• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention relates to a method and a device for applying magnetic fields to an object, which is in particular a layer or a layer-coated object, and more particularly to a coating comprising graphite particles, preferably for producing a negative electrode with oriented graphite particles. For example, for fast-charging lithium-ion batteries. The application of the magnetic fields should in particular be continuous. For this purpose, a Halbach arrays with permanent magnets (011) is used to apply magnetic fields, wherein the object is moved relative to the Halbach array. The application of the magnetic field takes place in particular before the initiation of a drying phase and / or during the drying phase.
    公开号:CH712912A2
    申请号:CH00165/17
    申请日:2017-02-13
    公开日:2018-03-15
    发明作者:Ebner Martin；Geldmacher Felix；Kory Max
    申请人:Battrion Ag；
    IPC主号:
    专利说明:

    Description: The invention relates to a method for applying magnetic fields to an object, the magnetic fields being applied in particular continuously and in particular to a graphite coating, and further in particular for producing an object in the form of a negative electrode with vertically oriented graphite particles for Example of fast-charging lithium-ion batteries. It further relates to a negative electrode with vertically aligned graphite particles produced by the method according to the invention.
    Carbon-based materials, in particular crystalline graphite, are used as active material in negative battery electrodes. Graphite has a layer-like structure consisting of individual carbon layers intercalated between the lithium ions, for example in a lithium-ion battery, when charging. The layer structure of graphite is reflected by its occurrence in flake form.
    When using flake-shaped graphite as an active material in an electrode, the flake-shaped graphite particles lie parallel (horizontally) to an underlying current collector foil. This leads to confused pore passages through the electrode. The lithium ions that diffuse from the positive electrode into the negative and vice versa must pass through this confused pore path. Particularly in the case of high charging rates, the lithium ions cannot move through the pore passages sufficiently quickly, which can lead to a reduction in the usable storage capacity. By aligning the graphite particles, the path lengths covered by the lithium ions during charging and discharging can be shortened and the charging and discharging properties of an electrochemical storage device can be improved.
    For the industrial production of negative graphite electrodes, the flake-shaped graphite is often rounded off. However, up to 70% of the original material is lost in the mechanical rounding process.
    The application of a magnetic field to an object is known. A Halbach array is a special configuration of permanent magnets. Such a configuration enables the magnetic flux on one side of the configuration to be almost canceled out, but strengthened on the other side, also known as “one-sided flux”. Another property of such a configuration is that the direction of the magnetic flux on the surface of the configuration changes depending on the location - the direction of the magnetic field rotates locally.
    EP 2 793 300 A1 discloses an application for the production of electrodes, magnetic nanoparticles being applied to electrochemically active particles, which in turn are applied to a substrate as a slurry ("suspension" or "paste") and then a magnetic field is applied the particle is applied. This suspension then has to be solidified, for example by drying. The addition of magnetic nanoparticles in the manufacture of the graphite paste can complicate the process. The addition of magnetic nanoparticles can also lead to undesired electrochemical processes, which can have an adverse effect on the end product. A method for continuously applying magnetic fields is not disclosed.
    The patent US 7 326 497 B2 describes a negative electrode and its manufacture for use in a rechargeable lithium-ion battery. A method is disclosed in which the graphite coating is aligned between two magnets in a magnetic field with a flux density greater than 0.5 T. To achieve good vertical alignments, flux densities of over 1 T or even 2.3 T are suggested. Flux densities in this area are technically difficult to implement, for example, superconducting magnets are required for such a high flux density.
    [0006] Another patent US Pat. No. 7,976,984 B2 describes a rechargeable battery in which mechanically rounded graphite particles are aligned in a magnetic field.
    By aligning the rounded graphite particles in a magnetic field, the path length of the lithium ions can be slightly shortened and thereby the charging and discharging properties can be improved, this improving effect being further enhanced by the use of flake-shaped graphite. However, as mentioned above, up to 70% of the original material is lost in the rounding process.
    The invention is therefore based on the object of a method for applying magnetic fields, in particular for the continuous application of magnetic fields to an object, which is in particular a layer or an object coated with a layer, and further in particular to a graphite coating for the production to develop an object in the form of a negative electrode.
    The object is achieved with the features of claim 1.
    The object, which can also be just one layer, can consist of, for example, graphite, a binder and a volatile solvent by drying, the method at least one quasi-continuous application, in particular during a manufacturing and / or processing method of negative electrodes for for example, enables fast-charging lithium-ion batteries and, due to the special magnetic field configuration, can vertically align diamagnetic graphite particles without the addition of magnetic nanoparticles with effective flux densities of less than 0.5 T.
