WO2025035640A1 - 一种锂电池负极及其制备方法和应用 - Google Patents

一种锂电池负极及其制备方法和应用 Download PDF

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Publication number
WO2025035640A1
WO2025035640A1 PCT/CN2023/133641 CN2023133641W WO2025035640A1 WO 2025035640 A1 WO2025035640 A1 WO 2025035640A1 CN 2023133641 W CN2023133641 W CN 2023133641W WO 2025035640 A1 WO2025035640 A1 WO 2025035640A1
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lithium
area
strip
negative electrode
buffer layer
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French (fr)
Inventor
郇庆娜
孙兆勇
孔德钰
贾海涛
陈强
牟瀚波
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CHINA ENERGY LITHIUM Co Ltd
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CHINA ENERGY LITHIUM Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Definitions

  • the present invention relates to the technical field of electrochemical energy storage, and in particular to a lithium negative electrode for a metal lithium battery, and a preparation method and application thereof.
  • Metal lithium is considered to be the best negative electrode material due to its capacity of 3860mAh/g and low potential of -3.04V.
  • metal lithium is considered to be the best negative electrode material due to its capacity of 3860mAh/g and low potential of -3.04V.
  • many battery manufacturers use pure metal lithium strips as negative electrodes for direct use.
  • the thickness of metal lithium is 50-80um. Metal lithium itself is very soft. When the thickness is less than 100um, it is very difficult to mechanize the production of rolls. It is even more difficult to roll out the pole ears of metal lithium strips.
  • the CN209641727 patent discloses that metal lithium is first die-cut into pieces of negative electrode sheets, and then the copper pole ears are attached to the single-piece pole sheet with a pressure of 0.3-0.5MPa to lead out the pole ears. This process is time-consuming and labor-intensive to lead out the pole ears, and cannot be used in large-scale production.
  • many research institutes use lithium copper laminated tape as negative electrode. Since the density of copper is 8.96g/ cm3 , which is 16 times the density of metallic lithium, 6um copper foil is equivalent to 100um thick lithium. The specific energy of products using the entire copper foil laminated with metallic lithium is limited. Therefore, the existing negative electrode still cannot meet the requirements of high specific energy batteries.
  • the present invention proposes a novel metal lithium negative electrode, in which the bonding area between the tab and the lithium belt is very narrow and accounts for a very small proportion, so that the specific energy of the battery is greatly improved, and the method of leading out the tab is relatively convenient, so that it can be rolled into a large-scale batch production for use.
  • the inventors designed a stress buffer layer, which is arranged in the area where the tab is to be combined with the lithium strip and is composed of protruding discontinuous metal particles.
  • these protruding particles are subjected to external force. It can be extended and deformed (the height of the protruding particles becomes smaller), so that the stress generated during the lamination can be buffered and released, reducing or avoiding the extension of the lithium material in the lamination area under stress.
  • the area where the lithium strip is to be combined with the pole ear can be pretreated to form a pretreated area with a reduced thickness.
  • the pretreated area has a new metal lithium surface (the original lithium surface has a passivation layer, which is not conducive to the lamination of lithium and copper together), which is conducive to better lamination of the stress buffer layer and the lithium strip.
  • the protruding particles in the stress buffer layer can also fill the thinned area after deformation, so as to obtain a metal lithium negative electrode with a flat surface and a pole ear.
  • One aspect of the present invention provides a negative electrode for a lithium battery, which is composed of a long strip of lithium or lithium alloy and a current collecting and gathering part combined with at least one side edge of the long strip of lithium or lithium alloy, wherein at least one side edge of the lithium or lithium alloy has a pretreatment area, the current collecting and gathering part includes an area with a stress buffer layer, and the pretreatment area and the area with the stress buffer layer overlap each other.
  • the current collecting and converging portion further includes a portion that is not overlapped with the pre-treated area and extends beyond the width of the lithium strip or the lithium alloy strip, and the portion is die-cut into a pole ear.
  • the metal lithium strip or lithium alloy strip has a thickness of 0.01-0.15 mm and a width of 10-1500 mm.
  • the metal lithium strip or lithium alloy strip has a thickness of 0.01-0.10 mm, more preferably 0.010-0.05 mm; the metal lithium strip or lithium alloy strip has a width of 20-1500 mm, more preferably 50-1500 mm, such as 150-1500 mm, 200-1500 mm, 250-1500 mm, 300-1500 mm, 350-1500 mm, 400-1500 mm, 450-1500 mm, or 500-1500 mm.
  • the width of the pre-treated area is 2-10 mm, and the thickness of the pre-treated area is 0.1-5 um thinner than the thickness at other locations, preferably 1-5 um; the pre-treatment methods include erasing, rolling, and gluing.
  • the lithium alloy comprises a binary alloy and/or a multinary alloy, preferably a binary alloy and/or a ternary alloy.
  • the lithium alloy is formed by a combination of metallic lithium and any one or at least two elements of Ag, Au, Sn, Si, Zn, Al, Mg, In, Ga, B, Mn, Sb, Cr, V, Cu, Fe or Ti, and the mass proportion of metallic lithium in the lithium alloy can be more than 50%, preferably more than 70%, more preferably more than 80%, or even more than 90%.
