CN108550808B - Composite metal lithium cathode and preparation method thereof - Google Patents
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- 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
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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
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides a composite metal lithium cathode, which comprises a primary network structure constructed by polymers; the nanoscale carbon material is filled into the primary network structure to form a secondary network structure; and lithium metal is filled into the secondary network structure to form a tertiary composite structure. Firstly, a secondary network structure filled with a carbon material is obtained by an accumulative roll-lamination method, and then metal lithium is inserted into the secondary network structure filled with the carbon material by the accumulative roll-lamination method, electro-deposition lithium or evaporation lithium plating to obtain the composite metal lithium cathode. The cathode with the structure can improve the lithium deposition morphology and solve the problem of growth of lithium dendrites, thereby improving the cycle performance and safety of the battery.
Description
Technical Field
The invention belongs to the field of lithium ion secondary batteries, and particularly relates to a composite metal lithium cathode and a preparation method thereof.
Background
A lithium ion secondary battery supplies electric energy to an external electrode by using lithium ion movement between a positive electrode and a negative electrode. Improving the specific energy of the lithium ion secondary battery is a major development direction of the development of the lithium ion secondary battery at present. One of the effective methods is to use metallic lithium as a negative electrode. This is because the lithium metal is a negative electrode active material having the highest energy by weight or volume ratio, which can release the most energy in the discharge process in which the lithium metal per weight or volume migrates from the negative electrode to the positive electrode. However, lithium dendrite grows on the surface of the lithium metal in the charging and discharging cycle process, which causes pulverization of the lithium negative electrode, increases the internal resistance of the battery, reduces the capacity of the battery and influences the service life. More seriously, lithium dendrites grow continuously and can pierce the separator and contact the positive electrode, causing internal short circuits and serious safety problems. Therefore, solving the growth of lithium dendrites is a problem that must be solved for practical use of a lithium negative electrode.
Scientists and engineers have made much research and effort to inhibit the growth of lithium dendrites. These efforts have focused on several aspects. (1) According to the documents Energy environ.sci.2014,7,513 and adv.sci.2016,3,1500213 and patent CN103531839, it is disclosed that by adding additives into the electrolyte, the SEI composition and morphology on the surface of the lithium metal negative electrode are regulated, and stable SEI is formed to inhibit dendritic growth. (2) An in-situ artificial SEI is constructed to protect the lithium metal negative electrode. (3) And a polymer electrolyte or an all-solid-state electrolyte is adopted to prevent the generation of lithium dendrites. However, these measures have major disadvantages. During the cyclic charge and discharge process of the lithium metal negative electrode, the lithium metal negative electrode undergoes large volume change, so that the electrolyte additive or the in-situ artificial SEI have insufficient strength and toughness and can bear the volume change of the lithium metal cycle without being broken. Especially when the current density is increased. According to theoretical calculations, lithium dendrite penetration is only completely blocked if the electrolyte strength exceeds 6Gpa, but none of the existing polymer electrolytes achieve such high strength. In addition, lithium dendrites diffuse along grain boundaries of the all-solid electrolyte, and short circuits occur through the all-solid electrolyte. Polymer electrolytes and all-solid-state electrolytes also do not address the lithium dendrite growth problem.
In addition to addressing the SEI and electrolyte directions, there have been some work focused on structural optimization of lithium metal anodes. Patent CN105845891A discloses a double-layer lithium metal negative electrode structure. The surface of the metal lithium is provided with a covering layer, and the covering layer is composed of one or more of carbon materials, polymer materials and glass fibers. The capping layer affects the electrochemical environment during lithium deposition, thereby inhibiting the growth of lithium dendrites. However, according to the research of the inventor, the thickness of the covering layer must be thicker enough to change the electrochemical environment of lithium deposition to achieve the effect of suppressing dendrites. The cap layer may decrease the energy density of the battery, increase the internal resistance of the battery, and affect the performance of the battery. In addition, the present invention cannot realize the double-layer structure by a mass production process. The document NATURE NANOTECHNOLOGY VOL 11, 2016, 7 proposes a new solution. And immersing the multilayer graphene oxide into liquid lithium, and forming a multilayer structure of graphene sheet layers/metallic lithium by virtue of capillary action. The lithium metal cathode with the structure has good electrochemical activity in the cyclic charge-discharge process, and can inhibit the growth of dendrites. However, the process is complex, the required graphene oxide sheet cannot be continuously produced, and the graphene oxide sheet can only be manufactured in a small area by adopting a suction filtration method. In particular, molten liquid lithium is required, and the operation can be carried out only under the protection of Ar gas. The method has no significance and value in amplification and practical application in general.
