Current collector, batteries comprising the same and related methods

Abstract

Described is a metallic current collector which is simultaneously capable of withstanding harsh chemical conditions, may be produced inexpensively and in a simple manner, exhibits favourably low ohmic resistance and enables production of batteries with prolonged lifetime and improved stability and performance. The current collector comprises a layer of copper or copper alloy, and a layer of amorphous nickel-phosphorus alloy provided over the layer of copper or copper alloy. Further aspects describes relate to the use of the aforementioned current collector in a battery, to a battery comprising the same, and to a method of manufacturing the same.

Description

CURRENT COLLECTOR, BATTERIES COMPRISING THE SAME AND RELATED METHODSFIELD OF INVENTION

[0001] This invention relates to a current collector having a structure which promotes corrosion resistance and is especially suitable for operation under harsh electrochemical conditions.

[0002] In certain embodiments, this invention relates to a method of manufacturing said current collector and its use, as well as to a battery comprising said current collector.BACKGROUND OF THE INVENTION

[0003] Battery technology has gained increased interest during the transformation towards a sustainable and environmentally friendly utilization and commercialization of sustainable and renewable energy generation sources, and finds various practical applications ranging from small scale applications (such as portable electronic devices or medical devices) to large scale applications including transportation to grid scale electrical energy storage.

[0004] A battery is a device that converts the chemical energy contained in its active materials directly into electric energy by means of an electrochemical redox reaction, and is typically composed of a cathode, an anode, a separator, electrolyte and two separate current collectors for the cathode and the anode side.

[0005] Current collectors are indispensable components for electrical connection of batteries with external circuits, and while they do not contribute to charge storage as their main function is to collect current and conduct electrons to the external circuit, they may substantially influence the energy density, capacity, rate capability and long-term stability of the batteries as such.

[0006] For instance, Al and Cu foils have been used as current collectors in the first commercial lithium-ion batteries, and over the past two decades, the thickness of these current collectors has decreased in order to increase the energy density. To further improve the performance, alternative materials and structures, as well as specific treatments such as etching and carbon coating, have also been investigated to enhance the electrochemical stability and electrical conductivity of current collectors. For example, Zhu et al., Journal of Power Sources 2021, 485, 229321, discloses a comparison of the performance of current collectors for lithium ion batteries, made from different materials such as Al, Cu, Ni, Ti,stainless steel and carbonaceous materials. It is also known to plate the current collector with Sn, Zn, Bi or In to establish a low electrical-contact resistance between the current collector and the electrode.

[0007] However, for certain applications, metallic current collectors not only require a high electrochemical stability throughout a wide potential range and have to exhibit low electrical resistivity, but simultaneously have to effectively resist harsh electrochemical conditions at the cathode and anode.

[0008] In this respect, the current collector is particularly required to have an excellent compatibility with the electrolyte in order to avoid corrosion and / or separation from the electrode active material.

[0009] This problem is especially pronounced in zinc ion batteries employing ZnCh-based aqueous electrolyte. While aqueous solutions are already well-known for their corrosiveness toward metals (such as Al, Cu and steel / Fe), chlorides are particularly corrosive. For example, Cu cannot be employed as the cathode current collector in chloride-based electrolytes because it is prone to oxidation to cuprous chloride complex ions, which are highly soluble in aqueous electrolytes and exhibit a high diffusivity coefficient, thus substantially promoting the corrosion of copper in chloride electrolytes under anodic conditions or in the presence of oxygen. In zinc-manganese dioxide (Zn-MnO2) batteries, efforts to improve the corrosion stability by applying a protective carbon layer could likewise not successfully prevent long-term corrosion of metallic current collectors due to high potential of the cathode active material MnC>2. Specifically, it has been found that electrolyte is transported through pinholes formed in the overprint layer and leads to creeping and dissolution of the underlying metal layer, thus destroying the stack integrity and ultimately the battery. Figures 1Aand 1B show photographs of the upper surface (electrode side) and lower surface (substrate side), respectively, of a copper foil extracted from a current collector consisting of carbon-coated copper, which has been used in a zinc-manganese dioxide (Zn-MnC>2) battery employing a zinc chloride electrolyte. Figs. 1A and 1B illustrate the dissolution of copper by the electrolyte throughout the entire thickness of the copper foil. Figure 2 illustrates the formation of pinholes on the surface of the carbon overprint layer.