  • the current collecting and gathering part is made of metal foil, and the metal foil is selected from copper foil, nickel foil, stainless steel foil or composite metal current collector; the thickness of the foil is 3-10um, preferably 3-8um.
  • the width of the current collecting and converging portion is 12-30 mm; and the width of the stress buffer layer is 2-10 mm.
  • the stress buffer layer comprises discontinuous protruding metal particles, which are formed by vapor deposition, and the particle size of the metal particles is 1-7um, preferably 1-5um.
  • the protruding height of the metal particles is 1-5um; the area ratio of the metal particles to the stress buffer layer is 1:3 to 9:10.
  • the metal particles include at least one of tin particles, zinc particles, magnesium particles, aluminum particles, silver particles, and lithium particles.
  • the type of the metal particles is the same as the alloy element contained in the lithium alloy ribbon.
  • the type of the metal particles is different from the alloying elements contained in the lithium alloy ribbon.
  • the pre-treated area and the area of the current collecting and gathering part having the stress buffer layer are laminated together by at least one of diffusion welding, ultrasonic welding, resistance welding and pressure welding processes; the width of the laminated area ranges from 2 to 10 mm.
  • the region where the stress buffer layer of the current collecting and converging part and the lithium strip or lithium alloy strip overlap can be continuous or discontinuous; because atoms are constantly diffusing, the discontinuous region will subsequently diffuse to a uniform state.
  • the stress buffer layer of the current collecting and converging part can be divided into several discontinuous parts, each of which is separated by a certain distance, for example, 0.1-1 mm.
  • the stress buffer layer can also have a grid shape.
  • the thickness of the stress buffer layer of the current collecting and converging part and the lithium belt or lithium alloy belt overlapping area is equal to or slightly greater than the thickness of the pure lithium belt or lithium alloy belt.
  • the thickness of the lithium belt is 50um, the thickness of the stress buffer layer of the current collecting and converging part and the lithium belt overlapping area is 55um; the thickness of the lithium belt is 60um, the thickness of the stress buffer layer of the current collecting and converging part and the lithium belt overlapping area is 60um; the thickness of the lithium magnesium (magnesium content 10%) alloy belt is 60um, the thickness of the stress buffer layer of the current collecting and converging part and the lithium belt overlapping area is 63um; the thickness of the lithium silver (silver content 1%) alloy belt is 40um, the thickness of the stress buffer layer of the current collecting and converging part and the lithium belt overlapping area is 40um.
  • Another aspect of the present invention provides a method for preparing the above-mentioned lithium battery negative electrode, comprising:
  • Step 1 depositing discontinuous protruding metal particles on the metal foil through a vapor deposition process to obtain a current collecting and gathering portion with a stress buffer layer covered in a partial area;
  • Step 2 pre-treating at least one side edge region of the lithium strip or lithium alloy strip by at least one of wiping, rolling and gluing to form a pre-treated region with a width of 2-10 mm;
  • Step 3 welding the region with the stress buffer layer of the current collecting and converging portion obtained in step 1 and the pre-treated region of the lithium strip or lithium alloy strip obtained in step 2 together by means of at least one of diffusion welding, ultrasonic welding, resistance welding, and pressure welding, so that the metal particles of the stress buffer layer and the lithium in the lithium strip or lithium alloy strip are fused together to form a fusion region of lithium and metal particles; and
  • Optional step four die-cutting the portion of the current collecting and gathering portion that is not overlapped with the pre-treated area and extends beyond the width of the lithium strip or lithium alloy strip to form a pole ear.
  • the conductive foil of the current collecting and gathering part is first subjected to a low-temperature plasma degreasing treatment; the degreased conductive foil is dried, and the dried conductive foil is subjected to a vapor deposition process to deposit discontinuous raised metal lithium particles to obtain a stress buffer layer, and the width of the stress buffer layer is 2-10 mm.
  • Another aspect of the present invention provides the use of the high-energy-density lithium battery negative electrode in a lithium-ion battery.
  • the high-energy-density metal lithium negative electrode can be used as the negative electrode of a metal lithium battery.
  • the present invention provides a lithium battery comprising the above-mentioned lithium battery negative electrode, and the positive electrode material is selected from ternary nickel-cobalt-manganese material, ternary nickel-cobalt-aluminum material, lithium-rich manganese-based positive electrode material, lithium cobalt oxide, lithium iron phosphate, and sulfur positive electrode material.
  • the electrolyte of the lithium battery can be selected from a liquid electrolyte or a solid electrolyte; the liquid electrolyte can be selected from an ester or an ether; the solid electrolyte can be selected from an oxide solid electrolyte, a sulfide solid electrolyte or a polymer electrolyte, such as a PEO (mixed oxide or sulfide powder) electrolyte.
  • a liquid electrolyte or a solid electrolyte can be selected from an ester or an ether
  • the solid electrolyte can be selected from an oxide solid electrolyte, a sulfide solid electrolyte or a polymer electrolyte, such as a PEO (mixed oxide or sulfide powder) electrolyte.
  • the diaphragm is made of PP, PE or a three-layer laminated diaphragm of PP and PE, and the diaphragm can have a ceramic coating.
