/mm, 12-18 layers/mm or 18-25 layers/mm of a lithium metal composite sheet laminated and attached.
In some embodiments, the surface capacity of the lithium metal layer is 0.2-10 mAh/cm2(ii) a If the surface capacity of the lithium metal layer is too low, it is difficult to provide sufficient active lithium for the lithium ion deposition exfoliation behavior, and the energy density of the negative electrode is reduced(ii) a If the surface capacity of the lithium metal layer is too high, the metal lithium is excessive, the mass energy density of the negative electrode is reduced, and meanwhile, due to the difference of electrochemical potentials of all points on the surface of the metal lithium, the deposition and peeling of the lithium are uneven due to too thick metal lithium, so that the stability of the metal lithium negative electrode in the charging and discharging process is affected. In some embodiments, the surface capacity of the lithium metal layer may be 0.2 to 1mAh/cm2、1～2mAh/cm2、2～5mAh/cm2、5～8mAh/cm2Or 8-10 mAh/cm2。
In some embodiments, the thickness of the conductive carbon material layer is 0.3-3 μm, and the conductive carbon material layer with the thickness ensures the covering effect of the conductive carbon material on the metal current collector mesh and the lithium ion guiding effect of the conductive carbon material on the lithium metal layer and the working surface of the negative electrode. If the thickness of the conductive carbon material layer is too low, the affinity guiding effect of the conductive carbon material on lithium ions on the working surface of the negative electrode is not facilitated, and the growth inhibiting effect on lithium dendrites is not good; if the content of the conductive carbon material layer is excessively high, the energy density of the lithium metal anode is reduced. In some embodiments, the conductive carbon material layer has a thickness of 0.3-0.8 μm, 0.8-1.5 μm, 1.5-2 μm, 2-2.5 μm, or 2.5-3 μm.
In some embodiments, the mass ratio of the conductive carbon material layer to the metal current collector mesh in the lithium metal composite sheet is 1: (5-15), the conductive carbon material prepared according to the proportion can form a complete conductive carbon material layer with uniform thickness on the surface of the metal current collector net, if the content of the conductive carbon material is too low, the complete conductive carbon material layer is difficult to form, the balanced guide adsorption effect of the conductive carbon material layer on lithium ions on the surface of the lithium metal layer is not facilitated, and local lithium dendrite on the working surface of the negative electrode can grow too fast to damage a diaphragm; if the content of the conductive carbon material is too high, the formed conductive carbon material layer is too thick, which is not beneficial to the stability of the conductive carbon material layer combined on the surface of the metal current collector net, and simultaneously reduces the energy density of the metal lithium negative electrode.
In some embodiments, the conductive carbon material layer comprises: an electrically conductive carbon material and a binder, wherein the electrically conductive carbon material is selected from the group consisting of: at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene; the binder is selected from: at least one of polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene butadiene rubber, polyvinylidene fluoride and epoxy resin. The conductive carbon material layer is deposited on the surface of the metal current collector net in a form of mixing the conductive carbon material and the binder to form the conductive carbon material layer, wherein the binder can improve the combination stability of the conductive carbon material and the metal current collector net, can inhibit the expansion problem between layers of the metal current collector net in the lithium deposition process to a certain extent, and reduces the aging and separation risks between the layers of the metal lithium negative electrode.
In some embodiments, in the conductive carbon material layer, the mass ratio of the conductive carbon material to the binder is (1-2): (0.4-3.5), the proportion can make the conductive carbon material relatively even and stable combination at the metal mass collector net surface, has guaranteed the cohesiveness between the conductive carbon material and between carbon material and the copper mesh simultaneously. In some embodiments, the mass ratio of the conductive carbon material and the binder may be 1: (0.4-1), 1: (1-2) and 1: (2-3) and 1: (3-3.5) and 2: (0.4-1), 2: (1-2) and 2: (2-3) and the like.
In some embodiments, the metallic current collector mesh comprises: the current collector nets made of the materials have high conductivity, and can collect the current generated by the battery so as to form large current to be output outwards.