Disclosure of Invention
The invention aims to provide a lithium ion secondary battery composite metal lithium negative electrode aiming at the defects of the prior art, and the electrode pulverization and the internal short circuit of the battery in the charging and discharging circulation process of the battery are avoided.
The technical scheme adopted by the invention is as follows: provided is a lithium metal anode having a three-stage composite structure, the lithium metal composite anode including: a primary network structure composed of polymers; the nanoscale carbon material is filled into the primary network structure to form a secondary network structure; and lithium metal is filled into the secondary network structure to form a tertiary composite structure.
The aperture range of the primary network structure of the composite metal lithium cathode is 0.1 mu m-1 mm, and the porosity is 10% -99%; the aperture range in the secondary network structure is 10 nm-1 mm, and the porosity is 9% -98%; the aperture range in the three-level composite structure is 0 nm-0.1 mm, and the porosity is 0% -50%.
The preferable three-level composite structure of the composite metal lithium negative electrode is as follows: the aperture in the primary network structure is 0.2-2 μm, and the porosity is 60-95%; the aperture in the secondary network structure is 0.05-1 μm, and the porosity is 50-85%; the aperture of the three-stage composite structure is 0nm to 100nm, and the porosity is 0 percent to 5 percent.
The thickness of the composite metal lithium negative electrode is 0.05 mu m-1 mm.
The polymer in the composite metal lithium cathode is one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyimide, polyacrylonitrile, polyaniline, polylactic acid, cellulose acetate and polylactic acid-glycolic acid copolymer, preferably polytetrafluoroethylene, and the mass content is 2-20%.
The nano-scale carbon material in the composite metal lithium cathode is one or more of natural graphite, artificial graphite, modified graphite, graphitized carbon, active carbon, hard carbon, soft carbon and graphene, and the mass content of the nano-scale carbon material is 15-70%.
The mass content of the lithium metal in the composite metal lithium negative electrode is 20-80%.
The invention also provides a preparation method of the composite metal lithium cathode, which comprises the following steps: rolling by a metal rolling method by utilizing the adhesive property of the polymer, wherein the pressing deformation is 10-50%, and obtaining a three-dimensional network polymer after one-time rolling; spreading a carbon material on the surface of the three-dimensional network polymer, then rolling, pressing down with the deformation amount of 20-50%, and filling carbon into the three-dimensional network structure to obtain a secondary structure filled with carbon; and (2) flatly laying metal lithium on the surface of a secondary structure, then rolling, wherein the pressing deformation amount is 20% -50%, a part of metal lithium is embedded into a carbon material, a part of metal lithium is filled into gaps of a three-dimensional structure to obtain a first composite metal lithium cathode, and the composite metal lithium cathode is cut, overlapped, rolled and repeated for 3-20 times to obtain the composite metal lithium cathode with uniform microstructure.
Further, the preparation method of the composite metal lithium negative electrode comprises the following steps: and the metal lithium is inserted into the secondary network structure filled by the carbon material by adopting electrodeposition lithium or the metal lithium is inserted into the secondary network structure filled by the carbon material by adopting evaporation lithium plating.
The inventors have made an inspection ofThe formation and growth of lithium dendrites was studied by reading literature and performing related experiments. During charging, lithium ions can generate electrochemical reaction on the surface of the negative electrode, and when the electrochemical potential of the surface is lower than that of Li+the/Li potential, lithium deposition on the surface of the negative electrode occurs. The electrochemical potential of the surface of the negative electrode is influenced by various factors, such as Li+Concentration, average potential of the negative electrode, and electrode surface micro-topography, etc. The surface appearance of the electrode has obvious influence on lithium deposition: in the regions with small curvature radius on the surface of the electrode, such as defect edges, bulges and the like, charges are easier to enrich, so that the potential of the regions is lower than that of other regions, and lithium precipitation often occurs preferentially; the deposited lithium metal in turn exacerbates the inconsistencies in surface morphology, resulting in lithium dendrite growth.
The prior art solves the problems from chemical and film manufacturing technologies, but the chemical method has the problems of complex process, difficult regulation and control and low practicability, and the degree of improving the cycle performance of the battery is limited; the film manufacturing technology has the problems of high cost, strict requirements on environment and difficult practicability. The problems of lithium pulverization and lithium dendrite existing in the lithium negative electrode can not be thoroughly solved.