    Continuously is defined in the sense of "in a continuous manufacturing process" such as "roll-to-roll processing" and not as "constant".
    CH 712 912 A2 According to the invention, a magnetic field is applied directly to the object by means of a Halbach array, in particular a graphite coating consisting of graphite particles, a binder and the solvent which is volatile during drying, with a preferably flat or cuboid configuration, the graphite coating being relative to a Halbach array (tool) is moved.
    [0012] There is a demand for technologies which enable rapid charging of electrochemical stores. The prior art already discloses the advantage of vertically aligned graphite particles in the negative electrode of battery electrodes. However, there is a lack of simple production or processing methods which make it possible to continuously apply magnetic fields during the production or processing method of graphite coatings which contain flake-shaped graphite.
    The method according to the invention enables magnetic fields to act on graphite coatings to align flaky graphite particles contained therein in a manner suitable for industrial production.
    [0013] Graphite is diamagnetic and has a diamagnetic anisotropy. This means that with a magnetic field acting perpendicular to the (002) plane of the graphite, the diamagnetic susceptibility is approximately 40-50 times as large as in the case of a magnetic field acting perpendicular to the (110) plane.
    Consequently, the energy stabilization of the graphite in the magnetic field leads to the (002) plane of the graphite being aligned parallel to the magnetic field. The method is based on a number of permanent magnets which are arranged in a special order. The permanent magnets can be arranged both planar and cylindrical. The relative movement of the graphite coating relative to the magnet arrangement described leads to the diamagnetic graphite particles being exposed to a rotating magnetic field which vertically aligns the diamagnetic graphite particles contained in the coating.
    The subsequent immobilization of the aligned graphite particles can take place, for example, by drying. Drying is characterized in that a solvent contained in the graphite coating leaves the graphite coating, which leads to the immobilization of the vertically aligned graphite particles.
    Drying can be both passive, e.g. due to the ambient temperature, i.e. not supported, as well as active, i.e. through targeted drying with, for example, a blower.
    The aim of the method according to the invention is to enable continuous application of magnetic fields, for example for producing negative electrodes with vertically oriented graphite particles by influencing the components of the graphite coating.
    The technical benefit lies in the possibility of having magnetic fields of a magnet packet or a magnetic roller act on, for example, a graphite coating consisting of diamagnetic graphite particles. As part of a continuous manufacturing process, the magnet package or the magnetic roller can change the properties, for example a graphite coating, in the manufacture of electrodes, for example for use in lithium-ion batteries.
    Preferred embodiments of the method according to the invention are disclosed in the dependent claims.
    The invention is described below in an embodiment with reference to a drawing. In the drawing they show
    1: a Halbach array with rigid, planar permanent magnets; (010)
    2: a Halbach array which is designed as a rotatable roller core;
    3: a scanning electron microscope image of a graphite coating in cross section;
    4: a histogram for the orientation of graphite particles;
    5: another scanning electron microscope image of the graphite coating. FIG. 6: another histogram for the orientation of graphite particles.
    97 g of flaky graphite is kneaded with 25 g of a carboxymethyl cellulose (CMC) solution (2 wt%) and 41 g of deionized water for 1 h and then with a further 25 g of the CMC solution (2 wt%) and 30 g of de-ionized water diluted with stirring.
    5 g of an SBR latex (40 wt%) are then added to this mixture and the mixture is stirred for 2 min.
    The graphite paste obtained is then applied with a doctor blade to an object 011, a copper foil (thickness of the copper foil 15 μm), which was previously clamped in a circle between two rubber rollers, not shown.
    Then the two rubber rollers are brought into rotation by means of an electric motor, so that the copper foil with the coating thereon is in the example at a speed of 3 m / min
    CH 712 912 A2 moved in a circle. A magnetic insert in the form of a rigid, planar magnetic insert 010 (FIG. 1), consisting of Halbach arrays, is then placed under the moving copper foil.
    The planar Halbach arrays with permanent magnets 010 act on the moving object 011.
    The copper foil with the coating 011 is moved past the magnetic insert, respectively. there is a relative movement between the magnetic insert and the copper foil. The distance to the copper foil is 3 mm in the example and the effective flux density determined with a Gauss meter is 0.35 T. The effective flux density corresponds to the flux density actually measured at the location of the graphite coating.
    After 3 minutes, warm air is blown onto the moving copper foil, including the liquid graphite coating, with heating guns, and in this way the graphite coating is dried. The solvent is removed and the vertically aligned graphite particles are immobilized.
    It is essential to apply the magnetic field before (and during) the active drying phase.
