Lithium ion battery electrode with uniformly dispersed electrode binder and conductive additive
11355744 · 2022-06-07
Assignee
Inventors
- Rajshekar Das Gupta (Toronto, CA)
- Elmira Memarzadeh (Mississauga, CA)
- Sankar Das Gupta (Mississauga, CA)
- Bjorn Haugseter (Skien, NO)
- Tom Henriksen (Skien, NO)
- Lars Ole Valøen (Porsgrunn, NO)
- Akhilesh Kumar Srivastava (Skien, NO)
Cpc classification
H01M4/62
ELECTRICITY
H01M4/5825
ELECTRICITY
H01M4/136
ELECTRICITY
H01M4/485
ELECTRICITY
Y02P70/50
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
Y10T29/49115
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
H01M4/525
ELECTRICITY
H01M4/0471
ELECTRICITY
H01M4/505
ELECTRICITY
H01M4/131
ELECTRICITY
Y02E60/10
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
H01M4/1391
ELECTRICITY
H01M2004/021
ELECTRICITY
H01M10/0525
ELECTRICITY
International classification
H01M4/36
ELECTRICITY
H01M4/485
ELECTRICITY
H01M4/1391
ELECTRICITY
H01M4/62
ELECTRICITY
H01M10/0525
ELECTRICITY
H01M4/58
ELECTRICITY
H01M4/525
ELECTRICITY
H01M4/131
ELECTRICITY
H01M4/136
ELECTRICITY
Abstract
The present disclosure relates generally to an electrode produced with a non-toxic solvent, resulting in a homogeneous mixture with uniform distributions of a conductive additive and a binder. Electrodes produced according to the present disclosure feature narrow binder particle size distribution, which distinguishes such electrodes from typical electrodes produced via a N-Methyl-Pyrrolidone (NMP) process. The resulting microstructure promotes the flow of current through the electrode and has an improved cycling stability due, in part, to the binder's and the conductive additive's ability to bind with the active material particles used in the fabrication of the electrode.
Claims
1. A positive electrode for a secondary battery, comprising: a current collector having at least one lateral surface, wherein the at least one lateral surface is coated with an electrode slurry to form a coating, wherein the coating comprises: a positive active material; substantially uniformly dispersed particles of conductive additive, wherein the conductive additive comprises carbon; and substantially uniformly dispersed particles of polyvinylidene fluoride (PVDF) binder; wherein the dispersed particles of PVDF binder have a particle size of between 150 and 450 nanometers; wherein the thickness of the coating on the at least one lateral surface of the current collector is between 425 and 500 microns; and wherein there is an average distance of 500 nm or less between adjacent dispersed particles of conductive additive.
2. The positive electrode of claim 1, wherein the current collector comprises a second lateral surface, wherein the second lateral surface is coated with the electrode slurry to form a second coating, wherein the thickness of the second coating on the second lateral surface is between 100 and 500 microns such that the combined thickness of the coatings on the at least one and the second lateral surfaces is between 625 and 1000 microns.
3. The positive electrode of claim 2, wherein the combined thickness of the coatings on the at least one and the second lateral surfaces is between 850 and 1000 microns.
4. The positive electrode of claim 1, wherein the dispersed particles of polyvinylidene fluoride binder comprise 1 to 10 percent by weight of the positive electrode.
5. The positive electrode of claim 4, wherein the dispersed particles of polyvinylidene fluoride binder comprise 2 to 5 percent by weight of the positive electrode.
6. The positive electrode of claim 1, wherein the dispersed particles of conductive additive comprise 1 to 10 percent by weight of the positive electrode.
7. The positive electrode of claim 6, wherein the dispersed particles of conductive additive comprise 3 to 5 percent by weight of the positive electrode.
8. The positive electrode of claim 1, wherein the average particle size of the dispersed particles of polyvinylidene fluoride binder is between 150 and 450 nm.
9. The positive electrode of claim 8, wherein the average particle size of the dispersed particles of polyvinylidene fluoride binder is between 200 and 300 nm.
10. The positive electrode of claim 1, wherein there is an average distance of 300 nm or less between adjacent dispersed particles of conductive additive.
11. The positive electrode of claim 10, wherein there is an average distance of 200 nm or less between adjacent dispersed particles of conductive additive.
