CN111033813A - Method for producing electrodes by adhesive fibrillation - Google Patents
Method for producing electrodes by adhesive fibrillation Download PDFInfo
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- CN111033813A CN111033813A CN201880050167.5A CN201880050167A CN111033813A CN 111033813 A CN111033813 A CN 111033813A CN 201880050167 A CN201880050167 A CN 201880050167A CN 111033813 A CN111033813 A CN 111033813A
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Classifications
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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
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for producing an electrode (E) for an electrochemical cell, in particular for a battery cell, for example for a lithium battery. In order to be able to produce, for example by dry coating, homogeneous mixtures of electrodes (E) for example for motor vehicle batteries, in particular for electric and/or hybrid vehicles, having improved properties and/or a layer thickness of significantly more than 100 μm, in a time-saving and cost-effective manner, at least one binder (B) is mixed with at least one electrode component (E1) in a high-shear-load mixing process to form a mixture (fB + E1) comprising a fibrillated binder, and then at least one further electrode component (E2) is added to the mixture (fB + E1) comprising a fibrillated binder by a lower-shear-load mixing process. The invention also relates to an electrode (E) produced thereby and to a battery equipped with an electrode (E) of said type.
Description
Technical Field
The present invention relates to a method for producing an electrode for an electrochemical cell, in particular for a battery cell; an electrode produced thereby; and an electrochemical cell equipped with an electrode of this type.
Background
Batteries based on, for example, lithium or sodium batteries (such as lithium or sodium ion batteries) offer great potential for energy saving and local avoidance of emissions when used in mobile and stationary applications.
Electrodes for lithium batteries are generally produced by wet coating methods. The procedure generally used here mixes the electrode component with at least one solvent to produce a (high-viscosity) liquid slurry or slip, which is then used to form a layer or coating, for example by means of a slot coater, a knife coater or a roll coater.
In order to remove the at least one solvent again, a long drying tunnel must be used for slow and controlled drying of the layer or coating. However, this leads to long production times and high production costs, for example in the form of energy costs for drying and for providing, recovering and/or catalytically combusting the at least one solvent.
Furthermore, wet coating methods can only produce electrodes with a limited layer thickness, for example up to 100 μm. However, for large batteries (such as large batteries required for electric vehicles), thicker electrodes would be desirable.
The documents US 2015/03030481 a1, WO 2005/008807 a2(EP 1644136 a2), WO 2005/049700 a1, US 4,556,618, US 4,379,772, US 4,354,958, US 3,898,099 and US 6,335,857B1 relate to a process for producing electrodes.
Disclosure of Invention
The present invention provides a method of producing an electrode (e.g., an anode and/or a cathode) for an electrochemical cell. The method can in particular be designed here for producing an electrode (for example an anode and/or a cathode) for a battery cell, in particular for a lithium battery or a sodium battery or for a metal-air battery, for example for a lithium ion battery and/or a lithium metal battery or for a sodium ion battery. The method may in particular be designed for producing electrodes (e.g. anodes and/or cathodes) for lithium batteries, for example for lithium ion batteries and/or lithium metal batteries.
In the process, in particular in process step a), at least one binder, in particular a polymeric binder, is mixed with at least one electrode component by means of a high shear mixing procedure to obtain a mixture comprising a fibrillated binder.
In the process (then), in particular in process step b), at least one further electrode component is admixed by means of a low-shear mixing procedure to the mixture comprising fibrillated binder, in particular from process step a).
By means of the high shear mixing procedure, in particular shear loads which are higher than those achieved by means of the low shear mixing procedure and which are capable of fibrillating the at least one binder can be achieved. Thus, the high shear mixing procedure may also be referred to as a higher shear mixing procedure, among others.
By the low shear mixing procedure, in particular a lower shear load than that achieved by the high shear mixing procedure can be achieved. Thus, the low shear mixing procedure may especially also be referred to as a lower shear mixing procedure.
The expression "high-shear mixing procedure" may here particularly denote a mixing procedure in which the particles move relative to one another, in particular in the absence of a lubricant (such as a liquid), in particular in which high-shear loads occur with a large velocity gradient between the particles themselves and/or between the particles and the mixer wall. Here, the particles under high shear load are particularly likely to undergo breakage, e.g. clean breakage. The high shear mixing procedure can be carried out, for example, by a jet method, in particular by a jet mill, and/or by a three-roll mill and/or by a twin-screw extruder.
The expression "low-shear mixing procedure" may in particular refer to a mixing procedure in which the streams of material are folded over one another, in particular in which the velocity gradients occurring between the particles themselves and/or between the particles and the mixer wall are small, and therefore low shear loads occur. Here, the particles under low shear load can in particular retain their shape and/or be subjected only to wear. The low-shear mixing procedure can be carried out, for example, by plow mixers and/or paddle mixers and/or static mixers (e.g., based on an elongated flow, for example, caused by a series of widening and narrowing in the channel system), and/or by gravity mixers.
By means of a high shear mixing procedure, for example by means of a jet mill, the at least one binder can be fibrillated, for example by means of relative motion and/or collision/bombardment on the particles of the at least one electrode component. Here, the at least one binder can be shaped in order to obtain in particular long fibrils (binder filaments). The fibrils of the at least one fibrillated binder (binder filaments) may then be attached in a distributed fashion on the surface of the at least one electrode component. The resulting mixture can then be made into an electrode by a dry production procedure, in other words a coating process which operates without solvent, for example by dry coating. As a result, it is possible to produce, for example, automotive batteries for electric and/or hybrid and/or plug-in hybrid vehicles and/or electrodes for stationary batteries having a layer thickness of significantly more than 100 μm in a time-saving and inexpensive manner and, in particular, without the use of flammable, toxic and/or carcinogenic solvents.
However, the high shear mixing procedure does impose high mechanical loads on the at least one electrode component.
For example, in high shear mixing procedures (e.g., by jet milling), soft, brittle, friable and coated electrode components, such as relatively soft intercalated graphite used as an anode active material, can be affected and/or altered by the mechanical forces acting on it; and/or brittle storage alloys (storage alloys) used as anode active materials, such as silicon alloys and/or tin alloys; and/or as a coated electrode component of an anode active material or a cathode active material (e.g., in the form of particles having a particle core and a particle shell surrounding the particle core (core-shell particles) and/or in the form of gradient material particles).
The term "gradient material particle" may particularly denote a particle that exhibits a property that varies within the particle and/or from the surface of the particle or from the periphery of the particle to the core of the particle and/or exhibits a gradient with respect to the material.
By means of a high shear mixing procedure, for example, soft, brittle and/or friable electrode components can be comminuted and/or ground, which may reduce their average particle size and/or optionally alter their particle shape.
For example in the case of intercalated graphite and/or storage alloys, this in turn may first lead to a reduction in its reversible storage capacity and/or an increase in its irreversible losses, due to, for example, the formation (in particular increased formation) of a covering layer by the bonding of lithium on its surface when the battery is first operated.
Secondly, the properties of the electrode, such as morphology, for example its porosity, and thus its wetting properties, current carrying capacity and/or capacitance, as well as its surface structure and surface reactivity, can be adversely affected by producing small particles and/or changing the particle shape, for example by converting spherical graphite particles into lamellar graphite particles via shearing along the sliding surface of the graphite.
Furthermore, by means of high-shear mixing procedures, for example, the functional and/or protective particle top coating on the coated electrode component in the form of particles, for example, having a particle core and a particle shell surrounding the particle core (core-shell particles) and/or gradient material particles can be disrupted. This may likewise lead to a reduction in its reversible storage capacity and/or an increase in irreversible losses, for example due to the formation (in particular increased formation) of a covering layer by lithium bonding at its surface when the battery is first operated, and may be detrimental to its long-term stability.
The subdivision into at least two separate mixing stages has the advantageous effect of being able to use the individual electrode components in the individual mixing stages depending on the nature and/or function of said components. For example, in a high shear mixing procedure, it is possible to use mechanically stable electrode components and/or electrode components which act as conductivity additives or conductivity agents and which retain their function even at low average particle sizes, in particular, which may still be advantageous; and/or in a low shear mixing procedure, it is possible to use mechanically sensitive electrode components and/or electrode components which are used as electrode active materials and whose function may be affected by the comminution.
Furthermore, by using at least one electrode component in a high shear mixing procedure, the at least one binder can advantageously be fibrillated by the material that functions in the electrode under production, and this can have a favourable effect on the specific energy density.
Thus, it is possible to produce a homogeneous mixture, in particular a mixture in which the at least one binder is homogeneously attached to the particles (e.g. all particles) of the at least one electrode component and the at least one further electrode component; and electrodes, such as anodes or cathodes, with improved performance and/or (also) with a layer thickness of significantly more than 100 μm, for example for use in automotive batteries, such as for use in electric and/or hybrid and/or plug-in hybrid vehicles, and/or for use in stationary battery packs, can be produced from the mixture in a time-saving and cost-effective manner, for example by a dry-process production procedure and/or by coating, for example by dry coating, for example a current collector or a carrier substrate.
The at least one electrode component and/or the at least one further electrode component may be formed from or comprise: for example at least one conductivity additive, especially for improving conductivity; and/or at least one electrode active material, in particular for energy storage, for example for the storage of lithium and/or surface-coated particles and/or gradient material particles.
For example, the at least one electrode component and/or the at least one further electrode component may be formed from or comprise: at least one conductive carbon, for example conductive graphite and/or at least one amorphous conductive carbon, in particular in the form of non-porous carbon particles, such as conductive carbon black, and/or carbon fibers and/or Carbon Nanotubes (CNTs) and/or graphene and/or expanded graphite; and/or at least one electrically conductive metal, such as silicon and/or tin and/or another metal and/or alloy, for example in the form of a metal powder; and/or at least one anode active material and/or at least one cathode active material, such as at least one intercalation material and/or composite material(s), in particular at least one intercalation material and/or composite material of lithium or sodium, such as intercalated graphite and/or at least one intercalated and/or intercalated amorphous carbon, such as hard carbon and/or soft carbon; and/or at least one storage alloy, for example at least one lithium storage alloy, for example a silicon alloy and/or a tin alloy, especially as anode active material; and/or at least one metal oxide and/or metal phosphate, for example a silicon oxide, in particular for forming or as an anode active material, and/or at least one metal oxide, for example at least one layered oxide and/or at least one spinel, for example at least one oxide of nickel and/or cobalt and/or manganese, for example an oxide of lithium nickel and/or cobalt and/or manganese, and/or at least one metal phosphate, for example at least one phosphate of iron and/or manganese and/or cobalt, for example a phosphate based on at least one lithium iron and/or manganese and/or cobalt, for example based on, for example, the following formulae: LiMPO4Wherein M ═ Fe, Mn and/orCo, especially as a cathode active material; and/or at least one conductive additive-electrode active material composite (composite), such as at least one conductive additive-anode active material composite or conductive additive-cathode active material composite, for example at least one carbon-electrode active material composite, for example at least one carbon-anode active material composite or at least one carbon-cathode active material composite, for example, at least one carbon-metal phosphate complex, for example coated with a conductive additive, for example, in the form of carbon-coated electrode active material particles, especially anode active material particles or cathode active material particles, for example in the form of carbon-coated metal phosphate particles and/or surface-coated particles, for example particles having a particle core and a particle shell surrounding the particle core (referred to as core-shell particles) and/or gradient material particles.
Expanded graphite may particularly refer to materials which are produced by expansion of graphite and which are used to provide graphene and/or materials comprising graphene.
Composite materials may especially refer to active materials whose mode of action is based on recombination and/or phase inversion reactions, such as Li + Al → LiAl.
Hard carbon is to be understood as meaning in particular carbon which can be inserted and/or intercalated, in particular relatively stable amorphous carbon, in particular carbon which is not graphitizable and can be used as anode active material.
Soft carbon is understood to mean, in particular, carbon which can be inserted and/or intercalated, in particular relatively stable amorphous carbon, in particular carbon which can be graphitized and which can be used as anode active material.
The high-shear mixing procedure, in particular in process step a), can take place or be carried out in particular by means of jet mills and/or three-roll mills and/or twin-screw extruders and/or counter-jet fluidized bed mills and/or ball mills and/or mortar mills and/or roller devices (in an operation known as rolling out) and/or tablet presses. Here, high shear forces can be formed, for example, by a relative movement of the at least one electrode component with respect to the at least one fibril forming binder (in particular the polymeric binder). The relative movement of the materials with respect to one another can be achieved here in a particularly simple manner by means of a roller device and/or a tablet press.
In the high shear rate mixing procedure, in particular in method step a), it may be advantageous to use a suitable particle size distribution of the at least one binder and the individual electrode components. In particular, the at least one electrode component may have a larger average particle size than the at least one binder.
In another embodiment, the high shear rate mixing procedure, especially in process step a), takes place or is carried out by means of a jet mill. By means of the jet mill, a uniform distribution of the at least one binder on the at least one electrode component can advantageously be achieved in a particularly simple and time-saving manner. With jet mills, especially gases (e.g. air) are used to mix the components at very high speeds (possibly up to sonic speeds). Here, the actual mixing procedure may advantageously last only about 1-2 seconds and may generate very high shear forces and thus very high shear loads. As a result, the at least one binder can advantageously be fibrillated very efficiently and quickly. The embodiments set forth above and below are particularly interesting with respect to the use of, for example, at least one electrode component with high mechanical stability and/or functionality that is very independent of comminution in high shear mixing procedures and at least one further electrode component with, for example, higher sensitivity and/or functionality that is dependent on comminution in low shear mixing procedures, based on the destructive effect of very high mechanical loads, for example accompanying very high shear loads, in the case of jet mills used in high shear mixing procedures.
The jet mill is preferably operated such that at least one electrode material is not damaged or at least is damaged only to a small extent, or, where appropriate, is damaged only in a controlled manner. For example, the jet mill may be operated at a minimum desired speed and/or residence time for application of the at least one binder. For example, the operating conditions of a jet mill can be determined through a series of experiments. In this case, the properties of at least one electrode component can be investigated, for example, by Scanning Electron Microscopy (SEM).
In the high-shear mixing procedure, the at least one binder can be fibrillated using, in particular, at least one electrode component which is, in particular, mechanically more stable in the high-shear mixing procedure or under the conditions of the high-shear mixing procedure than at least one further electrode component (in particular the component to be mixed in the low-shear mixing procedure) and/or whose mechanical loading and, for example, the functional ability to pulverize the electrode with which it is equipped have no or few adverse consequences in comparison with the at least one further electrode component (in particular the component to be mixed in the low-shear mixing procedure). In this case, mechanical loading or comminution of the at least one electrode component in the high shear mixing procedure may in particular be tolerated and/or the at least one electrode component may be used as sacrificial material.