    A rotating magnetic field for the graphite particles can alternatively also result from the fact that the graphite particles of an object 022 move relative to a rotatable, Halbach array 021 on a roller core 020, as shown in FIG. 2. A Halbach array is designed as a rotatable roller core (021) which can move around a fixed center (020) and past which an object (022) to be coated is moved.
    3 shows a scanning electrode microscope image of a cross section of a graphite coating with flaky graphite, which was obtained without the action of a magnetic field. The flaky graphite particles lie parallel to the underlying current collector foil.
    4 shows a histogram of the orientation of the graphite particles in a graphite coating which was obtained without the action of a magnetic field.
    6 shows a histogram of the orientation of the graphite particles in a graphite coating, which was obtained by the method described in the example in a magnetic field.
    The flake-shaped graphite particles are mostly vertical (at a 90 ° angle) to the underlying current collector foil. A scanning electrode microscope analysis of a cross section of the graphite coating obtained in the example shows the vertical alignment of the flake-shaped graphite particles (FIG. 5). 5 shows a scanning electrode microscope image of a cross section of an aligned graphite coating with flake-like graphite, which was obtained in a magnetic field by the method described in the example.
    The flake-shaped graphite particles are mostly vertical (at a 90 ° angle) to the underlying current collector foil.
    Analysis of the coating by means of an X-ray diffraction device (Riagaku SmartLab) shows a significantly increased amount of graphite particles whose (110) plane is vertical, i.e. 90 ° to the copper foil, compared to a graphite coating that is not exposed to a rotating magnetic field (FIGS. 3 and 4).
    The graphite coating obtained according to the invention with the vertically aligned flaky particles contained therein is then calendered to a porosity of 30%.
    A further, subsequent analysis of the compressed graphite coating by means of an X-ray diffraction device (Riagaku SmartLab) showed a further significantly increased intensity for graphite particles, the (110) plane of which is oriented vertically to the copper foil.
    List of terms [0026]
    010 Halbach array with permanent magnets
    011 moving object on which the magnetic field acts
    020 fixed center around which a rotatable roller core moves
    021 Rotatable Halbach array with permanent magnets
    022 moving object on which the magnetic field acts
    权利要求:
    Claims (13)
    [1]
    claims
    1. A method for application, in particular for continuous application, of magnetic fields to an object, which is in particular a layer or an object coated with a layer, in particular during manufacture and / or processing of the object (011, 022), permanent magnets in Arrangement of a Halbach array (010, 021) can be used for the application of magnetic fields, characterized in that the object (011, 022) is moved relative to the magnets for the application of at least one magnetic field.
    [2]
    2. The method according to claim 1, characterized in that the layer or coating contains particles, in particular magnetically influenceable particles.
    CH 712 912 A2
    [3]
    3. The method according to claim 1 or 2, characterized in that the layer or coating contains carbon, in particular crystalline carbon, preferably graphite, and particularly preferably graphite particles.
    [4]
    4. The method according to claim 1, characterized in that the object is exposed to a rotating magnetic field, in particular a temporally and / or locally rotating magnetic field.
    [5]
    5. The method according to claim 1 to 4, characterized in that the flux density of the magnetic field acting on the object is less than 0.5 T.
    [6]
    6. The method according to any one of claims 1 to 4, characterized in that the flux density of the magnetic field acting on the object is less than 0.45 T.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the mobility of the particles, in particular graphite particles, of the coating is actively changed, in particular reduced, during and / or after application of the magnetic field, in particular by volatilization of a component of the coating, especially by drying the coating.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the application of the magnetic field takes place before and / or during an active drying of the coating.
    [9]
    9. Device for application, in particular for continuous application, of magnetic fields to an object, which is in particular a layer or an object coated with a layer, in particular during manufacture and / or processing of the object (011, 022), permanent magnets in Arrangement of a Halbach array (010, 021) can be used to apply the magnetic fields, characterized in that the object (011,022) can be moved relative to the Halbach array (010, 021).
    [10]
    Device according to claim 9, characterized in that the object (011.022) is exposed to a rotating magnetic field, in particular a temporally and / or locally rotating magnetic field, due to the relative movement to the magnetic field of a magnetic roller core (021) or a magnet package (010).
    [11]
    11. The device according to claim 10, characterized in that it has a Halbach array in the form of a rotatable magnetic roll core (021) or a planar magnet package (020).
    [12]
    12. Object, in particular an electrode, and in particular an electrode coated with particles, preferably a negative electrode coated with graphite particles, characterized in that it is produced according to one of claims 1 to 9.
    [13]
    13. Object according to claim 12, characterized in that at least one magnetic field is applied to it and that the object is a negative electrode.
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    法律状态:
    优先权:
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