In some embodiments, the mesh length and width of the metallic current collector mesh are each independently 0.5-2 mm; the surface density of the metal current collector net is 150-500 g/m2(ii) a If the meshes of the metal current collector net are too large, current conduction is affected, the temperature rises too fast under a large multiplying power, and the safety performance of the battery is reduced; if the mesh of the metal current collector net is too small, the difficulty of the preparation process is high, and meanwhile, the coating effect of the conductive agent and the lithium metal deposition effect are reduced. In some embodiments, the mesh length and width of the metallic current collector mesh are independently 0.5-1 mm, 1-1.5 mm, 1.5-2 mm, etc.; the surface density of the metal current collector net can be 150-200 g/m2、200～300g/m2、300～400g/m2、400～500g/m2And the like.
In some embodiments, the metal current collector mesh has a thickness of 15-45 μm; if the thickness of the metal current collector mesh is too high, the mass energy density of the battery is reduced, and if the thickness of the metal current collector mesh is too low, the Direct Current Resistance (DCR) is excessively large. In some embodiments, the thickness of the metal current collector mesh may be 15-20 μm, 20-30 μm, 30-40 μm, 40-45 μm, or the like.
Examples of the present invention lithium metal negative electrodes can be prepared by the following example methods.
In a second aspect of the embodiments of the present invention, there is provided a method for preparing a lithium metal negative electrode, including the steps of:
s10, obtaining a metal current collector net, and combining a conductive carbon material on at least one surface of the metal current collector net to form a conductive carbon material layer;
s20, depositing metal lithium on the surface of the conductive carbon material layer to form a lithium metal layer to obtain a lithium metal composite sheet;
and S30, laminating and attaching a plurality of lithium metal composite sheets to obtain the lithium metal cathode.
In the method for manufacturing a lithium metal negative electrode according to the second aspect of the embodiments of the present invention, after the conductive carbon material is bonded to at least one surface of the metal current collector mesh to form the conductive carbon material layer with a stable structure, lithium metal is deposited on the surface of the conductive carbon material layer to form the lithium metal layer, so as to obtain the lithium metal composite sheet. And then laminating and attaching a plurality of lithium metal composite sheets to obtain the lithium metal cathode. The preparation method of the lithium metal cathode provided by the embodiment of the invention is simple in process and suitable for industrial large-scale production and application. The prepared metal lithium cathode can guide lithium ions into the metal lithium cathode through the lithium affinity performance of the conductive carbon material layer in the lamination, effectively reduces the influence of current density on the working surface of the cathode, inhibits the growth of lithium dendrites, and has positive effects on the application of a high-rate lithium metal battery.
In some embodiments, in the step S10, the step of bonding the conductive carbon material to the surface of the metal current collector mesh includes: after the metal current collector net is subjected to chemical modification treatment, mixed slurry of a conductive carbon material and a binder is deposited on one surface or two surfaces of the metal current collector net, and the conductive carbon material layer is formed through drying. According to the embodiment of the invention, the metal current collector net is subjected to chemical modification treatment, so that the surface of the metal current collector net is rough, and meanwhile, chemical active sites are formed, and the bonding stability of the conductive carbon material on the surface of the metal current collector net can be improved. And then, depositing the mixed slurry of the conductive carbon material and the binder on the surface of the metal current collector mesh to form a conductive carbon material layer, wherein the binder can further improve the combination stability of the conductive carbon material and the metal current collector mesh, and can inhibit the expansion problem between layers of the metal current collector mesh in the lithium deposition process to a certain extent, thereby reducing the risk of aging and separation between layers of the metal lithium cathode.
In some embodiments, the conductive carbon material layer comprises: an electrically conductive carbon material and a binder, wherein the electrically conductive carbon material is selected from the group consisting of: at least one of carbon black, conductive graphite, carbon fiber, single-walled or multi-walled carbon nanotube and graphene, wherein the carbon material has excellent conductivity; the binder is selected from: the binding agent is at least one of polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene butadiene rubber, polyvinylidene fluoride and epoxy resin, has strong cohesiveness, can improve the combination stability of the conductive carbon material and the metal current collector net, and has a certain inhibiting effect on the volume expansion between the middle layers of the negative electrode.
In some embodiments, in the mixed slurry of the conductive carbon material and the binder, the mass ratio of the conductive carbon material to the binder to the solvent is (1-2): (0.4-3.5): (0.3-3). The proportion can enable the conductive carbon material and the binder to form slurry with proper viscosity, is favorable for coating and depositing the slurry on the surface of the metal current collector net, forms a relatively uniform and stably combined conductive carbon material layer on the surface of the metal current collector net, and simultaneously ensures the cohesiveness between the conductive carbon materials and between the carbon materials and the copper net.