12. The positive electrode of claim 1, wherein there is an average distance of 500 nm or less between adjacent dispersed particles of polyvinylidene fluoride binder.
13. The positive electrode of claim 12, wherein there is an average distance of 300 nm or less between adjacent dispersed particles of polyvinylidene fluoride binder.
14. The positive electrode of claim 13, wherein there is an average distance of 200 nm or less between adjacent dispersed particles of polyvinylidene fluoride binder.
15. The positive electrode of claim 1, wherein the positive active material comprises lithium, manganese, nickel, cobalt, aluminum, or a combination thereof.
16. The positive electrode of claim 15, wherein the positive active material is selected from a group consisting of: LiCoO.sub.2, LiFePO.sub.4, LiMn.sub.2O.sub.4, LiNiO.sub.2, Li.sub.2FePO.sub.4F, LiCo.sub.1/3Ni.sub.1/3Mn.sub.1/3O.sub.2, and Li(Li.sub.aNi.sub.xMn.sub.yCo.sub.z).
17. The positive electrode of claim 1, wherein the conductive additive is selected from the group consisting of carbon black, acetylene black, and graphite, or combinations thereof.
18. The positive electrode of claim 1, wherein the positive active material is adhered strongly to the current collector.
Description
SHORT DESCRIPTION OF THE DRAWINGS
(1) The following is a brief description of the figures in the accompanying drawings. The figures are not necessarily to scale, and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in interest of clarity or conciseness.
(2) The available invention will be more easy to understand with support of the belonging figures, where
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(26) The foregoing summary, as well as the following detailed description of certain inventive techniques, will be better understood when read in conjunction with the figures. It should be understood that the claims are not limited to the arrangements and instrumentality shown in the figures. Furthermore, the appearance shown in the figures is one of many ornamental appearances that can be employed to achieve the stated functions of the apparatus.
DETAILED DESCRIPTION OF THE INVENTION
(27) In the following detailed description, numerous specific details may be set forth in order to provide a thorough understanding of embodiments of the present invention. However, it will be clear to one skilled in the art when embodiments of the present invention may be practiced without some or all of these specific details. In other instances, well-known features or processes may not be described in detail so as not to unnecessarily obscure the invention. In addition, like or identical reference numerals may be used to identify common or similar elements.
(28) One or more specific embodiments of the present disclosure will be described below. In an effort to provide a concise description of these embodiments, all features of an actual implementation may not be described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.
(29) When introducing elements of various embodiments of the present disclosure, the articles “a,” “an,” “the,” and “said” are intended to mean that there are one or more of the elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.
(30) In the following text, the available invention will be described with support from the belonging figure.
(31) It shall be understood that according to the invention, the foil that normally is used as cathodes and anodes also may comprise materials similar to fabrics or more generally, any conductive conductor which is compatible with the methods according to the available invention.
(32) First, there will be a description of a general implementation of the invention, followed by examples of the methods that will be shown.
(33) As indicated introductorily there exists a desire to change the process of manufacturing the slurry for coating of battery electrodes for lithium batteries.
(34) Lithium ion batteries normally consist of three active elements, namely anode, cathode plus an electrolyte. As indicated above, it is the purpose of the available invention to find an alternative to the disadvantageous use of solvents for coating of the electrode foils.
(35) The slurry that is applied to the electrode foils must have the correct body and viscosity so that the active layer that is applied to the electrodes will have a correct dry film thickness and homogeneity.
(36) In order to be able to form a paste or thinly liquid slurry from binder, such as PVDF and powder in the form of active materials, the mixture has to be added a liquid. By using a liquid which is entered as a component in the finished battery it is not necessary that the liquid is removed completely. This component will still be added at a later stage in the process. According to the execution of the available invention, a method for manufacturing of the slurry for coating of battery electrodes is provided, where the slurry, meaning active components and a binder will be diluted with a diluting agent, where the diluting agent is a component of the electrolyte which shall be used in the same lithium battery.
(37) In general the process for manufacturing of slurry according to the available patent can be described with support from
(38) After the homogenization step the slurry has obtained the desired body/viscosity and the electrode material D can be coated 2 with the slurry. The coating process may be in the form of extruding, rolling or tape casting, or other suitable coating processes known from the industry.