[0010] In view of the good chemical stability of Ti, Ti foil is generally considered as a suitable corrosion-resistant metallic current collector for aqueous zinc ion batteries. However, the relatively high costs of titanium foil as current collector material severely limits the large-scale commercialization of Zn ion batteries.

[0011] In view of the above, it remains desirable to provide a metallic current collector which is simultaneously capable of withstanding harsh chemical conditions, may be producedinexpensively and in a simple manner, exhibits favourably low ohmic resistance and enables production of batteries with prolonged lifetime and improved stability and performance.SUMMARY OF THE INVENTION

[0012] The present invention solves this object with the subject matter of the claims as defined herein. The advantages of the present invention will be further explained in detail in the section below and further advantages will become apparent to the skilled artisan upon consideration of the invention disclosure.

[0013] Generally speaking, in one aspect the present invention provides a current collector for a battery, comprising: a layer of copper or copper alloy, and a layer of amorphous nickelphosphorus alloy provided over the layer of copper or copper alloy.

[0014] In another aspect, the present invention relates to the use of the aforementioned current collector in a battery.

[0015] In a further aspect, the present invention relates to a battery, comprising: a first current collector; a positive electrode including a positive electrode active material and being in contact with the first current collector; a negative electrode including a negative electrode active material; a second current collector in contact with the negative electrode; a separator between the positive electrode and the negative electrode; and an electrolyte; wherein the first current collector and / or the second current collector is the aforementioned current collector.

[0016] In yet another aspect, the present invention provides a method of manufacturing the aforementioned current collector, comprising a step of depositing the layer of amorphous nickel-phosphorus alloy over the layer of copper or copper alloy via electroplating.BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Fig. 1A is a photograph of the electrode side surface of a prior art copper foil extracted from a prior art current collector consisting of carbon-coated copper.

[0018] Fig. 1 B is a photograph of the substrate side surface of a prior art copper foil extracted from a prior art current collector consisting of carbon-coated copper.

[0019] Fig. 2 is a photograph of the surface of the carbon layer of a prior art current collector consisting of carbon-coated copper, illustrating pinhole formation upon exposure to chloride-containing electrolyte.

[0020] Fig. 3A is a schematic representation of an exemplary embodiment of the current collector according to the present invention.

[0021] Fig. 3B is a schematic representation of a preferred embodiment of the current collector according to the present invention.

[0022] Fig. 3C is a schematic representation of another preferred embodiment of the current collector according to the present invention including a substrate.

[0023] Fig. 4 is a schematic representation of an exemplary battery.DETAILED DESCRIPTION OF THE INVENTION

[0024] For a more complete understanding of the present invention, reference is now made to the following description of the illustrative embodiments thereof:Current Collector

[0025] In a first embodiment, the present invention relates to a current collector for a battery, comprising: a layer of copper or copper alloy, and a layer of amorphous nickel-phosphorus alloy provided over the layer of copper or copper alloy.

[0026] The term “current collector”, as used herein, relates to a conductive material that facilitates the flow of electric current between the electrode active material in an energy storage device (e.g. a battery) and the external circuit. Although during a manufacturing process, current collector layers are sometimes deposited on or laminated onto an electrode active material layer, it is noted that the current collector of the present invention is distinct from an electrode active material layer in that it does not comprise electrode active material, i.e. material which is involved in the electrochemical redox reactions in a battery. Current collectors of the present invention may also be used as traces, i.e. energization element components capable of connecting together circuit components, e.g. in lead frames.

