US20220320520A1 - Devices and methods for preparing a slurry and coating a substrate with a slurry - Google Patents
Devices and methods for preparing a slurry and coating a substrate with a slurry Download PDFInfo
- Publication number
- US20220320520A1 US20220320520A1 US17/843,055 US202217843055A US2022320520A1 US 20220320520 A1 US20220320520 A1 US 20220320520A1 US 202217843055 A US202217843055 A US 202217843055A US 2022320520 A1 US2022320520 A1 US 2022320520A1
- Authority
- US
- United States
- Prior art keywords
- slurry
- powder
- substrate
- cylinder
- passage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 239000000758 substrate Substances 0.000 title claims abstract description 102
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- 239000002904 solvent Substances 0.000 claims abstract description 61
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
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- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 description 1
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- 239000001814 pectin Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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- 229920000765 poly(2-oxazolines) Polymers 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
- B01F25/4521—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through orifices in elements, e.g. flat plates or cylinders, which obstruct the whole diameter of the tube
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- B01F31/65—Mixers with shaking, oscillating, or vibrating mechanisms the materials to be mixed being directly submitted to a pulsating movement, e.g. by means of an oscillating piston or air column
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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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
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/50—Mixing mined ingredients and liquid to obtain slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
- B01F23/565—Mixing liquids with solids by introducing liquids in solid material, e.g. to obtain slurries
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure is directed to devices and methods for preparing a slurry and coating the slurry onto a substrate.
- Forming slurries containing powders and optionally binders dispersed within a solvent often involves considerable energy and equipment. Such is the case when forming slurries for the manufacture of substrates used in forming electrodes for batteries.
- viscous slurries containing powders, like carbon black powder or other active/non-active materials, and organic polymers as binders are coated onto substrates to form current collectors by drawing or delivering either the slurries or the substrates via various methods, such as doctor blades, roll-to-roll coaters, etc.
- Conventional devices used in wet coating require a large amount of space because of the required use of the doctor blades, the roll-to-roll coaters, etc. All of the devices and workstations related to the conventional mixing, kneading, coating, and drying are massive.
- Dry coating processes are an alternative to wet coating for the manufacture of electrodes.
- dry coating has several drawbacks. For example, it is necessary to pulverize dried carbon composite powder into fine powder for coating, which requires two machines to pulverize and distribute the fine powder onto the substrate. Specific hoppers and complex arrangements of coaters also are required to disperse the fine powder onto the substrate.
- Dry coating also suffers from inconsistent results of battery performance based on the irregular distribution of the fine powder on the substrate.
- the resultant unevenness of powder density on the substrate has a direct effect on many issues, like the adhesive force between the coating and the substrate and the porosity uniformity, which eventually leads to lack of reaction uniformity.
- An aspect of the present disclosure includes a process of coating a substrate with a slurry for forming an electrode.
- the slurry contains a powder.
- the powder can be formed of carbon black powder, or any conductive/non-conductive material or blends thereof.
- the slurry further contains one or more solvents and binders.
- the slurry can optionally include one or more dispersion agents.
- the process further includes freeze drying the coated substrate and heating the freeze-dried coated substrate under a vacuum at elevated temperatures to remove residual solvents.
- the process further includes calendering the resulting coated substrate to be used as battery electrodes.
- a further aspect of the disclosure is a device configured to mix and knead a slurry, and then coat the slurry simultaneously on both sides of a substrate.
- the device includes two cylinders connected via a narrow tube, with a piston in each cylinder configured to repeatedly force the slurry back and forth between the cylinders and through the tube. The repeated movement of the slurry through the tube applies a shearing force to the slurry, which mixes and kneads the slurry.
- the device includes a die configured to extrude the slurry onto the substrate so that the slurry contacts both surfaces of the substrate simultaneously.
- Another aspect of the present disclosure includes a method of coating a substrate including providing a slurry in a closed volume with at least one passage.
- the slurry includes a solvent, a powder, a binder, and a dispersion agent.
- the method further includes forcing the slurry repeatedly under high pressure through the at least one passage in a first flow direction and then back through the at least one passage in a second flow direction, opposite the first flow direction, to homogenously disperse the powder and the binder within the solvent.
- the method further includes coating both sides of the substrate simultaneously with the slurry extruded from the closed volume after the forcing.
- aspects of the present disclosure also include an electrode that is coated according to the above method, a battery having an electrode that is coated according to the above method, and a battery system having a plurality of battery cells, with each battery cell having an electrode that is coated according to the above method.
- An additional aspect of the present disclosure includes a method of curing a coated substrate including providing a substrate coated on both sides with a slurry.
- the slurry includes a solvent, a powder, a binder, and a dispersion agent.
- the method further includes freezing at least the solvent and the dispersion agent coated on the substrate, and sublimating at least the solvent and the dispersion agent frozen on the substrate.
- the method further includes heating the substrate under vacuum to above the freezing points of the at least one solvent and the dispersion agent after the sublimating and calendering the substrate after the heating.
- a further aspect of the present disclosure includes a system with a first cylinder assembly with a first cylinder and a first piston.
- the first piston is configured to reciprocally move within the first cylinder.
- the system also includes a second cylinder assembly with a second cylinder and a second piston.
- the second piston is configured to reciprocally move within the second cylinder.
- the system also includes a passage connecting the first cylinder assembly to the second cylinder assembly. In the operation of the system, the first cylinder assembly and the second cylinder assembly are configured to alternatingly apply compression and suction to a slurry within the first cylinder and the second cylinder to cause the slurry to reciprocally move through the passage.
- FIG. 1 illustrates a cross-sectional view of a device used to prepare a slurry, according to aspects of the present disclosure.
- FIG. 2A illustrates a perspective view of a die assembly, according to aspects of the present disclosure.
- FIG. 2B illustrates an exploded view of the die assembly of FIG. 2A , with two die parts, according to aspects of the present disclosure.
- FIG. 2C illustrates a top view of the die assembly of FIG. 2A , according to aspects of the present disclosure.
- FIG. 2D illustrates a bottom view of the die assembly of FIG. 2A , according to aspects of the present disclosure.
- FIG. 3A illustrates a cross-sectional view of the device of FIG. 1 configured for applying the slurry onto a substrate, according to aspects of the present disclosure.
- FIG. 3B illustrates an optically transparent perspective view of the die of FIG. 3A applying the slurry onto the substrate, according to aspects of the present disclosure.
- FIG. 3C illustrates a cross-sectional view of the substrate of FIG. 3B , along the line 3 B- 3 B, being coated with the slurry, according to aspects of the present disclosure.
- FIG. 4 is a flowchart of a process for coating a substrate, according to aspects of the present disclosure.
- FIG. 5 is a flowchart of a process for curing a coated substrate, according to aspects of the present disclosure.
- the devices and processes of the present disclosure significantly reduce the complexity and time required to form and apply the slurries to the substrate.
- the disclosed devices and processes can be used in the manufacture of an electrode for a battery.
- the devices and processes can be used for the formation and application of any type of slurry onto any type of substrate, not specifically limited to a substrate intended for an electrode.
- the devices and methods of the present disclosure decrease or eliminate the use of toxic chemicals as solvents and/or dispersion agents, such as NMP, DMF, acetone etc., in the formation of slurries for electrodes.
- the devices and methods also shorten and simplify the overall process of battery electrode manufacturing by removing complicated conventional processes in the preparation of slurries, the treatment of substrates, the manipulation of equipment, and the like.
- the devices and methods also scale down the size or exclude the use of the expensive and massive devices used in condensation, pulverization, and powder distribution for the processes discussed above in the background.
- the methods of the present disclosure use only one device, which performs all of the mixing, kneading, and coating.
- the device coats a slurry directly onto a substrate in situ, without the hassle of, for example, transferring the slurry from a mixing device to a coating device.
- the device also coats both sides of the substrate simultaneously.
- the methods also include freeze drying the coated substrate, which removes the solvents. The freeze drying helps reduce damage or changes in the pore structures of the slurry and substrate formed during coating.
- the present disclosure also provides a slurry coating process along with a coating device for the manufacture of an electrode for an electrochemical cell.
- the electrochemical cell can be, for example, a primary cell or a secondary cell, such as a lithium cell or a fuel cell.
- the slurries of the present disclosure are formed of a solvent, a powder, and a binder.
- the slurries can also include a dispersion agent.
- the solvent can be any chemical that can dissolve a binder, and any chemical can be chosen according to the desired binders' properties.
- the solvent can be water with a water-soluble binder, such as polytetrafluoroethylene (PTFE).
- PTFE polytetrafluoroethylene
- the solvent can be acetone (or nearly pure acetone), NMP, or DMF with a non-water soluble binder, such as polyvinylidene fluorine (PVDF) powder or resin.
- the solvent can be any chemical that can form a dispersion with the binder and the powder.
- the powder can be any powder used in the manufacture of a dispersion.
- the powder can be any powder used in the manufacture of an electrode.
- the powder can be any electrochemically activatable, active, or inactive inorganic or organic material, or combinations thereof.
- the conductive powder serves as the electrode or the conductive additive within the electrode for an electrochemical cell.
- the conductive powder can be carbon black powder, graphite, carbon fibers, etc., or blends thereof.
- Non-carbon powders can be, for example, silicon carbide (SiC), barium sulfate (BaSO 4 ), lithium iron phosphate (LiFePO 4 ), lithium manganese iron phosphate (LiMnFePO 4 ), and various oxides, such as silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), lithium nickel cobalt aluminum oxide (LiNiCoAlO 2 ), lithium nickel cobalt manganese oxide (LiNiCoMnO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O 4 ), lithium cobalt oxide (LiCoO 2 ), and the like, and other natural minerals, and combinations thereof.
- silicon dioxide SiO 2
- Al 2 O 3 aluminum oxide
- LiNiCoAlO 2 lithium nickel cobalt aluminum oxide
- LiNiCoMnO 2 lithium nickel cobalt manganese oxide
- LiMn 2 O 4 lithium
- the foregoing non-carbon powders are all water soluble and hydrophilic.
- the ratio of the water-based solvent to the powder within the slurry can be lowered further down to about 0.6:1 by weight because of the mixing as described below and the material hydrophilicity. This is in contrast to the ratio for hydrophilic powders and water-based solvents in conventional wet methods, which is about 1.25:1 by weight.
- the ratio of solvent to powder within the slurry can be about 4.5-8:1 by weight. This provides an advantage over conventional slurries, which require solvent to powder ratios of about 24-27:1 by weight. Thus, significantly less solvent must be used in the methods of the present disclosure, which reduces the amount of solvent that must be removed during the cure.
- the binder aids in adhering the powder to the substrate after coating and curing.
- the binder can be a resin binder.
- the binder can be soluble within the solvent, such as being water soluble, or can be in the form of a dispersion, such as a water-based polytetrafluoroethylene emulsion.
- Na-CMC sodium carboxymethyl cellulose
- the amount of binder used in the slurry depends on how the binder affects the conductivity of the resulting electrode.
- the ratio of binder to the powder within the slurry can be about 0.02:1 to about 0.1:1.
- the binder content of above about 10 wt % relative to the combined weight of the binder and the powder is not suitable for large-scale electrode production due to viscosity and energy-density considerations.
- the dispersion agent aids in mixing hydrophobic inorganic components, such as carbon powders, with the water-based solvents and binders.
- the dispersion agent is selected to be in a liquid state and have similar or inferior physical properties to the solvent, such as lower melting/precipitating point.
- the similar or inferior physical properties of the dispersion agent compared to the solvent cause the dispersion agent to evaporate along with or before the solvent so that a resulting film on a substrate after freeze drying contains mainly the powder.
- isopropyl alcohol having precipitation point of ⁇ 89° C. can be used with water as the solvent.
- Extra solvent residue including a non-aqueous solvent, can be extracted during freeze drying, such as in a freeze dryer condenser at ⁇ 60° C. to ⁇ 80° C., or during the subsequent heating of the coated substrate at an elevated temperature, as further discussed below.
- Dispersion agents that can be used within the slurry include, for example, isopropyl alcohol, ethanol, methanol, acetic acid, acetonitrile, acetone, NMP, DMF, and the like. Further, in one or more embodiments, some dispersion agents can also function as both the dispersion agent and the solvent. Further, although dispersion agents such as NMP and DMF are not preferably used because of their toxic qualities, they can still be used in slurries of the present disclosure because of the much lower required concentrations. For example, because of the benefits of the mixing and associated device discussed below, the amounts of these dispersion agents can be much lower than conventional wet methods, which still reduces the related expense of their use.
- the amount of dispersion agent used in a slurry depends on the other components within the slurry, including the solvent. However, the slurry can be as low as 0.01 weight percent (wt %) dispersion agent. This is in contrast to conventional slurries mixed using conventional methods, which may be required to be up to 30 wt % dispersion agent in an aqueous solvent. For example, in a slurry of the present disclosure of carbon powder, water as the solvent, and PTFE emulsion as the binder, when isopropyl alcohol is used as the dispersion agent, the slurry is about 1 wt % isopropyl alcohol. When using NMP as the dispersion agent, the slurry can be as low as 0.01 wt % NMP.
- FIG. 1 illustrated is a cross-sectional view of a device 100 used to prepare a slurry 102 and coat the slurry 102 on a substrate, according to aspects of the present disclosure.
- the device 100 includes a pair of cylinders 104 a , 104 b and a pair of pistons 106 a , 106 b .
- Each piston 106 a , 106 b is within one of the cylinders 104 a , 104 b (e.g., piston 106 a is within cylinder 104 a , and piston 106 b is within cylinder 104 b ).
- the pistons 106 a , 106 b are connected to one or more devices (not shown) that are configured to drive the pistons 106 a , 106 b in a linear and reciprocal movement along the length of the cylinders 104 a , 104 b (e.g., stroke length or direction), as indicated by the line A.
- the one or more devices that drive the pistons 106 a , 106 b can be one or more linear actuators that can be controlled by a programmable drive.
- the one or more devices can be any type of mechanical and/or electromechanical device that can impart a reciprocal linear movement to the pistons 106 a , 106 b . Actuation of the pistons 106 a , 106 b is synchronized so that one piston applies a compressive force on the slurry 102 as the other piston applies a suction force.
- the cylinders 104 a , 104 b are fluidically connected via a narrow tube 108 .
- the narrow tube 108 allows the slurry 102 to flow between the cylinders 104 a , 104 b under the compressive forces generated by actuation of the pistons 106 a , 106 b .
- the slurry 102 can be repeatedly passed through the tube 108 .
- the slurry 102 flows from cylinder 104 a through the tube 108 and to cylinder 104 b in a first flow direction, such as left to right in the direction of line A in FIG. 1 .
- the slurry 102 then flows from cylinder 104 b through the tube 108 and to cylinder 104 a , such as right to left in the direction of line A in FIG. 1 .
- the second flow direction is opposite to the first flow direction.
- the flow direction illustrated in FIG. 1 is linear along the line A, in one or more embodiments the flow direction can be non-linear.
- the tube 108 can be in the shape of a U, an S, or have any number of the same and/or different bends that creates a tortuous path for the slurry 102 to travel.
- the repeated movement of the slurry 102 through the tube 108 mixes the slurry 102 .
- the mixing is aided further by the narrow diameter of the tube 108 as compared to, for example, the diameters of the cylinders 104 a , 104 b in the stroke directions of the pistons 106 a , 106 b or the direction of the flow (e.g., line A).