Has the advantages that:
according to the composite metal lithium cathode structure provided by the invention, the cathode can improve the lithium deposition morphology and solve the problem of lithium dendrite growth, so that the cycle performance and safety of the battery are improved: firstly, the micron-sized polymer skeleton has high stability and electrochemical inertia, the performance of the battery cannot be influenced, and the carbon and the lithium distributed in the network structure can ensure that the structure has good electronic conductivity and normal deposition/dissolution of the lithium; secondly, lithium is uniformly distributed in the network structure, and the lithium carbon layer serves as a lithium source in the lithium dissolution process to provide partial capacity; the lithium carbon layer can balance the surface potential of the negative electrode during lithium deposition and inhibit the growth of dendritic crystals; thirdly, the micron-sized polymer skeleton in the composite lithium cathode structure can provide a space for lithium deposition/dissolution, so that the volume change of the cathode is relieved, and the structural stability is improved.
Drawings
FIG. 1 is a schematic structural diagram of a composite lithium metal anode of the present invention;
FIG. 2 is a cycle diagram of a symmetric battery fabricated using a composite lithium metal anode of the present invention;
FIG. 3 is a graph of cycle results for a symmetrical battery fabricated using a conventional lithium metal negative electrode;
Detailed Description
Example 1
The content of the polymer in the composite metal lithium negative electrode is 2%, the content of the nano carbon material is 25%, and the content of the lithium metal is 73%.
The composite metal lithium cathode is obtained by adopting an accumulative pack rolling method, and the specific method comprises the following steps: by utilizing the caking property of the polymer PTFE, rolling by adopting a metal rolling method, wherein the pressing deformation is 10-50%, and obtaining a three-dimensional network polymer after one-time rolling; spreading a carbon material on the surface of the three-dimensional network polymer, then rolling, pressing down with the deformation amount of 20-50%, and filling carbon into the three-dimensional network structure to obtain a secondary structure filled with carbon; and flatly spreading the metallic lithium on the surface of the secondary structure, then rolling, wherein the pressing deformation amount is 20-50%, a part of the metallic lithium is embedded into the carbon material, and a part of the metallic lithium is filled into the gap of the three-dimensional structure, so that the first-pass composite metallic lithium cathode is obtained. And cutting, superposing and rolling the composite lithium metal cathode, and repeating for 3-20 times to obtain the composite lithium metal cathode with uniform microstructure. According to the characteristic that a polymer, nano-scale carbon and lithium metal are easy to deform, a framework is formed by using huge shearing force generated by severe plastic deformation of the polymer, and the carbon material and the lithium metal are dispersed in the framework. The composite metal lithium cathode with a three-level composite structure compounded by micron-level polymer/nano-level carbon/metal lithium is formed, and has a unique microstructure structure and excellent mechanical properties.
Fig. 2 and 3 show that the overpotential of the composite lithium metal cathode of the present invention is significantly lower than that of the conventional lithium cathode, and the cycling stability is better.
Example 2
The content of the polymer in the composite metal lithium negative electrode is 10%, the content of the nano carbon material is 50%, and the content of the lithium metal is 40%.
The lithium composite metal negative electrode was obtained by the accumulative pack rolling method, which was the same as in example 1.
Example 3
The content of the polymer in the composite metal lithium negative electrode is 20%, the content of the nano carbon material is 30%, and the content of the lithium metal is 50%.
The lithium composite metal negative electrode was obtained by the accumulative pack rolling method, which was the same as in example 1.
Example 4
The specific method for obtaining the composite metal lithium negative electrode comprises the following steps: by utilizing the caking property of the polymer PTFE, rolling by adopting a metal rolling method, wherein the pressing deformation is 10-50%, and obtaining a three-dimensional network polymer after one-time rolling; spreading a carbon material on the surface of the three-dimensional network polymer, then rolling, pressing down with the deformation amount of 20-50%, and filling carbon into the three-dimensional network structure to obtain a secondary structure filled with carbon; and then, adopting electro-deposition lithium to embed metal lithium into a secondary network structure filled with a carbon material to prepare the composite metal lithium cathode with the three-level composite structure.
Example 5
The specific method for obtaining the composite metal lithium negative electrode comprises the following steps: by utilizing the caking property of the polymer PTFE, rolling by adopting a metal rolling method, wherein the pressing deformation is 10-50%, and obtaining a three-dimensional network polymer after one-time rolling; spreading a carbon material on the surface of the three-dimensional network polymer, then rolling, pressing down with the deformation amount of 20-50%, and filling carbon into the three-dimensional network structure to obtain a secondary structure filled with carbon; and then, embedding the metal lithium into a secondary network structure filled with the carbon material by adopting evaporation lithium plating to prepare the composite metal lithium cathode with the three-level composite structure.