(39) Step 3 in the process comprises evaporation of the thinner which was added to the homogenization process 1. The applied slurry will consequently change from being viscous slurry to become a more solid material.
(40) In parallel with step 3 there may be an active recycling step 4 which recycles the thinner that evaporates.
(41) The following step 5 that is the step following step 3 and 4 is a step where the electrode material with the applied coating is rolled.
(42) The following step 6 comprises baking of the rolled electrode, this baking will among other things secure that the binder adheres sufficiently to the active electrode materials and to the electrode foil.
(43) The final step 7 comprises further finishing of the lithium ion batteries.
(44) It shall be understood that manufacturing according to the steps 1 to 7 may be run consecutively and continuously, so that when step 1 is finished and a batch from step 1 moves onto step 2, then new materials can be added a homogenization of step 1, same is valid for the 10 following steps, so that a manufacturing process can run continuously.
(45) Implementation According to the Available Invention
(46) In the following the available invention will be described with an example.
(47) In this example in accordance with the available invention, the materials that will be used in the manufacturing of a lithium ion battery cell will comprise the following.
(48) The anode, that is the positive electrode, consists of a copper foil; this copper foil shall be coated with an active material, generally in the form of a graffiti powder (LiC.sub.6). Also other active materials such as titanat (Li.sub.4Ti.sub.5O.sub.12), Si(Li.sub.4,4Si) or Ge(Li.sub.4,4Ge) can be used as active anode material. The graffiti powder shall be applied to the copper foil, in order for such a 20 coating process to be successful and give a homogeneous surface then the graffiti powder must be mixed with 1 PVDF, PVDF and the graffiti powder must consequently be given a viscosity which is suitable for coating and thus the mixture will be added an organic carbonate, such as ethylene carbonate (EC) C. This blending step corresponds to the homogenization step 1 according to the general process description. The mixture may be heated to a temperature above the melting point of the thinner, i.e. the ingredient that was blended in order to give the right viscosity. The temperature may well be above the melting point of the thinner and close to the transition temperature of the binder.
(49) The cathode, i.e. the negative electrode consists of an aluminum foil this aluminum foil shall be coated by an active material in the form of a lithium metal oxide. The lithium metal oxide 30 shall be coated on the copper foil, so that such a coating process shall be successful and give a homogeneous surface then the lithium metal oxide A must be mixed with 1 PVDF, PVDF and lithium metal oxide must consequently be given a viscosity suitable for coating therefore the mixture will be added ethylene carbonate (EC) C. This step of the mixing corresponds with the homogenization step 1 according to the general process description.
(50) The following steps for cathode and anode follow roughly the same process as described in
(51) Another Performance Specification According to the Available Invention
(52) In the following the available invention will be described with another example.
(53) In this example in accordance with the performance specification of the available invention the material used during the manufacturing of a lithium ion battery cell comprises the following.
(54) The anode, that is the positive electrode consists of a copper foil, this copper foil shall typically be coated by an active material in the form of a graffiti powder, thus the process for the anode is according to the description above.
(55) The cathode that is the negative electrode consists of an aluminum foil this aluminum foil shall be coated by an active material in the form of a metal oxide such like one of Lithium cobalt oxide (LiCoO.sub.2), a polyanion such like Lithium iron phosphate (LiFePO.sub.4) or a lithium manganese oxide (LiMn.sub.2O.sub.4). Further cathode materials are found in the not supplementary group, LiNiO.sub.2, Li.sub.2FePO.sub.4F, LiCo.sub.1/3Ni.sub.1/3Mn.sub.1/3O.sub.2Li(Li.sub.aNi.sub.xMn.sub.yCo.sub.z)O.sub.2. For simplicity the term metal oxide will be used in the following for these mentioned phosphates/oxides.
(56) The metal oxide shall be coated on the copper foil, in order for such a coating process shall be successful and give a homogeneous surface, the metal oxide A must be mixed 1 with a binder B, for instance PVDF and the metal oxide must in addition be given a viscosity suitable for coating therefore the mixture is added an organic carbonate such as ethylene carbonate (EC) C or diethyl carbonate. This mixing step corresponds to the homogenization step 1 according to the general process description.