In some embodiments, the step of chemically modifying comprises: treating the metal current collector net by using an alkaline solution; the smooth surface of the metal current collector net is etched by the alkaline solution, so that the current collector net forms a rough and irregular surface, and the conductive carbon material can be more firmly combined physically; meanwhile, the alkaline solution can form alkaline hydroxyl and other chemical active groups on the irregular surface of the current collector net, so that the chemical combination of the conductive carbon material is facilitated, and the combination stability of the conductive carbon material and the metal current collector net is further improved. In some embodiments, the metal current collector mesh may be immersed in an alkaline solution, such that the alkaline solution etches the metal current collector mesh throughout.
In some embodiments, the alkaline solution comprises: at least one of ammonium chloride, ferric trichloride and ammonia water, wherein the alkaline solutions can chemically modify the metal current collector net to form a rough and irregular surface containing active groups, so that the combination of conductive carbon materials is facilitated.
In some embodiments, the concentration of the alkaline solution is 0.5mol/L to 3mol/L, the alkaline solution in the concentration range has the best chemical modification effect on the metal current collector net, and if the concentration is too low, the modification effect of the alkaline solution on the surface of the metal current collector is not facilitated; if the concentration is too high, the etching effect of the alkaline solution on the metal current collector is too strong, and the network structure of the metal current collector is easily damaged.
In some embodiments, the metal current collector net is immersed in at least one alkaline solution of ammonium chloride, ferric chloride and ammonia water with the concentration of 0.5mol/L-3mol/L for 0.2-2 hours, so that the alkaline solution can completely etch the metal current collector net.
In some embodiments, the metallic current collector mesh comprises: at least one metal selected from copper, nickel and titanium; the current collector nets made of the materials have high conductivity, and can collect the current generated by the battery so as to form large current to be output outwards.
In some embodiments, the mesh length and width of the metallic current collector mesh are each independently 0.5-2 mm; the surface density of the metal current collector net is 150-500 g/m2(ii) a If the meshes of the metal current collector net are too large, current conduction is affected, the temperature rises too fast under a large multiplying power, and the safety performance of the battery is reduced; if the mesh of the metal current collector net is too small, the difficulty of the preparation process is highAnd at the same time, the conductive agent coating and lithium metal deposition effects are reduced.
In some embodiments, the thickness of the metal current collector mesh is 15-45 μm, which may reduce the mass energy density of the battery if the thickness of the metal current collector mesh is too high, and may cause a large Direct Current Resistance (DCR) if the thickness of the metal current collector mesh is too low.
In some embodiments, the conductive carbon material layer has a thickness of 0.3 to 3 μm; the conductive carbon material layer with the thickness not only ensures the covering effect of the conductive carbon material on the metal current collector net, but also ensures the lithium ion guiding effect of the conductive carbon material on the lithium metal layer and the working surface of the negative electrode.
In some embodiments, the mass ratio of the conductive carbon material layer to the metallic current collector mesh is 1: (5-15); the conductive carbon material prepared according to the proportion can form a complete conductive carbon material layer with uniform thickness on the surface of the metal current collector net, if the content of the conductive carbon material is too low, the complete conductive carbon material layer is difficult to form, the balanced guide adsorption effect of the conductive carbon material layer on lithium ions on the surface of the lithium metal layer is not facilitated, and the local lithium dendrite on the working surface of the negative electrode possibly grows too fast to damage a diaphragm; if the content of the conductive carbon material is too high, the formed conductive carbon material layer is too thick, which is not beneficial to the stability of the conductive carbon material layer combined on the surface of the metal current collector net, and simultaneously reduces the energy density of the metal lithium negative electrode.
In some embodiments, in step S20, the step of depositing lithium metal on the surface of the conductive carbon material layer includes: and under the inert atmosphere of nitrogen, argon and the like with the water oxygen content of less than 0.5ppm, assembling the composite layer of the conductive carbon material layer and the metal current collector net and the metal lithium into a half cell, and depositing the metal lithium on the surface of the conductive carbon material layer under the current driving to form a lithium metal layer. According to the embodiment of the invention, the composite layer and the lithium metal are assembled into the half-cell, and the lithium metal is deposited in an electrochemical mode, so that the formed lithium metal layer is compact and stable, and the surface capacity of the lithium metal layer can be flexibly regulated and controlled.