  • the battery can be made into square, soft pack and cylindrical batteries.
  • the high specific energy metal lithium negative electrode of the present invention can be produced in batches in rolls, which solves the problem of difficulty in engineering the tabs of pure lithium strip negative electrodes.
  • the high specific energy metal lithium negative electrode of the present invention has its own tabs, which can be directly die-cut for use without the need for additional tabs.
  • the high specific energy metal lithium negative electrode of the present invention can be used directly as a negative electrode, because the current collecting and gathering part has a small area and occupies a small proportion.
  • this negative electrode in conjunction with a high-capacity positive electrode material, a battery with an energy density exceeding 500wh/kg can be prepared.
  • the stress buffer layer can be in close contact with the lithium strip or lithium alloy strip, and the current collecting effect is good.
  • FIG. 1 is a schematic diagram of the planar structure of the negative electrode of a lithium battery of the present invention.
  • FIG2 is a cross-sectional view of the negative electrode of the lithium battery of the present invention, in which the thickness of the lithium and the current collecting portion is greater than the thickness of the lithium strip or the lithium alloy strip.
  • FIG3 is another cross-sectional view of the negative electrode of the lithium battery of the present invention, in which the thickness of the lithium and the current collecting portion is equal to the thickness of the lithium strip or lithium alloy strip.
  • FIG. 4 is a physical picture of lithium metal particles in the stress buffer layer in Example 2.
  • FIG. 5 is a physical picture of magnesium metal particles in the stress buffer layer in Example 5.
  • FIG1 is a schematic diagram (top view) of the planar structure of the negative electrode of a lithium battery of the present invention, wherein the negative electrode of the lithium battery comprises a lithium strip or a lithium alloy strip 1 and a current collecting and gathering portion 2 bonded to one edge of the lithium strip or the lithium alloy strip.
  • FIG2 and FIG3 show cross-sectional views of the negative electrode of a lithium battery of the present invention, wherein the pre-treated region of the lithium strip or the lithium alloy strip 1 and the region of the current collecting and gathering portion 2 having a stress buffer layer are laminated together to form a bonding portion 3 (a fusion region of lithium and metal particles).
  • the thickness of the laminated region in FIG2 is greater than the thickness of the lithium strip or the lithium alloy strip, and the thickness of the laminated region in FIG3 is equal to the thickness of the lithium strip or the lithium alloy strip.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the rolled copper foil (current collecting part) has a thickness of 5um and a width of 20mm. Under the conditions of a vacuum degree of 10-3 Pa and a temperature of 500°C, lithium particles with a particle size of 2um are deposited on the surface of the edge area (3mm width area) of one side of the copper foil, and the area of the lithium particles accounts for one-half, thereby obtaining a stress buffer layer.
  • the edge area (3mm wide) of one side of the rolled lithium strip (50um thick, 100mm wide) was erased to a thickness of 1um; the stress buffer layer area on the copper foil and the erased area of the lithium strip were welded together by pressure welding (pressure of 50MPa, temperature of 40°C) to obtain a lithium negative electrode with a lithium-copper coating area thickness of 55um.
  • the surface of the lithium strip is flat.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the rolled copper foil (current collecting part) has a thickness of 3.5um and a width of 15mm. Under the conditions of a vacuum degree of 10-3 Pa and a temperature of 500°C, lithium particles with a particle size of 1um are deposited on the surface of an edge area (5mm width area) on one side of the copper foil, and the area of the lithium particles accounts for three-fifths, thereby obtaining a stress buffer layer.
  • FIG4 shows a physical picture of the lithium metal particles in the stress buffer layer in this embodiment.
  • the edge area (5mm wide) on one side of the rolled lithium strip (60um thick, 200mm wide) was rolled to a thickness of 4um; the stress buffer layer area on the copper foil and the rolled area of the lithium strip were welded together by pressure welding (pressure 80MPa, temperature is 30°C) to obtain a lithium negative electrode with a lithium-copper coating area thickness of 60um.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the rolled copper foil (current collecting part) is 4um thick and 20mm wide. Under the conditions of vacuum degree of 10 -3 Pa and temperature of 500°C, lithium particles with a particle size of 1um are deposited on the surface of the copper foil (3mm width area), and the area of lithium particles accounts for one-half, to obtain a stress buffer layer.
  • the edge area (3mm wide) on one side of the rolled lithium tape (50um thick, 500mm wide) was erased with an erased thickness of 3um; the stress buffer layer area on the copper foil and the erased area of the lithium tape were welded together by pressure welding (pressure 40MPa, temperature 30°C) to obtain a lithium negative electrode with a lithium-copper coating area thickness of 50um.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the rolled stainless steel foil (current collecting part) has a thickness of 10um and a width of 20mm. Under the conditions of vacuum degree of 10 -5 Pa and temperature of 1000°C, tin particles with a particle size of 1um are deposited on the surface of the stainless steel foil (5mm width area), and the area of the tin particles accounts for one-half, thereby obtaining a stress buffer layer.
