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    • 专利摘要:
    Lithium ion battery cathode, battery and method for treating a battery cathode a cathode (10) of a lithium ion battery containing a conductive substrate (12), a first layer (14) coating at least a portion is described. of the conductive substrate (12) comprising a pretreatment composition comprising a group IIIb and/or a group IV metal and a second layer (16) coating at least a portion of the conductive substrate (12) and the first layer (14) , the second layer (16) comprising a coating composition comprising a lithium containing compound. a method for treating a battery cathode and a battery containing the treated cathode is also described.
    公开号:BR112015023240B1
    申请号:R112015023240-0
    申请日:2014-03-07
    公开日:2021-08-03
    发明作者:Randy E. Daughenbaugh；Richard F. Karabin；Edward F. Rakiewicz；Kevin Thomas Sylvester；Nathan J. Silvernail；Stuart D. Hellring
    申请人:Ppg Industries Ohio, Inc.；
    IPC主号:
    专利说明:

    technical field
    [0001] The present invention relates to pretreatment compositions and methods for coating a battery electrode. The present invention also relates to coated battery electrodes. Invention History
    [0002] Electrodes for use in lithium ion batteries are manufactured by bonding an active material to a conductive substrate through the use of a binder. The performance and life of a Li-ion battery depends, at least in part, on the anti-corrosive properties of the electrode and an adhesive resistance between the active material and the conductive substrate. Electrode corrosion can lead to a reduction in adhesive strength, which can result in electrode corrosion. Thus, it is important to optimize both the anticorrosive properties of the electrode and the adhesive resistance between the active material and the conductive substrate.
    [0003] Although increased amounts of binder can increase bond strength, high amounts of binder reduce electrode capacity, and therefore negatively impact battery performance. Accordingly, it would be desirable to provide compositions and methods for treating a conductive substrate and improving the adhesive strength of lithium-containing material to the conductive substrate and/or adhesive properties, without requiring increased amounts of binding material. In addition, it would be desirable to provide compositions and methods for treating a conductive substrate that, in at least some cases, impart adhesive strength equivalent or even superior to the adhesive properties obtained through the use of increased amounts of binding material. It would also be desirable to provide related treated electrodes. Invention Summary
    [0004] In certain embodiments, the invention relates to a cathode of a lithium ion battery comprising a conductive substrate, a first layer coating at least a portion of the conductive substrate, comprising a pretreatment composition comprising a metal of the Group IIIB and/or Group IV, and a second layer coating at least a portion of the first layer, the second layer comprising a coating composition comprising a lithium-containing compound.
    [0005] In certain embodiments, the invention relates to a battery comprising a cathode comprising a conductive substrate, a first layer coating at least a portion of the conductive substrate comprising a pretreatment composition comprising a Group IIIB and/or a metal. Group IV, and a second layer coating at least a portion of the first layer, the second layer comprising a coating composition comprising a lithium-containing compound. The battery also contains an anode, a separator between the anode and cathode, and an electrolyte in contact with the anode and cathode.
    [0006] In certain other embodiments, the invention relates to a method for treating a battery cathode, comprising contacting a conductive substrate of the battery cathode with a pretreatment composition comprising a Group IIIB and/or Group IV metal , and depositing a coating composition comprising lithium-containing compounds onto at least a portion of the pretreated conductive substrate.
    [0007] The attached drawings, which are incorporated and which form part of this report, illustrate some non-restrictive embodiments of the invention Brief Description of Drawings
    [0008] Figure 1 is a partially schematic side sectional view of a battery including a cathode comprising a first layer comprising a pretreatment composition according to an embodiment of the present invention; and
    [0009] Figure 2 is a partially schematic side sectional view of a cathode according to an embodiment of the present invention. Detailed Description of the Invention
    [00010] For the purpose of describing the invention in detail, it is understood that the invention may assume many variations and alternative step sequences, unless otherwise specified. Furthermore, except in the operating examples, or where otherwise indicated, all numbers expressing, for example, amounts of ingredients used in the report and claims are to be understood to be modified in all circumstances by the term "about". Accordingly, unless otherwise indicated, the numerical parameters set forth in the following report and appended claims are approximate and may vary depending on the desired properties to be achieved by the present invention. As a minimum, and not as an attempt to restrict the application of the equivalents doctrine to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of significant digits reported and applying common rounding techniques.