In some embodiments, the surface capacity of the lithium metal layer is 0.2-10 mAh/cm2(ii) a If the surface capacity of the lithium metal layer is too low, it is difficult to provide sufficient active lithium for lithium ion depositionThe energy density of the negative electrode is reduced due to the peeling behavior; if the surface capacity of the lithium metal layer is too high, the metal lithium is excessive, the mass energy density of the negative electrode is reduced, and meanwhile, due to the difference of electrochemical potentials of all points on the surface of the metal lithium, the deposition and peeling of the lithium are uneven due to too thick metal lithium, so that the stability of the metal lithium negative electrode in the charging and discharging process is affected.
In some embodiments, in step S30, the step of laminating the plurality of lithium metal composite sheets includes: and laminating the plurality of lithium metal composite sheets, and then performing rolling treatment to fix the plurality of lithium metal composite sheets to form the lithium metal cathode. According to the embodiment of the invention, the plurality of lithium metal composite sheets are laminated and then rolled, so that the stability of the binding capacity between layers in the lithium metal cathode is improved, and the lithium metal cathode is ensured not to fall off among the lithium metal composite sheets in the subsequent circulation process; the stability and the safety of the metal lithium cathode and the battery are improved.
In some embodiments, the lithium metal anode comprises 3-25 layers/mm of lithium metal composite sheet laminated and arranged; the metal lithium cathode made of the lithium metal composite sheets with the laminated number not only ensures the energy density of the cathode, but also has the lithium releasing and embedding effect; but also ensures the stability of the lithium metal cathode structure. The number of the laminated layers of the lithium metal composite sheet in the metal lithium cathode can be flexibly selected according to the application requirements of the energy density, the volume and the like of an actual battery.
In some embodiments, a side surface formed by laminating a plurality of lithium metal composite sheets is used as a working surface of the negative electrode; in the embodiment of the invention, the side surface formed by laminating and attaching a plurality of lithium metal composite sheets is used as the working surface of the negative electrode, that is, the working surface of the negative electrode is the laminating arrangement plane of the lithium metal composite sheets, such as: the negative electrode plane is formed by an alternate laminated structure of a metal current collector net, a conductive carbon material layer and a lithium metal layer, or the negative electrode plane is formed by an alternate laminated structure of the lithium metal layer, the conductive carbon material layer, the metal current collector net, the conductive carbon material layer and the lithium metal layer. On the one hand, the current density of the working surface of the negative electrode can be greatly reduced under the condition of high-rate current test, and the high-rate cycle life of the battery cell can be obviously prolonged. On the other hand, the normal lithium ion exfoliation deposition behavior occurs on the lithium metal surface, however, in the embodiment of the present invention, the laminated side surface is adopted as the negative working surface, since the metal current collector mesh has lithium-phobic property, and the conductive carbon material has lithium-philic property, the conductive carbon material can sufficiently guide the lithium ions on the negative working surface into and enrich in the conductive carbon material layer inside the negative electrode, thereby reducing the current density of the negative working surface, reducing the rate of lithium ions depositing on the negative working surface to form lithium dendrites, and reducing the safety risk of the lithium dendrites growing to pierce the diaphragm.
In a third aspect of the embodiments of the present invention, there is provided a lithium ion battery, which includes the above-mentioned metallic lithium negative electrode, or includes the metallic lithium negative electrode prepared by the above-mentioned method.
According to the lithium ion battery provided by the third aspect of the embodiment of the invention, the lithium ion battery comprises the metal lithium negative electrode with the characteristics of high energy density, low surface current density, slow growth of lithium dendrite and the like, so that the rate capability, the cycle charge and discharge life and the safety performance of a battery material are effectively improved.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and to make the advanced performance of the lithium metal negative electrode, the preparation method thereof, and the lithium ion battery of the embodiments of the present invention obviously manifest, the above technical solutions are illustrated by a plurality of examples below.