- the slurry 102 passing through the tube 108 experiences high shear forces rendered from the velocity disproportion of particles within the slurry 102 based on the particles at the edges of the tube 108 experiencing lower velocities than the particles at the center of the tube 108 , according to the Bernoulli principle.
- the shear forces exerted while charging and/or discharging the cylinders 104 a , 104 b with the slurry 102 results in a high mixing efficiency and produces enormous kneading effects.
- the mixing efficiency is dependent on the flow speed of the slurry 102 through the tube 108 , the diameter of the tube 108 , and the mixing time.
- a flow speed of 430 millimeters per second through a three-eighth inch inner diameter tube takes only 15 minutes of mixing.
- a flow speed of 380 millimeters per second through a three-eighth inch inner diameter tube takes only 25 minutes of mixing.
- a flow speed of 170 millimeters per second through a one-eighth inch inner diameter tube takes only 10 minutes of mixing.
- the diameter of the tube 108 can be about 1/16 to 1 ⁇ 2 inch.
- the configuration of the device 100 provides for a higher mixing efficiency than conventional devices, such as conventional planetary mixers. For example, mixing 30 grams of carbon black powder takes only about 0.3 kilowatt-hours (kWh) of energy. For larger amounts of mixed material, the power consumed can be up to about 10 to 15 kilowatt-hours per kilogram of powder.
- a device 100 was formed of cylinders (i.e., cylinders 104 a , 104 b ) having three-inch inner diameters.
- the cylinders were connected by a tube (i.e., tube 108 ) that was seven inches long and had a one-eighth inch inner diameter.
- a slurry i.e., slurry 102
- pistons i.e., pistons 106 a , 106 b
- the slurry which was formed of a carbon black-polymer blend, was completely mixed and kneaded by the reciprocal movement of the pistons and being forced through the tube in less than a half hour and ready for coating.
- the actual mixing and kneading times can vary depending on the size of particle, the size of tube 108 (e.g., inner diameter, length) and the speed of the pistons 106 a , 106 b and, therefore, the resulting speed of the slurry 102 passing through the tube 108 .
- tube 108 is shown connecting the cylinders 104 a , 104 b , in one or more embodiments there can be more than one tube 108 connecting the cylinders 104 a , 104 b . More than one tube 108 can be used when the diameter of the cylinders 104 a , 104 b in the stroke direction is large relative to the diameter of the tube 108 .
- the device 100 can be formed of one or more metals, metal alloys, or other materials (e.g., plastics).
- the material used for the device 100 can depend on the solvents used to form the slurry. With water as the main solvent of a slurry, the device 100 can be formed of a material resistant to corrosion by water and the other dispersion agents, such as 316 stainless steel.
- the device 100 can include a third cylinder.
- the third cylinder can be attached to one of the cylinders 104 a , 104 b and/or the tube 108 .
- the third cylinder can be used to accumulate the slurry prior to coating the slurry onto a substrate, as discussed below.
- the third cylinder can have any working volume larger than that of the cylinder 104 a or 104 b so that the third cylinder can accumulate the slurry 102 for coating later, after mixing, as described further below.
- a die 200 is illustrated that is used to apply the slurry 102 onto a substrate, according to aspects of the present disclosure.
- the die 200 is formed of two die parts 202 a , 202 b .
- the die parts 202 a , 202 b can be symmetrical, as shown, or identical.
- the die parts 202 a , 202 b can be asymmetrical.
- the die parts 202 a , 202 b are shown and described as each being a single part, in one or more embodiments the die parts 202 a , 202 b can each be formed of multiple parts.
- the die parts 202 a , 202 b are configured to apply thin planar layers of the slurry 102 simultaneously on both sides of a substrate, as further described below.
- the die 200 includes an interface 204 ( FIG. 2A ) that is configured to connect the die 200 to one of the cylinders 104 a , 104 b or to the tube 108 (or to the third cylinder, if present).
- the interface 204 includes two slurry inlet ports 206 a , 206 b —one inlet port 206 a , 206 b for each die part 202 a , 202 b , respectively.
- the inlet ports 206 a , 206 b are configured to accept the slurry 102 extruded from the device 100 , either from one of the cylinders 104 a , 104 b or from the tube 108 , depending on where the die 200 is attached.
- each die part 202 a , 202 b further includes a slurry outlet port 208 a , 208 b .
- the outlet ports 208 a , 208 b are configured to apply the slurry 102 evenly on a substrate as the substrate passes by the outlet ports 208 a , 208 b .
- the outlet ports 208 a , 208 b are approximately the same width as the substrate, but can be longer or shorter in width than the substrate.
- Passages 210 a , 210 b connect the outlet ports 208 a , 208 b to the inlet ports 206 a , 206 b .
- the inlet ports 206 a , 206 b are configured to divide the slurry 102 into two separate streams. Thereafter, the passages 210 a , 210 b are configured to evenly distribute the slurry 102 to the outlet ports 208 a 208 b for subsequent distribution of the slurry onto the substrate.
- the die parts 202 a , 202 b coupled together to form the die 200 and define a slit 212 through the die 200 .
- the slit 212 allows a substrate to pass through the die 200 .
- slurry 102 extruded from the outlet ports 208 a , 208 b is applied simultaneously to both sides of the substrate passing through the slit 212 .
- FIG. 3A illustrated is a cross-sectional view of the device 100 configured for coating the slurry 102 onto a substrate 300 , according to aspects of the present disclosure.
- the device 100 has been modified by disconnecting the tube 108 from the cylinder 104 a .
- the die 200 is connected to the cylinder 104 a via the interface 204 .
- the die 200 can instead be connected to the tube 108 or the cylinder 104 b (or a third cylinder).
- the tube 108 may have an interface that connects to the interface 204 of the die 200 .
- the ability to re-configure the device 100 from the mixing, kneading configuration of FIG. 1 to the application configuration of FIG. 3A allows for coating to be done simply and directly in situ without transferring the slurry 102 from one device (i.e., device 100 ) to another device.
- the substrate 300 can be any type of substrate, such as a substrate used in forming an electrode.
- the substrate can be a foam, a mesh, or any type of porous, semi-porous, or non-porous material.
- FIG. 3B illustrates the slurry 102 passing into the inlet ports 206 a , 206 b , being directed into the passages 210 a , 210 b , out of the die 200 through the outlet ports 208 a , 208 b , and then onto the substrate 300 .
- the pressure of the slurry 102 exiting the outlet ports 208 a , 208 b forces the slurry 102 into the substrate 300 , such as into the pores of the substrate 300 .
- the application of the slurry 102 onto the substrate 300 also causes the substrate 300 to advance through the die 200 through the slit 212 .
- application of the slurry 102 onto the substrate 300 can move the substrate 300 in a desired direction, such as downward in the orientation of FIG. 3B .
- the substrate 300 can be driven through the die 200 using another driving force, such as a take-up device (not shown).
- FIG. 3C illustrates the applied slurry 102 on the substrate 300 .
- the slurry 102 forms thin films 302 a , 302 b on both sides of the substrate 300 .
- the thin films can be about 8 ⁇ m to about 25 ⁇ m (micrometer) thick.
- Application of the thin films 302 a , 302 b according to the disclosed process results in an even thickness on both sides of the substrate 300 .
- the thickness can be controlled by the speed of the piston 106 a during extrusion of the slurry 102 from the cylinder 104 a , in combination with the speed of the substrate 300 passing through the slit 212 within the die 200 .
- the slurry 102 can be exposed to a vacuum within one or both of the cylinders 104 a , 104 b (or the third cylinder).
- the vacuum aids in removing gas within the slurry 102 before coating.
- Gas within the slurry 102 can affect surface evenness and adhesion of the resulting thin films 302 a , 302 b of the slurry 102 on the substrate 300 .
- removal of the gas improves the evenness and adhesion of the slurry 102 .
- FIG. 4 is a flowchart of a process 400 for coating a substrate, according to aspects of the present disclosure.
- the process 400 is conducted using the device 100 disclosed above.
- the process 400 begins at step 402 with a slurry in the device 100 .
- the device 100 as disclosed above, has a closed volume with at least one passage defined by the cylinders 104 a , 104 b and the tube 108 .
- the slurry can be any slurry disclosed herein, and can contain a solvent, a powder, a binder, and a dispersion agent. In one or more embodiments, the slurry can lack the dispersion agent.
- the binder in the slurry cannot exceed 10 wt % relative to the combined weight of the binder and the powder.
- the ratio of the water-based solvent to the powder in the slurry can be about 4.5-8:1 by weight.
- the amount of dispersion agent in the slurry can be as low as 0.01 wt %. However, the amount of dispersion agent, if any, within the slurry is generally about 1 to 2 wt %.
- the slurry can be formed of water as the solvent, carbon black as the powder, polytetrafluoroethylene emulsion as the binder, and an alcohol as the dispersion agent, although any component disclosed above can be used.
- the slurry does not require n-methyl-2-pyrrolidone or another toxic dispersion agent based on the ability of the device 100 to create a dispersion out of the slurry without the toxic dispersion agents.
- each of the two cylinders includes a piston, and a reciprocal actuation of the two pistons forces the slurry to flow in the first flow direction and the second flow direction.
- the cylinders are configured so that a cross section of the at least one passage is smaller than cross sections of the cylinders in stroke directions of the two pistons. This causes a high shear force on the slurry at it passes through the tube, which causes mixing of the slurry.
- an inner diameter of each passage can be about 1/16 inch to 1 ⁇ 2 inch, and an inner diameter of the cylinders can be much larger, such as about 3 inches or more. In one or more embodiments, the inner diameter can be smaller than 3 inches depending on the speed of the pistons within the cylinders.
- both sides of a substrate are coated simultaneously with the slurry extruded from the closed volume.
- the coating can be a thin film of the slurry at a desired thickness, as discussed above.
- a vacuum can be applied to the slurry within the device 100 to remove gas that may have developed within the slurry during earlier process steps.
- the solvents and dispersion agents used in forming the slurry allow for a different process of curing the slurry on the substrate than conventional processes. Specifically, because small portions of volatile organic solvents, such as alcohols mentioned above, are used to disperse hydrophobic materials, like the carbon powders, in a water dominant solution, it is possible to use a freeze-drying process to remove the solvents and dispersion agents and dry the coatings.
- the freeze-drying process decreases the possibility of issues found in conventional electrode manufacturing processes. These issues include uncontrollable deformations of pore structures and defects in morphologies and porosities of the thin films while drying.
- FIG. 5 is a flowchart of a process 500 for curing a coated substrate as a final product, according to aspects of the present disclosure.
- the process 500 begins at step 502 with a substrate coated on both sides with a slurry.
- the substrate can be coated according to the process 400 disclosed above, and the slurry can be any slurry based on the aspects of the present disclosure.
- the solvent and the dispersion agent coated on the substrate are frozen.
- the freezing can occur according to any process that reduces the temperature of the solvent and the dispersion agent to below their freezing points. However, in one or more embodiments, it is not necessary to freeze the dispersion agent when the amount of dispersion agent used is negligible relative to the amount of solvent, such as in the case of 1 wt % isopropyl alcohol in the current invention.
- the solvent and the dispersion agent within the coated substrate are sublimated to freeze dry the substrate. Sublimation can occur according to any process that causes the solvent and the dispersion agent to sublimate.
- the substrate is heated in vacuum to above the standard freezing points of the solvent and the dispersion agent.
- the heating and vacuuming further aid in removing any remaining solvent and dispersion agent in the substrate.
- the substrate is calendered.
- the calendering includes cold calendering the substrate to stabilize the coating on the substrate.
- the calendering also includes hot rolling the substrate after the cold calendering.
- the hot rolling can be about 100° C. to about 150° C. to improve the adhesion of the thin films on the substrate. In addition to improving adhesion, the hot rolling also increases the electrical conductivity through the improved adhesion.
- the coating method produces a uniform coating on a substrate having a porosity that is superior to porosity achieved by conventional methods heretofore.
- the coating is relatively defect-free compared to conventional approaches, producing a very low rate of pinholes, blisters, divots, barring, striping, foreign contaminants, exaggerated non-uniform coating areas, or agglomerates on the coating surfaces.
- the methods and devices of the present disclosure lower the use or the amount of, or remove entirely, toxic materials in the formation of slurries, such as toxic solvents that cause undesirable vapors during the production of electrodes for batteries. Reduction or removal of the toxic materials reduces or eliminates specialty equipment required to prevent the release of the toxic materials into the environment and other issues, such as explosion. The methods and devices of the present disclosure also decrease the required work space needed for electrode manufacture as compared to conventional processes.
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Abstract
Devices and methods for preparing a slurry for coating onto a substrate. The devices and methods of the present disclosure relate to providing a slurry in a closed volume with at least one passage. The slurry includes a solvent, a powder, and a binder. The slurry can also include a dispersion agent. The slurry is forced repeatedly under high pressure through the at least one passage in a first flow direction and then back through the at least one passage in a second flow direction, opposite the first flow direction. The forcing homogenously disperses the powder and the binder within the solvent. Both sides of the substrate are then coated simultaneously with the slurry extruded from the closed volume after the forcing. Curing of the coated slurry includes freeze drying to preserve the porosity of the slurry on the substrate.
Description
- The present application is a divisional of pending U.S. patent application Ser. No. 17/140,932, filed Jan. 4, 2021, now allowed, which is a continuation of U.S. Non-Provisional patent application Ser. No. 15/964,051, filed Apr. 26, 2018, and entitled “Devices and Methods for Preparing a Slurry and Coating a Substrate with a Slurry,” now abandoned, which is incorporated by reference in its entirety.
- The present disclosure is directed to devices and methods for preparing a slurry and coating the slurry onto a substrate.
- Forming slurries containing powders and optionally binders dispersed within a solvent often involves considerable energy and equipment. Such is the case when forming slurries for the manufacture of substrates used in forming electrodes for batteries. For example, in conventional wet electrode coating processes, viscous slurries containing powders, like carbon black powder or other active/non-active materials, and organic polymers as binders, are coated onto substrates to form current collectors by drawing or delivering either the slurries or the substrates via various methods, such as doctor blades, roll-to-roll coaters, etc. Conventional devices used in wet coating require a large amount of space because of the required use of the doctor blades, the roll-to-roll coaters, etc. All of the devices and workstations related to the conventional mixing, kneading, coating, and drying are massive.
- Long periods of time also are required to mix the slurries by using conventional planetary mixers. Typically, a large amount of toxic solvents also is used in the slurries for conventional wet coating to aid in the formation and application of the slurries onto the substrate. Such toxic solvents include, for example, n-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, etc. After coating the slurry on the substrate, the toxic solvents must be removed. Removal requires elaborate evaporation techniques in the drying process to prevent environmental pollution and explosions. Bulky dryers with long belt conveyors combined with heating systems are required for the drying to evaporate the toxic solvents. Along with drying systems, it is necessary to install systems for collecting the evaporated toxic solvents to prevent environmental pollution.
- Dry coating processes are an alternative to wet coating for the manufacture of electrodes. However, dry coating has several drawbacks. For example, it is necessary to pulverize dried carbon composite powder into fine powder for coating, which requires two machines to pulverize and distribute the fine powder onto the substrate. Specific hoppers and complex arrangements of coaters also are required to disperse the fine powder onto the substrate.
