WO2019104365A1 - Collecteur de courant - Google Patents

Collecteur de courant Download PDF

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Publication number
WO2019104365A1
WO2019104365A1 PCT/AU2017/051322 AU2017051322W WO2019104365A1 WO 2019104365 A1 WO2019104365 A1 WO 2019104365A1 AU 2017051322 W AU2017051322 W AU 2017051322W WO 2019104365 A1 WO2019104365 A1 WO 2019104365A1
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WO
WIPO (PCT)
Prior art keywords
current collector
mechanical strength
electrical conductivity
measured
fibres
Prior art date
Application number
PCT/AU2017/051322
Other languages
English (en)
Inventor
Manuel WIESER
Original Assignee
Nano-Nouvelle Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Nano-Nouvelle Pty Ltd filed Critical Nano-Nouvelle Pty Ltd
Priority to PCT/AU2017/051322 priority Critical patent/WO2019104365A1/fr
Publication of WO2019104365A1 publication Critical patent/WO2019104365A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • 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 a current collector for use in electrochemical cells of batteries.
  • Batteries such as lithium ion batteries, typically comprise a number of
  • electrochemical cells each of which comprises an anode, a separator and a cathode. Reactions take place during discharge of the battery at the anode and cathode that cause positive ions to be generated at the anode, with those ions travelling through an electrolyte, through the separator and through an electrolyte on the cathode side to the cathode. The positive ions are reduced at the cathode. This results in generation of an electric current, which can be collected through an external circuit. Charging of the batteries involves applying an external voltage to cause the reactions that occur during discharge to be reversed.
  • a current collector is a highly conductive material which serves the purpose of collecting electrons in electrode type applications, such as lithium ion batteries, capacitors, fuel cells and the like.
  • the anodes (negative electrodes) and cathodes (positive electrodes) typically include respective active material substances that are responsible for storing charge carriers, with the active material substances being applied to flat metal foils.
  • the flat metal foils normally serve as the current collector.
  • the material chosen for the current collector on the anode is commonly copper, whereas aluminium is commonly used as the cathode collector material on the cathode.
  • the current industry standard for current collectors for anodes is a copper foil having a thickness of 9 to 10 ⁇ m.
  • the required thickness is dependent upon the type of application.
  • high-energy applications tend to use anode current collectors in the form of copper foil having thicknesses between 9 and 1 m m whilst high power applications tend to use copper foils as current collectors with a thickness between 10 to 25 ⁇ m.
  • the size and volume of the battery components has to be reduced. For current collector foils, this translates into a reduction in thickness, which strongly impacts the weight of the battery cell and also has a minor impact on its volume.
  • Metal foams with a thickness in the millimetre range are commonly used as current collectors in nickel battery systems. In practice, it is difficult to create metal foams that have a very thin thickness whilst maintaining a high percentage of porosity. Further, metal foams typically have pore structures that may best be described as interconnected pores that are randomly distributed in space with no particular directionality or anisotropy.
  • the current industry standard for cathode current collectors in lithium ion batteries is to use an aluminium foil having a thickness of from 10 to 25 ⁇ m, with the lower thickness being applied to energy type applications and the larger thickness being applied in power type applications.
  • Sakamoto This patent application is now abandoned.
  • Sakamoto described a positive electrode for an alkaline storage battery.
  • the electrode comprises a polymeric material that is formed as a foamed resin, a non- woven fabric or a woven fabric, that has a three dimensional network stmcture and has a void portion in which a plurality of pores are coupled in three dimensions.
  • the resin skeleton is coated with a nickel coating layer.
  • the thickness of the nickel coating layer ranges from 0.5 to 5 ⁇ m.
  • the average pore diameter of the pores forming the void portion of the positive electrode substrate falls in the range of from not less than 15 ⁇ m to not more than 450 ⁇ m. By adjusting the average pore diameter to within this range, the current collectivity is improved.
  • the nickel coated porous resin material of Sakamoto is filled with a positive electrode active material containing nickel hydroxide particles wherein the filling amount of the positive electrode active material is not less than 3 times and not more than 10 times of weight of the positive electrode substrate. Further, a proportion of the nickel coating layer to the positive electrode substrate is not less than 30wt% and not more than 80wt%.
  • PCT/AU2013/000088 are also incorporated herein by cross-reference.
  • the present invention is directed to a current collector, which may at least partially overcome at least one of the abovementioned disadvantages or provide the consumer with a useful or commercial choice.
  • the present invention in one form, resides broadly in a current collector for an electrochemical cell or a battery, the current collector comprising a porous polymeric substrate coated with a conductive material, characterised in that the current collector has anisotropic properties.
  • the current collector having anisotropic properties it is meant that one or more properties of the current collector when measured along one direction differ from the one or more properties measured in a different direction.
  • the current collector has one or more properties measured in a longitudinal direction or a machine direction (MD) that is different to the one or more properties measured in a transverse direction (TD) or a cross-machine direction.
  • MD machine direction
  • TD transverse direction
  • TD cross-machine direction
  • the anisotropic property of the current collector is mechanical strength. In another embodiment, the anisotropic property of the current collector is electrical conductivity.
  • the current collector has a mechanical strength in one direction that is at least 10% higher than a mechanical strength when measured in a transverse direction to the one direction.
  • the current collector has a mechanical strength in one direction that is at least 20% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 30% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 40% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 50% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 60% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 70% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 80% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 90% higher than a mechanical strength when measured in a transverse direction, or has a mechanical strength in one direction that is at least 20% higher than a mechanical
  • the current collector has an electrical conductivity in one direction that is at least 10% higher than an electrical conductivity when measured in a transverse direction to the one direction.
  • the current collector has an electrical conductivity in one direction that is at least 20% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 30% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 40% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 50% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 60% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 70% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 80% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is at least 90% higher than an electrical conductivity when measured in a transverse direction, or has an electrical conductivity in one direction that is that is at least 20% higher than an
  • the current collector has a mechanical strength in the machine direction that is from 18% to 307% higher than compared to the mechanical strength in the transverse direction. In one embodiment, the current collector has a mechanical strength in the machine direction that is from 1.2 to 4.1 times higher than the mechanical strength in the transverse direction.
  • the current collector has an electrical conductivity that is from 25% to 346% higher in the machine direction when compared to the transverse direction. In one embodiment, the current collector has an electrical conductivity that is from 1.2 to 4.5 times higher than the electrical conductivity in the transverse direction.
  • the current collector exhibits higher mechanical strength in a machine direction when compared to mechanical strength in a transverse machine direction.
  • the current collector exhibits higher mechanical strength in a transvers machine direction when compared to mechanical strength in a machine direction.
  • the current collector exhibits higher electrical conductivity in a machine direction when compared to electrical conductivity in a transverse machine direction.
  • the current collector exhibits higher electrical conductivity in a transverse machine direction when compared to electrical conductivity in a machine direction.
  • the porous polymeric substrate comprises an electrically non- conductive polymeric substrate.
  • the porous polymeric substrate may be selected from materials including cellulose and its derivatives including cellulose acetate, cellulose nitrate, mixed cellulose esters, polyolefins including polyethylene, polypropylene, polybutene, polyisobutylene, ethylene propylene rubber and variations thereof, polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyvinylchloride (PVC), polyether sulfone (PES), polyamides including Nylon and variations thereof, polyimides and variations thereof, polyurethanes and variations thereof, polytetrafluoroethylene (PTFE), polyvinylidene fluoride PVDF, polycarbonate, and or a mixture of those.
  • the porous substrate may comprise a porous carbon substrate or a graphene substrate or a carbon nanofiber substrate or a carbon nanotube substrate.
  • the substrate may comprise fibres of single polymer or several different polymer fibres mixed together.
  • the substrate may constitute a woven or non-woven substrate.
  • the substrate may comprise a continuous structure containing a single polymer or the substrate may comprise a layered or laminated structure where individual layers may be comprised of different polymers.
  • a more preferred thickness of the porous polymeric substrate would be from l ⁇ m to 5000 ⁇ m, or from l ⁇ m to lOOO ⁇ m, or from l ⁇ m to 500 ⁇ m, or from l ⁇ m to 400 ⁇ m, or from l ⁇ m to 250 ⁇ m, or from 1 ⁇ m to 150 ⁇ m, or from l ⁇ m to 100 ⁇ m, or from l ⁇ m to 50 ⁇ m or from l ⁇ m to 20 ⁇ m.
  • the porous polymeric substrate comprises a porous polyethylene terephthalate (PET) substrate.
  • PET is suitable for use in this application due to its good temperature stability and no known toxicity.
  • the PET substrate is made from PET fibres having a circular cross-section with small diameter. This substrate can be used for the creation of the current collectors.
  • the substrate is made from PET fibres having a large diameter, which can be used to create thicker current collectors. It will also be appreciated that current collectors made from substrates having smaller diameter fibres will tend to have smaller pores than current collectors made from substrates having larger diameter fibres.
  • the porous polymeric substrate comprises a plurality of fibres, with a greater proportion of the fibres extending in the one direction and a lesser proportion of the fibres extending in the other direction.
  • the porous polymeric material is coated with an electrically conductive material.
  • the electrically conductive material comprises a metal.
  • the metal may be selected from copper, nickel, aluminium, iron, titanium, gold, platinum or mixtures or alloys of two or more thereof. Other metals may also be used.
  • the electrically conductive porous material may have pore sizes that range from 0.1 ⁇ m to 3000 ⁇ m.
  • the electrically conductive porous material may have a porosity of 30% to 95% (by volume).
  • the electrically conductive porous material may have a specific surface area that ranges from 0.005m 2 /cm 3 to 100m 2 /cm 3 , 0.005m 2 /cm 3 to 50m 2 /cm 3 , or from 0.005m 2 /cm 3 to 20m 2 /cm 3 , or from 0.005m 2 /cm 3 to 10m 2 /cm 3 , or from 0.005m 2 /cm 3 to 2m 2 /cm 3 , or from 0.005m 2 /cm 3 to 0.2m 2 /cm 3 .
  • At least part of the porosity in the substrate is interconnected and open to the surface.
  • pore sizes, porosity and surface area of the unit conductive porous material may be varied or selected to accord with the specific requirements of the application of use.
  • One way of describing conductivity in porous solids is to use an‘equivalent solid’ conductivity. For example, if the material has a volume fraction of solid of only 20%, and the measured conductivity is x, the‘equivalent solid’ conductivity would be 5 times x. Similarly, if the material has a volume fraction of solid of 50%, and the measured conductivity is y, the ‘equivalent solid’ conductivity would be 2 times y. This way of comparison is useful for comparing the quality of solids in stmctures with different volume fraction of solids.