In a subsequent separate low shear mixing procedure, the at least one further electrode component is less mechanically stable or more sensitive than the at least one electrode component mixed in the high shear mixing procedure, e.g. based on its mechanical stability and/or sensitivity coating, and may then be homogeneously incorporated into the mixture comprising the fibrillated binder with a lower mechanical load.
In one embodiment, the at least one electrode component is more mechanically stable than the at least one further electrode component, especially in or under the conditions of the high shear mixing procedure, and/or the functionality of the at least one electrode component is less affected than the functionality of the at least one further electrode component, especially by the high shear mixing procedure or under the conditions of the high shear mixing procedure and/or by mechanical loading, such as comminution. Thus, the individual electrode components can be advantageously used in terms of their properties and/or their functionality.
A higher mechanical stability and/or a lower impact on functionality of the at least one electrode component relative to the at least one further electrode component may be achieved in various ways.
In another embodiment, for example, the at least one electrode component, for example in the case of spherical particles, has an average particle diameter, in particular a primary particle diameter, of less than 10 μm; and/or, for example, in the case of fibrous and/or tubular particles, have an average particle length (e.g., average fiber length and/or tube length) of, for example, less than 10 μm; and/or, for example, in the case of lamellar particles, have a mean planar particle diameter (particle plane diameter) of less than 10 μm, or such a size/length/diameter is used. For example, the at least one electrode component may have or use an average particle size, in particular a primary particle size, of less than or equal to 8 μm, in particular less than or equal to 6 μm; and/or an average particle length (e.g. average fibre length and/or tube length) of less than or equal to 8 μm, especially less than or equal to 6 μm; and/or an average plane particle size of less than or equal to 8 μm, in particular less than or equal to 6 μm.
Experimental studies have shown that: the high shear mixing procedure (e.g., by jet milling) produces a minimum achievable and thus stable average particle size or particle length (e.g., fiber length and/or tube length) or planar particle size, particularly in the range of greater than or equal to 4 μm to less than or equal to 6 μm; and in this case particles having a particle size or particle length (e.g. fiber length and/or tube length) or a plane particle size in this range are not further comminuted, especially in view of the physical boundary conditions of the mixer, e.g. mill, and the properties of the material.
Since the at least one electrode component has an average particle diameter or average particle length (for example average fiber length and/or tube length) or average plane particle diameter of less than 10 μm, for example less than or equal to 8 μm, in particular less than or equal to 6 μm, the comminution effect acting thereon by the high-shear mixing procedure can be reduced, since in this case the particles are mostly only comminuted to an average particle diameter or average particle length (for example average fiber length and/or tube length) or average plane particle diameter, for example in the range of greater than or equal to 4 μm to less than or equal to 6 μm. In this way, mechanical stability of the at least one electrode component can be obtained in a high shear mixing procedure.
In one particular configuration, the at least one electrode component has an average particle size in a range of greater than or equal to 0.01 μm to less than or equal to 6 μm, for example, in a range of greater than or equal to 4 μm to less than or equal to 6 μm; and/or have an average particle length (e.g., average fiber length and/or tube length) in a range of greater than or equal to 0.01 μm to less than or equal to 6 μm, such as in a range of greater than or equal to 4 μm to less than or equal to 6 μm; and/or having an average planar particle size in the range of greater than or equal to 0.01 μm to less than or equal to 6 μm, for example in the range of greater than or equal to 4 μm to less than or equal to 6 μm; or use such size/length/diameter. Thus, the comminuting effect acting thereon during the high shear mixing procedure can be minimized and a high mechanical stability of the at least one electrode component can be achieved during the high shear mixing procedure.
In another embodiment, the at least one further electrode component has a larger average particle size, in particular a primary particle size, than the at least one electrode component, for example in the case of spherical particles; and/or have a greater average particle length (e.g., a greater average fiber length and/or tube length), such as in the case of fibers and/or tubular particles; and/or have a larger average planar particle size, for example in the case of lamellar particles; or use such size/length/diameter. Because the at least one electrode component has a smaller average particle size and/or a smaller average particle length (e.g., a smaller average fiber length and/or tube length), and/or a smaller average planar particle size than the at least one other electrode component, the at least one electrode component may be more mechanically stable in a high shear rate mixing procedure than the at least one other electrode component.
For example, the at least one further electrode component may have or use an average particle size, in particular a primary particle size, of greater than or equal to 10 μm or greater than 8 μm or greater than 6 μm; and/or average particle length (e.g., average fiber length and/or tube length) and/or average plane particle size. For example, the at least one further electrode component may have or use an average particle size, in particular a primary particle size, of greater than or equal to 10 μm or greater than or equal to 12 μm or greater than or equal to 15 μm, for example in the range of greater than or equal to 10 μm to less than or equal to 20 μm; and/or greater than or equal to 10 μm or greater than or equal to 12 μm or greater than or equal to 15 μm, such as an average particle length (e.g., average fiber length and/or tube length) in a range from greater than or equal to 10 μm to less than or equal to 20 μm; and/or an average planar particle size of 10 μm or more or 12 μm or more or 15 μm or more, for example, in a range of 10 μm or more to 20 μm or less.
By using the at least one further electrode component in a low shear mixing procedure, the at least one further electrode component may be protected against, for example, severe mechanical loading and/or comminution, especially as a result of a high shear mixing procedure, and may therefore be treated in such a way that the material is retained as much as possible, even for materials which are less sensitive or mechanically stable, such as relatively soft, intercalated graphite, and/or coated particles, such as core-shell particles, and/or gradient material particles.
Alternatively or additionally, with regard to the above-mentioned gradient between the at least one electrode component and the at least one further electrode component based on their average particle size, particle length (e.g. fiber length and/or tube length) and/or planar particle size, it is possible to select the at least one electrode component to be less affected in its functionality than the at least one further electrode component due to the high shear mixing procedure.
In another embodiment, the at least one electrode component comprises or is formed from, for example: at least one conductivity additive, in particular for improving the conductivity. More particularly, the at least one electrode component may comprise or be formed from: at least one conductive carbon and/or at least one conductive metal.
The functionality of the conductive additive (e.g. conductive carbon, e.g. conductive graphite and/or amorphous conductive carbon, such as conductive carbon black, and/or carbon fibers and/or Carbon Nanotubes (CNTs) and/or graphene and/or expanded graphite and/or conductive metals, especially for improving the conductivity) is typically much less affected by high mechanical loads and/or crushing than the functionality of e.g. electrode active materials, especially for energy storage (e.g. for storage of lithium), e.g. anode active materials and/or cathode active materials, e.g. intercalation and/or composite materials, such as intercalation graphite and/or intercalatable amorphous carbon, such as hard carbon and/or soft carbon and/or storage alloys. Furthermore, the depolymerization and subsequent fibrillation of the at least one binder may advantageously be assisted by the application of conductive additives, for example conductive carbon, such as conductive graphite and/or conductive carbon black.
In one configuration of this embodiment, the at least one electrode component comprises or is formed from electrically conductive graphite. Electrically conductive graphite has a lower average particle size, for example in the range of greater than or equal to 4 μm to less than or equal to 10 μm, and a lower reversible storage capacity and/or a higher reaction surface area, and therefore has a higher irreversible capacity loss upon first lithiation or first operation of the battery, as compared to, for example, intercalated graphite, and is therefore not ideal for intercalation of lithium. The at least one electrode component used in the process steps of high mechanical loading, in particular in method step a), can be, for example, electrically conductive graphite sold under the trade names KS4 and/or KS6 by imerys (timcal) or sold under different trade names by different manufacturers.