    [00011] Notwithstanding the fact that the numerical ranges and parameters establishing the broad scope of the invention are approximate, the numerical values established in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective test measurements.
    [00012] Likewise, it is to be understood that any numerical range cited herein is intended to include all sub-ranges included therein. For example, a range from "1 to 10" is intended to include all subranges between (and including) the minimum quoted value of 1 and the maximum quoted value of 10, that is, a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.
    [00013] In the present application, the use of the singular includes the plural and the plural includes the singular, unless specifically noted otherwise. Furthermore, in this application, the use of “or” means “and/or”, unless specifically noted otherwise, although “and/or” may be explicitly used in certain cases.
    [00014] Unless otherwise stated, as used herein, the term "substantially free" means that a specific material is not purposefully added to a composition but is only present in trace amounts or in the form of impurity. As used herein, the term "completely free" means that a composition does not comprise a specific material. That is, the composition comprises 0 percent by weight of such material.
    [00015] Figure 1 schematically illustrates a battery 100, according to an embodiment of the present invention. Although a single cathode layer 10 and a single anodic layer 20 are illustrated, it is understood that batteries 100 may have multiple cathode 10 and anodic layers 20, each separated by a separator 40. Figure 2 schematically illustrates a cathode 10 according to an embodiment of the present invention that can be used in a battery in which multiple alternating anodic and cathodic layers are used.
    [00016] As illustrated in Figures 1 and 2, certain embodiments of the invention refer to a cathode 10 of a lithium ion battery 100 comprising a conductive substrate 12 (sometimes referred to as a "collector" or as an "electron collector" ), a first layer 14 covering at least a portion of the conductive substrate comprising a pretreatment composition comprising a Group IIIB and/or Group IV metal, and a second layer 16 covering at least a portion of the first layer, the second layer 16 comprising a coating composition comprising a lithium containing compound. Treatment of the conductive substrate 12 with the pretreatment composition can result in improved anticorrosive properties of the electrode and improved adhesion of the coating composition comprising the lithium-containing compound to the conductive substrate compared to conductive substrates that have not been pretreated with the pretreatment composition.
    [00017] Certain embodiments of the present invention relate to compositions and methods for treating a conductive substrate 12.
    [00018] As illustrated in Figure 1, the battery 100 may include a cathode 10, an anode 20, a spacer 40 between the anode 20 and the cathode 10, and an electrolyte 30 in contact with the cathode 10 and the anode. An enclosure 50 that is in contact with one of electrodes 10, 20 may contain electrodes 10, 20, electrolyte 30 and separator 40. A terminal 60 is in contact with cathode 10. Suitable conductive substrates 12 for use in the present invention include those that are often used as electrodes, such as a cathode 10 or anode 20, in a lithium ion battery 100. Specific examples of suitable conductive substrates 12 include, but are not limited to, aluminum, copper, iron, nickel, steel stainless steel, and combinations thereof. In certain embodiments, conductive substrate 12 of cathode 10 can comprise aluminum. In certain embodiments, the conductive substrate of anode 20 can comprise copper. In certain embodiments, the conductive substrate may be sheet-shaped with a thickness of 1 µm to 500 µm, such as 15 µm.