[0027] The layer of amorphous nickel-phosphorus (Ni-P) alloy provides a dense barrier which is resistant towards pinhole formation, and thus effectively reduces electrolyte migration between grain boundaries. In addition, the amorphous Ni-P layer advantageously enables direct soldering. Hence, the amorphous Ni-P layer simultaneously provides excellent corrosion and wear resistance, good solderability, high electrical conductivity, smooth and uniform surface morphology, a low friction coefficient, electrocatalytic activity, and paramagnetic characteristics, and may be produced through simple electrochemical methods.

[0028] In preferred embodiments, the layer of amorphous Ni-P alloy is deposited over the layer of copper or copper alloy (henceforth Cu or Cu alloy) via electroplating.

[0029] The layer of amorphous Ni-P alloy may be electrodeposited through co-deposition of Ni and P via reduction of Ni ions and POs3' ions. It is known that the amount of P in the alloyaffects its crystallographic structure and increasing the P content changes the microstructure from crystalline to nano-crystalline and finally to an amorphous state. Typically, coatings with P content higher than 8 wt.-%, based on the total weight of the layer of amorphous Ni-P alloy, will exhibit an amorphous microstructure which lacks the long-range order that is characteristic of a crystal. The boundary P content for the transition to an amorphous state may vary depending on the electrodeposition bath used (e.g. due to presence of brighteners or other additives).

[0030] In order to further reduce pinhole formation which may lead to dissolution of the underlying metal layer and to ensure excellent solderability, the layer of amorphous Ni-P alloy preferably has a phosphorus (P) content higher than 12 wt.-%, preferably in a range of from 13 to 19 wt.-%, more preferably in a range of from 14 to 18 wt.-%, and especially preferably in a range of from 15 to 17 wt.-%, based on the total weight of the layer of amorphous Ni-P alloy.

[0031] The layer of amorphous Ni-P alloy may be made of a binary Ni-P alloy essentially consisting of nickel and phosphorus. However, it is also possible to use ternary or quaternary alloys comprising one or more components other than Ni in minor amounts (e.g. < 5 wt.-% per metal component, based on the total weight of the layer of amorphous Ni-P alloy), provided that the resulting layer exhibits a stable amorphous microstructure. Exemplary metal components other than Ni include, but are not limited to Co, Cr, Cu, Fe, Sn, Zn, W, Mo and Re, for example, while preferred examples of ternary alloys in terms of corrosion resistance and / or thermal stability include Ni-Cr-P, Ni-Co-P, Ni-Sn-P, Ni-Zn-P and Ni-Mo-P. Examples of quaternary alloys include, but are not limited to Ni-W-Cu-P and Ni-Fe-Co-P, for instance.

[0032] In preferred embodiments, the layer of amorphous Ni-P alloy has a thickness of 0.01 to 5 pm, more preferably from 0.05 to 3 pm.

[0033] The layer of Cu or Cu alloy may essentially consist of Cu or a Cu alloy preferably comprising more than 50 wt.-%, more preferably at least 60 wt.-% and especially preferably at least 80 wt.-% of Cu based on the total weight of the layer and preferably less than 50 wt.-%, more preferably less than 40 wt.-% and especially preferably less than 20 wt.-% of one or more components other than Cu. As an example thereof, bronze alloy consisting primarily of Cu and Sn and minor amounts of optional non-metals (e.g. P), metalloids, (e.g., As and / or Si), and metals (e.g., Al, Mn, Ni, Fe, Pb, Bi and / or Zn) may be mentioned. Notably, the expression “essentially consists of” used herein is understood to define that the respective layer consists of the material except from unavoidable impurities, which may be present in an amount of up to 0.5 wt.-% of the respective layer.

[0034] The thickness of the layer of Cu or Cu alloy is not particularly limited.

[0035] In a preferred embodiment of the current collector (10), an example of which is illustrated in Fig. 3A, the layer of Cu or Cu alloy (11 ) may be in direct contact with the layer of amorphous Ni-P alloy (12).