  • the edge area (5mm wide) on one side of the rolled lithium-tin alloy strip (60um thick, 300mm wide, tin content 5%) was rolled away with a thickness of 3um; the stress buffer layer area on the stainless steel foil and the rolled away area of the lithium-tin alloy strip were welded together by pressure welding (pressure 80MPa, temperature 40°C) to obtain a high-energy-density lithium metal negative electrode product.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the rolled copper foil (current collecting part) has a thickness of 5um and a width of 20mm. Under the conditions of a vacuum degree of 10-5 Pa and a temperature of 700°C, magnesium particles with a particle size of 2um are deposited on the surface of the copper foil (3mm width area), and the area of the magnesium particles accounts for one third, thereby obtaining a stress buffer layer.
  • FIG5 shows a physical picture of the magnesium metal particles in the stress buffer layer in this embodiment.
  • the edge area (5mm wide) on one side of a rolled lithium-magnesium alloy strip (50um thick, 100mm wide, magnesium content 10%) was erased with an erased thickness of 3um; the stress buffer layer area on the copper foil and the erased area of the lithium-magnesium alloy strip were welded together by pressure welding (pressure 60MPa, temperature is 30°C) to obtain a high-energy-density lithium metal negative electrode product.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the rolled copper foil (current collecting part) has a thickness of 5um and a width of 20mm. Under the conditions of vacuum degree of 10 -5 Pa and temperature of 700°C, magnesium particles with a particle size of 2um are deposited on the surface of the copper foil (3mm width area), and the area of magnesium particles accounts for one third to obtain a stress buffer layer.
  • the edge area (5mm wide) on one side of the rolled lithium strip (50um thick, 300mm wide) was erased with a thickness of 3um; the stress buffer layer area on the copper foil and the erased area of the lithium strip were welded together by pressure welding (pressure 50MPa, temperature 40°C) to obtain a high-energy-density lithium metal negative electrode product.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • the high specific energy metal lithium negative electrode, NCM ternary positive electrode and diaphragm of Example 1 were assembled into a soft pack battery by means of a laminating machine, and the capacity of the battery cell was 2Ah.
  • test voltage range is 3-4.25V, and the charge and discharge current is 0.5C.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • the high specific energy metal lithium negative electrode, NCM ternary positive electrode and diaphragm of Example 5 are assembled into a soft pack battery with the help of a laminating machine, and the capacity of the battery cell is 2Ah.
  • the test voltage range is 3-4.25V, and the charge and discharge current is 0.5C.
  • the rolled copper foil has a thickness of 5um and a width of 20mm; the rolled lithium strip (60um thick) has a width of 100mm; the edge area on one side of the copper foil (3mm wide) and the edge area on one side of the lithium strip (3mm wide) are rolled together, and the pressure is set to 70MPa.
  • the length of the lithium strip in the rolled laminated area and the unlaminated pure lithium strip area is inconsistent.
  • the laminated area is prone to pulling the lithium in the unlaminated pure lithium strip area to deform.
  • the length of the product reaches about 20 meters, the lithium strip is severely stretched and deformed, and many pits and bumps appear on the surface of the lithium strip, which cannot be used as a negative electrode, so the winding is stopped.
  • the rolled copper foil (current collecting area) has a thickness of 5um and a width of 120mm; the lithium tape has a thickness of 25um and a width of 100mm.
  • the lithium tape is laminated on both sides onto the rolled copper foil to obtain a product with metallic lithium laminated on both sides of the copper foil (using the entire copper foil as the current collecting area).
  • This negative electrode and NCM positive electrode were used, and the battery was dried at 130°C for 12 hours.
  • the positive electrode and the separator are assembled into a soft pack battery with the help of a laminating machine.
  • the capacity of the battery cell is 2Ah.
  • the test voltage range is 3-4.25V, and the charge and discharge current is 0.5C.
  • Examples 7 and 8 use very narrow copper foil as the current collector, and the specific energy can exceed 500wh/kg.
  • Comparative Example 2 uses a whole copper foil as the current collector. Because the density of the copper foil is very large and the copper foil has a large use area, the specific energy is only 413.5Wh/kg.