- Dry coating also suffers from inconsistent results of battery performance based on the irregular distribution of the fine powder on the substrate. The resultant unevenness of powder density on the substrate has a direct effect on many issues, like the adhesive force between the coating and the substrate and the porosity uniformity, which eventually leads to lack of reaction uniformity. Even with specially designed powder coating machines equipped with sophisticated distributors, the same kind of problems of inconsistent cell performance exist.
- Accordingly, needs exist for coating devices and coating processes that decrease the issues mentioned above in slurry formation in general, and as applied to battery electrode manufacturing.
- An aspect of the present disclosure includes a process of coating a substrate with a slurry for forming an electrode. The slurry contains a powder. In some aspects, the powder can be formed of carbon black powder, or any conductive/non-conductive material or blends thereof. The slurry further contains one or more solvents and binders. The slurry can optionally include one or more dispersion agents. The process further includes freeze drying the coated substrate and heating the freeze-dried coated substrate under a vacuum at elevated temperatures to remove residual solvents. The process further includes calendering the resulting coated substrate to be used as battery electrodes.
- A further aspect of the disclosure is a device configured to mix and knead a slurry, and then coat the slurry simultaneously on both sides of a substrate. The device includes two cylinders connected via a narrow tube, with a piston in each cylinder configured to repeatedly force the slurry back and forth between the cylinders and through the tube. The repeated movement of the slurry through the tube applies a shearing force to the slurry, which mixes and kneads the slurry. In some aspects, the device includes a die configured to extrude the slurry onto the substrate so that the slurry contacts both surfaces of the substrate simultaneously.
- Another aspect of the present disclosure includes a method of coating a substrate including providing a slurry in a closed volume with at least one passage. The slurry includes a solvent, a powder, a binder, and a dispersion agent. The method further includes forcing the slurry repeatedly under high pressure through the at least one passage in a first flow direction and then back through the at least one passage in a second flow direction, opposite the first flow direction, to homogenously disperse the powder and the binder within the solvent. The method further includes coating both sides of the substrate simultaneously with the slurry extruded from the closed volume after the forcing.
- Aspects of the present disclosure also include an electrode that is coated according to the above method, a battery having an electrode that is coated according to the above method, and a battery system having a plurality of battery cells, with each battery cell having an electrode that is coated according to the above method.
- An additional aspect of the present disclosure includes a method of curing a coated substrate including providing a substrate coated on both sides with a slurry. The slurry includes a solvent, a powder, a binder, and a dispersion agent. The method further includes freezing at least the solvent and the dispersion agent coated on the substrate, and sublimating at least the solvent and the dispersion agent frozen on the substrate. The method further includes heating the substrate under vacuum to above the freezing points of the at least one solvent and the dispersion agent after the sublimating and calendering the substrate after the heating.
- A further aspect of the present disclosure includes a system with a first cylinder assembly with a first cylinder and a first piston. The first piston is configured to reciprocally move within the first cylinder. The system also includes a second cylinder assembly with a second cylinder and a second piston. The second piston is configured to reciprocally move within the second cylinder. The system also includes a passage connecting the first cylinder assembly to the second cylinder assembly. In the operation of the system, the first cylinder assembly and the second cylinder assembly are configured to alternatingly apply compression and suction to a slurry within the first cylinder and the second cylinder to cause the slurry to reciprocally move through the passage.
- These and other capabilities of the disclosed devices, systems, and methods will be more fully understood after a review of the following figures, detailed description, and claims.
-
FIG. 1 illustrates a cross-sectional view of a device used to prepare a slurry, according to aspects of the present disclosure. -
FIG. 2A illustrates a perspective view of a die assembly, according to aspects of the present disclosure. -
FIG. 2B illustrates an exploded view of the die assembly ofFIG. 2A , with two die parts, according to aspects of the present disclosure. -
FIG. 2C illustrates a top view of the die assembly ofFIG. 2A , according to aspects of the present disclosure. -
FIG. 2D illustrates a bottom view of the die assembly ofFIG. 2A , according to aspects of the present disclosure. -
FIG. 3A illustrates a cross-sectional view of the device ofFIG. 1 configured for applying the slurry onto a substrate, according to aspects of the present disclosure. -
FIG. 3B illustrates an optically transparent perspective view of the die ofFIG. 3A applying the slurry onto the substrate, according to aspects of the present disclosure. -
FIG. 3C illustrates a cross-sectional view of the substrate ofFIG. 3B , along the line 3B-3B, being coated with the slurry, according to aspects of the present disclosure. -
FIG. 4 is a flowchart of a process for coating a substrate, according to aspects of the present disclosure. -
FIG. 5 is a flowchart of a process for curing a coated substrate, according to aspects of the present disclosure. - While the devices, systems, and methods discussed herein are susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and will be described in detail herein. It should be understood, however, that the description is not intended to be limited to the particular forms disclosed. Rather, the description is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
- There is shown in the drawings and will herein be described in detail one or more embodiments of the device, system, and method with the understanding that the present disclosure is to be considered as an exemplification of the principles of the disclosed herein and is not intended to limit the broad aspects solely to the embodiments illustrated. For purposes of the present detailed description, the singular includes the plural and vice versa (unless specifically disclaimed); the word “or” shall be both conjunctive and disjunctive; the word “all” means “any and all”; the word “any” means “any and all”; and the word “including” means “including without limitation.” Additionally, the singular terms “a,” “an,” and “the” include plural referents unless context clearly indicates otherwise. Every range of numbers disclosed herein includes the upper and lower numbers and every rational number, including every integer, therebetween.
- Disclosed are devices and processes for preparing a slurry, and then applying the slurry onto a substrate. The devices and processes of the present disclosure significantly reduce the complexity and time required to form and apply the slurries to the substrate. Disclosed also are processes for curing substrates coated with the slurry. The disclosed devices and processes can be used in the manufacture of an electrode for a battery. However, the devices and processes can be used for the formation and application of any type of slurry onto any type of substrate, not specifically limited to a substrate intended for an electrode.
- As applied to the manufacture of electrodes for batteries, the devices and methods of the present disclosure decrease or eliminate the use of toxic chemicals as solvents and/or dispersion agents, such as NMP, DMF, acetone etc., in the formation of slurries for electrodes. The devices and methods also shorten and simplify the overall process of battery electrode manufacturing by removing complicated conventional processes in the preparation of slurries, the treatment of substrates, the manipulation of equipment, and the like. The devices and methods also scale down the size or exclude the use of the expensive and massive devices used in condensation, pulverization, and powder distribution for the processes discussed above in the background.
- In particular, the methods of the present disclosure use only one device, which performs all of the mixing, kneading, and coating. The device coats a slurry directly onto a substrate in situ, without the hassle of, for example, transferring the slurry from a mixing device to a coating device. The device also coats both sides of the substrate simultaneously. The methods also include freeze drying the coated substrate, which removes the solvents. The freeze drying helps reduce damage or changes in the pore structures of the slurry and substrate formed during coating. The present disclosure also provides a slurry coating process along with a coating device for the manufacture of an electrode for an electrochemical cell. The electrochemical cell can be, for example, a primary cell or a secondary cell, such as a lithium cell or a fuel cell.
- The slurries of the present disclosure are formed of a solvent, a powder, and a binder. The slurries can also include a dispersion agent. In one or more embodiments, the solvent can be any chemical that can dissolve a binder, and any chemical can be chosen according to the desired binders' properties. For example, the solvent can be water with a water-soluble binder, such as polytetrafluoroethylene (PTFE). Alternatively, the solvent can be acetone (or nearly pure acetone), NMP, or DMF with a non-water soluble binder, such as polyvinylidene fluorine (PVDF) powder or resin. In one or more alternative embodiments, the solvent can be any chemical that can form a dispersion with the binder and the powder.