Example 1
A lithium metal anode, the preparation of which comprises the steps of:
1. and soaking the copper mesh in 1.5mol/L ammonium chloride solution for 15min, taking out and washing with deionized water. Mixing single-walled carbon nanotube and 60% polytetrafluoroethylene aqueous solution at a ratio of 2:1, and spray-coating the mixture with a thickness of 10 μm and an areal density of 280g/m2A conductive carbon material layer with a thickness of 0.5 μm is formed on the surface of the copper mesh.
2. Under the condition that the oxygen content of water is lower than 0.5ppm in the argon environment, a half cell is assembled by a composite layer of a copper mesh and a conductive carbon material layer and metal lithium, the metal lithium is deposited under the current of 0.1mA, and the surface capacity is 3mAh/cm2And obtaining the lithium metal composite sheet.
3. And (3) superposing 160 layers of lithium metal composite sheets, and then rolling to obtain the lithium metal cathode.
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching 523 ternary cathode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Example 2
A lithium metal anode, the preparation of which comprises the steps of:
1. and soaking the copper mesh in 1.0mol/L ammonium chloride solution for 30min, taking out and washing with deionized water. Mixing super P and 60% styrene butadiene rubber aqueous solution according to the proportion of 1:3, and spraying on the mixture with the thickness of 16 μm and the surface density of 160g/m2A conductive carbon material layer with a thickness of 1.5 μm is formed on the surface of the copper mesh.
2. Under the condition that the oxygen content of water is lower than 0.5ppm in the argon environment, a half cell is assembled by a composite layer of a copper mesh and a conductive carbon material layer and metal lithium, the metal lithium is deposited under the current of 0.05mA, and the surface capacity is 2mAh/cm2And obtaining the lithium metal composite sheet.
3. And (4) stacking 150 layers of lithium metal composite sheets, and then rolling to obtain the lithium metal cathode.
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Example 3
A lithium metal anode, the preparation of which comprises the steps of:
1. and soaking the copper mesh in 0.5mol/L ammonia water solution for 60min, taking out and washing with deionized water. Mixing carbon nano tube with styrene-butadiene rubber aqueous solution with the mass fraction of 60% according to the proportion of 2:1, spraying and coating the mixture on a layer with the thickness of 18 mu m and the surface density of 240g/m2A conductive carbon material layer with a thickness of 3 μm is formed on the surface of the copper mesh.
2. Under argon atmosphere, water oxygenUnder the condition that the content is lower than 0.5ppm, a half cell is assembled by a composite layer of the copper mesh and the conductive carbon material layer and the metallic lithium, the metallic lithium is deposited under the current of 0.05mA, and the surface capacity is 4mAh/cm2And obtaining the lithium metal composite sheet.
3. And (3) laminating 100 layers of lithium metal composite sheets, and then rolling to obtain the lithium metal cathode.
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Example 4
A lithium ion battery which differs from example 1 in that: cutting the prepared lithium metal cathode into a proper size, taking the surface of a lithium metal layer as a cathode working surface, matching with a lithium iron phosphate cathode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 1
A lithium ion battery which differs from example 1 in that: adopts a conventional lithium metal cathode with the same size to match with a lithium iron phosphate cathode material, and commercializes LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 2
A lithium metal anode, the preparation of which differs from example 2 in that: the mixing ratio of the super P to the styrene butadiene rubber aqueous solution with the mass fraction of 60% is 10: 1.
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 3
A lithium metal anode, the preparation of which differs from example 2 in that: the mixing ratio of the super P to the styrene butadiene rubber aqueous solution with the mass fraction of 60% is 1: 10.
Lithium ion batteryA cell, the preparation of which comprises the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 4
A lithium metal anode, the preparation of which differs from example 2 in that: the surface capacity of the lithium metal layer is 20mAh/cm2。
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 5
A lithium metal anode, the preparation of which differs from example 3 in that: the surface density of the copper mesh surface is 100g/m2。
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 6
A lithium metal anode, the preparation of which differs from example 3 in that: the thickness of the copper mesh was 10 μm.
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, matching with the lithium iron phosphate anode material, and commercializing LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Comparative example 7
A lithium metal anode, the preparation of which differs from example 3 in that: the thickness of the conductive carbon material layer was 3.5 a.
A lithium ion battery prepared by the steps of: cutting the prepared lithium metal cathode into a proper size, taking the cut section as the working surface of the cathode, and matching with the lithium iron phosphate anodeMaterial, commercial LiPF6And assembling the electrolyte and the diaphragm to obtain the lithium ion battery.