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Abstract

一种锂电池负极及其制备方法和应用，所述锂电池负极由长条状的锂带或锂合金带和结合于所述长条状的锂带或锂合金带的至少一侧边缘上的集流汇集部组成，其中所述锂带或锂合金带的至少一侧边缘具有预处理区域，所述集流汇集部包含具有应力缓冲层的区域，所述预处理区域和所述具有应力缓冲层的区域彼此覆合在一起。

Description

一种锂电池负极及其制备方法和应用 技术领域
本发明涉及电化学储能技术领域，特别涉及用于金属锂电池的锂负极及其制备方法和应用。
背景技术
随着社会对锂离子电池的能量密度要求越来越高。首先要采用更高比容量的负极材料，金属锂由于3860mAh/g的容量和-3.04V的低电位，认为是最优的负极材料。目前很多电池厂家采用纯金属锂带做负极直接使用，金属锂厚度为50-80um，金属锂本身很软，厚度小于100um时成卷机械化生产难度很大，金属锂带材成卷引出极耳的难度更大。CN209641727专利公开了将金属锂先模切成一片一片的负极片，之后采用0.3～0.5MPa压强的力将铜极耳贴合到单片的极片上引出极耳，采用此种工艺引出极耳费时费力，无法大规模生产应用。另很多科研院采用锂铜覆合带做负极使用，由于铜的密度是8.96g/cm3，是金属锂密度的16倍，6um铜箔相当于100um厚的锂，采用整面铜箔覆合金属锂的产品比能量有限，因此现有的负极仍不能满足高比能电池的要求。
发明内容
本发明提出了一种新型的金属锂负极，此款锂负极中极耳与锂带的结合区域很窄，所占比重很小，使得电池的比能量得到很大提升，并且引出极耳方式比较方便，可以成卷大规模批量化生产使用。
目前锂铜覆合的工艺大多数采用压力覆合工艺。本申请的发明人发现，当仅在锂带边缘覆合铜箔作为极耳时，因铜和锂覆合区域很窄(3-10mm)，作用力只作用到很窄的覆合区域，覆合时压力小，锂和铜附着不好，锂很容易从铜上剥离下来，集流效果差；而覆合时压力大，覆合区域的锂材料会相应延展，但是其它未覆合区域的锂材料未受力不会延展，金属锂负极产品成卷生产过程中，覆合区域的锂和未覆合区域的锂因在长度上不一致(这种不一致随着长度的增加更明显)，造成未覆合区域的锂出现拉伸变形的现象。
针对上述问题，发明人设计了应力缓冲层，该应力缓冲层设置在极耳要与锂带结合的区域中，由凸起的不连续金属颗粒构成，这些凸起颗粒在极耳与锂带覆合时在外力作 用下可以延展变形(凸起颗粒的高度变小)，从而使覆合时产生的应力能够被缓冲释放，减小或避免覆合区域的锂材料在应力作用下的延展。另外，还可以对锂带要与极耳结合的区域进行预处理，形成厚度消薄的预处理区域，该预处理区域具有新的金属锂表面(原先锂表面上有钝化层，不利于锂和铜覆合到一起)，有利于应力缓冲层和锂带更好的覆合到一起，同时，应力缓冲层中的凸起颗粒在变形后也可以填补消薄区域，得到表面平整的自带极耳的金属锂负极。
本发明的技术方案如下。
本发明的一个方面提供一种锂电池负极，所述锂电池负极由长条状的锂带或锂合金带和结合于所述长条状的锂带或锂合金带的至少一侧边缘上的集流汇集部组成，其中所述锂带或锂合金带的至少一侧边缘具有预处理区域，所述集流汇集部包含具有应力缓冲层的区域，所述预处理区域和所述具有应力缓冲层的区域彼此覆合在一起。
根据一个实施方式，所述集流汇集部还包括未与所述预处理区域覆合的、延伸超过锂带或锂合金带宽度的部分，该部分模切成极耳。
根据一个实施方式，金属锂带或锂合金带厚度为0.01-0.15mm，宽度为10-1500mm。优选地，金属锂带或锂合金带厚度为0.01-0.10mm，更优选0.010-0.05mm；金属锂带或锂合金带的宽度为20-1500mm，更优选50-1500mm，例如150-1500mm，200-1500mm，250-1500mm，300-1500mm，350-1500mm，400-1500mm，450-1500mm，或者500-1500mm。
根据一个实施方式，预处理区域的宽度为2-10mm，预处理区域的厚度比其他处的厚度薄0.1-5um，优选1-5um；预处理方式包括擦除、辊除、胶粘。
根据一个实施方式，锂合金包括二元合金和/或多元合金，优选为二元合金和/或三元合金。
根据一个实施方式，锂合金由金属锂与Ag、Au、Sn、Si、Zn、Al、Mg、In、Ga、B、Mn、Sb、Cr、V、Cu、Fe或Ti中的任意一种或至少两种元素组合形成，锂合金中金属锂所占质量比例可以为50％以上，优选70％以上，更优选80％以上，甚至90％以上。
根据一个实施方式，集流汇集部由金属箔材制成，所述金属箔材选自铜箔、镍箔、不锈钢箔或复合金属集流体；箔材厚度为3-10um，优选3-8um。
根据一个实施方式，集流汇集部的宽度为12-30mm；应力缓冲层的宽度为2-10mm。
根据一个实施方式，应力缓冲层包含不连续的凸起金属颗粒，金属颗粒通过气相沉积形成，金属颗粒的粒径大小为1-7um，优选1-5um。金属颗粒的凸起高度为1-5um；金属颗粒在应力缓冲层的面积占比为1：3至9：10。
根据一个实施方式，金属颗粒包括锡颗粒、锌颗粒、镁颗粒、铝颗粒、银颗粒以及锂颗粒中的至少一种。
根据一个实施方式，金属颗粒的种类与锂合金带中所含的合金元素相同。
根据一个实施方式，金属颗粒的种类与锂合金带中所含的合金元素不相同。
根据一个实施方式，预处理区域和集流汇集部的具有应力缓冲层的区域借助扩散焊、超声焊、电阻焊、压力焊工艺中的至少一种覆合到一起；覆合区域的宽度范围为2-10mm。
根据一个实施方式，集流汇集部的应力缓冲层和锂带或锂合金带覆合的区域可以是连续的，也可以是非连续的；因原子是不断扩散的，非连续的区域后续也会扩散到均匀一致的状态。例如，集流汇集部的应力缓冲层可以分为不连续的几个部分，每个部分间隔一定距离，例如，0.1-1mm。应力缓冲层也可以具有网格形状。
根据一个实施方式，集流汇集部的应力缓冲层和锂带或锂合金带覆合区域的厚度等于或略大于纯锂带或锂合金带厚度。例如：锂带厚度为50um，集流汇集部的应力缓冲层和锂带覆合区域的厚度为55um；锂带厚度为60um，集流汇集部的应力缓冲层和锂带覆合区域的厚度为60um；锂镁(镁含量10％)合金带厚度为60um，集流汇集部的应力缓冲层和锂带覆合区域的厚度为63um；锂银(银含量1％)合金带厚度为40um，集流汇集部的应力缓冲层和锂带覆合区域的厚度为40um。
本发明的另一个方面提供一种制备上述锂电池负极的方法，包括：
步骤一：通过气相沉积工艺，在金属箔材上沉积不连续的凸起金属颗粒，得到部分区域覆有应力缓冲层的集流汇集部；
步骤二：通过擦除、辊除、胶粘中的至少一种，对锂带或锂合金带的至少一侧边缘区域进行预处理，形成宽度为2-10mm的预处理区域；
步骤三：将步骤一得到的集流汇集部的具有应力缓冲层的区域和步骤二得到的锂带或锂合金带的预处理区域借助扩散焊、超声焊、电阻焊、压力焊中的至少一种焊接到一起，使应力缓冲层的金属颗粒和锂带或锂合金带中的锂融合在一起，形成锂和金属颗粒的融合区；和
任选的步骤四：对所述集流汇集部的未与所述预处理区域覆合的、延伸超过锂带或锂合金带宽度的部分进行模切，形成极耳。
根据一个实施方式，在步骤一中，对集流汇集部的导电性的箔材先进行低温等离子除油处理；对除油后导电性箔材进行干燥处理，干燥后导电性箔材通过气相沉积工艺，沉积不连续的凸起的金属锂颗粒，得到应力缓冲层，应力缓冲层的宽度为2-10mm。
本发明的再一个方面提供上述高比能锂电池负极在锂离子电池中的应用，上述高比能金属锂负极可以用作金属锂电池的负极。
根据一个实施方式，本发明提供一种锂电池，其包含上述的锂电池负极，正极材料选自三元镍钴锰材料，三元镍钴铝材料，富锂锰基正极材料，钴酸锂，磷酸铁锂，硫正极材料。
根据一个实施方式，锂电池的电解液可以选择液态电解液或者固态电解质；液态电解液选择酯类或者醚类；固态电解质可以选择氧化物固态电解液、硫化物固态电解质或者聚合物类电解质，例如PEO(已混合氧化物或者硫化物粉体)类电解质。
对于液态电池，隔膜选用PP、PE或者PP和PE三层覆合隔膜，隔膜可带陶瓷涂层。
电池可以组成方型、软包、圆柱型电池。
本发明具有以下优点中的至少一种：
(1)本发明的高比能金属锂负极可以成卷批量化生产，解决了纯锂带负极工程化引出极耳难的问题。
(2)本发明的高比能的金属锂负极自带极耳，可以直接模切出极耳使用，不需要额外引出极耳。
(3)本发明的高比能金属锂负极可以直接作负极使用，因集流汇集部使用面积小，占的比重小，使用此负极配套高容量的正极材料可以制备能量密度超500wh/kg的电池。
(4)解决了锂和集流汇集部覆合不牢固的问题，应力缓冲层可以和锂带或锂合金带接触紧密，集流效果好。
附图说明
图1为本发明的锂电池负极的平面结构的一个示意图。
图2为本发明的锂电池负极的一个截面图，图中锂和集流汇集部覆合的厚度大于锂带或锂合金带厚度。
图3为本发明的锂电池负极的另一个截面图，图中锂和集流汇集部覆合的厚度等于锂带或锂合金带厚度。
图4为实施例2中应力缓冲层中锂金属颗粒的实物图。
图5为实施例5中应力缓冲层中镁金属颗粒的实物图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
又及，在如下实施例之中所采用的各种产品结构参数、各种反应参与物及工艺条件均是较为典型的范例，但经过本案发明人大量试验验证，于上文所列出的其它不同结构参数、其它类型的反应参与物及其它工艺条件也均是适用的，并也均可达成本发明所声称的技术效果。
图1为本发明的锂电池负极的平面结构的一个示意图(俯视图)，其中，锂电池负极包括锂带或锂合金带1和结合于锂带或锂合金带一侧边缘上的集流汇集部2。图2和图3显示了本发明的锂电池负极的截面图，其中，锂带或锂合金带1的预处理区域与集流汇集部2的具有应力缓冲层的区域覆合在一起形成结合部3(锂和金属颗粒的融合区)。图2中覆合区域的厚度大于锂带或锂合金带厚度，图3中覆合区域的厚度等于锂带或锂合金带厚度。
实施例1：
成卷铜箔(集流汇集部)厚度为5um，宽度20mm；在真空度为10-3Pa，温度为500℃条件下，在铜箔的一侧边缘区域(3mm宽度区域)表面沉积粒径2um的锂粒，锂粒面积占比为二分之一，得到应力缓冲层；
对成卷的锂带(50um厚，100mm宽)一侧边缘区域(3mm宽)进行擦除处理，擦除的厚度为1um；将铜箔上的应力缓冲层区域和锂带擦除区域通过压力焊(压力为50MPa，温度为40℃)的方式焊接到一起，得到锂铜覆合区域厚度为55um的锂负极。该实施例获得的锂铜复合带中，锂带表面平整。
实施例2：
成卷铜箔(集流汇集部)厚度为3.5um，宽度15mm；在真空度为10-3Pa，温度为500℃条件下，在铜箔的一侧边缘区域(5mm宽度区域)表面沉积粒径1um的锂粒，锂粒面积占比为五分之三，得到应力缓冲层；图4显示了该实施例中应力缓冲层中锂金属颗粒的实物图。
对成卷的锂带(60um厚，200mm宽)一侧边缘区域(5mm宽)进行辊除处理，辊除的厚度为4um；将铜箔上的应力缓冲层区域和锂带的辊除区域通过压力焊(压力80MPa，温度是30℃)方式焊接到一起，得到锂铜覆合区域厚度为60um的锂负极。
实施例3：
成卷铜箔(集流汇集部)厚度为4um，宽度20mm；在真空度为10-3Pa，温度为500℃条件下，在铜箔(3mm宽度区域)表面沉积粒径1um的锂粒，锂粒面积占比为二分之一，得到应力缓冲层；
对成卷的锂带(50um厚，500mm宽)一侧边缘区域(3mm宽)进行擦除处理，擦除的厚度为3um；将铜箔上的应力缓冲层区域和锂带的擦除区域通过压力焊(压力40MPa，温度是30℃)的方式焊接到一起，得到锂铜覆合区域厚度为50um的锂负极。
实施例4：
成卷不锈钢箔(集流汇集部)厚度为10um，宽度20mm；在真空度为10-5Pa，温度为1000℃条件下，在不锈钢箔(5mm宽度区域)表面沉积粒径1um的锡粒，锡粒面积占比为二分之一，得到应力缓冲层；
对成卷的锂锡合金带(60um厚，300mm宽，锡含量5％)一侧边缘区域(5mm宽)进行辊除处理，辊除的厚度为3um；将不锈钢箔上的应力缓冲层区域和锂锡合金带的辊除区域通过压力焊(压力80MPa，温度是40℃)的方式焊接到一起，得到高比能金属锂负极产品。
实施例5：
成卷铜箔(集流汇集部)厚度为5um，宽度20mm；在真空度为10-5Pa，温度为700℃条件下，在铜箔(3mm宽度区域)表面沉积粒径2um的镁粒，镁粒面积占比为三分之一，得到应力缓冲层；图5显示了该实施例中应力缓冲层中镁金属颗粒的实物图。
对成卷的锂镁合金带(50um厚，100mm宽，镁含量10％)一侧边缘区域(5mm宽)进行擦除处理，擦除的厚度为3um；将铜箔上的应力缓冲层区域和锂镁合金带的擦除区域通过压力焊(压力60MPa，温度是30℃)的方式焊接到一起，得到高比能金属锂负极产品。
实施例6：
成卷铜箔(集流汇集部)厚度为5um，宽度20mm；在真空度为10-5Pa，温度为700℃条件下，在铜箔(3mm宽度区域)表面沉积粒径2um的镁粒，镁粒面积占比为三分之一，得到应力缓冲层；
对成卷的锂带(50um厚，300mm宽)一侧边缘区域(5mm宽)进行擦除处理，擦除的厚度为3um；将铜箔上的应力缓冲层区域和锂带的擦除区域通过压力焊(压力50MPa，温度是40℃)的方式焊接到一起，得到高比能金属锂负极产品。
实施例7：
负极使用实施例1的高比能金属锂负极；正极使用NCM三元正极，经130℃烘干12小时待做电池；隔膜使用Celgard2500，电解液采用1M LiPF6，EC：EMC＝3:7(vol/vol)。将实施例1的高比能金属锂负极、NCM三元正极和隔膜借助叠片机组装成软包电池，电芯的容量2Ah。
测试电压范围3-4.25V，充放电流为0.5C。
实施例8：
负极选用实施例5的高比能金属锂负极，正极使用NCM三元正极，经130℃烘干12小时待做电池；隔膜使用Celgard2500，电解液采用1M LiPF6，EC：EMC＝3:7(vol/vol)。将实施例5的高比能金属锂负极、NCM三元正极和隔膜借助叠片机组装成软包电池，电芯的容量2Ah。测试电压范围3-4.25V，充放电流为0.5C。
对比例1：
成卷铜箔厚度为5um，宽度20mm；成卷的锂带(60um厚)，宽度100mm；将铜箔一侧边缘区域(3mm宽)和锂带一侧的边缘区域(3mm宽)辊压覆合到一起，设置压力为70MPa，生产产品的过程中发现辊压覆合的区域和没有覆合的纯锂带区域的锂带长度不一致，覆合区域容易拉扯没有覆合的纯锂带区域锂变形，生产产品长度达到20米左右时，锂带拉伸变形严重，锂带表面出现很多坑坑洼洼，无法做负极使用，停止收卷。
对比例2：
成卷铜箔(集流汇集区)厚度为5um，宽度120mm；锂带厚度25um，锂带宽度100mm，将锂带双面覆合到成卷的铜箔上，得到铜箔双面覆合金属锂的产品(使用整面铜箔作为集流汇集区)。
使用此款负极，正极使用NCM三元正极，经130℃烘干12小时待做电池；隔膜使用Celgard2500，电解液采用1M LiPF6，EC：EMC＝3:7(vol/vol)。将负极、NCM三元 正极和隔膜借助叠片机组装成软包电池，电芯的容量2Ah。测试电压范围3-4.25V，充放电流为0.5C。
表1：不同负极组装电池的比能量对比
从表1可以看出，实施例7和实施例8采用很窄铜箔做集流体，比能量能突破500wh/kg，对比例2使用整面铜箔做集流体，因铜箔的密度很大，铜箔使用面积很大，所以比能量只有413.5Wh/kg。
应当理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种锂电池负极，其特征在于，所述锂电池负极由长条状的锂带或锂合金带和结合于所述长条状的锂带或锂合金带的至少一侧边缘上的集流汇集部组成，其中
    所述锂带或锂合金带的至少一侧边缘具有预处理区域，所述集流汇集部包含具有应力缓冲层的区域，所述预处理区域和所述具有应力缓冲层的区域彼此覆合在一起，
    其中，所述预处理为：对锂带要与极耳结合的区域进行预处理，形成厚度消薄的预处理区域，该预处理区域具有新的金属锂表面；
    所述应力缓冲层为：应力缓冲层在极耳要与锂带结合的区域中，由凸起的不连续金属颗粒构成，这些凸起颗粒在极耳与锂带覆合时在外力作用下可以延展变形。
  2. 根据权利要求1所述的锂电池负极，其特征在于，所述集流汇集部还包括未与所述预处理区域覆合的、延伸超过锂带或锂合金带宽度的部分，该部分模切成极耳。
  3. 根据权利要求1所述的锂电池负极，其特征在于，所述锂带或锂合金带厚度为0.01-0.15mm，宽度为10-1500mm；所述预处理区域的宽度为2-10mm，预处理区域的厚度比其他处的厚度薄0.1-5um，预处理方式包括擦除、辊除、胶粘。
  4. 根据权利要求1所述的锂电池负极，其特征在于，所述锂合金由金属锂与Ag、Au、Sn、Si、Zn、Al、Mg、In、Ga、B、Mn、Sb、Cr、V、Cu、Fe或Ti中的任意一种或至少两种元素组合形成。
  5. 根据权利要求1所述的锂电池负极，其特征在于，所述集流汇集部由金属箔材制成，所述金属箔材选自铜箔、镍箔、不锈钢箔或复合金属集流体；
    所述集流汇集部的厚度为3-10um；宽度为12-30mm；应力缓冲层的宽度为2-10mm。
  6. 根据权利要求1所述的锂电池负极，其特征在于，所述应力缓冲层中的不连续的凸起金属颗粒通过气相沉积形成，金属颗粒的粒径大小为1-7um；金属颗粒的凸起高度为1-5um；金属颗粒在应力缓冲层的面积占比为1：3至9：10。
  7. 根据权利要求6所述的锂电池负极，其特征在于，所述金属颗粒包括锡颗粒、锌颗粒、镁颗粒、铝颗粒、银颗粒以及锂颗粒中的至少一种。
  8. 根据权利要求1所述的锂电池负极，其特征在于，所述预处理区域和所述集流汇集部的具有应力缓冲层的区域借助扩散焊、超声焊、电阻焊、压力焊工艺中的至少一种覆合到一起；覆合区域的宽度范围为2-10mm。
  9. 一种制备如权利要求1至8中任一项所述的锂电池负极的方法，包括：
    步骤一：通过气相沉积工艺，在金属箔材上沉积不连续的凸起金属颗粒，得到部分区域覆有应力缓冲层的集流汇集部；
    步骤二：通过擦除、辊除、胶粘中的至少一种，对锂带或锂合金带的至少一侧边缘区域进行预处理，形成宽度为2-10mm的预处理区域；
    步骤三：将步骤一得到的集流汇集部的具有应力缓冲层的区域和步骤二得到的锂带或锂合金带的预处理区域借助扩散焊、超声焊、电阻焊、压力焊中的至少一种焊接到一起，使应力缓冲层的金属颗粒和锂带或锂合金带中的锂融合在一起，形成锂和金属颗粒的融合区；和
    任选的步骤四：对所述集流汇集部的未与所述预处理区域覆合的、延伸超过锂带或锂合金带宽度的部分进行模切，形成极耳。
  10. 一种锂电池，其特征在于，所述锂电池包含如权利要求1-8中任一项所述的锂电池负极，正极材料选自三元镍钴锰材料，三元镍钴铝材料，富锂锰基正极材料，磷酸铁锂，钴酸锂和硫正极材料。
PCT/CN2023/133641 2023-08-14 2023-11-23 一种锂电池负极及其制备方法和应用 Pending WO2025035640A1 (zh)

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