(57) The following steps for cathode and anode will roughly follow the same process as described in
(58) It shall be understood that a number of binders and active raw materials can be combined, where the central issue is that the thinner shall be a component in the final battery.
(59) In the following is a description of the electrolyte and the properties associated with the materials composing the parts of the electrolyte. The electrolyte in a normal battery normally consists of organic carbonates such as EC (ethylene carbonate), diethyl carbonate. EC which is the most common is a waxy material which melts at approximately 40° C. and is then a liquid with low viscosity. EC is not poisonous; it is without smell and is only flammable at higher temperatures (above 140° C.).
(60) According to an aspect of the invention the desired viscosity of this slurry may be generated by mixing the binder B (such as PVDF), the powder A (active, materials) and molten EC C. The amount of EC is adjusted according to the desired viscosity of the mixture.
(61) This mixture is homogenized vigorously at a temperature above the melting point of EC and below the melting point of the binder (for example at approx. 180° C. for PVDF). The particles with the binder will then because of the vigorous mixture be dispersed between all the particles in the mixture. If the homogenization takes place at a temperature above the melting temperature of the binder B, the mixture will obtain a lower viscosity.
(62) When the mixture is homogenized sufficiently so that the binder particles B are dispersed evenly between all the particles in the mixture, the metal foil D can be coated with the mixture. This may be done by extrusion, rolling or tape-casting. The battery film will then have to be heated in order to evaporate the EC till the EC concentration is equal to or less than the desired EC concentration of the finished battery cell.
(63) The consequent rolling of the battery film will press the particles together and will improve the binding between the particles.
(64) The EC-vapor which is formed by drying of the battery film can be condensed, filtered and reused in the process. EC is a harmless liquid with few health and environmental impacts.
(65) A: Active materials, such as graffiti and lithium oxide
(66) B: Binder, for example PVDF
(67) C: Thinner according to the available invention, an electrolyte component such as organic carbonates
(68) D: Leading foil, such as aluminum foil, copper foil, aluminum canvas and copper canvas among others
(69) 1: Homogenization
(70) 2: Coating, for instance by extruding, tape-casting, rolling or similar
(71) 3: Evaporation of solvents
(72) 4: Recycling of solvents
(73) 5: Rolling
(74) 6: Baking, to melt the binder
(75) 7: Further processing to build up the battery
(76) In certain embodiments of the present disclosure, an electrode comprises an active material in which a conductive additive and a binder are homogeneously dispersed. Although the present disclosure focuses primarily on a positive electrode (a cathode), the inventors envisage that certain embodiments may be produced as a negative electrode (an anode).
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(78) According to the present disclosure, the electrode slurry coating, including the active material, is adhered strongly to the current collector. In coatings that are not adhered strongly, there is often a depletion of binder near the current collector. In embodiments according to the present disclosure, binder remains dispersed and present near to the current collector. In conventional electrodes, the thickness of the electrode is often limited by a few factors, including that if the electrode is too thick, the active material will not adhere to the current collector. According to the present disclosure, the strong adhesion of the active material to the current collector allows for the electrode to be produced as a thicker electrode. The electrode may be produced by extrusion. The electrode may be extruded to be thick or thin. According to certain aspects of the present disclosure, the positive electrode may have a thickness of between 10 and 500 microns, or between 40 and 300 microns, or approximately 200 microns. The positive electrode may comprise a current collector having at least one lateral surface that has been coated with an electrode slurry. Thicker electrodes produced according to the present disclosure may have a coating on the at least one lateral surface of the electrode having a thickness of between 50 and 500 microns. The current collector may comprise a second lateral surface, wherein the second lateral surface may be coated with the electrode slurry. The coating on the second lateral surface of the positive electrode may have a thickness of between 50 and 500 microns, such that the combined thickness of the coatings on the at least one and the second lateral surfaces is between 100 and 1000 microns. In certain embodiments, the combined thickness of the coatings on the at least one and the second lateral surfaces may be between 200 and 600 microns, or approximately 300 microns.
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(91) Particle size distribution increases, and uniformity of dispersion decreases as one moves from cathodes according to the present disclosure, to typical supplier cathodes, to typical NMP cathodes. These characteristics suggest a more uniform and homogeneous binder distribution through the thickness of a cathode prepared according to the present disclosure despite the relatively high thickness of the cathode.
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(97) While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims.