NO347301B1 - Cu-al electrode for lithium ion cell and method of manufacturing the cell - Google Patents

Cu-al electrode for lithium ion cell and method of manufacturing the cell Download PDF

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Publication number
NO347301B1
NO347301B1 NO20211346A NO20211346A NO347301B1 NO 347301 B1 NO347301 B1 NO 347301B1 NO 20211346 A NO20211346 A NO 20211346A NO 20211346 A NO20211346 A NO 20211346A NO 347301 B1 NO347301 B1 NO 347301B1
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alloy
lithium
lithium ion
foil
layer
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NO20211346A
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NO20211346A1 (en
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Børre Tore BØRRESEN
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Equinor Energy As
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Priority to NO20211346A priority Critical patent/NO347301B1/en
Priority to PCT/EP2022/081313 priority patent/WO2023083880A1/en
Publication of NO20211346A1 publication Critical patent/NO20211346A1/en
Publication of NO347301B1 publication Critical patent/NO347301B1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
    • 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
    • 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
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/36—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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/36—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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Description

Cu-Al electrode for lithium ion cell and method of manufacturing the cell
The present invention relates to an anode/negative electrode for a lithium ion cell and a method of manufacturing the anode/negative electrode.
Background
Fossil fuels stand presently for about 4/5 of the global energy demand, resulting in emissions of around 40 billion tons of CO2 to the atmosphere per year. One consequence of these emissions is an enhanced greenhouse-effect in the atmosphere causing a potentially dangerous global warming. Thus, the ongoing global warming issue increases the awareness of and factual need for a green shift of our economy.
According to the International Panel on Climate Change of the United Nations, the global net CO2-emissions need to be decreased to zero by the year 2050 to reach the goal of maximum 1.5 °C global warming set by the Paris agreement. One key factor to reach net zero CO2-emissions is electrification of machines and devices running on fossil fuel derived fuels such as petrol, diesel, kerosene, natural gas etc.
The electrification of mobile and/or portable machines/devices requires the ability to store and carry along a sufficient supply of electric energy. Electrochemical storage devices (batteries) attract therefore much interest. Lithium ion batteries (LIBs) are presently the most commonly applied secondary high-capacity batteries for portable electronics, tools, and transportation vehicles due to their combination of high energy density and high delivering capacity of electric effect.
Prior art
Presently commercially available secondary LIBs typically have electrochemical cells made up of a layer of a separator/electrolyte interposed between a layered anode/negative electrode and a layered cathode/positive electrode. Both electrodes, anode and cathode, are typically made up of a layer of active material (lithium ion delivering or up-taking material) facing the separator and a metallic current collecting substrate on the opposite/outer side of the active metal layer. The layers are typically 10 to 50 µm thick. The cathode usually applies an intercalation-type transition-metal-oxide as the active material of the cathode and an intercalation-type carbonaceous material (graphite) as the active material of the anode [ref 1]. The carbonaceous material may contain a certain fraction of silicon or silicon oxide to increase the energy storage capacity.
The energy density of present commercially available secondary LIBs is typically up to about 250 Wh/kg or 650 Wh/litres. Many mobile/portable appliances require a higher storage capacity than this to be enabled to be fully electrified and/or satisfying consumer/market demands. However, the energy density of the present LIBs are approaching their theoretical limit, causing a search for new material systems of the cathode and/or the anode enabling developing superior secondary LIBs.
Alloy-type materials such as Si, Sn, Ge, Sb, and Al, which may form alloys with Li, have attracted much interest due to their high theoretical capacity and appropriate lithiation/delithiation potentials. Aluminium can alloy with lithium forming AlLi, Al2Li3, and Al4Li9. The theoretical capacity from Al to AlLi is 993 mAh/gAl, or approx. three times the theoretical capacity of graphite [ref 2]. However, these alloy-type materials undergo an isotropic volume changes during lithiation and delithiation. For example, Aluminium will expand to about twice its size when lithiated to LiAl. Such huge volume changes cause damage to the aluminium matrix, potentially causing fragmentation into a fine powder drifting into the electrolyte. Fragmentation of electrode may also deteriorate the electric connection and integrity of the system, hence destroy the performance of the battery cell.
Hongyi Li et al. [1] have studied and found that the hardness of the matrix material has a profound effect on the structural stability of the aluminium matrix after lithiation. They lithiated aluminium foils of various hardness in coin-type cells with a Li counter-electrode and found that soft aluminium of Vickers hardness of 30 or less become locally deformed when lithiated to a cathodic charge of 5 mAh/cm<2 >at a current density of 0.5 mA/cm<2>. In contrast, hard aluminium of Vickers hardness of 60, did not deform. Instead protruding AlLi grains cracked and caused ductile fractures in the aluminium matrix. However, aluminium foils with Vickers hardness of around 35 achieved homogeneous lithiation on the front side and no damaged Almatrix on the back side. Hongyi Li et al. suggested therefore using a single aluminium foil of Vickers hardness of around 35 as both the active material and the current collecting substrate of an anode of secondary LIBs.
Handong Jiao et al. [3] have studied the problem of disintegration and pulverization of aluminium foils when applied as negative electrode in aluminium ion batteries. The document proposes applying a composite material of an aluminium plated copper foil which was found to deliver remarkable stability and long cycle life. The Al-Cu-foil was made by washing the surface in ethanol and distilled water followed by an acidic etching in hydrochloric acid of a copper foil (of thickness 10 µm) to make the foil surface free from impurities and oxides, and then electroplating the cupper foil by chronopotentiometry in a AlCl3 and 1-ethyl-3-methylimidazolium chloride system.
From US 2006/121351 it is known a negative electrode for a non-aqueous electrolyte secondary battery including an active material portion capable of electrochemically absorbing and desorbing Li, a current collector carrying the active material portion, and a buffer interposed between the active material portion and the current collector, the active material portion includes at least one selected from the group consisting of a Si simple substance, a Si alloy, and a Si compound, the current collector includes Cu, and the buffer has a first layer contacting the current collector and including a group A element which is at least one selected from the group A consisting of Sn, Al, and In, and a second layer contacting the active material portion and including a group B element which is at least one selected from the group B consisting of transition metal elements other than Cu.
US 2005/014068 discloses an anode capable of inhibiting collapse of a shape of an anode active material layer and a side reaction with an electrolyte in accordance with the collapse, and inhibiting reduction in a battery capacity, and a battery using it. The anode comprises an anode current collector and the anode active material layer. The anode active material layer has a first layer containing Sn and a second layer containing an element other than Sn capable of electrochemically inserting and extracting Li. A component element of the anode current collector is preferably diffused in both the first layer and the second layer.
Objective of the invention
The main objective of the invention is to provide a lithium ion cell comprising a negative electrode made of alloy-type materials.
A further objective is to provide a method of manufacturing the negative electrode of the lithium ion cell.
Description of the invention
The present invention is based on the realisation that a layer of copper may act stabilising for a layer of an alloy-type material enhancing the alloy-type material ability to tolerate the volume changes associated with lithiation and delithiation cycles. Furthermore, the copper foil may enhance the transport of electricity and heat.
Thus, in a first aspect, the invention relates to a lithium ion electrochemical cell, comprising:
a negative electrode,
a positive electrode, and
an electrolyte,
characterised in that
the negative electrode comprises a layered composite consisting of a layer of Cu or a Cu-alloy and a first composite layer of one of: Al, an Al-alloy, an Al/Lialloy, Sn, a Sn-alloy, Si, or a Si-alloy, and wherein the layer (7) of Cu or a Cu-alloy is diffusion bonded to the first composite layer 6.
The term “positive electrode” as used herein refers to an electric current conducting part of the electrochemical cell comprising an active material able to take up lithium ions and recombine them with electrons to electrical neutrality when the electrochemical cell discharges. The positive electrode may also de denoted as the cathode in the literature. The terms positive electrode and cathode may herein be used interchangeably. In one embodiment, the positive electrode may comprise a metallic substrate functioning both as a mechanical support for the active material and as the current collecting and conducting part of the electrode. The invention may apply any positive electrode known to the skilled person suited for lithium ion batteries. Examples of suited active materials of the cathode/positive electrode includes, but is not limited to, lithium nickel manganese cobalt oxides (LiNixMnyCozO2), lithium nickel cobalt aluminium oxides (LiNiCoAlO2), lithium manganese oxide (LiMn2O4), lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), sulphur (S8), sulphur coated carbon nanotubes, and sulphurised graphene.
The term “negative electrode” as used herein encompasses any negative electrode known to the skilled person suited for use in a lithium ion cell as long as it comprises a layered composite consisting of a layer of Cu or a Cu-alloy and a first composite layer of: Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy. The negative electrode may also be denoted as the anode in the literature. The terms negative electrode and anode may herein be used interchangeably. Examples of aluminium alloys include but is not limited to AA1xxx series aluminium alloys, manganese containing alloys (AA3xxx, AA6xxx and AA7xxx series), according to the Aluminium Association Standard, examples of tin alloys include but is not limited to aluminium-tin alloys (5-40% Sn).
The term “electrochemical cell” as applied herein refers to a device which produces an electric current from energy released by a spontaneous redox reaction involving a lithium compound when its two conductive electrodes are electrically connected, i.e. when the electrochemical cell discharges. In one embodiment, the electrochemical cell may be a secondary (rechargeable) electrochemical cell. The term “secondary” as applied herein refers to the electrochemical cell being able to reverse its redox reaction when an electric potential is applied to its electrodes, i.e. when the electrochemical cell is charged. The term “battery” us used herein refers to a single or to an assembly of a plurality of electrochemical cells.
The term “electrolyte” as used herein refers to the component of the electrochemical cell being in contact with the anode and the cathode, and which facilitates transport of Li<+ >ions between the anode and cathode and electrically insulates the anode and the cathode to keep self-discharging currents in the electrochemical cell at a minimum. The invention is not tied to any specific electrolyte but may apply any electrolyte known to the skilled person to be suited for lithium ion type electrochemical cells including non-aqueous electrolytes such as for example lithium hexafluorophosphate (LiPF6) dissolved in organic carbonates such as a mixture of ethylene carbonate with of one or more of dimethyl carbonate, propylene carbonate, diethyl carbonate, and ethyl methyl carbonate, or a Li2B12F12-xHx electrolyte with addition of lithium difluoro(oxalato)borate, aqueous electrolytes such as e.g. an aqueous solution of lithium nitrate (LiNO3) and/or lithium sulphate (Li2SO4), or ionic liquids having a cation chosen from one or more of imidazolium, quaternary ammonium, pyrrolidinium, and piperidinium and an anion chosen from one or more of PF , BF , and bis(trifluoromethanesulfonyl)imide (TFSI ). In one embodiment, the electrolyte may be a solid electrolyte, for example based on polymeric or ceramic (e.g. oxides or sulphides) compounds. Examples of a solid state electrolytes include but is not limited to a poly(ethylene oxide) complexed with an alkali metal ion with or without addition of a lithium salt, a lithium orthosilicate, a glass, a sulphide, or RbAg4I5.
In one embodiment, the lithium ion cell may further comprise a separator mechanically separating the anode from the cathode. The invention is not tied to any specific separator but may apply any separator known to the skilled person to be suited for lithium ion batteries. Examples of suited separators include but are not limited to a polymeric membrane of polyethylene (PE), polypropylene (PP), or PE/PP with pore sizes in the range of micrometres.
In one embodiment, the Cu layer of the layered composite of the negative electrode according to the first aspect of the invention may have a thickness in the range of from 5 to 200 µm, preferably from 10 to 150 µm, more preferably from 15 to 100 µm, and most preferably from 20 to 80 µm.
In one embodiment, the first composite layer of the negative electrode according to the first aspect of the invention may have a thickness in the range of from 5 to 100 µm, preferably from 10 to 75 µm, more preferably from 15 to 50 µm, and most preferably from 20 to 40 µm.
In one embodiment, the layered composite of the negative electrode according to the first aspect of the invention is made by diffusion bonding a stacked foil of the first composite layer and foil of copper.
Thus, in a second aspect, the invention relates to a method for producing a negative electrode for a lithium ion cell, wherein the method comprises:
forming a stack of foils comprising:
a first foil of one of: Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy, and
a foil of Cu or a Cu-alloy,
and
bonding together the stack of foils by diffusion bonding.
In one embodiment, the diffusion bonding of the method according to the second aspect of the invention may comprise pressurising the stack of foils to a pressure in the range of from 1 to 15 MPa, preferably from 8 to 13 MPa, and most preferably from 10 – 12 MPa and heating the stack of foils to a temperature in the range of from 200 to 650 °C, preferably from 300 to 600 °C, and most preferably from 400 to 500 °C, and maintain this pressure and temperature for a period of from 10 to 90 minutes, preferably from 20 to 75 minutes, and most preferably from 30 to 60 minutes. The pressure may be applied in a continuous manner by static pressing or periodic pressing action using rolling techniques. The use of a reducing environment, e.g. a hydrogen enriched atmosphere, during the bonding process may be beneficial.
In one embodiment, the method according to the second aspect of the invention further comprises forming a stack of foils further comprising a second foil of one of: Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy laid onto the foil of Cu or Cu-alloy at the opposite side of the first composite layer.
In one embodiment, the method according to the second aspect of the invention further comprises forming a stack of foils comprising a first bonding layer laid between the first foil of Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Sialloy and the foil of Cu or Cu-alloy.
In one embodiment, the method according to the second aspect of the invention further comprises forming a stack of foils further comprising, if a second foil of Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy is present in the stack, a second bonding layer laid between the second foil of Al, an Al-alloy, an Al/Lialloy, Sn, a Sn-alloy, Si, or a Si-alloy and the foil of Cu or Cu-alloy.
Example embodiment
The invention will be described in further detail by way of an example embodiment of a lithium ion cell according to the invention.
The electrochemical cell according to the embodiment is schematically drawn in figure 1. The figure is a cut-drawing as seen from the side. As seen from the figure, the example embodiment comprises a three-layered cathode 1 comprising a first layer 2 of lithium nickel cobalt aluminium oxide (LiNiCoAlO2) mixed with carbonaceous particles and binder and deposited to a thickness of 70 µm onto one side of an aluminium foil 3 of thickness 20 µm and a second layer 4 of lithium nickel cobalt aluminium oxide ) mixed with carbonaceous particles and binder and deposited to a thickness of 70 µm onto the other side of the aluminium foil 3.
The anode 5 is, as the cathode, a three-layered structure comprising a first layer 6 of aluminium of 99.999 % purity (based on weight) of a thickness of 20 µm being diffusion bonded to a copper foil 7 of thickness 10 µm and a second layer 8 of aluminium of 99.999 % purity (based on weight) of a thickness of 20 µm being diffusion bonded to the other side of the copper foil 7.
In-between the anode 5 and the cathode 1, there is a first separator 9 of thickness 12 µm made of microporous polyethylene (PE). The micropores is filled with an electrolyte comprising lithium hexafluorophosphate (LiPF6) dissolved in a mixture of ethylene carbonate and dimethyl carbonate.
References
1. Hongyi Li et al., “Circumventing huge volume strain in alloy anodes of lithium batteries”, Nature Communications, (2020)11:1584 | https://doi.org/10.1038/s41467-020-15452-0
2. Haidong Wang et al., “The progress on aluminium-based anode materials for lithium-ion batteries”, J. Mater. Chem., A, 2020, 8, 25649 – 25662 DOI: 10.1039/d0ta09672d
3. Handong Jiao et al., “Cu-Al Composite as the Negative Electrode for Long-Life Al-Ion Batteries”, Journal of the Electrochemical Society, 2019, 166 (15), A3539 – A3545,
DOI: 10.1149/2.0131915jes

Claims (14)

1. A lithium ion electrochemical cell, comprising:
a negative electrode (5),
a positive electrode (1), and
an electrolyte,
characterised in that
the negative electrode (5) comprises a layered composite consisting of a layer (7) of Cu or a Cu-alloy and a first composite layer (6) of one of: Al, an Alalloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy, and wherein the layer (7) of Cu or a Cu-alloy is diffusion bonded to the first composite layer (6).
2. The lithium ion cell according to claim 1, wherein the first composite layer (6) is an Al alloy in either the AA1xxx series, the AA3xxx series, the AA6xxx series of the AA7xxx series according to the Aluminium Association Standard, or a tin alloy, or an aluminium-tin alloy having 5 to 40 weight% Sn.
3. The lithium ion cell according to claim 1 or 2, wherein an active material of the positive electrode (1) is one of: lithium nickel manganese cobalt oxides (LiNixMnyCozO2), lithium nickel cobalt aluminium oxides (LiNiCoAlO2), lithium manganese oxide (LiMn2O4), lithium iron phosphate (LiFePO4), and lithium cobalt oxide (LiCoO2), sulphur (S8), sulphur coated carbon nanotubes, and sulphurised graphene.
4. The lithium ion cell according to any one of claims 1 to 3, wherein the electrolyte is
either:
a non-aqueous solution of lithium hexafluorophosphate (LiPF6) dissolved in organic carbonates, preferably a mixture of ethylene carbonate with of one or more of dimethyl carbonate, propylene carbonate, diethyl carbonate, and ethyl methyl carbonate,
or:
Li2B12F12-xHx with addition of lithium difluoro(oxalato)borate,
or:
an aqueous solution of lithium nitrate (LiNO3) and/or lithium sulphate (Li2SO4),
or:
an ionic liquid having a cation chosen from one or more of: imidazolium, quaternary ammonium, pyrrolidinium, and piperidinium, and an anion chosen form oner or more of PF , BF and bis(trifluoromethanesulfonyl)-imide (TFSI ).
5. The lithium ion cell according to any preceding claim, wherein the lithium ion cell further comprises a separator (9) mechanically separating the negative electrode (5) from the positive electrode (1), and wherein the separator preferably is a polymeric membrane with pore sizes in the range of micrometres made of either a polyethylene (PE), a polypropylene (PP), or a polyethylene/ polypropylene (PE/PP).
6. The lithium ion cell according to any one of claims 1 to 4, wherein the the electrolyte is a solid electrolyte, preferably chosen from one of: a poly(ethylene oxide) complexed with an alkali metal ion with or without addition of a lithium salt, a lithium orthosilicate, a glass, a sulphide, or RbAg4I5.
7. The lithium ion cell according to any preceding claim, wherein the Cu-layer (7) of the layered composite of the negative electrode has a thickness in the range of from 5 to 200 µm, preferably from 10 to 150 µm, more preferably from 15 to 100 µm, and most preferably from 15 to 80 µm, and
the first (6) composite layer of the negative electrode has a thickness in the range of from 5 to 100 µm, preferably from 10 to 75 µm, more preferably from 15 to 50 µm, and most preferably from 15 to 40 µm.
8. The lithium ion cell according to any preceding claim, wherein the electrochemical cell is a secondary electrochemical cell.
9. A method for producing a negative electrode for a lithium ion cell, wherein the method comprises:
forming a stack of foils comprising:
a first foil of one of: Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy, and
a foil of Cu or a Cu-alloy,
and
bonding together the stack of foils by diffusion bonding.
10. The method according to claim 9, wherein the diffusion bonding comprises:
pressurising the stack of foils to a pressure in the range of from 1 to 15 MPa, preferably from 8 to 13 MPa, and most preferably from 10 – 12 MPa,
heating the stack of foils to a temperature in the range of from 200 to 650 °C, preferably from 300 to 600 °C, and most preferably from 400 to 500 °C, and maintaining this pressure and temperature for a period of from 10 to 90 minutes, preferably from 20 to 75 minutes, and most preferably from 30 to 60 minutes.
11. The method according to claim 9 or 10, wherein the pressure is applied in a continuous manner by static pressing or periodically by rolling.
12. The method according to any one of claims 9 to 11, wherein the stack of foils further comprises a second foil of one of: Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy laid onto the foil of Cu or Cu-alloy at the opposite side of the first composite layer.
13. The method according to claim 12, wherein the stack of foils further comprises a second bonding layer laid between the second foil of Al, an Al-alloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy and the foil of Cu or Cu-alloy.
14. The method according to any one of claims 9 to 13, wherein the stack of foils further comprises a first bonding layer laid between the first foil of Al, an Alalloy, an Al/Li-alloy, Sn, a Sn-alloy, Si, or a Si-alloy and the foil of Cu or Cu-alloy.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050014068A1 (en) * 2003-07-15 2005-01-20 Tomoo Takada Anode and battery using it
US20060121351A1 (en) * 2004-12-08 2006-06-08 Matsushita Electric Industrial Co., Ltd. Negative electrode for non-aqueous electrolyte secondary battery, manufacturing method therefor, and non-aqueous electrolyte secondary battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050014068A1 (en) * 2003-07-15 2005-01-20 Tomoo Takada Anode and battery using it
US20060121351A1 (en) * 2004-12-08 2006-06-08 Matsushita Electric Industrial Co., Ltd. Negative electrode for non-aqueous electrolyte secondary battery, manufacturing method therefor, and non-aqueous electrolyte secondary battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HANDONG J. et al. Cu-Al Composite as the Negative Electrode for Long- Life Al-Ion Batteries, Journal of the Electrochemical Society, 2019, 166, 15, A3539 – A3545, Dated: 01.01.0001 *

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