- The powder can be any powder used in the manufacture of a dispersion. In one or more embodiments, the powder can be any powder used in the manufacture of an electrode. For example, the powder can be any electrochemically activatable, active, or inactive inorganic or organic material, or combinations thereof. When the powder is a conductive powder, the conductive powder serves as the electrode or the conductive additive within the electrode for an electrochemical cell. The conductive powder can be carbon black powder, graphite, carbon fibers, etc., or blends thereof. Other non-carbon powders can be, for example, silicon carbide (SiC), barium sulfate (BaSO4), lithium iron phosphate (LiFePO4), lithium manganese iron phosphate (LiMnFePO4), and various oxides, such as silicon dioxide (SiO2), aluminum oxide (Al2O3), lithium nickel cobalt aluminum oxide (LiNiCoAlO2), lithium nickel cobalt manganese oxide (LiNiCoMnO2), lithium manganese oxide (LiMn2O4), lithium nickel manganese spinel (LiNi0.5Mn1.5O4), lithium cobalt oxide (LiCoO2), and the like, and other natural minerals, and combinations thereof.
- The foregoing non-carbon powders are all water soluble and hydrophilic. Thus, in using water soluble and hydrophilic powders as described above, the ratio of the water-based solvent to the powder within the slurry can be lowered further down to about 0.6:1 by weight because of the mixing as described below and the material hydrophilicity. This is in contrast to the ratio for hydrophilic powders and water-based solvents in conventional wet methods, which is about 1.25:1 by weight. For the carbon-based powders, the ratio of solvent to powder within the slurry can be about 4.5-8:1 by weight. This provides an advantage over conventional slurries, which require solvent to powder ratios of about 24-27:1 by weight. Thus, significantly less solvent must be used in the methods of the present disclosure, which reduces the amount of solvent that must be removed during the cure.
- The binder aids in adhering the powder to the substrate after coating and curing. In one or more embodiments, the binder can be a resin binder. The binder can be soluble within the solvent, such as being water soluble, or can be in the form of a dispersion, such as a water-based polytetrafluoroethylene emulsion. Specific binders that can be used in battery manufacture include, for example, sodium carboxymethyl cellulose (Na-CMC), poly(sodium acrylate) (PAA-Na), poly(ethylene oxide) (PEO), poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly(3,4-ethylendioxythiophene), water-soluble acrylate (Acryl S020), polyvinyl alcohol (PVA), polyacrylamides and poly-methylacrylamides, divyinly ether-maleic anhydride, polyoxazoline, various types of polyphosphates used in tissue engineering, starch, liquid glucose, hydroxypropyl methyl cellulose (HPMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), carnauba wax, guar gum, xanthan gum (XG), pectin, and the like, and combinations thereof.
- In the manufacture of an electrode, the amount of binder used in the slurry depends on how the binder affects the conductivity of the resulting electrode. In one or more embodiments, the ratio of binder to the powder within the slurry can be about 0.02:1 to about 0.1:1. However, the binder content of above about 10 wt % relative to the combined weight of the binder and the powder is not suitable for large-scale electrode production due to viscosity and energy-density considerations.
- The dispersion agent aids in mixing hydrophobic inorganic components, such as carbon powders, with the water-based solvents and binders. In one or more preferable embodiments, the dispersion agent is selected to be in a liquid state and have similar or inferior physical properties to the solvent, such as lower melting/precipitating point. The similar or inferior physical properties of the dispersion agent compared to the solvent cause the dispersion agent to evaporate along with or before the solvent so that a resulting film on a substrate after freeze drying contains mainly the powder. For an example, isopropyl alcohol having precipitation point of −89° C. can be used with water as the solvent. Extra solvent residue, including a non-aqueous solvent, can be extracted during freeze drying, such as in a freeze dryer condenser at −60° C. to −80° C., or during the subsequent heating of the coated substrate at an elevated temperature, as further discussed below.
- Dispersion agents that can be used within the slurry include, for example, isopropyl alcohol, ethanol, methanol, acetic acid, acetonitrile, acetone, NMP, DMF, and the like. Further, in one or more embodiments, some dispersion agents can also function as both the dispersion agent and the solvent. Further, although dispersion agents such as NMP and DMF are not preferably used because of their toxic qualities, they can still be used in slurries of the present disclosure because of the much lower required concentrations. For example, because of the benefits of the mixing and associated device discussed below, the amounts of these dispersion agents can be much lower than conventional wet methods, which still reduces the related expense of their use.
- The amount of dispersion agent used in a slurry depends on the other components within the slurry, including the solvent. However, the slurry can be as low as 0.01 weight percent (wt %) dispersion agent. This is in contrast to conventional slurries mixed using conventional methods, which may be required to be up to 30 wt % dispersion agent in an aqueous solvent. For example, in a slurry of the present disclosure of carbon powder, water as the solvent, and PTFE emulsion as the binder, when isopropyl alcohol is used as the dispersion agent, the slurry is about 1 wt % isopropyl alcohol. When using NMP as the dispersion agent, the slurry can be as low as 0.01 wt % NMP.
- Referring to
FIG. 1 , illustrated is a cross-sectional view of adevice 100 used to prepare aslurry 102 and coat theslurry 102 on a substrate, according to aspects of the present disclosure. Thedevice 100 includes a pair ofcylinders pistons piston cylinders piston 106 a is withincylinder 104 a, andpiston 106 b is withincylinder 104 b). Thepistons pistons cylinders pistons pistons pistons slurry 102 as the other piston applies a suction force. - The
cylinders narrow tube 108. Thenarrow tube 108 allows theslurry 102 to flow between thecylinders pistons pistons cylinders slurry 102 can be repeatedly passed through thetube 108. Thus, theslurry 102 flows fromcylinder 104 a through thetube 108 and tocylinder 104 b in a first flow direction, such as left to right in the direction of line A inFIG. 1 . Theslurry 102 then flows fromcylinder 104 b through thetube 108 and tocylinder 104 a, such as right to left in the direction of line A inFIG. 1 . The second flow direction is opposite to the first flow direction. Although the flow direction illustrated inFIG. 1 is linear along the line A, in one or more embodiments the flow direction can be non-linear. For example, thetube 108 can be in the shape of a U, an S, or have any number of the same and/or different bends that creates a tortuous path for theslurry 102 to travel. - The repeated movement of the
slurry 102 through thetube 108 mixes theslurry 102. The mixing is aided further by the narrow diameter of thetube 108 as compared to, for example, the diameters of thecylinders pistons slurry 102 passing through thetube 108 experiences high shear forces rendered from the velocity disproportion of particles within theslurry 102 based on the particles at the edges of thetube 108 experiencing lower velocities than the particles at the center of thetube 108, according to the Bernoulli principle. The shear forces exerted while charging and/or discharging thecylinders slurry 102 results in a high mixing efficiency and produces enormous kneading effects. - The mixing efficiency is dependent on the flow speed of the
slurry 102 through thetube 108, the diameter of thetube 108, and the mixing time. The narrower the diameter of thetube 108 and the higher the flow speed of theslurry 102 through thetube 108, then the more effective the mixing and kneading. By way of example, a flow speed of 430 millimeters per second through a three-eighth inch inner diameter tube takes only 15 minutes of mixing. A flow speed of 380 millimeters per second through a three-eighth inch inner diameter tube takes only 25 minutes of mixing. And a flow speed of 170 millimeters per second through a one-eighth inch inner diameter tube takes only 10 minutes of mixing. In practice, the diameter of thetube 108 can be about 1/16 to ½ inch. Thus, the configuration of thedevice 100 provides for a higher mixing efficiency than conventional devices, such as conventional planetary mixers. For example, mixing 30 grams of carbon black powder takes only about 0.3 kilowatt-hours (kWh) of energy. For larger amounts of mixed material, the power consumed can be up to about 10 to 15 kilowatt-hours per kilogram of powder. - According to one example, a
device 100 was formed of cylinders (i.e.,cylinders pistons pistons slurry 102 passing through thetube 108. - Although only one