  • the electrically conductive porous material may have an electrical equivalent solid conductivity in the range of from 0.01 S/cm to 500,000S/cm.
  • a more preferred electrical equivalent solid conductivity would be in the range of 10,000S/cm and 500,000S/cm, or 30,000S/cm and 500,000S/cm, or 500,000S/cm and 500,000S/cm, or l00,000S/cm and
  • the electrically conductive porous material comprises a porous polymeric material having a thin coating of a metal applied thereto.
  • the metal may be applied to the porous polymeric materials such that the metal coating has a thickness that is less than 8000nm, or less than 5000nm, or less than 3000nm, or less than 2000nm or less than lOOOnm, or less 500nm, or less than 300nm, or less than 200nm, or less than lOOnm, or less than 50nm, or less than 30nm.
  • the metal coating may have a thickness that is at least lnm thick, or at least 2nm thick, or at least 5nm thick, or at least lOnm thick or at least 20nm thick.
  • the current collector may have total weight values that fall in the range of from 2.5mg/cm to 8.0mg/cm , or from 3.0mg/cm to 8.0mg/cm , or from 3.5mg/cm to 8.0mg/cm , or from 4.0mg/cm to 8.0mg/cm 2 , or from 4.5mg/cm 2 to 8.0mg/cm 2 , or from 5.0mg/cm 2 to 8.0mg/cm 2 , or from 5.5mg/cm 2 to 8.0mg/cm 2 , or from 7.0mg/cm 2 to 8.0mg/cm 2 , or from 3.0mg/cm 2 to
  • the pores/openings created by the fibres and their spatial orientation establishes a certain directionality of pores/openings, extending into the current collector’s structure in a largely downwardly facing pattern (in other words, generally perpendicular to the surface of the current collector).
  • the current collector of the present invention may be manufactured by selecting an appropriate substrate that has anisotropic properties and then applying an electrically conductive coating to the substrate. Any of the methods disclosed in our international patent applications mentioned in the introductory part of the specification, or in our US patent application number 15/295647, the entire contents of which are herein incorporated by cross-reference, may be used to produce the current collector in accordance with the present invention.
  • the current collector may have a porosity that falls in the range of from 60% to 95%, or from 70% to 95%.
  • the current collector has a weight percentage of metal (calculated by dividing the weight of metal by the combined weight of metal plus substrate) of from 80 to 95%.
  • the substrate has a volume fraction of metal of from 2 to 30%, or from 2 to 20%.
  • the current collector may have a thickness that falls in the range of from 5 ⁇ m to 1 mm or even higher, or from 5 ⁇ m to 400 ⁇ m, or from 5 ⁇ m to lO ⁇ m, or from 25 ⁇ m to 400 ⁇ m.
  • the thickness of the current collector in accordance with the present invention can vary quite greatly, depending upon the desired thickness in the end application.
  • the present invention provides a current collector for an electrochemical cell or a battery, the current collector comprising a porous polymeric substrate coated with a conductive material, characterised in that the porous polymeric substrate comprises a woven or nonwoven substrate comprising a plurality of fibres that have a width that is greater than a height of the fibres.
  • the fibres that are used in the porous polymeric substrate may be described as flat or flattened fibres.
  • the fibres may have a width that is at least 1.2 times the height of the fibres, or at least 1.4 times the height of the fibres, or at least 1.5 times the height of the fibres, or at least 1.75 times the height of the fibres, or at least 2 times the height of the fibres, or at least 3 times the height of the fibres, or at least 4 times the height of the fibres, or at least 5 times the fibres, or at least 6 times the height of the fibres, or at least 7 times the height of the fibres, or at least 8 times the height of the fibres, or at least 9 times the height of the fibres, or at least 10 times the height of the fibres, or up to 20 times the height of the fibres.
  • the porous polymeric substrate used in the second aspect of the invention may have anisotropic properties.
  • Embodiments of the second aspect of the present invention may advantageously combine the requirement for low thickness (because even if 2 or 3 fibres are stacked on top of each other in the substrate, the thickness of the substrate will be relatively low due to the flattened nature of the fibres) with high-strength in the machine and/or transverse direction due to the geometry of the fibres.
  • the present invention provides a current collector for an electrochemical cell or a battery, the current collector comprising a porous polymeric substrate coated with a conductive material, characterised in that the porous polymeric substrate coated with the conductive material is reduced in thickness after application of the conductive material.
  • the present invention provides a method for producing a current collector for an electrochemical cell or a battery, the method comprising coating a porous polymeric substrate with a conductive material and subsequently reducing a thickness of the porous polymeric substrate coated with the conductive material.
  • the thickness of the porous polymeric substrate coated with the conductive material is reduced by subjecting it to rolling or calendaring or stamping. [0061] In one embodiment, the thickness of the porous polymeric substrate coated with the conductive material is reduced by at least 10%, or reduced by at least 20%, or reduced by at least 30%, or reduced by at least 40%, or reduced by at least 50%. In one embodiment, the thickness of the porous polymeric substrate coated with a conductive material is reduced by 10 to 60%, or by 20 to 55%, all by 30 to 50%, or by 40 to 50%, or by about 50%, or by about 60%.