Further, in order to verify the improvement of the examples of the present invention, the cycle stability of the examples and comparative examples was tested, and the test results are shown in table 1 below:
TABLE 1
| Sample (I) | Test conditions | Capacity retention rate |
| Example 1 | 3C | 98.2％ |
| Example 2 | 3C | 99.3％ |
| Example 3 | 3C | 98.3％ |
| Example 4 | 3C | 94.3％ |
| Comparative example 1 | 3C | 87.9％ |
| Comparative example 2 | 3C | 86.1％ |
| Comparative example 3 | 3C | 90.4％ |
| Comparative example 4 | 3C | 88.8％ |
| Comparative example 5 | 3C | 89.8％ |
| Comparative example 6 | 3C | 90.1％ |
| Comparative example 7 | 3C | 87.5％ |
From the above test results, it can be seen that the lithium ion batteries prepared in examples 1 to 3 of the present invention using the metallic lithium negative electrode have better cycle stability than the lithium ion battery prepared in comparative example 1 using the conventional lithium metallic negative electrode. In the example 4, the lithium ion battery does not adopt the cutting section of the metal lithium negative electrode as the negative electrode working surface, but adopts the lithium metal layer as the negative electrode working surface, and compared with the lithium ion battery directly adopting the lithium metal layer as the negative electrode in the comparative example 1, the cycle performance is also improved.
In addition, when the content of the conductive carbon material in the metallic lithium negative electrode is too high (comparative example 2) or too low (comparative example 3), and the conductive carbon material layer is too thick (comparative example 7), the cycle stability of the lithium ion battery may be reduced. When the lithium metal layer plane capacity in comparative example 4 is too high, the cycle stability of the lithium ion battery is also lowered. When the areal density of the copper mesh is too small (comparative example 5) and the thickness of the copper mesh is too low (comparative example 6), the cycle stability of the lithium ion battery is also lowered.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (28)
1. The utility model provides a lithium metal negative pole which characterized in that, lithium metal negative pole includes the lithium metal composite piece of a plurality of stromatolite laminating settings, lithium metal composite piece includes: the lithium battery comprises a metal current collector mesh, a conductive carbon material layer combined on at least one surface of the metal current collector mesh, and a lithium metal layer deposited on the surface of the conductive carbon material layer; taking the side surface formed by the plurality of laminated and attached lithium metal composite sheets as a working surface of the negative electrode; the side surface is a lamination arrangement plane of the lithium metal composite sheet.
2. The lithium metal anode of claim 1, wherein the lithium metal anode comprises 3 to 25 layers/mm of the lithium metal composite sheet laminated together, i.e., 3 to 25 layers per mm of the lithium metal anode.
3. The lithium metal anode of claim 1 or 2, wherein the conductive carbon material layer has a thickness of 0.3 to 3 μm.
4. The lithium metal negative electrode according to claim 1 or 2, wherein the surface capacity of the lithium metal layer is 0.2 to 10mAh/cm2。
5. The metallic lithium anode of claim 1 or 2, wherein a mass ratio of the conductive carbon material layer to the metallic current collector mesh in the lithium metal composite sheet is 1: (5-15).
6. The lithium metal anode of claim 1 or 2, wherein the conductive carbon material layer comprises: an electrically conductive carbon material and a binder, wherein the electrically conductive carbon material is selected from the group consisting of: at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene; the binder is selected from: at least one of polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene butadiene rubber, polyvinylidene fluoride and epoxy resin.
7. The metallic lithium anode of claim 5, wherein the metallic current collector mesh comprises: at least one metal selected from copper, nickel and titanium.
8. The lithium metal anode of claim 5, wherein the mesh length and the width of the metal current collector mesh are each independently 0.5 to 2 mm; the surface density of the metal current collector net is 150-500 g/m2。
9. The lithium metal anode of claim 5, wherein the thickness of the metallic current collector mesh is 15 to 45 μm.
10. The lithium metal negative electrode according to claim 6, wherein the conductive carbon material layer has a mass ratio of the conductive carbon material to the binder of (1 to 2): (0.4-3.5).