[0036] In an alternatively preferred embodiment, a nickel (Ni) layer may be provided between the layer of Cu or Cu alloy and the layer of amorphous Ni-P alloy. While not being limited thereto, the nickel layer is preferably in contact with the layer of Cu or Cu alloy and / or the layer of amorphous Ni-P alloy. The presence of the Ni-based layer provides an improved adhesion to subsequent coating layers, especially to the layer of amorphous Ni-P owing to the excellent compatibility.

[0037] The Ni layer essentially consists of Ni or an alloy which has Ni as its principal component and preferably comprises at least 90 wt.-%, more preferably at least 95 wt.-% Ni based on the total weight of the Ni layer.

[0038] In preferred embodiments, the Ni layer is in contact with the layer of Cu or Cu alloy and / or the layer of amorphous Ni-P alloy, and more preferably in contact with both the layer of Cu or Cu alloy and the layer of amorphous Ni-P alloy.

[0039] The Ni layer preferably has a thickness of 0.1 to 10 pm, more preferably from 0.5 to 5 pm. In general, it may be preferred that the total thickness of the Ni layer and the amorphous Ni-P layer is between 0.5 to 10 pm, more preferably from 1 to 5 pm.

[0040] The layer of amorphous Ni-P alloy can likewise serve as the underlayer for other top coatings.

[0041] In a preferred embodiment, the current collector of the present invention comprises a carbon layer provided over and preferably in contact with the layer of amorphous nickelphosphorus alloy, which further inhibits corrosion, enhances electric conductivity and improves performance of the current collector. In addition, a carbon layer may provide enhanced adhesion between electrode active materials and the current collector due to the typically rough surface structure and the expansive surface area of carbon. Finally, in view of the mechanical strength of the carbon layer, the robustness of the current collector may be improved and internal short circuits caused by dendritic growth may be prevented. The carbon layer may include or consist of graphitic carbon (e.g., carbon nanotubes (CNTs), graphene, graphene oxide, reduced graphene oxide, graphdiyne and derivatives thereof), amorphous carbon, doped carbon (e.g. N-doped or O-doped carbon), carbon-metal composites (e.g. CNT-Cu composites), and combinations thereof, for example. An example of a carbon-layer containing current collector (10) is illustrated in Fig. 3B, with the carbon layer (13) being provided in direct contact with the amorphous Ni-P layer (12) covering the layer of Cu or Cu alloy (11).

[0042] In preferred embodiments, the current collector of the present invention may further comprise a non-conductive substrate, which may be flexible. As an example thereof, polymer, silicon, a ceramic substrate, glass, fabric, paper and combinations thereof may be mentioned. Further preferred examples thereof include a polymer, silicon, ceramic, glass, and combinations thereof. Even further preferably, the substrate is selected from a polymer or glass, more preferably from a polymer, and especially preferably from a polymer selected from polyetheretherketone (PEEK), polyphenylsulfone (PPSLI), polyethylene terephthalate (PET), polyimide (PI), polyetherimide (PEI), liquid crystal polymer (LCP) or epoxy glass.

[0043] Typically, the substrate thickness ranges from 20 to 500 pm, more preferably between 50 and 150 pm.

[0044] While, in principle, other layers may be interposed between the layer of Cu or Cu alloy and the non-conductive substrate, the layer of Cu or Cu alloy is preferable placed, deposited onto or adhered to (via chemical adhesives) the non-conductive substrate.

[0045] Overall, it is particularly preferred that the current collector of the present invention comprises the following configuration:a) a non-conductive substrate;b) a layer of Cu or Cu alloy provided over and in contact with the non-conductive substrate;c) a layer of amorphous Ni-P provided over and in contact with the layer of Cu or Cu alloy; andd) a carbon layer provided over and in contact with the layer of amorphous Ni-P.

[0046] In an alternatively preferred embodiment, the current collector (10) of the present invention comprises the following configuration, which is also illustrated in Fig. 3C:a) a non-conductive substrate (15);b) a layer of Cu or Cu alloy (11 ) provided over and in contact with the non-conductive substrate (15);c) a Ni layer (14) provided over and in contact with the layer of Cu or Cu alloy (11); d) a layer of amorphous Ni-P (12) provided over and in contact with the Ni layer (14); ande) a carbon layer (13) provided over and in contact with the layer of amorphous Ni-P (12).