  • the step of reducing the thickness of the porous polymeric substrate coated with the conductive material also reduces the porosity of the current collector.
  • the reduction in porosity closely follows the reduction in thickness.
  • the porous polymeric substrate coated with the conductive material is subjected to rolling or calendaring at a temperature ranging from 10°C to 300°C, or from 10°C to 250°C, or from 10°C to 200°C, or from 10°C to 150°C, or from 10°C to 100°C, or from 10°C to 70°C, or from 10°C to 50°C.
  • the rolling or calendaring step is carried out at room temperature.
  • the present invention provides a method for assembling a battery comprising, producing a current collector for an electrochemical cell or a battery by coating a porous polymeric substrate with a conductive material and subsequently applying a layer of active material to the current collector.
  • the present invention provides a method for assembling a battery comprising, producing a current collector for an electrochemical cell or a battery by coating a porous polymeric substrate with a conductive material and subsequently reducing a thickness of the porous polymeric substrate coated with the conductive material, followed by applying a slurry comprising active material particles to the current collector.
  • the layer of active material comprises a film of active material.
  • the layer of active material comprises active material particles.
  • a slurry of active material particles is applied to the current collector.
  • the slurry is applied to only a single side of the current collector. In another aspect, the slurry is applied to both sides of the current collector. In another embodiment, the layer of active material is applied to only one side of the current collector. In another embodiment, the layer of active material is applied to both sides of the current collector.
  • Embodiments of the third, fourth and fifth aspect of the present invention may use the porous substrate coated with the conductive material of the first and/or second aspects of the present invention.
  • the coating may be applied by any suitable technique.
  • the coating may be applied to the surface by various means.
  • an initial layer may be applied by atomic layer deposition, electrodeposition, electroless deposition, hydrothermal methods, electrophoresis, photocatalytic methods, sol-gel methods, other vapour phase methods such as chemical vapour deposition, physical vapour deposition and close-spaced sublimation.
  • Further layers of the same coating or of a different coating or coatings using one or more of these methods may also be applied. It may be useful to coat the material such that the composition of the material is not uniform throughout. For example, a coating method may be used that only penetrates partway into the porous material.
  • the coating may also be applied by sequential use of different coating methods. Any of the methods disclosed in our international patent applications mentioned in the introductory part of the specification, or in our US patent application number 15/295647, the entire contents of which are herein incorporated by cross-reference, may be used to produce the current collector in accordance with the present invention.
  • the current collector may be heated to an elevated temperature, such as up to 300°C, without any noticeable loss of functionality as a current collector being observed.
  • the current collector may be heated to an elevated temperature of up to 300°C without changing its dimension or suffering from shrinkage.
  • the current collector may be heated to the elevated temperature for a period of up to 12 hours or longer without any loss of functionality or without changing dimensions.
  • Figure 1 shows a plan-view SEM photomicrograph of an uncoated substrate suitable for the use in fabricating current collectors in accordance with example 8;
  • Figure 2 shows a cross-section photomicrograph of the obtained electrode, with active material particles being integrated into the void spaces of the current collector in accordance with example 8;
  • Figure 3 shows a cross-section photomicrograph of the obtained electrode, with active material particles being coated on one side of a 6 ⁇ m solid copper current collector foil in accordance with example 9;
  • Figure 4 shows a cross-section SEM photomicrograph of the obtained electrode, with active material particles being coated on the current collector in accordance with example 10.
  • Figures 5A and 5B show plan-view SEM photomicrographs of the obtained current collector in its original state and after being calendared at calendaring condition number 3 in accordance with example 11.
  • PET substrate made from circular PET fibres (fibre diameter ⁇ 10 ⁇ m )
  • PET substrate made from circular PET fibres (fibre diameter > 10 ⁇ m ) • Membrane 4: 105 ⁇ m thickness
  • Membrane 6 30 ⁇ m thickness; basis weight: 18.0 g/m 22 ; non-woven fibrous composite structure consisting out of three different types of polymer fibres
  • PET substrate made from flat PET fibres
  • composite structure including flat PET fibres and a second polymeric fibre.
  • An electroless copper coating was applied to a porous polymeric, non-woven substrate consisting of polyethylene terephthalate fibres (PET).
  • PET polyethylene terephthalate fibres
  • the thickness of the substrate before the application of the copper coating was 10 ⁇ m.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride. The activation step took place at 26.5°C for a period of three minutes.
  • a copper layer was then applied by contacting the substrate with Enthone Envision copper plating chemistry at a temperature of 46°C for a period of 70 minutes.
  • a copper loading of 2.87mg/cm 2 was applied to the polymeric substrate.
  • the copper coating was estimated to be 980 nm in thickness on average.
  • the current collector had the following properties:
  • an electroless copper coating was applied to a porous polymeric, non-woven substrate consisting of polyethylene terephthalate fibres (PET).
  • PET polyethylene terephthalate fibres
  • the thickness of the substrate before the application of the copper coating was 15 ⁇ m.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride. The activation step took place at 26.5°C for a period of three minutes.
  • a copper layer was then applied by contacting the substrate with Enthone Envision copper plating chemistry at a temperature of 46°C for a period of 45 minutes.
  • a copper loading of 4.25mg/cm was applied to the polymeric substrate.
  • the copper coating was estimated to be 936 nm in thickness on average.