11. A method for preparing a lithium metal anode according to any one of claims 1 to 10, comprising the steps of:
obtaining a metal current collector net, and bonding a conductive carbon material to at least one surface of the metal current collector net to form a conductive carbon material layer;
depositing metal lithium on the surface of the conductive carbon material layer to form a lithium metal layer, so as to obtain a lithium metal composite sheet;
laminating and attaching a plurality of lithium metal composite sheets to obtain a lithium metal cathode; taking the side surface formed by the plurality of laminated and attached lithium metal composite sheets as a working surface of the negative electrode; the side surface is a lamination arrangement plane of the lithium metal composite sheet.
12. The method of making a metallic lithium negative electrode of claim 11, wherein the step of bonding a conductive carbon material to the surface of the metallic current collector mesh comprises: and after the metal current collector net is subjected to chemical modification treatment, depositing the mixed slurry of the conductive carbon material and the binder on at least one surface of the metal current collector net, and drying to form the conductive carbon material layer.
13. The method of making a lithium metal anode of claim 11, wherein the step of depositing lithium metal on the surface of the conductive carbon material layer comprises: and under the inert atmosphere with the water oxygen content of less than 0.5ppm, assembling the composite layer of the conductive carbon material layer and the metal current collector net and metal lithium into a half cell, and depositing the metal lithium on the surface of the conductive carbon material layer under the current driving to form the lithium metal layer.
14. The method of making a lithium metal anode of claim 11, wherein the step of laminating the layers comprises: and (3) laminating and laminating a plurality of lithium metal composite sheets, and then performing rolling treatment to fix the plurality of lithium metal composite sheets to form the lithium metal cathode.
15. The method of making a lithium metal anode of claim 12, wherein the step of chemically modifying comprises: and treating the metal current collector net by adopting an alkaline solution.
16. The method for producing a lithium metal anode according to claim 12, wherein in the mixed slurry of the conductive carbon material and the binder, a mass ratio of the conductive carbon material, the binder, and the solvent is (1 to 2): (0.4-3.5): (0.3-3).
17. The method of making a lithium metal anode of claim 15, wherein the alkaline solution comprises: at least one of ammonium chloride, ferric trichloride and ammonia water.
18. The method of making a lithium metal anode of claim 15, wherein the alkaline solution has a concentration of 0.5mol/L to 3 mol/L.
19. The method of any one of claims 11 to 18, wherein the lithium metal anode comprises 3 to 25 layers/mm of lithium metal composite sheets laminated together.
20. The method for preparing a lithium metal anode according to any one of claims 11 to 18, wherein a side surface formed by laminating a plurality of the lithium metal composite sheets is used as an anode working surface.
21. The method of manufacturing a lithium metal anode according to any one of claims 11 to 18, wherein the conductive carbon material layer has a thickness of 0.3 to 3 μm; the surface capacity of the lithium metal layer is 0.2-10 mAh/cm2。
22. The method for preparing the lithium metal anode according to any one of claims 11 to 18, wherein the mass ratio of the conductive carbon material layer to the metal current collector mesh in the lithium metal composite sheet is 1: (5-15).
23. The method of making a lithium metal anode of any one of claims 11 to 18, wherein the conductive carbon material layer comprises: an electrically conductive carbon material and a binder, wherein the electrically conductive carbon material is selected from the group consisting of: at least one of carbon black, conductive graphite, carbon fiber, carbon nanotube and graphene; the binder is selected from: at least one of polytetrafluoroethylene, carboxymethyl cellulose, polyacrylic acid, styrene butadiene rubber, polyvinylidene fluoride and epoxy resin.
24. The method of making a lithium metal anode of any of claims 11 to 18, wherein the metallic current collector mesh comprises: at least one metal selected from copper, nickel and titanium.
25. The method of manufacturing a lithium metal anode according to any one of claims 11 to 18, wherein the mesh length and the width of the metal current collector mesh are each independently 0.5 to 2 mm.
26. The method of preparing the lithium metal negative electrode of any one of claims 11 to 18, wherein the areal density of the metal current collector mesh is 150 to 500g/m2。
27. The method of manufacturing a lithium metal anode according to any one of claims 11 to 18, wherein the thickness of the metal current collector mesh is 15 to 45 μm.
28. A lithium ion battery comprising the lithium metal negative electrode according to any one of claims 1 to 10 or the lithium metal negative electrode prepared by the method according to any one of claims 11 to 27.
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