tube 108 is shown connecting thecylinders tube 108 connecting thecylinders tube 108 can be used when the diameter of thecylinders tube 108. - The
device 100 can be formed of one or more metals, metal alloys, or other materials (e.g., plastics). The material used for thedevice 100 can depend on the solvents used to form the slurry. With water as the main solvent of a slurry, thedevice 100 can be formed of a material resistant to corrosion by water and the other dispersion agents, such as 316 stainless steel. - In one or more embodiments, the
device 100 can include a third cylinder. The third cylinder can be attached to one of thecylinders tube 108. The third cylinder can be used to accumulate the slurry prior to coating the slurry onto a substrate, as discussed below. In one embodiment, the third cylinder can have any working volume larger than that of thecylinder slurry 102 for coating later, after mixing, as described further below. - Referring to
FIGS. 2A-2D , adie 200 is illustrated that is used to apply theslurry 102 onto a substrate, according to aspects of the present disclosure. As shown inFIGS. 2A and 2B , thedie 200 is formed of two dieparts die parts die parts die parts die parts die parts slurry 102 simultaneously on both sides of a substrate, as further described below. Thedie 200 includes an interface 204 (FIG. 2A ) that is configured to connect thedie 200 to one of thecylinders interface 204 includes twoslurry inlet ports inlet port part inlet ports slurry 102 extruded from thedevice 100, either from one of thecylinders tube 108, depending on where thedie 200 is attached. - Referring to
FIG. 2B , each diepart slurry outlet port outlet ports slurry 102 evenly on a substrate as the substrate passes by theoutlet ports outlet ports -
Passages outlet ports inlet ports inlet ports slurry 102 into two separate streams. Thereafter, thepassages slurry 102 to theoutlet ports 208 a 208 b for subsequent distribution of the slurry onto the substrate. - Referring to
FIGS. 2C and 2D , thedie parts die 200 and define aslit 212 through thedie 200. As described further below, theslit 212 allows a substrate to pass through thedie 200. As the substrate passes through thedie 200,slurry 102 extruded from theoutlet ports slit 212. - Referring to
FIG. 3A , illustrated is a cross-sectional view of thedevice 100 configured for coating theslurry 102 onto asubstrate 300, according to aspects of the present disclosure. Thedevice 100 has been modified by disconnecting thetube 108 from thecylinder 104 a. In place of thetube 108, thedie 200 is connected to thecylinder 104 a via theinterface 204. However, in one or more embodiments, thedie 200 can instead be connected to thetube 108 or thecylinder 104 b (or a third cylinder). For example, thetube 108 may have an interface that connects to theinterface 204 of thedie 200. The ability to re-configure thedevice 100 from the mixing, kneading configuration ofFIG. 1 to the application configuration ofFIG. 3A allows for coating to be done simply and directly in situ without transferring theslurry 102 from one device (i.e., device 100) to another device. - Prior to connecting the
die 200, as much of theslurry 102 as possible can be collected within thecylinder 104 a. Theslurry 102 within thecylinder 104 a then is extruded from thecylinder 104 a via actuation of thepiston 106 a. The extrudedslurry 102 passes into thedie 200 and is applied simultaneously to both sides of thesubstrate 300 from theoutlet ports substrate 300 can be any type of substrate, such as a substrate used in forming an electrode. For example, the substrate can be a foam, a mesh, or any type of porous, semi-porous, or non-porous material. -
FIG. 3B illustrates theslurry 102 passing into theinlet ports passages outlet ports substrate 300. The pressure of theslurry 102 exiting theoutlet ports slurry 102 into thesubstrate 300, such as into the pores of thesubstrate 300. - In one or more embodiments, the application of the
slurry 102 onto thesubstrate 300 also causes thesubstrate 300 to advance through thedie 200 through theslit 212. In other words, application of theslurry 102 onto thesubstrate 300 can move thesubstrate 300 in a desired direction, such as downward in the orientation ofFIG. 3B . Alternatively, or in addition, thesubstrate 300 can be driven through thedie 200 using another driving force, such as a take-up device (not shown). -
FIG. 3C illustrates the appliedslurry 102 on thesubstrate 300. Specifically, theslurry 102 forms thin films 302 a, 302 b on both sides of thesubstrate 300. The thin films can be about 8 μm to about 25 μm (micrometer) thick. Application of the thin films 302 a, 302 b according to the disclosed process results in an even thickness on both sides of thesubstrate 300. Moreover, the thickness can be controlled by the speed of thepiston 106 a during extrusion of theslurry 102 from thecylinder 104 a, in combination with the speed of thesubstrate 300 passing through theslit 212 within thedie 200. - In one or more embodiments, after mixing the
slurry 102 but prior to coating theslurry 102 onto thesubstrate 300, theslurry 102 can be exposed to a vacuum within one or both of thecylinders slurry 102 before coating. Gas within theslurry 102 can affect surface evenness and adhesion of the resulting thin films 302 a, 302 b of theslurry 102 on thesubstrate 300. Thus, removal of the gas improves the evenness and adhesion of theslurry 102. -
FIG. 4 is a flowchart of aprocess 400 for coating a substrate, according to aspects of the present disclosure. Theprocess 400 is conducted using thedevice 100 disclosed above. Theprocess 400 begins atstep 402 with a slurry in thedevice 100. Thedevice 100, as disclosed above, has a closed volume with at least one passage defined by thecylinders tube 108. The slurry can be any slurry disclosed herein, and can contain a solvent, a powder, a binder, and a dispersion agent. In one or more embodiments, the slurry can lack the dispersion agent. As disclosed above, the binder in the slurry cannot exceed 10 wt % relative to the combined weight of the binder and the powder. The ratio of the water-based solvent to the powder in the slurry can be about 4.5-8:1 by weight. The amount of dispersion agent in the slurry can be as low as 0.01 wt %. However, the amount of dispersion agent, if any, within the slurry is generally about 1 to 2 wt %. As an example, the slurry can be formed of water as the solvent, carbon black as the powder, polytetrafluoroethylene emulsion as the binder, and an alcohol as the dispersion agent, although any component disclosed above can be used. Importantly, the slurry does not require n-methyl-2-pyrrolidone or another toxic dispersion agent based on the ability of thedevice 100 to create a dispersion out of the slurry without the toxic dispersion agents. - At
step 404, the slurry is forced repeatedly under high pressure through the at least one passage in a first flow direction and then back through the at least one passage in a second flow direction, opposite the first flow direction, to homogenously disperse the powder and the binder within the solvent. As disclosed above, each of the two cylinders includes a piston, and a reciprocal actuation of the two pistons forces the slurry to flow in the first flow direction and the second flow direction. The cylinders are configured so that a cross section of the at least one passage is smaller than cross sections of the cylinders in stroke directions of the two pistons. This causes a high shear force on the slurry at it passes through the tube, which causes mixing of the slurry. For example, an inner diameter of each passage can be about 1/16 inch to ½ inch, and an inner diameter of the cylinders can be much larger, such as about 3 inches or more. In one or more embodiments, the inner diameter can be smaller than 3 inches depending on the speed of the pistons within the cylinders. - At
step 406, both sides of a substrate are coated simultaneously with the slurry extruded from the closed volume. The coating can be a thin film of the slurry at a desired thickness, as discussed above. In one or more embodiments, prior to step 406 but afterstep 404, a vacuum can be applied to the slurry within thedevice 100 to remove gas that may have developed within the slurry during earlier process steps. - The solvents and dispersion agents used in forming the slurry allow for a different process of curing the slurry on the substrate than conventional processes. Specifically, because small portions of volatile organic solvents, such as alcohols mentioned above, are used to disperse hydrophobic materials, like the carbon powders, in a water dominant solution, it is possible to use a freeze-drying process to remove the solvents and dispersion agents and dry the coatings. The freeze-drying process decreases the possibility of issues found in conventional electrode manufacturing processes. These issues include uncontrollable deformations of pore structures and defects in morphologies and porosities of the thin films while drying.