  • the current collector had the following properties:
  • An electroless copper coating was applied to a porous polymeric, non-woven substrate as described in example 2.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride.
  • the activation step took place at 26.5°C for a period of three minutes.
  • the substrate was then contacted with an accelerator comprising Macuplex 9338 with 12M HC1. Contact between the accelerator and the substrate took place at 48.5°C for a period of one minute.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46.5°C for a period of 120 minutes.
  • a copper loading of 2.5 lmg/cm was applied to the polymeric substrate.
  • the cross- section SEM photomicrograph was used to estimate the coating thickness of the applied copper coating.
  • the copper coating was estimated to be 900 nm to 1200 nm in thickness.
  • Example 3 Membrane 4
  • an electroless copper coating was applied to a porous polymeric, non-woven substrate consisting out of polyethylene terephthalate fibres (PET).
  • PET polyethylene terephthalate fibres
  • the thickness of the substrate before the application of the copper coating was 104 ⁇ m.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride. The activation step took place at 26.5°C for a period of three minutes.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46°C for a period of 60 minutes.
  • the current collector had the following properties:
  • an electroless copper coating was applied to a porous polymeric, non-woven substrate consisting out of polyethylene terephthalate fibres (PET).
  • PET polyethylene terephthalate fibres
  • the thickness of the substrate before the application of the copper coating was 160 ⁇ m.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride. The activation step took place at 26.5°C for a period of three minutes.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46°C for a period of 60 minutes.
  • the current collector had the following properties:
  • a porous polymeric membrane with a non-woven fibrous composite structure and a thickness of 30 ⁇ m was coated with copper using electroless deposition.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride.
  • the activation step took place at 26.5°C for a period of three minutes.
  • the substrate was then contacted with an accelerator comprising Macuplex 9338 with 12M HC1. Contact between the accelerator and the substrate took place at 48.5°C for a period of one minute.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46.5°C for a period of 30 minutes.
  • a copper loading of 4.30 mg/cm was applied to the polymeric substrate.
  • the copper coating was estimated to be 59nm in thickness on average.
  • the current collector had the following properties:
  • a porous polymeric membrane with a non- woven fibrous composite structure and a thickness of 30 ⁇ m was coated with nickel using electroless deposition.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride.
  • the activation step took place at 26.5°C for a period of three minutes.
  • the substrate was then contacted with an accelerator comprising Macuplex 9338 with 12M HC1. Contact between the accellerator and the substrate took place at 48.5°C for a period of one minute.
  • a nickel layer was then applied by contacting the substrate with a solution containing, 28.3g/L nickel(II)sulfate hexahydrate, 42g/L citric acid, 3.5g/L DMAB and 26g/L sodium hydroxide for a period of 10 minutes at a temperature of 50°C.
  • a nickel loading of 0.57mg/cm 2 was applied to the polymeric substrate.
  • the current collector had the following properties:
  • Example 7 Membrane 6 coated with copper and then nickel
  • a porous polymeric membrane with a non-woven fibrous composite structure and a thickness of 30m m was coated with copper using electroless deposition.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride.
  • the activation step took place at 26.5°C for a period of three minutes.
  • the substrate was then contacted with an accelerator comprising Macuplex 9338 with 12M HC1. Contact between the accellerator and the substrate took place at 48.5°C for a period of one minute.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46.5°C for a period of 47.5 minutes.
  • a copper loading of 3.78mg/cm 2 was applied to the polymeric substrate. This material had the following properties:
  • a nickel layer was applied to the initial copper layer by contacting the substrate with an electroless nickel solution containing, 28.3g/L nickel(II)sulfate hexahydrate, 42g/L citric acid, 3.5g/L DMAB and 26g/L sodium hydroxide for a period of lOmin at a temperature of 50°C.
  • a nickel loading of 0.06mg/cm 2 was applied. The following properties were obtained:
  • porous polymeric substrates made from flat or flattened fibres can be used to make current collectors in accordance with the present invention, including the following:
  • Membrane 7 a PET substrate made from flat PET fibres.
  • the membrane was of 140m m thickness; Fibre type: 20 ⁇ m in width and 3 ⁇ m in thickness.
  • Figure 1 shows a plan-view SEM photomicrograph of the alternative uncoated substrate suitable for the use in fabricating current collectors by the invention described in this patent.
  • Membrane 8 is a PET membrane made from flattened fibres. The membrane was of 100 ⁇ m thickness; Fibre type: 18 ⁇ m in width and 2.5 ⁇ m in thickness.
  • Membrane 9 is a PET membrane made from flattened fibres. The membrane was of 30 ⁇ m thickness; non-woven fibrous composite structure including flat PET fibres and a second polymeric fibre.
  • an electroless copper coating was applied to a porous polymeric, non-woven substrate consisting out of polyethylene terephthalate fibres (PET).
  • PET polyethylene terephthalate fibres
  • the thickness of the substrate before the application of the copper coating was 15 ⁇ m.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride. The activation step took place at 26.5°C for a period of three minutes.
  • a copper layer was then applied by contacting the substrate with Enthone Envision copper plating chemistry at a temperature of 46°C for a period of 50 minutes.
  • a copper loading of 2.71mg/cm 2 was applied to the polymeric substrate.
  • the copper coating was estimated to be 822 nm in thickness on average.