[0047] The layer of amorphous Ni-P is not necessarily provided over the entire surface of the current collector, as long as it is at least present at the surface section of the current collector which is supposed to contact the electrode and / or which is supposed to come into contact with electrolyte. The same applies to the optional carbon layer and the optional Ni-layer.

[0048] The layer of amorphous Ni-P may extend over and cover the sides of the underlying layer(s) to ensure additional corrosion protection.

[0049] Additional layers may be provided over the amorphous Ni-P layer or the carbon layer (if present). As examples thereof, metallic layers made of gold (Au) or its alloys and / or platinum and its alloys may be mentioned, for example.Battery

[0050] In a second embodiment, the present invention relates to the use of a current collector according to the first embodiment in a battery. Preferred embodiments of the battery will be described in conjunction with the third embodiment hereinbelow.

[0051] In particular, in a third embodiment, the present invention relates to a battery, comprising: a first current collector; a positive electrode including a positive electrode active material and being in contact with the first current collector; a negative electrode including a negative electrode active material; a second current collector in contact with the negative electrode; a separator between the positive electrode and the negative electrode; and an electrolyte; wherein the first current collector and / or the second current collector is a current collector according to the first embodiment. It is noted that in the battery of the present invention, the current collector does not contain electrode active material, i.e. material which is involved in the electrochemical redox reactions in the battery.

[0052] An exemplary battery (100) is illustrated in Fig. 4, wherein an electrolyte-containing separator (112) is provided between a positive electrode (111A) including a positive electrode active material and a negative electrode (111 B) including a negative electrode active material. A first current collector (110A) is provided in contact with the positive electrode (111A) and a second current collector (110B) is provided in contact with the negative electrode (111 B). The assembly is covered by a non-conductive top substrate (113A) and a non-conductive bottom substrate (113B) and the sides thereof are sealed with a sealant (114A, 114B, 114C and 114D) to protect the inner section of the battery from the environment. The sides of both current collectors (110A, 110B) extend beyond the width of the top and bottom substrates (113A, 113B) and are exposed to facilitate connection with an electrical consumer. According to the present invention, at least one of the first current collector (110A) and the second current collector (110B) and preferably both are independently selected from a current collector described in relation to the first embodiment. It is noted that within the battery, the layer of amorphous Ni-P alloy is not necessarily provided over the entire surface of the currentcollector, as long as it is at least present at the surface section of the current collector contacting the electrode.

[0053] In principle, the battery chemistry is not particularly limited and exemplary batteries may include, but are not limited to zinc ion batteries and lithium ion batteries for example.

[0054] In a preferred embodiment, the battery is a primary battery.

[0055] In another preferred embodiment, the battery is a primary or secondary Zn-MnC>2 battery, more preferably a primary Zn-MnC>2 battery, which uses manganese dioxide (MnC>2) as the positive electrode active material of the positive electrode (i.e. cathode) and zinc (Zn) as the negative electode active material of the negative electrode (i.e. anode). As examples thereof, zinc-carbon batteries may be mentioned. In case of Zn-MnC>2 batteries, it is particularly preferred that at least the current collector contacting the cathode is a current collector according to the first embodiment. In comparison with lithium ion batteries, aqueous Zn-MnC>2 batteries have the advantage that they do not pose large safety risks while still providing a high theoretical capacity and low toxicity, and may be produced by abundant and / or inexpensive starting materials.

[0056] As indicated above, the advantages of the current collector according to the present invention are especially pronounced in presence of corrosive battery chemistry, for instance, when the electrolyte is a halide-containing electrolyte (e.g. an aqueous chloride-containing electrolyte). In general, the electrolyte of a battery is selected for compatibility with the electrode active materials. For the Zn anode and a MnC>2 cathode, a Leclanche electrolyte, or ammonium chloride (NH4CI) solution, zinc chloride (ZnCh), zinc acetate and mixture thereof may be employed, for example. By adding zinc chloride to zinc acetate-based electrolytes, the battery capacity of a Zn-MnC>2 battery may be significantly improved. For dilute solutions, salines, such as sodium chloride (NaCI), magnesium chloride (MgCh) and potassium chloride (KCI) solutions together with additives such as sodium borate, boric acid and sodium ethylenediamine tetraacetate may alternatively be used. The current collector of the present invention exhibits excellent compatibility with aqueous halide-containing electrolyte and is resistant towards pinhole formation and corrosion, thus prolonging lifetime of the battery and improving the battery performance (e.g. high peak currents due to low impedance). Furthermore, unlike foils comprising titanium, platinum and / or tantalum that have been widely used as current collectors for batteries with aqueous halide containing electrolytes, the current collectors of the present invention may be produced inexpensively, thus widening the commercial application of aqueous battery systems.

[0057] The battery of the present invention may be produced in a variety of shapes, including cylindrical, prismatic, pouch-type or arcuate shapes. For the use in smart labels, smart cards(i.e. chip cards, or integrated circuit cards (ICC or IC cards)) or other flat electronic devices, for example, prismatic battery designs may be preferred.

[0058] The battery of the present invention may be connected with other devices that require a power source for operation. When biocompatible materials are used for the battery, the battery may be designed to be implantable or otherwise associated with a medical device (e.g., in pacemakers, hearing aids, heart pumps, defibrillators, neuromodulation devices), or incorporated into or connected with a biosensor. In this manner, aqueous Zn-MnC>2 batteries, for example, can be produced with a good biocompatibility.Current Collector Manufacturing Method

[0059] In principle, the current collector of the present invention may be produced by any method known in the art which enables formation of a layer of amorphous Ni-P alloy over the layer of Cu or Cu alloy, such as electroplating or electroless plating, for example.

[0060] In a fourth embodiment, the present invention relates to a method of manufacturing a current collector according to the first embodiment, comprising a step of depositing the layer of amorphous Ni-P alloy over the layer of Cu or Cu alloy via electroplating (also known as electrodeposition). Electroplating of Ni-P has the advantage over electroless plating that it is more adapted to roll-to-roll (R2R) processing and facilitates high-volume production at high line speeds.

[0061] Common electrodeposition baths known in the art may be employed for electroplating Ni-P over the Cu or Cu alloy layer or the intermediate Ni layer, if present. Typical baths comprise a Ni source (such as nickel sulfate and nickel chloride, for example), a P source (e.g., H3PO3), and optional additives, which may include stabilizing agents (e.g., H3PO4), buffering agents (e.g., H3BO3), surfactants (e.g. sodium lauryl sulfate), accelerators (e.g., sulfur compounds), complexing agents and / or brightening agents (e.g., saccharine, glycine, pyridinium propyl sulfonate (PPS), coumarine, alkali metal citrate, cerium sulfate or combinations thereof), the content of which may be suitably adjusted by the skilled artisan.

[0062] The method of providing the layer of Cu or Cu alloy is not particularly limited any may be brought about by any method known to the skilled artisan. For instance, the layer of Cu or Cu alloy may be deposited by electroless plating or electroplating on a non-conductive substrate known in the art, or provided as a Cu / Cu alloy foil or wire.

[0063] The method of providing the optional intermediate Ni layer is not particularly limited either and may be brought about by any method known to the skilled artisan, including, but not limited to electroless plating or electroless plating.

[0064] In general, the electrodeposition step for electroplating can as such be performed by galvanostatic, potentiostatic or by potentiocyclic methods, which may be suitably selected by the skilled artisan depending on the desired surface roughness and layer stability, for example. Pulsed electrodeposition can be employed to alternate different potentials and thus different processes. As will be further known by the skilled artisan, alloy layers can be fabricated by codeposition of two or more metals from their salts.

[0065] As outlined above, a carbon layer may be provided over the amorphous Ni-P layer to improve the corrosion stability, interlayer adhesion and / or electric conductivity of the current collector. The method of depositing the carbon layer is not particularly limited and may be suitably selected by the skilled artisan depending on the type of carbon (e.g. graphitic carbon, graphene, graphene oxide, reduced graphene oxide, graphdiyne and derivatives thereof, amorphous carbon, doped carbon, carbon-metal composites) and the desired properties.

[0066] Notably, the steps of manufacturing the current collector of the present invention may be carried out efficiently and economically through a reel-to-reel process.

[0067] It will be appreciated that the present invention may employ any of the preferred features specified above with respect to the description of the first to fourth embodiments, and that the preferred features may be combined in any combination, except for combinations, where at least some of the features are mutually exclusive.

[0068] Once given the above disclosure, many other features, modifications, and improvements will become apparent to the skilled artisan.Reference Numerals10 current collector11 Cu / Cu alloy layer12 amorphous Ni-P layer13 (optional) carbon layer14 (optional) Ni layer15 (optional) non-conductive substrate100 battery110A first current collector110B second current collector111 A positive electrode111 B negative electrode112 separator113A top substrateB bottom substrate A-114D sealant

Claims

CLAIMS1. Current collector for a battery, comprising:a layer of copper or copper alloy, anda layer of amorphous nickel-phosphorus alloy provided over the layer of copper or copper alloy.

2. The current collector according to claim 1 , wherein the layer of copper or copper alloy is in contact with the layer of amorphous nickel-phosphorus alloy.

3. The current collector according to claim 1, further comprising a nickel layer between the layer of copper or copper alloy and the layer of amorphous nickel-phosphorus alloy.

4. The current collector according to claim 3, wherein the nickel layer is in contact with the layer of copper or copper alloy and / or the layer of amorphous nickel-phosphorus alloy.

5. The current collector according to claim 3 or claim 4, wherein the nickel layer has a thickness of 0.1 to 10 pm, preferably from 0.5 to 5 pm.

6. The current collector according to any one of claims 1 to 5, further comprising a carbon layer provided over and preferably in contact with the layer of amorphous nickel-phosphorus alloy.

7. The current collector according to any one of claims 1 to 6, wherein the layer of amorphous nickel-phosphorus alloy has a phosphorus (P) content higher than 12 wt.-%, preferably in a range of from 13 to 19 wt.-%, more preferably in a range offrom 14 to 18 wt.-%, and especially preferably in a range offrom 15 to 17 wt.-%, based on the total weight of the layer of amorphous nickel-phosphorus alloy.

8. The current collector according to any one of claims 1 to 7, wherein the layer of amorphous nickel-phosphorus alloy has a thickness of 0.01 to 5 pm, preferably from 0.05 to 3 pm.

9. The current collector according to any one of claims 1 to 8, further comprising a non-conductive substrate, preferably selected from a polymer, silicon, ceramic, glass, and combinations thereof, more preferably from a polymer or glass, further preferably from a polymer, and especially preferably from a polymer selected from polyetheretherketone(PEEK), polyphenylsulfone (PPSLI), polyethylene terephthalate (PET), polyimide (PI), polyetherimide (PEI), liquid crystal polymer (LCP) or epoxy glass.

10. Use of a current collector according to claims 1 to 9 in a battery.

11. Battery, comprising:a first current collector;a positive electrode including a positive electrode active material and being in contact with the first current collector;a negative electrode including a negative electrode active material;a second current collector in contact with the negative electrode;a separator between the positive electrode and the negative electrode; and an electrolyte;wherein the first current collector and / or the second current collector is a current collector according to any one of claims 1 to 9.

12. Battery according to claim 11, wherein the battery is a primary battery.

13. Battery according to claim 11 or claim 12, wherein the battery is a Zn-MnC>2 battery.

14. Battery according to any one of claims 11 to 13, wherein the electrolyte is an aqueous halide-containing electrolyte, preferably a chloride-containing electrolyte.

15. Method of manufacturing a current collector according to any one of claims 1 to 9, comprising a step of depositing the layer of amorphous nickel-phosphorus alloy over the layer of copper or copper alloy via electroplating.

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