In another alternative or additional configuration of this embodiment, the at least one electrode component comprises or is formed from: amorphous conductive carbon, particularly in the form of non-porous carbon particles. The at least one electrode component may, for example, comprise or consist of conductive carbon black.
In another alternative or additional configuration of this embodiment, the at least one electrode component comprises or is formed from: carbon fibers and/or Carbon Nanotubes (CNTs).
Carbon fibers and/or carbon nanotubes are advantageously particularly suitable for fibrillation of the at least one binder. Furthermore, by using carbon fibers and/or carbon nanotubes in the high shear mixing procedure, the carbon fibers and/or carbon nanotubes can be dispersed particularly well, and problems that may occur in other mixing procedures (especially low shear mixing procedures) during dispersion or during uniform incorporation can be solved by dispersing the carbon fibers and/or carbon nanotubes. The jet mill is capable of incorporating or dispersing carbon fibers and/or carbon nanotubes by mixing in a particularly simple manner. For example, the at least one electrode component may comprise or be formed from: an average diameter much less than 1 μm, typically less than or equal to 200 nm; and/or carbon fibers having an average particle length, such as a fiber length and/or a tube length, in a range of greater than or equal to 2 μm to less than or equal to 200 μm, such as in a range of greater than or equal to 2 μm to less than or equal to 20 μm; and/or an average diameter of less than or equal to 50nm, for example in the range of greater than or equal to 0.3nm to less than or equal to 50 nm; and/or carbon nanotubes having an average particle length, such as an average fiber length and/or tube length, in a range of greater than or equal to 10nm to less than or equal to 50cm, such as greater than or equal to 10nm to less than or equal to 20 μm.
If the already described mechanical stabilization is to be achieved additionally by a low average particle length (for example fiber length and/or tube length), the at least one electrode component may comprise or use carbon fibers having an average particle length (for example average fiber length and/or tube length), for example in the range from greater than or equal to 2 μm to less than 10 μm or less than or equal to 8 μm or less than or equal to 6 μm, and/or carbon nanotubes having an average particle length (for example average fiber length and/or tube length), for example in the range from greater than or equal to 10nm to less than 10 μm or less than or equal to 8 μm or less than or equal to 6 μm.
In another alternative or additional configuration of this embodiment, the at least one electrode component comprises or is formed from: graphene and/or expanded graphite.
In another alternative or additional configuration of this embodiment, the at least one electrode component comprises: at least one conductive additive-electrode active material composite, for example at least one conductive additive-anode active material composite or at least one conductive additive-cathode active material composite, for example at least one carbon-electrode active material composite, such as at least one carbon-anode active material composite or at least one carbon-cathode active material composite, for example at least one carbon metal phosphate composite, in particular in the form of conductive additive-coated electrode active material particles, for example in the form of conductive additive-coated anode active material particles or in the form of conductive additive-coated cathode active material particles, for example in the form of carbon-coated electrode active material particles, for example in the form of carbon-coated anode active material particles or in the form of carbon-coated cathode active material particles, for example in the form of particles of carbon-coated metal phosphate, in particular having an average particle diameter of less than 10 μm, for example less than or equal to 8 μm or less than or equal to 6 μm, for example less than or equal to 4 μm or less than or equal to 2 μm or less than or equal to 1 μm. This type of compound can be processed into a conductive additive, used in part as an active material, and mechanically stable.
In another alternative or additional configuration of this embodiment, the at least one electrode component comprises or is formed from: at least one electrically conductive metal, such as silicon and/or tin and/or another metal and/or alloy, for example in the form of a metal powder.
In a further alternative or additional embodiment, the at least one further electrode component comprises at least one electrode active material, in particular for energy storage, for example for storing lithium. For example, the at least one further electrode component may comprise or be formed from: at least one anode active material and/or cathode active material, such as at least one intercalation material and/or composite material, such as at least one lithium or sodium intercalation and/or composite material.
In one configuration of this embodiment, the at least one further electrode component may comprise or be formed from: intercalated graphite and/or intercalated amorphous carbon, such as hard carbon and/or soft carbon, especially as anode active material. By blending relatively soft intercalated graphite in a low shear mixing procedure and especially not in a high shear mixing procedure, it is advantageously possible to prevent the particle size of the intercalated graphite from drastically reducing and/or severely damaging the intercalated graphite, for example due to slippage thereof, in a high shear mixing procedure, for example by means of a jet mill.
In another alternative or additional configuration of this embodiment, the at least one further electrode component comprises or is formed from: and storing the alloy. In particular, the at least one further electrode component may comprise or be formed from: lithium storage alloys such as silicon and/or tin alloys.
In another alternative or additional configuration of this embodiment, the at least one further electrode component comprises or is formed from: at least one metal oxide and/or metal phosphate. For example, the at least one further electrode component may comprise or be formed from: silicon oxides, particularly for forming or as anode active materials; and/or at least one metal oxide, in particular at least one layered oxide and/or at least one spinel, for example at least one oxide of nickel and/or cobalt and/or manganese, for example an oxide of lithium nickel and/or cobalt and/or manganese; and/or at least one metal phosphate, for example at least one iron and/or manganese and/or cobalt phosphate, for example at least one lithium iron and/or manganese and/or cobalt phosphate based, for example, on the formula: LiMPO4And M ═ Fe, Mn, and/or Co, particularly as a cathode active material.
In principle, the at least one electrode component and/or the at least one further electrode component may comprise or be formed from: spherical and/or non-spherical particles.
Alternatively or in addition to the above measures, a higher mechanical stability and/or a less impaired functionality of the at least one electrode component compared to the at least one further electrode component can be achieved by a corresponding particle shape.
In another alternative or additional embodiment, the at least one electrode component comprises or is formed from spherical particles. For example, the at least one electrode component may comprise or be formed from: stable and/or compact spherical particles. Spherical particles, such as MCMB (mesocarbon microbeads), may have a higher mechanical stability compared to non-spherical particles, such as layered graphite, e.g. intercalated graphite.
In a further alternative or additional embodiment, the at least one further electrode component accordingly comprises non-spherical particles, for example, if non-spherical particles are to be used in the process, in particular on the basis of lower mechanical loads in the low-shear mixing procedure (as already explained).
Alternatively or in addition to the above measures, a higher mechanical stability and/or a less impaired functionality of the at least one electrode component compared to the at least one further electrode component can be achieved by a corresponding particle structure.
Thus, in another alternative or additional embodiment, the at least one electrode component is free of surface-coated particles and/or gradient material particles. For example, the at least one electrode component may be free of particles having a particle core and a particle shell surrounding the particle core (referred to as core-shell particles), and/or free of gradient material particles. This method can be used in particular if the surface-coated particles or the gradient material particles are known to have a relatively low mechanical stability. During the high shear mixing procedure, the surface coating of the particles and/or the gradient material particles may be damaged and/or destroyed. Thus, it may be advantageous to incorporate them by mixing in a low shear mixing procedure.
Thus, in a further alternative or additional embodiment, the at least one further electrode component comprises surface-coated particles, for example particles having a particle core and a particle shell surrounding the particle core (referred to as core-shell particles), and/or gradient material particles.
In a further alternative or additional embodiment, the at least one electrode component is free of electrode active material, in particular for energy storage, for example for the storage of lithium, for example free of anode active material and/or free of cathode active material. As already explained, the functionality of the electrode active material is generally more affected by mechanical loading and/or crushing than the functionality of the conductive additive.