  • the current collector had the following properties:
  • An anode slurry mixture was prepared for the purpose of applying an active material coating to the current collector.
  • the slurry mixture contained 94.5% of the graphite active material by weight, 2.5% SBR binder by weight and 1.5% CMC binder by weight and 1.5% Super P Carbon Black by weight as the conductive additive. Water was used as the solvent and the active material slurry was applied to the current collector by a blade-type coating mechanism.
  • the graphite active material used in this example was artificial MCMB (Meso- porous Carbon Microbeads) sourced from Gelon LIB Co., Limited.
  • a total coating weight of 13.88mg/cm was applied to the current collector. It has to be noted that for a substrate where the coating forms an integrated electrode structure meaning that the active material occupies the void space within the volume of the current collector, the notion of a coating per side is not applicable.
  • the total electrode thickness obtained after the coating process was measured to be 124 ⁇ m with a calculated porosity of 54%.
  • the coated electrode was then calendered at a pressure of 100bar which reduced the total electrode thickness tol09 ⁇ m and a calculated porosity of 37%.
  • the total calculated capacity based on active material loading weight and specific active material capacity of the obtained electrode was 4.40mAh/cm 2 (which would correspond to a capacity of 2.20mAh/cm per side for a conventional foil based electrode.
  • Figure 2 shows a cross-section photomicrograph of the obtained electrode, with active material particles being integrated into the void spaces of the current collector.
  • Example 9 Comparative Example - 6 ⁇ m copper foil electrode [00112] Electrodeposited battery grade solid copper foil with a thickness of 6 ⁇ m was sourced form Targray Technology International Inc.
  • An anode slurry mixture was prepared for the purpose of applying an active material coating to the current collector.
  • the slurry mixture contained 94.5% of the graphite active material by weight, 2.5% SBR binder by weight and 1.5% CMC binder by weight and 1.5% Super P Carbon Black by weight as the conductive additive. Water was used as the solvent and the active material slurry was applied to the current collector by a blade-type coating mechanism.
  • a total coating weight of 7.8mg/cm 2 was applied to one side of the 6 ⁇ m thick solid copper foil. This would correspond to an active material coating weight of 15.60mg/cm for the weight of a two sided coating on the current collector.
  • the total electrode thickness obtained after the coating process was measured to be 75 ⁇ m with a calculated porosity of 47%.
  • the coated electrode was then calendered at a pressure of lOObar which reduced the total electrode thickness to 68 ⁇ m and a calculated porosity of 41 %.
  • the total calculated capacity based on active material loading weight and specific active material capacity of the obtained electrode was 2.48mAh/cm 2 for the one-sided coating on the current collector. This would correspond to a total capacity of 4.96mAh/cm for a two sided coating on the current collector.
  • Figure 3 shows a cross-section photomicrograph of the obtained electrode, with active material particles being integrated into the void spaces of the current collector.
  • a porous polymeric membrane with a non- woven fibrous composite structure and a thickness of 30 ⁇ m was coated with copper using electroless deposition.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride.
  • the activation step took place at 27.5°C for a period of three minutes.
  • the substrate was then contacted with an accelerator comprising Macuplex 9338 with 12M HC1. Contact between the accellerator and the substrate took place at 48.5°C for a period of one minute.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46.5°C for a period of 60 minutes.
  • a copper loading of 4.95 mg/cm 2 was applied to the polymeric substrate.
  • the copper coating was estimated to be 61nm in thickness on average.
  • the copper coated current collector was calendered to reduce its thickness before coating the current collector with graphite active material.
  • the calendering process reduced the thickness of the current collector from 59 ⁇ m and a porosity of 66% before calendering to a thickness of 30 ⁇ m and a porosity of 34% after calendering.
  • the solid equivalent conductivity of the current collector remained unchanged.
  • An anode slurry mixture was prepared for the purpose of applying an active material coating to the current collector.
  • the slurry mixture contained 96.5 % of the graphite active material by weight, 2.5% PVDF binder by weight and 1.0% Super P C-65 Carbon Black by weight as the conductive additive. NMP was used as the solvent and the active material slurry was applied to the current collector by a blade-type coating mechanism.
  • the graphite active material used in this example was BTR 918S, a natural graphite, sourced from Tianjin BTR New Energy Technology Co., Ltd.
  • the active material has a particle size distribution of d 10 : 9- 13 ⁇ m; d 50 : 17-23 ⁇ m; d 90 : 27-36 ⁇ m and the specific capacity of the graphite active material is 338mAh/g.
  • a total coating weight of 24.72mg/cm 2 was applied to the current collector. This corresponds to a coating weight of 12.36mg/cm per side of the current collector.
  • the electrode was then calendered to adjust the porosity of the active material coating.
  • the total electrode thickness after calendering was measured to be 1 88m m and the active material coating had an average calculated coating porosity of 34%.
  • the total calculated capacity based on active material loading weight and specific active material capacity of the obtained electrode was 8.08mAh/cm 2 . This corresponds to a capacity of 4.04mAh/cm 2 per side of the electrode.
  • Figure 4 shows a plan-view and a cross-section SEM photomicrograph of the obtained current collector.
  • Examples 11 and 12 show examples that involved calendering of the current collector before the application of an active material coating.
  • an electroless copper coating was applied to a porous polymeric, non-woven substrate consisting out of polyethylene terephthalate fibres (PET).
  • PET polyethylene terephthalate fibres
  • the thickness of the substrate before the application of the copper coating was 15 ⁇ m.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HCh Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride. The activation step took place at 26.5°C for a period of three minutes.
  • a copper layer was then applied by contacting the substrate with Enthone Envision copper plating chemistry at a temperature of 46°C for a period of 45 minutes.
  • a copper loading of 1.12mg/cm 2 was applied to the polymeric substrate.
  • the obtained current collector was then calendered using three different calendering conditions to achieve the desired reduction in thickness.
  • the letter A denotes the properties of the uncalendered current collector and the letter B, C and D denote the properties of the current collector after the calendering at condition 1, 2, and 3.
  • Calendering condition 2 Pressure: 100bar; Temperature: RT; Number of passes: 1
  • Calendering condition 3 Pressure: lOObar; Temperature: 70°C; Number of passes: 1
  • Calendaring condition 3 obtained a compacted current collector with a thickness of 6m m and good levels of conductivity. A reduction in thickness from 19 ⁇ m to 6 ⁇ m corresponds to a 68% thickness reduction through the calendaring process.
  • Figures 5 A to 5D show plan-view SEM photomicrographs of the obtained current collector in its original state and after being calendared at calendaring conditions number 3.
  • a porous polymeric membrane with a non-woven fibrous composite structure and a thickness of 30 ⁇ m was coated with copper using electroless deposition.
  • the substrate was pretreated with an activator comprising Macuplex D34C with 12M HC1.
  • Macuplex D34C is a proprietary commercially available activator that contains palladium chloride and tin chloride.
  • the activation step took place at 26.5°C for a period of three minutes.
  • the substrate was then contacted with an accelerator comprising Macuplex 9338 with 12M HC1. Contact between the accellerator and the substrate took place at 48.5°C for a period of one minute.
  • a copper layer was then applied by contacting the substrate with MacDermid Copper 85 at a temperature of 46.5°C for a period of 30 minutes.
  • a copper loading of 4.30mg/cm was applied to the polymeric substrate.
  • a second substrate was prepared in the same way but the substrate was contacted with MacDermid Copper 85 at a temperature of 46.5°C for a period of 27 minutes. A copper loading of 3.71mg/cm was applied to the polymeric substrate.
  • the first current collector with a copper loading of 4.30mg/cm was calendered using the following conditions: [00139] Calendaring condition: Force: 240 Tons; Temperature: RT; Number of passes: 1
  • Calendaring at such conditions yielded a reduction in thickness of the current collector from 53 ⁇ m to 28 ⁇ m which corresponds to a reduction of current collector thickness of 47%. It also has to be noted that the conductivity of the current collector improved with the calendaring process.
  • the letter A denotes the properties of the uncalendared current collector and the letter B denotes the current collector after the calendaring process.
  • Calendering at such conditions yielded a reduction in thickness of the current collector from 52 ⁇ m to 26 ⁇ m which corresponds to a reduction of current collector thickness of 50%. It also has to be noted that the conductivity of the current collector improved with the calendering process.
  • the letter A denotes the properties of the uncalendered current collector and the letter B denotes the properties of the current collector after the calendering process.
  • Metals useful as the conductive material for current collector applications can be selected from the following: copper, nickel, aluminium, iron, titanium, gold, platinum or mixtures or alloys of two or more thereof.
  • the directional characteristics for some of the membranes are imparted by the fact that a higher percentage of the fibres in the substrate are aligned and are running in the machine direction. A lower percentage of the fibres is running into the transverse direction.
  • the fibre distribution imparts a certain degree of anisotropy to the current collector leading to three unique aspects described below.
  • a range of membrane thicknesses and corresponding basis weights are possible. Examples include:
  • Base membrane 8 - 10 ⁇ m thickness and a weight of 2- 4g/m 2
  • Base membrane 12 - 20 ⁇ m thickness and a weight of 5 - 8g/m 2
  • Base membrane 20 -30 ⁇ m thickness and a weight of 8 - 12g/m 2 [00150] Other thicknesses and weights can also be used.
  • the calculated porosity of these membranes before a metal coating is applied will typically lie in the range of 50 to 98%, or from 60 to 95%, or from 70 to 95%, or from 70-80%.
  • the fibres of the substrate give a gross thickness with larger“pores” without taking space from the active materials. The aim is to maximise the active material content in the given current collector volume without sacrificing on the performance of the current collector.
  • the metal content with the current collector can be expressed in several ways.
  • the metal content of the current collector can be expressed as a weight percentage of metal, determined as a weight of metal as a fraction of the total current collector weight (polymer + metal).
  • the thin micro-porous membranes may possess a weight percentage of metal of 80-95%.
  • the metal content could be described as the volume fraction of metal contained within the structure.
  • the volume fraction of metal such as copper usually ranges between 2% and 20%. Of course higher levels between 20% and 40% may also be useful in certain applications.
  • the openings ideally have a size that allows the active material particle to infiltrate the volume of the current collector but do not allow the active material paste to simply fall through the structure due to its low thickness, as this can cause difficulties during electrode manufacture or assembly of the cells.
  • the active material (which is typically applied in the form of a paste or slurry containing graphite, binders and other components) can easily pass through the current collector, this can lead to the active material passing through the current collector and causing a build-up of material on the supporting surface underneath the current collector, which can cause difficulty in obtaining and even coating of the active material on the current collector and can also form sites for potential breakage of the current collector during electrode coating or cell assembly.
  • Standard graphite active material particles have an average diameter of 15 -23 ⁇ m with some particles being only 10 ⁇ m in diameter and the largest ones being up to 50 ⁇ m in diameter. Various graphites with a smaller average particle diameter size of 5-15 ⁇ m may also be used.
  • Electrodes need to be calendered after graphite coating to provide the optimal density of the active material. This process applies high forces on the current collector structure and an open current collector will allow the particles to nestle in the structure whilst minimising damaging the structure.
  • particulate active materials such as silicon, tin, carbons in various forms, and composite particles such as graphite/silicon, graphite/lithium, or carbon/silicon and
  • carbon/lithium and core shell particle structures incorporating one or more of the aforementioned materials of graphite, carbon, silicon, lithium, copper or composites thereof may only have an average diameter of l- 10 ⁇ m or less than l ⁇ m.
  • the openings in the micro-porous current collector may be designed to match the active material in use.
  • a thick microporous current collector having a thickness in the range of from 25 to 400 ⁇ m can be used.
  • the current collector is a thick current collector
  • the current collector has a very low weight per volume/thickness of these thicker current collectors.
  • the thick porous polymeric substrate can comprise a substrate made from PET fibres having a circular cross-section with diameter of 10-15 ⁇ m (alternatively fibres with a larger diameter of up to 30 ⁇ m or a fibre diameter as little as 5 ⁇ m could be used). It is expected that this“thicker current collector” is likely to be predominantly used in combination with lithium metal batteries where lithium metal is plated into the void space of the 3D porous structure. However, filling the current collector with active material particles of a given shape and dimension may also be feasible. Active material particles with a smaller diameter such as 1- 10 ⁇ m may be preferred in combination with this thicker structure.
  • the thicker micro-porous current collector structure also possesses a certain degree of anisotropy through the plane of the current collector as opposed to the in-plane anisotropic features of strength and conductivity.
  • This current collector provides an alternative to the structure of copper foams while being able to achieve thicknesses and porosities at such thicknesses that are unattainable for copper foams.
  • this current collector allows for the creation of thicker current collector structures with thicknesses thin enough to be out of reach of metal foams ( ⁇ 400 ⁇ m), while maintaining high levels of porosity (>70%) of up to 95%, while being able to create pores/openings in the 50-100 ⁇ m range or larger. This is not something that can be achieved with metal foams, while creating a structure of sufficient strength for commercial processing and while creating a structure where the directionality of pores/opening is such that they are extending into current collector's structure in a largely downwardly facing pattern.
  • a range of membrane thicknesses and corresponding basis weights are possible. Examples include:
  • Base membrane 80- 120 ⁇ m thickness and a weight of 8 - 14g/m 22
  • Base membrane 140 - 180 ⁇ m thickness and a weight of 18 - 25g/m 22
  • the calculated porosity of these membranes before a metal coating is applied lies in the range of 85-95%. Porosity ranges of 70% to 95% are useful.
  • the openings of the pores ideally have a size and orientation that in the case of a lithium metal battery allows the lithium ions supplied by the opposing electrode (cathode) to migrate into the porous structure and deposit as metallic lithium.
  • the openings should allow the particles to easily infiltrate the volume of the current collector but do not allow the active material paste to simply fall through the structure.
  • Standard graphite active material particles have an average diameter of 15-23 ⁇ m with some particles being only 10 ⁇ m in diameter and the largest ones being up to 50 ⁇ m in diameter.
  • Various graphite’s with a smaller average particle diameter size of 5-15 ⁇ m may also be used.
  • particulate active materials such as silicon, tin, carbons in various forms, and composite particles such graphite/silicon, graphite/lithium, or carbon/silicon and carbon/lithium and core shell particle structures incorporating one or more of the aforementioned materials of graphite, carbon, silicon, lithium, copper or composites thereof may only have an average diameter of 1-10 ⁇ m or less than 1 ⁇ m.
  • the openings in the micro-porous current collector may be designed to match the active material in use.
  • the shape of the openings could be varied by the anisotropy of the fibre structure to maximise the capacity, particularly with a large pore to particle ratio. It is expected that the average pore size required will decrease with a decrease in active material particle size.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

La présente invention concerne un collecteur de courant pour une cellule électrochimique ou une batterie, le collecteur de courant comprenant un substrat polymère poreux enduit d'un matériau conducteur, l'invention étant caractérisée en ce que le collecteur de courant présente des propriétés anisotropes.
PCT/AU2017/051322 2017-11-30 2017-11-30 Collecteur de courant WO2019104365A1 (fr)

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CN114678515A (zh) * 2022-04-12 2022-06-28 珠海中科先进技术研究院有限公司 一种多孔聚合物涂层铜电极及其制备方法和应用
CN114678515B (zh) * 2022-04-12 2024-05-31 珠海中科先进技术研究院有限公司 一种多孔聚合物涂层铜电极及其制备方法和应用

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EP2846384A1 (fr) * 2013-09-04 2015-03-11 VARTA Microbattery GmbH Cellule électrochimique mince et souple
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CN114678515B (zh) * 2022-04-12 2024-05-31 珠海中科先进技术研究院有限公司 一种多孔聚合物涂层铜电极及其制备方法和应用

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