-
FIG. 5 is a flowchart of aprocess 500 for curing a coated substrate as a final product, according to aspects of the present disclosure. Theprocess 500 begins atstep 502 with a substrate coated on both sides with a slurry. The substrate can be coated according to theprocess 400 disclosed above, and the slurry can be any slurry based on the aspects of the present disclosure. - At
step 504, the solvent and the dispersion agent coated on the substrate are frozen. The freezing can occur according to any process that reduces the temperature of the solvent and the dispersion agent to below their freezing points. However, in one or more embodiments, it is not necessary to freeze the dispersion agent when the amount of dispersion agent used is negligible relative to the amount of solvent, such as in the case of 1 wt % isopropyl alcohol in the current invention. - At
step 506, after freezing the solvent and the dispersion agent, the solvent and the dispersion agent within the coated substrate are sublimated to freeze dry the substrate. Sublimation can occur according to any process that causes the solvent and the dispersion agent to sublimate. - At
step 508, after sublimating the solvent and the dispersion agent, the substrate is heated in vacuum to above the standard freezing points of the solvent and the dispersion agent. The heating and vacuuming further aid in removing any remaining solvent and dispersion agent in the substrate. - At
step 510, after the heating, the substrate is calendered. In one or more embodiments, the calendering includes cold calendering the substrate to stabilize the coating on the substrate. In one or more embodiments, the calendering also includes hot rolling the substrate after the cold calendering. The hot rolling can be about 100° C. to about 150° C. to improve the adhesion of the thin films on the substrate. In addition to improving adhesion, the hot rolling also increases the electrical conductivity through the improved adhesion. - Although it is possible to lose porosity within the thin films during the calendering, the properties of the pore structure of the thin films after freeze drying are still superior in terms of evenness and uniformity to pores for any coating made by the conventional methods in battery electrode manufacture. Thus, the coating method produces a uniform coating on a substrate having a porosity that is superior to porosity achieved by conventional methods heretofore. The coating is relatively defect-free compared to conventional approaches, producing a very low rate of pinholes, blisters, divots, barring, striping, foreign contaminants, exaggerated non-uniform coating areas, or agglomerates on the coating surfaces.
- Thus, the methods and devices of the present disclosure lower the use or the amount of, or remove entirely, toxic materials in the formation of slurries, such as toxic solvents that cause undesirable vapors during the production of electrodes for batteries. Reduction or removal of the toxic materials reduces or eliminates specialty equipment required to prevent the release of the toxic materials into the environment and other issues, such as explosion. The methods and devices of the present disclosure also decrease the required work space needed for electrode manufacture as compared to conventional processes.
- While the present disclosure relates discloses one or more particular embodiments, those skilled in the art will recognize that many changes may be made thereto without departing from the spirit and scope of the present invention. Each of these embodiment(s) and obvious variations thereof is contemplated as falling within the spirit and scope of the invention. It is also contemplated that additional embodiments according to aspects of the present invention may combine any number of features from any of the embodiments described herein.
Claims (15)
1. A system comprising:
a first cylinder assembly having a first cylinder and a first piston, the first piston being configured to reciprocally move within the first cylinder;
a second cylinder assembly having a second cylinder and a second piston, the second piston being configured to reciprocally move within the second cylinder; and
a passage interconnecting the first cylinder assembly to the second cylinder assembly, the first cylinder, the second cylinder and the passage forming a closed volume;
wherein, in operation, the first cylinder assembly and the second cylinder assembly are configured to alternatingly and repeatedly apply compression and suction under high pressure to a slurry within the first cylinder and the second cylinder to cause the slurry to flow through the passage in a first flow direction and then back again through the passage in a second flow direction that is opposite the first flow direction, in response to a reciprocal actuation of the first and second pistons of the first and second cylinders, the slurry including a solvent, a powder, a binder, and a dispersion agent selected for forming a battery cell electrode applied to a substrate, the reciprocal actuation homogenously dispersing the powder and the binder within the solvent.
2. The system of claim 1 , further comprising:
a die assembly connected to the first cylinder assembly and having two sub-die parts,
wherein each sub-die part has an inlet passage for receiving the slurry from the first cylinder assembly and an outlet configured to extrude the slurry onto a substrate passing through the die assembly.
3. The system of claim 1 , wherein the two sub-die parts assembled form a passage for a substrate to pass through for extruding the slurry onto both sides of the substrate simultaneously.
4. The system of claim 1 , wherein a ratio of the binder to the powder is about 0.02:1 to about 0.1:1 by weight.
5. The system of claim 1 , wherein the powder is a carbon black powder, and a ratio of the solvent to the carbon black powder is about 4.5:1 to about 8:1 by weight.
6. The system of claim 1 , wherein the slurry is about 0.01-2 wt % of the dispersion agent.
7. The system of claim 1 , wherein about 10 to 15 kWh of energy per kilogram of solid powder is required to form the dispersion of the powder and the binder in the slurry.
8. The system of claim 1 , wherein a cross section in the first flow direction of the passage is smaller than cross sections of the cylinders in stroke directions of the two pistons.
9. The system of claim 8 , wherein a diameter of the passage is 1/16 inch to ½ inch.
10. The system of claim 1 , wherein the slurry lacks n-methyl-2-pyrrolidone.
11. The system of claim 1 , wherein the solvent is water.
12. The system of claim 1 , wherein the binder is a polytetrafluoroethylene emulsion.
13. The system of claim 1 , wherein the dispersion agent is an alcohol.
14. The system of claim 1 ,
wherein a ratio of the binder to the powder is about 0.02:1 to about 0.1:1 by weight,
wherein the powder is a carbon black powder, and a ratio of the solvent to the carbon black powder is about 4.5:1 to about 8:1 by weight,
wherein the slurry is about 0.01-2 wt % of the dispersion agent, and
wherein about 10 to 15 kWh of energy per kilogram of solid powder is required to form the dispersion of the powder and the binder in the slurry.
15. The system of claim 1 , wherein a diameter of the passage is 1/16 inch to ½ inch.
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US17/843,055 US20220320520A1 (en) | 2018-04-26 | 2022-06-17 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
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US15/964,051 US20190334176A1 (en) | 2018-04-26 | 2018-04-26 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
US17/140,932 US11398628B2 (en) | 2018-04-26 | 2021-01-04 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
US17/843,055 US20220320520A1 (en) | 2018-04-26 | 2022-06-17 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
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US17/140,932 Active US11398628B2 (en) | 2018-04-26 | 2021-01-04 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
US17/843,055 Pending US20220320520A1 (en) | 2018-04-26 | 2022-06-17 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
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US17/140,932 Active US11398628B2 (en) | 2018-04-26 | 2021-01-04 | Devices and methods for preparing a slurry and coating a substrate with a slurry |
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EP3942607A1 (en) | 2019-03-18 | 2022-01-26 | Intematix Corporation | Led-filament |
CN113826225A (en) | 2019-03-18 | 2021-12-21 | 英特曼帝克司公司 | Encapsulated white light emitting device including photoluminescent layered structure |
CN112473516A (en) * | 2020-12-11 | 2021-03-12 | 天新福(北京)医疗器材股份有限公司 | Mixing arrangement of colloidal solution |
CN113078294B (en) * | 2021-04-01 | 2022-09-27 | 山东天瀚新能源科技有限公司 | Equipment convenient to wet thick liquids of big lithium-ion battery pole piece adhesion in batches |
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US20190334176A1 (en) | 2019-10-31 |
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