However, as already explained, damage and/or destruction of the surface coating on the particles and/or the gradient material particles and/or the influence on the functionality of the electrode active material can optionally be counteracted by a low average particle size and/or a low average particle length (e.g. a low average fiber length and/or tube length) and/or a low average planar particle size, in particular of less than 10 μm, for example less than or equal to 8 μm, for example less than or equal to 6 μm. Thus, for example, any conductive additive-electrode active material composite (especially in the form of conductive additive coated electrode active material particles), such as carbon-metal phosphate composites (for example in the form of carbon coated metal phosphate particles), having an average particle size of less than 10 μm, for example less than or equal to 6 μm, especially less than or equal to 4 μm or less than or equal to 2 μm or less than or equal to 1 μm, may be mechanically stable in a high shear mixing procedure.
In addition to the influence on the gradient and/or the functionality of the mechanical stability of at least one electrode component relative to at least one other electrode component, which is produced by the average particle diameter and/or the average particle length (for example the average fibre length and/or the tube length) and/or the average plane particle diameter, and/or by the use as a conductivity additive or electrode active material, and/or by the particle shape and/or by the particle configuration, the influence on the gradient and/or the functionality of the mechanical stability of the different electrode components can be difficult, in particular in the case of electrode components having one or more of the same above-mentioned properties, and can for example be determined, in particular only on the basis of a series of experiments: electrode compositions that are graded with respect to each other, and the particular type of high shear mixer to be used, such as a jet mill or other high shear mixer, and mixtures produced under comparable mixing conditions are investigated, for example, by Scanning Electron Microscopy (SEM) and/or cell function testing.
The at least one binder (especially a polymeric binder) may comprise or be formed from: for example at least one lithium ion-conducting or lithium ion-conducting polymer, for example at least one polyalkylene oxide, for example polyethylene oxide (PEO), and/or at least one polyester and/or at least one polyacrylate and/or at least one polymethacrylate, for example polymethyl methacrylate (PMMA), and/or at least one polyacrylonitrile and/or at least one fluorinated and/or non-fluorinated polyolefin, for example polyvinylidene fluoride (PvdF) and/or polytetrafluoroethylene (PTFE, teflon) and/or Polyethylene (PE) and/or polypropylene (PP), and/or copolymers thereof, for example polyethylene oxide-polystyrene copolymer (PEO-PS copolymer) and/or acrylonitrile-butadiene-styrene copolymer (ABS).
In a further alternative or additional embodiment, the at least one binder (in particular the polymeric binder) comprises or is formed by: at least one lithium ion conducting or lithium ion conducting polymer and/or copolymer thereof. Accordingly and advantageously, it is possible to provide not only adhesion, but also lithium ion conductivity within the electrode by means of the at least one binder. For example, the at least one binder (especially a polymeric binder) may comprise or be formed from: at least one polyalkylene oxide, such as polyethylene oxide; and/or at least one polyester and/or at least one polyacrylate and/or at least one polymethacrylate, such as polymethylmethacrylate, and/or at least one polyacrylonitrile; and/or copolymers thereof, such as polyethylene oxide-polystyrene (PEO-PS copolymer) and/or acrylonitrile-butadiene-styrene copolymer (ABS). For example, the at least one binder (especially a polymeric binder) can comprise or be formed from: at least one polyalkylene oxide, especially polyethylene oxide, and/or copolymers thereof.
The at least one binder may be used in an amount to ensure that the at least one binder is capable of adhering equally to all of the particles of the at least one electrode component and the at least one further electrode component. In this case, it is possible to avoid, in particular, completely covering the particle surfaces of the at least one electrode component and the at least one further electrode component. Preferably, only point contacts are formed between the at least one binder and the particles of the at least one electrode component and the at least one further electrode component. In this way, the surface area available for actual storage reactions can be maximized.
In another alternative or additional embodiment, the at least one binder is used in an amount greater than or equal to 0.1 wt% to less than or equal to 10 wt%, for example greater than or equal to 0.2 wt% to less than or equal to 5 wt%, based on the total weight of the electrode components of the electrode. This has proven to be advantageous in order to achieve a uniform attachment of the at least one binder to all particles of the electrode component in the form of point contacts and thus to maximize the surface area available for the actual storage reaction.
In another alternative or additional embodiment, greater than or equal to 0.1 wt% to less than or equal to 50 wt%, such as greater than or equal to 0.1 wt% to less than or equal to 30 wt%, such as greater than or equal to 0.25 wt% to less than or equal to 20 wt%, such as greater than or equal to 0.5 wt% to less than or equal to 15 wt% or less than or equal to 10 wt% or less than or equal to 5 wt% of at least one electrode component is used, based on the total weight of the electrode components of the electrode.
In another alternative or additional embodiment, from greater than or equal to 0.1 wt% to less than or equal to 98 wt%, such as from greater than or equal to 0.1 wt% to less than or equal to 90 wt%, such as from greater than or equal to 0.1 wt% to less than or equal to 80 wt%, based on the total weight of the electrode components of the electrode, of at least one additional electrode component is used.
In this method, for example, the at least one binder (for example if two or more different binders are to be used) and/or the at least one electrode component (if for example two or more electrode components are to be used) can be added in multiple stages during the high shear mixing procedure. For example, in a high shear mixing procedure, in particular in method step a), it is possible to first add the first binder and then to add the one or more further binders and to mix them with the at least one electrode component; and/or the at least one binder is first blended with a first electrode component of the at least one electrode component and then blended with a second electrode component of the at least one electrode component and mixed.
However, in another embodiment, in particular in method step a), a first high shear mixing procedure is used for mixing the at least one first binder with the at least one electrode component to obtain a first mixture comprising the fibrillated binder; and at least one second high shear mixing procedure is used to mix the at least one second binder with the at least one electrode component (which may, for example, be the same or different from the at least one electrode component used in the first mixing procedure) to obtain at least one second mixture comprising the fibrillated binder. This may facilitate binder fibrillation and/or mixing of the binder with the electrode components.
In a further alternative or additional embodiment, in particular in method step a), a first high shear mixing procedure is used for mixing at least one binder, optionally at least one first binder, with the first electrode component of the at least one electrode component to obtain a first mixture comprising a fibrillated binder; and at least one second high shear mixing procedure is used to mix at least one binder (which may, for example, be the same as or different from the at least one binder used in the first mixing procedure; e.g., at least one second binder) with the second electrode component of the at least one electrode component to obtain at least one second mixture comprising the fibrillated binder. This may facilitate mixing of the binder with the electrode components and/or fibrillation of the binder.
In the above embodiments, in particular in method step b), the first mixture comprising the fibrillated binder and the second mixture comprising the fibrillated binder may then be mixed with the at least one further electrode component by a low shear mixing procedure.
In another embodiment, the method is designed for producing an anode. In this case, the at least one further electrode component may comprise or be formed from: in particular at least one anode active material, such as intercalated graphite and/or intercalated amorphous carbon, such as hard carbon and/or soft carbon, and/or a storage alloy, such as a lithium storage alloy, such as a silicon alloy and/or a tin alloy, and/or a metal oxide, in particular a silicon oxide. For example, greater than or equal to 80 wt%, alternatively greater than or equal to 90 wt%, of at least one anode active material can be used based on the total weight of the electrode components of the anode.
In one configuration of this embodiment, from greater than or equal to 5% to less than or equal to 10% by weight of at least one conductive carbon, for example an amorphous conductive carbon, in particular a conductive carbon black, and/or a conductive graphite and/or carbon fibers and/or carbon nanotubes and/or graphene and/or expanded graphite, and/or from greater than or equal to 5% to less than or equal to 10% by weight of at least one conductive metal, based on the total weight of the electrode components of the anode (in particular in the form of at least one electrode component), is used.
In such a case, a first high shear mixing procedure may be used to mix the at least one binder with the at least one conductive carbon (e.g., in the form of conductive carbon black) to obtain a first mixture comprising a fibrillated binder; and a second high shear mixing procedure may be used to mix the at least one binder with the at least one conductive metal to obtain a second mixture comprising a fibrillated binder.
The first mixture comprising the fibrillated binder and the second mixture comprising the fibrillated binder may then be mixed with the at least one anode active substance, such as intercalated graphite and/or intercalated amorphous carbon, such as hard carbon and/or soft carbon, and/or a storage alloy, such as a lithium storage alloy, such as a silicon alloy and/or a tin alloy, and/or a metal oxide, especially a silicon oxide, by a low shear mixing procedure.
In another embodiment, the method is designed for producing a cathode. In this case, the at least one further electrode component may comprise or be formed from: in particular at least one cathode active material, for example at least one metal oxide and/or metal phosphate, for example at least one metal oxide, in particular at least one layered oxide and/or at least one spinel, for example at least one oxide of nickel and/or cobalt and/or manganese, for example lithium nickel and/or cobalt and/or ∑ erOr manganese oxides, and/or at least one metal phosphate, for example at least one iron and/or manganese and/or cobalt phosphate, for example at least one lithium iron and/or manganese and/or cobalt phosphate based, for example, on the following formula: LiMPO4Wherein M ═ Fe, Mn, and/or Co. The at least one additional electrode component, in particular the at least one cathode active material, may be used, for example, in an amount of greater than or equal to 80 weight percent, alternatively greater than or equal to 90 weight percent, based on the total weight of the electrode components of the cathode. Here, the at least one further electrode component, in particular the at least one cathode active material, may have an average particle size, for example a primary particle size, for example in the range of greater than or equal to 10 μm to less than or equal to 20 μm.
Here, the at least one electrode component may be or comprise, for example, at least one conductive carbon, such as conductive graphite and/or conductive carbon black.
In one configuration of this embodiment, greater than or equal to 0.25 wt.% to less than or equal to 20 wt.%, such as greater than or equal to 0.5 wt.% to less than or equal to 10 wt.%, and in particular greater than or equal to 0.5 wt.% to less than or equal to 5 wt.%, of the at least one electrode component, such as at least one conductive carbon, such as conductive graphite and/or conductive carbon black, is used, based on the total weight of the electrode components of the cathode.
In another particular configuration of this embodiment, the at least one further electrode component, in particular the at least one cathode active material, comprises or is formed from: at least one metal oxide, for example at least one layered oxide and/or at least one spinel, for example at least one oxide of nickel and/or cobalt and/or manganese, for example an oxide of lithium nickel and/or cobalt and/or manganese. In this case, the at least one further electrode component, in particular the at least one cathode active material, may also have an average particle size, for example a primary particle size, for example in the range from greater than or equal to 10 μm to less than or equal to 20 μm. The at least one additional electrode component, such as at least one metal oxide, may be used, for example, in an amount of greater than or equal to 50 weight percent, such as greater than or equal to 70 weight percent or greater than or equal to 80 weight percent or greater than or equal to 85 weight percent, alternatively greater than or equal to 90 weight percent, based on the total weight of the electrode components of the cathode.
In another alternative or additional particular configuration of this embodiment, the at least one electrode component comprises or is formed from: at least one conductive additive, for example at least one conductive carbon, for example conductive graphite and/or conductive carbon black, and/or at least one metal phosphate, for example at least one iron and/or manganese and/or cobalt phosphate, for example at least one lithium iron and/or manganese and/or cobalt phosphate based, for example, on the formula: LiMPO4Where M ═ Fe, Mn and/or Co, for example, the average particle diameter, for example, the primary particle diameter, is less than 10 μ M or less than or equal to 8 μ M or less than or equal to 6 μ M, e.g., less than or equal to 4 μm, e.g., less than or equal to 2 μm or less than or equal to 1 μm, and/or at least one conductive additive-cathode active material composite, such as at least one carbon-cathode active material composite, such as at least one carbon-metal phosphate composite, for example in the form of particles of cathode active material coated with a conductive additive (e.g. carbon coated), for example in the form of particles of carbon coated metal phosphate, having an average particle size of less than 10 μm or less than or equal to 8 μm or less than or equal to 6 μm, for example less than or equal to 4 μm or less than or equal to 2 μm or less than or equal to 1 μm.
Based on the total weight of the electrode components of the cathode, it is possible to use, for example, from greater than or equal to 0.1% to less than or equal to 50% by weight, for example from greater than or equal to 0.1% to less than or equal to 30% by weight, in particular from greater than or equal to 0.5% to less than or equal to 15% by weight, of the at least one electrode component, for example at least one conductive additive, for example conductive carbon, for example conductive graphite and/or conductive carbon black, and/or the at least one metal phosphate and/or combinations thereof, in particular the at least one conductive additive-cathode active material composite, for example the at least one carbon-cathode active material composite, for example at least one carbon-metal phosphate composite, for example in the form of conductive additive-coated cathode active material particles, for example in the form of carbon-coated cathode active material particles, for example in the form of carbon-coated metal phosphate particles, for example having an average particle diameter of less than 10 μm or less than or equal to 8 μm or less than or equal to 6 μm, for example less than or equal to 4 μm, in particular less than or equal to 2 μm or less than or equal to 1 μm.
In another embodiment, the at least one binder is mixed with the at least one electrode component in a low shear premixing procedure upstream of the high shear mixing procedure to obtain a premix which is then mixed in the high shear mixing procedure, in particular in process step a), to obtain a mixture comprising the fibrillated binder. The premixing procedure can be carried out in particular in method step a0) upstream of method step a).
In another embodiment, the low-shear mixing procedure and/or the low-shear premixing procedure is carried out by means of a gravimetric mixer and/or a mixer based on the turbulent principle, for example by means of an elongated flow and/or tube widening and/or by means of a kneader and/or an extruder and/or by means of a plow mixer and/or a paddle mixer and/or by means of a drum mixer, or with such an apparatus. Mixing assemblies of this type may advantageously impart low shear loads to the electrode components, for example lower shear loads than jet mills and/or three-roll mills and/or through twin-screw extruders, especially lower shear loads than jet mills. In particular in the case of mixers based on the turbulent principle, it may be advantageous for only low material loads to occur, for example because no internals are required and/or no "contact mixing" is present.
In a further embodiment, for example in process step c) downstream of process step b), the electrode (in particular the anode and/or the cathode) is formed, for example by dry production and/or by coating, for example by dry coating, of the current collector or the carrier substrate, in particular the mixture comprising at least one fibrillated binder, at least one electrode component and at least one further electrode component from process step b). From this mixture, it is possible, for example, to form electrodes having a defined porosity and/or a defined thickness (for example in the form of a film). The current collector may for example be a metal current collector foil or a different kind of current collector, such as expanded metal, mesh, metal braid, metalized fabric and/or a foil perforated or punched or otherwise suitably prepared.
For further technical features and advantages of the method according to the invention, reference is hereby made explicitly to the description relating to the electrode according to the invention and to the battery according to the invention, and also to the figures and the description of the figures.
The invention also provides an electrode (e.g. an anode and/or a cathode) produced by the method of the invention.
The electrodes (e.g. anodes and/or cathodes) produced by the method of the invention can be studied, for example by Scanning Electron Microscopy (SEM), and are, for example, based on the deterioration of the individual components.
For further technical features and advantages of the electrode according to the invention, reference is hereby explicitly made to the description relating to the method according to the invention and to the battery according to the invention, and also to the figures and the description of the figures.
The invention also relates to an electrochemical cell, in particular a battery cell, for example a lithium or sodium cell or a metal-air cell, for example a lithium ion cell and/or a lithium metal cell or a sodium ion cell, in particular a lithium cell, for example a lithium ion cell and/or a lithium metal cell, comprising at least one electrode according to the invention or an electrode produced according to the invention.
For further technical features and advantages of the battery according to the invention, reference is hereby explicitly made to the description relating to the method according to the invention and to the electrode according to the invention, and also to the figures and the description of the figures.
Drawings
Further advantages and advantageous configurations of the inventive subject matter are illustrated by the accompanying drawings and are set forth in the description that follows. Here, it should be kept in mind: the drawings are merely illustrative in nature and are not intended to limit the invention in any manner. In the drawings, there is shown in the drawings,
FIG. 1 shows a schematic flow chart illustrating one embodiment of the production process of the present invention.
Detailed Description
Fig. 1 shows an embodiment of the inventive method for producing an electrode, in particular an anode or a cathode, for an electrochemical cell, in particular for a battery cell, for example a lithium battery.
Fig. 1 shows: optionally, first, in a low-shear premixing procedure, in an optional upstream process step a0), at least one binder B is mixed with at least one electrode component E1 to give a premix B + E1. The at least one binder B may for example comprise at least one lithium ion conducting polymer or lithium ion conducting polymer, such as polyethylene oxide (PEO) and/or polymethyl methacrylate (PMMA), and/or at least one fluorinated and/or non-fluorinated polyolefin, such as polyvinylidene fluoride (PVDF) and/or Polytetrafluoroethylene (PTFE) and/or Polyethylene (PE) and/or polypropylene (PP), and/or copolymers thereof.
Fig. 1 also shows: in the high shear mixing procedure, in process step a), the at least one binder B is optionally mixed with the at least one electrode component E1 in the form of a premix from optional upstream process step a0 to give a mixture fB + E1 comprising fibrillated binder. The high shear rate mixing procedure may be carried out, for example, by a jet mill.
Further, fig. 1 shows: in process step b), at least one further electrode component E2 is admixed to the mixture fB + E1 comprising fibrillated binder from process step a) by a low shear mixing procedure.
In particular, during the high shear mixing procedure, the at least one electrode component E1 may be more mechanically stable than the at least one further electrode component E2, and/or the functionality of the at least one electrode component E1 may be less affected by the high shear mixing procedure and/or the comminution than the functionality of the at least one further electrode component E2.
For example, the at least one electrode component E1 may have an average particle diameter or average particle length or average planar particle diameter of less than 10 μm, for example in the range of greater than or equal to 4 μm to less than or equal to 6 μm. It has been shown that such small sized particles undergo little or no further comminution in a high shear mixing procedure (e.g., in a jet mill), and are therefore mechanically metastable in that procedure. Conversely, the at least one further electrode component E2 may have, for example, a larger average particle size or a larger average particle length or a larger average in-plane particle size of, for example, greater than or equal to 10 μm to less than or equal to 20 μm, and thus may be mechanically sensitive or unstable in a high shear mixing procedure (e.g., in a jet mill) from a comparative point of view.
Alternatively, for example, the at least one electrode component E1 may comprise at least one conductive additive, such as at least one conductive carbon, for example conductive graphite and/or amorphous conductive carbon, for example conductive carbon black, and/or carbon fibers and/or carbon nanotubes and/or graphene and/or expanded graphite, and/or at least one conductive metal; and the at least one further electrode component E2 may comprise at least one electrode active material, for example at least one anode active material or cathode active material, for example at least one intercalation material and/or composite material. The functionality of the conductive additive is significantly less affected by comminution in the high shear mixing procedure than the functionality of the electrode active material (e.g., anode active material or cathode active material, e.g., intercalation material and/or composite material).
Alternatively, the at least one electrode component E1 may, for example, be free of surface-coated particles and/or free of gradient material particles, while the at least one further electrode component E2 may comprise surface-coated particles and/or gradient material particles. In high shear mixing procedures, such as in jet milling, the surface coating of the gradient material particles and/or surface-coated particles may be damaged and/or destroyed and thus their function may be affected.
Furthermore, fig. 1 shows: in process step c), the electrode E is formed from the mixture fB + E1+ E2 from process step b) comprising the at least one fibrillated binder fB, the at least one electrode component E1 and the at least one further electrode component E2, for example by a dry production procedure and/or by coating, for example by dry coating.
Claims (22)
1. A method for producing an electrode (E) for an electrochemical cell, in particular for a battery cell, for example for a lithium battery, in which,
-mixing at least one binder (B) and at least one electrode component (E1) by a high shear mixing procedure to obtain a mixture (fB + E1) comprising a fibrillated binder, and
-admixing at least one further electrode component (E2) to the mixture comprising fibrillated binder (fB + E1) by a low shear mixing procedure.
2. The method of claim 1, wherein, especially in the high shear mixing procedure, the at least one electrode component (E1) is more mechanically stable than the at least one further electrode component (E2); and/or wherein the functionality of the at least one electrode component (E1) is less affected by the high shear mixing procedure and/or comminution than the functionality of the at least one further electrode component (E2).
3. The method according to claim 1 or 2, wherein the at least one electrode component (E1) is used with an average particle size or average particle length or average planar particle size of less than 10 μ ι η, in particular less than or equal to 6 μ ι η.
4. The method according to any one of claims 1 to 3, wherein the at least one electrode component (E1) is used with an average particle size or an average particle length or an average planar particle size in the range of greater than or equal to 0.01 μm to less than or equal to 6 μm, in particular in the range of greater than or equal to 4 μm to less than or equal to 6 μm.
5. The method according to any one of claims 1 to 4, wherein the at least one further electrode component (E2) is used which has a larger average particle size or a larger average particle length or a larger average planar particle size than the at least one electrode component (E1),
in particular, wherein the at least one further electrode component (E2) has an average particle diameter or an average particle length or an average planar particle diameter of greater than or equal to 10 μm or greater than 6 μm is used.
6. The method according to any one of claims 1 to 5, wherein the at least one electrode component (E1) is formed from or comprises: at least one conductive additive, in particular at least one conductive carbon and/or at least one conductive metal.
7. The method according to any one of claims 1 to 6, wherein the at least one electrode component (E1) comprises:
-electrically conductive graphite, and/or
Amorphous conductive carbon in the form of non-porous carbon particles, in particular conductive carbon black, and/or
-carbon fibres, and/or
-carbon nanotubes, and/or
Graphene and/or expanded graphite, and/or
At least one electrically conductive metal, and/or
-at least one conductive additive-electrode active material complex, in particular at least one carbon-metal phosphate complex.
8. The process according to any one of claims 1 to 7, wherein the at least one further electrode component (E2) comprises at least one electrode active material, in particular at least one anode active material or at least one cathode active material, such as at least one intercalation material and/or composite material.
9. The method according to any one of claims 1 to 8, wherein the at least one further electrode component (E2) comprises:
-intercalated graphite and/or insertable and/or intercalatable amorphous carbon, especially hard and/or soft carbon, and/or
At least one storage alloy, and/or
At least one metal oxide and/or metal phosphate, in particular silicon oxide and/or at least one layered oxide and/or at least one spinel and/or at least one metal phosphate.
10. The method according to any one of claims 1 to 9, wherein the at least one electrode component (E1) comprises spherical particles.
11. The method of any one of claims 1 to 10,
wherein the at least one electrode component (E1) is free of electrode active material, in particular free of anode active material or free of cathode active material, and/or free of surface-coated particles and/or free of gradient material particles, and/or
Wherein the at least one further electrode component (E2) comprises surface-coated particles and/or gradient material particles.
12. The method of any one of claims 1 to 11, wherein the high shear rate mixing procedure is performed by a jet mill.
13. The process according to any one of claims 1 to 12, wherein the at least one binder (B) comprises at least one lithium ion conducting polymer or lithium ion conducting polymer and/or copolymer thereof, in particular polyethylene oxide and/or copolymer thereof.
14. The method according to any one of claims 1 to 13, wherein, based on the total weight of the electrode components (E1, E2) of the electrode, use is made of
-from greater than or equal to 0.1% to less than or equal to 10% by weight of said at least one binder (B), and/or
-from greater than or equal to 0.1% to less than or equal to 50% by weight of said at least one electrode component (E1), and/or
-from greater than or equal to 0.1% to less than or equal to 98% by weight of said at least one further electrode component (E2).
15. The method of any one of claims 1 to 14,
-mixing at least one first binder and at least one electrode component by a first high shear mixing procedure to obtain a first mixture comprising a fibrillated binder; and
-mixing at least one second binder and at least one electrode component by at least one second high shear mixing procedure to obtain at least one second mixture comprising a fibrillated binder; and/or
-mixing at least one binder and a first electrode component of the at least one electrode component by a first high shear mixing procedure to obtain a first mixture comprising a fibrillated binder; and
-mixing at least one binder and a second electrode component of the at least one electrode component by at least one second high shear mixing procedure to obtain at least one second mixture comprising a fibrillated binder; and
-mixing the first mixture comprising fibrillated binder and the second mixture comprising fibrillated binder with the at least one further electrode component by the low shear mixing procedure.
16. Process according to any one of claims 1 to 15, wherein the process is designed for producing anodes, wherein the at least one further electrode component (E2) comprises at least one anode active material, in particular intercalated graphite and/or intercalated amorphous carbon, in particular hard carbon and/or soft carbon, and/or a storage alloy and/or a metal oxide, in particular a silicon oxide.
17. The method according to any one of claims 1 to 16, wherein the method is designed for producing a cathode, wherein the at least one further electrode component (E2) comprises at least one cathode active material, in particular at least one metal oxide and/or metal phosphate, in particular at least one layered oxide and/or at least one spinel and/or at least one metal phosphate.
18. The method according to any one of claims 1 to 17, wherein the at least one binder (B) and the at least one electrode component (E1) are mixed in a low shear pre-mixing procedure upstream of the high shear mixing procedure to obtain a pre-mix (B + E1), and then the pre-mix (B + E1) is mixed in the high shear mixing procedure to obtain a mixture (fB + E1) comprising fibrillated binder.
19. The process according to any one of claims 1 to 18, wherein the low-shear mixing procedure and/or the low-shear premixing procedure is carried out by means of a gravimetric mixer and/or by means of a mixer based on the turbulent flow principle and/or by means of a kneader and/or by means of an extruder and/or by means of a coulter mixer and/or a paddle mixer and/or by means of a drum mixer.
20. The method according to any one of claims 1 to 19, wherein electrode (E) is formed from a mixture (fB + E1+ E2) comprising the at least one fibrillated binder, the at least one electrode component (E1) and the at least one further electrode component (E2), in particular by a dry production procedure and/or by coating, for example by dry coating.
21. An electrode, in particular an anode or a cathode, produced by a method according to any one of claims 1 to 20.
22. Electrochemical cell, in particular a battery cell, such as a lithium battery, comprising at least one electrode according to claim 21.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102017213403.8A DE102017213403A1 (en) | 2017-08-02 | 2017-08-02 | Electrode production process by binder fibrillation |
| DE102017213403.8 | 2017-08-02 | ||
| PCT/EP2018/070536 WO2019025336A1 (en) | 2017-08-02 | 2018-07-30 | Method for producing electrodes by means of binder fibrillation |
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| CN111033813A true CN111033813A (en) | 2020-04-17 |
| CN111033813B CN111033813B (en) | 2023-10-24 |
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| EP (1) | EP3642894A1 (en) |
| CN (1) | CN111033813B (en) |
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| DE102020210614A1 (en) | 2020-08-20 | 2022-02-24 | Robert Bosch Gesellschaft mit beschränkter Haftung | Method for producing an electrode of a battery cell, battery cell and use of the same |
| CN112038579A (en) * | 2020-09-28 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Metal lithium composite electrode, preparation method thereof and electrochemical energy storage device |
| CN112420975B (en) * | 2020-10-20 | 2022-02-22 | 浙江南都电源动力股份有限公司 | Production method of electrode plate in battery |
| KR20220065124A (en) * | 2020-11-12 | 2022-05-20 | 에스케이온 주식회사 | Anode active material including core-shell composite and method for manufacturing same |
| DE102022105656A1 (en) | 2022-03-10 | 2023-09-14 | Volkswagen Aktiengesellschaft | Process for the continuous production of a battery electrode |
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| JP2000149954A (en) * | 1998-11-11 | 2000-05-30 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery, and its manufacture |
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| CN106463267A (en) * | 2014-04-18 | 2017-02-22 | 麦斯韦尔技术股份有限公司 | Dry energy storage device electrode and methods of making the same |
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| US4379772A (en) | 1980-10-31 | 1983-04-12 | Diamond Shamrock Corporation | Method for forming an electrode active layer or sheet |
| US4354958A (en) | 1980-10-31 | 1982-10-19 | Diamond Shamrock Corporation | Fibrillated matrix active layer for an electrode |
| US4556618A (en) | 1983-12-01 | 1985-12-03 | Allied Corporation | Battery electrode and method of making |
| US5393617A (en) * | 1993-10-08 | 1995-02-28 | Electro Energy, Inc. | Bipolar electrochmeical battery of stacked wafer cells |
| EP0735093B1 (en) * | 1994-10-19 | 2001-03-21 | Daikin Industries, Ltd. | Binder for cell and composition for electrode and cell prepared therefrom |
| JP2000049055A (en) | 1998-07-27 | 2000-02-18 | Asahi Glass Co Ltd | Electric double layer capacitor and electrode for it |
| WO2005049700A1 (en) | 2003-11-20 | 2005-06-02 | Bayerische Julius-Maximilians- Universität Würzburg | Polymer bonded functional materials |
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2017
- 2017-08-02 DE DE102017213403.8A patent/DE102017213403A1/en active Pending
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2018
- 2018-07-30 EP EP18756376.2A patent/EP3642894A1/en active Pending
- 2018-07-30 CN CN201880050167.5A patent/CN111033813B/en active Active
- 2018-07-30 WO PCT/EP2018/070536 patent/WO2019025336A1/en unknown
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| JP2000149954A (en) * | 1998-11-11 | 2000-05-30 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery, and its manufacture |
| CN1838999A (en) * | 2003-07-09 | 2006-09-27 | 麦斯韦尔技术股份有限公司 | Dry particle based electrochemical apparatus and methods of making same |
| CN106463267A (en) * | 2014-04-18 | 2017-02-22 | 麦斯韦尔技术股份有限公司 | Dry energy storage device electrode and methods of making the same |
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| WO2019025336A1 (en) | 2019-02-07 |
| DE102017213403A1 (en) | 2019-02-07 |
| EP3642894A1 (en) | 2020-04-29 |
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