CN110875476A - Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery - Google Patents
Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery Download PDFInfo
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- CN110875476A CN110875476A CN201810993887.7A CN201810993887A CN110875476A CN 110875476 A CN110875476 A CN 110875476A CN 201810993887 A CN201810993887 A CN 201810993887A CN 110875476 A CN110875476 A CN 110875476A
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- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 1
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Provided are an anode for a lithium secondary battery, a method of preparing the same, and a lithium secondary battery including the same. The negative electrode of the lithium secondary battery includes a five-layer structure formed of a current collector, a lithium ribbon or a lithium alloy ribbon positioned at both sides of the current collector, and a carbonaceous layer positioned between and in direct contact with the current collector and the lithium ribbon or the lithium alloy ribbon.
Description
Technical Field
The invention relates to the field of secondary batteries, in particular to a secondary battery cathode with simple preparation process and a secondary battery using the same.
Background
In recent years, with the demand of electrical appliances such as smart phones, tablet computers, electric vehicles, and the like for high-energy chemical power sources, as well as the non-renewable nature of petroleum and coal resources and the pollution of burning fossil resources to the environment, secondary batteries with high energy density have become a hot point of research. At present, the specific energy development space of a secondary battery taking graphite as a negative electrode and lithium iron phosphate, lithium cobaltate, ternary materials and the like as a positive electrode is limited and almost reaches a limit value. In the lithium secondary battery, the lithium metal has the most negative electrode potential (-3.045V) and the highest specific capacity (3860mAh/g), can meet the requirement of high energy density of an electrode material, and many scientific research institutes and companies at home and abroad turn to the research, development and application of the secondary battery taking lithium as the negative electrode.
Disclosure of Invention
In an effort to develop a lithium or lithium alloy tape as a negative electrode material for a lithium secondary battery, the inventors of the present application have found that, although it is generally believed that the two metal materials are directly pressure-bonded together to achieve good contact and adhesion between the two metal materials, when the lithium or lithium alloy tape is directly bonded to a metal current collector (e.g., copper foil), there may be some places where adhesion is not tight, which may result in poor electron conduction between the negative electrode material and the current collector, large interfacial resistance, and reduced battery capacity.
In order to solve the above problems, the inventors have conducted intensive studies and, as a result, have found that: by adopting a laminated composite structure, namely, firstly forming a carbon layer (especially the carbon layer containing the porous carbon material) on the surface of the metal current collector and then compounding a lithium belt or a lithium alloy belt on the carbon layer, the adhesion and the electron conduction capability between the lithium belt or the lithium alloy belt and the metal current collector can be improved, the growth of lithium dendrite can be inhibited, and the capacity retention rate of the battery can be improved.
One aspect of the present invention provides a negative electrode for a lithium secondary battery, the negative electrode including a five-layer structure formed of a current collector, a lithium ribbon or a lithium alloy ribbon positioned at both sides of the current collector, and a carbonaceous layer positioned between and in direct contact with the current collector and the lithium ribbon or the lithium alloy ribbon.
Another aspect of the present invention provides a method of preparing the above negative electrode, comprising: forming a carbon layer on two surfaces of the current collector by a coating method or a vapor deposition method, and compounding a lithium ribbon or a lithium alloy ribbon onto the carbon layer by pressure compounding.
In a further aspect of the present invention, there is provided a secondary battery comprising the above negative electrode, preferably the lithium secondary battery is a lithium sulfur battery, a lithium air battery, a lithium polymer battery or a lithium all-solid battery.
According to the invention, the carbonaceous layer is arranged between the lithium belt or the lithium alloy belt and the metal current collector, the carbonaceous layer can ensure the adhesion between the lithium belt or the lithium alloy belt and the metal current collector and simultaneously improve the electron conduction capability, and particularly under the condition of adopting the porous carbon material, the specific surface area of the porous carbon material is large, the deposition sites of lithium ions are increased, the effective current density is reduced, the growth of lithium dendrites is effectively inhibited, and the electrochemical performance is improved.
Drawings
Fig. 1 shows a front view of a negative electrode of a secondary battery according to an embodiment of the present invention
Fig. 2 is a cross-sectional view of the rolled negative electrode of fig. 1 taken along line a-a.
Fig. 3 shows a cycle performance test chart of the secondary batteries of examples 1, 2 and 3.
Detailed Description
Fig. 1 shows a front view of a negative electrode of a secondary battery according to an embodiment of the present invention. The negative electrode is in a coiled form and is in a composite form of two surfaces of a current collector, namely, two surfaces of the current collector 3 are provided with carbon layers 2; the double-sided composite lithium or lithium alloy tape 1 of the carbonaceous layer 2.
Fig. 2 is a cross-sectional view of the rolled negative electrode of fig. 1 taken along line a-a. It should be noted that the widths of the lithium ribbon or lithium alloy ribbon 1, the carbonaceous layer 2, and the current collector 3 in fig. 1 and 2 may be arbitrarily set, and are not necessarily in proportion to the drawing.
The negative electrode active material in the present invention is metallic lithium or a lithium alloy, and is provided in the form of a metallic lithium ribbon or a lithium alloy ribbon. The thickness of the metallic lithium or lithium alloy ribbon may be 0.02-0.20mm, preferably 20-50 um. The lithium alloy is composed of metallic lithium and at least one other element, which may include: magnesium, boron, aluminum, silicon, indium, zinc, silver, calcium and manganese. The content of the other elements accounts for 0.1-40%, preferably 1-20% of the total mass of the lithium alloy.
The current collector of the present invention comprises a metal foil, a metal foam, preferably at least one of a copper foil, a nickel foil, a copper foam and a nickel foam. The metal foil, such as copper foil, may have a thickness of 6 to 10 microns. The thickness of the foam metal can be 0.1-0.5 mm. The width of the current collector may be 10-3000 mm.
The carbonaceous layer of the present invention may comprise conductive carbon particles of micro-or nano-scale. The conductive carbon particles can be at least one selected from carbon black, graphite, acetylene black, ketjen black, activated carbon fiber, mesoporous carbon, carbon nanotubes, carbon molecular sieves and graphene. Porous conductive carbon particles including at least one of activated carbon, activated carbon fiber, mesoporous carbon, carbon nanotube microsphere, carbon molecular sieve, carbon nanofiber, carbon hollow nanosphere, and hollow carbon sphere are preferable. Preferably, the pore size of the porous conductive carbon particles is in the range of 0.1 to 100nm, preferably 0.1 to 20 nm. The thickness of the single side of the carbonaceous layer is 0.5-5 um. The density of the single-side surface of the carbonaceous layer is 0.5-1.5g/m2。
In the present invention, the carbonaceous layer may be formed on both sides of the current collector by a coating method or by a vapor deposition method. For example, the carbonaceous layer may be formed by mixing porous conductive carbon particles, a binder, and a solvent in a certain ratio to form a slurry, coating the slurry on a current collector, and curing and drying the slurry. The binder can be selected from polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC) and the like; the solvent can be selected from N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), p-xylene (PX), Tetrahydrofuran (THF), etc. The slurry of the carbonaceous layer comprises the following components in percentage by mass: 5 to 15 percent of conductive carbon particles, 0.1 to 0.5 percent of binder and the balance of solvent.
In the invention, after the carbon layers are formed on the two sides of the current collector, the coiled current collector with the carbon layers and the coiled lithium belt or lithium alloy belt can be combined together by a coiling and uncoiling device and mechanical pressure, and then the secondary battery cathode can be prepared. The manufacturing process is simple and can be used for batch production.
The lithium secondary battery of the present invention includes the above negative electrode, and further includes a positive electrode, an electrolytic solution, a separator, and a case.
The positive electrode of the lithium secondary battery of the present invention includes a current collector and a positive electrode material layer formed on both sides of the current collector. The positive electrode material layer is obtained by coating positive electrode material slurry on two surfaces of a current collector.
According to certain embodiments, the positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and a solvent. The positive active material includes active materials that are used in the art for a positive electrode of a secondary battery, such as lithium iron phosphate, lithium cobaltate, nickel-cobalt-aluminum ternary, nickel-cobalt-manganese ternary material, elemental sulfur doped with a conductive agent, oxygen, vanadium pentoxide, and the like. The conductive agent and the binder include those usable in the art for a positive electrode of a secondary battery, for example, the conductive agent may include graphite, graphene, carbon nanotubes, carbon fibers, conductive carbon black (Super P), acetylene black, ketjen black, and the like; the binder may include polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and the like. The solvent may include N-methyl-2-pyrrolidone (NMP) and the like.
The positive electrode collector that may be used in the present invention may be a positive electrode collector commonly used in the art, for example, an aluminum foil, a carbon-coated aluminum foil.
The electrolyte solution that may be used in the secondary battery of the present invention may include esters, ethers, polymer electrolytes, ionic liquids, solid electrolytes, and the like. For example: ethylene carbonate, propylene carbonate, diethyl carbonate; 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME); li2S-P2S5Class i, Li10GeP2S12LLZO (lithium lanthanum zirconium oxide) solid electrolytes, PEO (polyethylene oxide) polymers; cations and iminium anions of piperidines, pyrroles or quaternaries (TFSI)-) The formed ionic liquid, and the like.
The separator and the case that can be used in the secondary battery according to the present invention may be a separator and a case that are commonly used in the art, for example, the separator may be a polymer separator such as a Polyethylene (PE) film, a polypropylene (PP) film, a polyethylene-polypropylene-polyethylene (PE-PP-PE) film, or the like; the outer shell can be a flexible package of composite film or a metal shell package.
The secondary battery of the present invention may adopt a laminate type or a winding type structure.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, which are merely illustrative and should not be construed as limiting the scope of the present invention.
Example 1
Preparation of copper foil with carbonaceous layer: the carbonaceous layer slurry comprises the following components in percentage by mass: 6.5 percent of active carbon (with the aperture of 2.0-2.2nm, Jicann nanometer), 0.2 percent of binder PVDF (New chemical material Co., Ltd., same below) and the balance of solvent NMP (same below) are stirred and mixed evenly by magnetic force to obtain even carbon slurry. Coating slurry on the two sides of a coiled current collector copper foil (Lingbaoxinxin copper foil, Inc., thickness 9 microns, the same below) by using an automatic coating machine, and curing and drying to obtain a coiled copper foil with a carbon layer, wherein the thickness of the single-side carbon layer is 1 micron.
Preparing a negative electrode: and (3) covering a lithium tape on the double-sided composite with the carbon layer copper foil by using a winding and unwinding device and liner film protection and using mechanical pressure, wherein the thickness of the lithium tape is 35 microns, and thus obtaining the cathode.
Preparing a positive electrode: according to the positive active material LiFePO4(Hunancedar new materials Co., Ltd.): artificial graphite (tianjinbei new energy science and technology ltd): the PVDF binder is mixed according to the mass ratio of 8:1:1, the NMP solvent is added, the mixture is mixed into slurry, the slurry is coated on a current collector aluminum foil (the Tianlong aluminum industry Co., Ltd., the Shenyi city, the thickness is 10 microns, the same below) to prepare a positive electrode, and the positive electrode is dried in a vacuum drying oven for 24 hours at the temperature of 80 ℃ for standby.
1mol/L LiPF is selected as electrolyte6EC/EMC (volume ratio 1:1, EC: ethylene carbonate, EMC: ethyl methyl carbonate)Eastern fir battery materials ltd); the diaphragm is a PP (polypropylene) diaphragm, and is assembled into a battery for testing electrochemical performance, the voltage range is 3.0-4.2V, and the battery is charged and discharged at the multiplying power of 0.2C.
Example 2
Preparation of copper foil with carbonaceous layer: the carbonaceous layer slurry comprises the following components in percentage by mass: 6.5% of artificial graphite, 1.5% of conductive carbon black, 0.2% of binder PVDF and the balance of solvent NMP, and uniformly mixing by magnetic stirring to obtain uniform carbon slurry. And coating slurry on the two sides of the coiled current collector copper foil by using an automatic coating machine, wherein the thickness of the single-side carbon layer is 1 micron, and thus the coiled copper foil with the carbon layer is obtained.
Preparing a negative electrode: and compounding a lithium tape on the double surfaces of the copper foil with the carbon layer by using a winding and unwinding device and the protection of the lining film and using mechanical pressure, wherein the thickness of the lithium tape is 35 microns, and thus obtaining the cathode.
The positive electrode material, the electrolyte and the separator were the same as those of example 1. The battery is assembled to test the electrochemical performance, the voltage range is 3.0-4.2V, and the battery is charged and discharged at the multiplying power of 0.2C.
Example 3
Preparing a negative electrode: compounding lithium tapes on two surfaces of the coiled current collector copper foil (with the thickness of 9 microns) by virtue of a coiling and uncoiling device and protection of a lining film, wherein the thickness of the lithium tapes is 35 microns, and obtaining the negative electrode
The positive electrode material, the electrolyte and the separator were the same as those of example 1. The battery is assembled to test the electrochemical performance, the voltage range is 3.0-4.2V, and the battery is charged and discharged at the multiplying power of 0.2C.
The cycle performance of the examples 1, 2 and 3 is shown in fig. 3, and the cycle performance graph shows that the batteries of the examples 1 and 2 with the carbon layer compounded on the copper foil have better performance; example 1 compares with example 2, the conductive carbon material in the carbonaceous layer performs better when porous carbon is used. The specific surface area of the porous carbon is large, so that the effective current density is reduced, the deposition sites of lithium ions are increased, and the generation of lithium dendrites is inhibited. Specific values are given in table one below.
Claims (10)
1. A negative electrode for a lithium secondary battery, comprising a five-layer structure formed of a current collector, a lithium ribbon or a lithium alloy ribbon on both sides of the current collector, and a carbonaceous layer between and in direct contact with the current collector and the lithium ribbon or the lithium alloy ribbon.
2. The negative electrode of claim 1, wherein the lithium or lithium alloy ribbon has a thickness of 0.020 to 0.20mm, preferably 0.020 to 0.050 mm.
3. The negative electrode of claim 1, wherein the lithium alloy is comprised of metallic lithium and at least one other element, the other element comprising: magnesium, boron, aluminum, silicon, indium, zinc, silver, calcium and manganese, wherein the content of the other elements accounts for 0.1-40 percent of the total mass of the lithium alloy, and preferably 1-20 percent.
4. The negative electrode of claim 1, wherein the carbonaceous layer has a thickness of 0.5 to 5 μm on one side.
5. The negative electrode of claim 1, wherein the carbonaceous layer comprises porous conductive carbon particles, preferably the porous conductive carbon particles comprise at least one of activated carbon, activated carbon fibers, mesoporous carbon, carbon nanotube microspheres, carbon molecular sieves, carbon nanofibers, carbon hollow nanospheres, hollow carbon spheres; preferably, the pore size of the porous conductive carbon particles is in the range of 0.1-100 nm, preferably 0.1-20 nm.
6. The negative electrode of claim 1, wherein the current collector is a metal foil or a metal foam, preferably at least one of a copper foil, a nickel foil, a copper foam and a nickel foam.
7. A method of preparing the anode of any one of claims 1-6, comprising:
forming a carbon layer on two surfaces of the current collector by a coating method or a vapor deposition method, and compounding a lithium ribbon or a lithium alloy ribbon onto the carbon layer by pressure compounding.
8. The method of claim 7, wherein the carbonaceous layer is formed by coating a slurry containing conductive carbon particles on both sides of a current collector, the slurry comprising porous conductive carbon particles, a binder, and a solvent.
9. A lithium secondary battery comprising the negative electrode according to any one of claims 1 to 6, preferably a lithium sulfur battery, a lithium air battery, a lithium polymer battery or a lithium all-solid-state battery.
10. The lithium secondary battery according to claim 9, wherein the lithium secondary battery is of a laminated type or a wound type.
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| CN114068871A (en) * | 2020-07-31 | 2022-02-18 | 天津中能锂业有限公司 | Composite belt with ultrathin lithium layers coated on two surfaces and preparation method thereof |
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