Comparative example
Patent CN 106784635 a provides a method for preparing a composite lithium negative electrode for a solid-state battery, which is to deposit lithium metal in the gaps of a three-dimensional carbon material or a foam porous material by a thermal infusion method or an electrodeposition method to prepare the composite lithium negative electrode, wherein the application of a three-dimensional framework provides sufficient space for pre-storing lithium in the preparation process and provides a carrier for receiving metal lithium in the battery circulation process, and has the advantages of inhibiting the growth of lithium dendrites in the battery circulation process, stabilizing the volume change of the electrode, having good circulation stability and long service life.
The composite metal lithium cathode in the invention adopts a polymer as a three-dimensional framework, and has better strength and toughness compared with a carbon framework, so that the structure is more stable; moreover, the method can be realized by adopting various methods, and the processability is strong; the structure of the material can be regulated and controlled by adjusting the components of the polymer, the carbon and the metallic lithium, and the structure has variability and controllability; more importantly, the polymer framework is more stable than the carbon framework, so that the volume change of the electrode can be better stabilized, the cycling stability is good, and the service life is longer.
The above description is of the preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. It should be noted that modifications and equivalents may be made to the technical solution of the present invention by those skilled in the art without departing from the scope of the present invention.
Claims (8)
1. A composite lithium metal anode characterized by: the negative electrode includes: a primary network structure composed of polymers; the nanoscale carbon material is filled into the primary network structure to form a secondary network structure; lithium metal is filled into a tertiary composite structure formed in the secondary network structure to form a composite metal lithium cathode; the content of the nanoscale carbon material is 15% -70%, and the content of the lithium metal is 20% -80%.
2. The composite lithium metal anode of claim 1, wherein: the aperture in the primary network structure is 0.1 mu m-1 mm, and the porosity is 10% -99%; the aperture in the secondary network structure is 10 nm-1 mm, and the porosity is 9% -98%; the aperture of the three-stage composite structure is 0 nm-0.1 mm, and the porosity is 0% -50%.
3. The composite lithium metal anode of claim 2, wherein: the aperture in the primary network structure is 0.2-2 μm, and the porosity is 60-95%; the aperture in the secondary network structure is 0.05-1 μm, and the porosity is 50-85%; the aperture of the three-stage composite structure is 0nm to 100nm, and the porosity is 0 percent to 5 percent.
4. The composite lithium metal anode of claim 1, wherein: the thickness of the composite metal lithium negative electrode is 0.05 mu m-1 mm.
5. The composite lithium metal anode of claim 1, wherein: the polymer is one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyimide, polyacrylonitrile, polyaniline, polylactic acid, cellulose acetate and polylactic-co-glycolic acid, and the content of the polymer is 2-20%.
6. The composite lithium metal anode of claim 1, wherein: the nano-scale carbon material is one or more of natural graphite, artificial graphite, modified graphite, graphitized carbon, activated carbon, hard carbon, soft carbon and graphene.
7. A method of preparing the lithium composite metal anode of claim 1, wherein: the preparation method comprises the following steps: rolling the polymer by a metal rolling method, wherein the pressing deformation is 10-50%, and obtaining a three-dimensional network polymer after one-time rolling; spreading a carbon material on the surface of the three-dimensional network polymer, rolling, pressing down with the deformation amount of 20-50%, and filling carbon into the three-dimensional network structure to obtain a secondary structure filled with carbon; and (2) flatly laying metal lithium on the surface of a secondary structure, then rolling, wherein the pressing deformation amount is 20% -50%, a part of metal lithium is embedded into a carbon material, a part of metal lithium is filled into gaps of a three-dimensional structure to obtain a first composite metal lithium cathode, and the composite metal lithium cathode is cut, overlapped, rolled and repeated for 3-20 times to obtain the composite metal lithium cathode with uniform microstructure.
8. The method of producing a lithium composite metal anode according to claim 7, characterized in that: the preparation method of the composite metal lithium negative electrode comprises the following steps: and the metal lithium is inserted into the secondary network structure filled by the carbon material by adopting electrodeposition lithium or the metal lithium is inserted into the secondary network structure filled by the carbon material by adopting evaporation lithium plating.
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| CN109411694A (en) * | 2018-10-22 | 2019-03-01 | 天齐锂业（江苏）有限公司 | A kind of lithium metal composite negative pole and the preparation method and application thereof |
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