    [00019] The electrolyte 30 may comprise a non-aqueous solution prepared by dissolving a salt in an organic solvent. The electrolytic salt used in the electrolyte can be any electrolytic salt suitable for batteries of this type. Examples of the electrolytic salts include LiClO4, LiAsF6, LiPF6, LiBF4, LiB(C6H5)4, LiB(C2O4)2, CH3SO3Li, CF3SO3Li, LiCl, LiBr and the like. In embodiments, the organic solvent can include any suitable type that has generally been used in batteries of this type. Examples of such organic solvents include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, Y-butyrolactone, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, methylsulfolane, acetonitrile, propionitrile, anisole, acetate, butyrate, propionate and the like. In certain embodiments, cyclic carbonates such as propylene carbonate, or chain carbonates such as dimethyl carbonate and diethyl carbonate are used. These organic solvents can be used singly or in combination of two types or more. In certain embodiments, the electrolyte may also comprise additives or stabilizers, such as VC (vinyl carbonate), VEC (ethylene vinyl carbonate), EA (ethylene acetate), TPP (triphenylphosphate), phosphazenes, LiBOB, LiBETI, LiTFSI, BP (biphenyl), PS (propylene sulfite), ES (ethylene sulfite), AMC (allylmethylcarbonate) and APV (divinyladipate).
    [00020] In certain embodiments, anode 20 can be prepared by mixing a negative active material, a conductive material, and a binder by any method known in the prior art, as described, for example, in lithium ion batteries : Science and Technologies, Yoshio et al., 2009. In certain embodiments, the anode can be prepared by mixing about 93% by weight of graphite as negative active material, about 3% by weight of conductive carbon (eg, acetylene black ) and about 4% by weight of a binder such as, for example, polyvinylidene difluoride (PVDF) and using a current collector copper sheet, typically 10-15 µm thick.
    [00021] In certain embodiments, the cathode 10 can be prepared by mixing a positive active material, a conductive material and a binder, by any method known in the prior art, as described, for example, in lithium ion batteries ; Science and Technologies, Yoshio et al., 2009. In certain embodiments, the cathode can be prepared by mixing about 90% by weight of LiNiCoMnO2 as lithium active material, about 5% by weight of conductive carbon (eg, black of acetylene), and about 5% by weight of a binder, such as PVDF, and using an aluminum collector sheet, typically 10-15 µ thick.
    [00022] In certain embodiments, and as illustrated in Fig. 1, anode 20 and cathode 10 (described below) may be separated by a separator 40. In certain embodiments, the separator may be formed of a polymer film such as such as polyethylene or polypropylene, containing micropores that can be laminated. In certain embodiments, anode 20, cathode 10, and spacer 40 can be spirally wound to produce a spiral-type electrode element. In certain embodiments, the roller can be oblong in shape.
    [00023] According to embodiments of the invention, and as schematically illustrated in Fig 2, the cathode 10 comprises a conductive substrate 12, a first layer 14 coating at least a portion of the conductive substrate 12 comprising a pretreatment composition comprising a metal of Group IIIB and/or Group IV and a second layer 16 coating at least a portion of the first layer 14, the second layer 16 comprising a coating composition comprising a lithium-containing compound.
    [00024] The conductive substrate 12 to be treated according to the methods of the present invention may be first cleaned to remove grease, dirt, or other foreign matter. This is often accomplished by employing mild or strong alkaline cleaners, such as those commercially available and conventionally used in metal pretreatment processes. Examples of alkaline cleaners suitable for use in the present invention include Chemkleen 163, Chemkleen 177, Chemkleen 490MZ, Chemkleen 2010LP/Chemkleem 181 ALP, each commercially available from PPG Industries, Inc. Such cleaners are often followed and/or preceded by water washing. .
    [00025] In certain embodiments, the conductive substrate 12 to be treated in accordance with the methods of the present invention may first be washed with a fluoride solution to etch its surface. As used herein, "etch" refers to a composition that, upon contact with a substrate, activates the surface for better reaction with subsequent coating steps, including, for example, a pre-treatment step. In certain embodiments, the step of washing the substrate with fluoride solution can remove oxide layers and/or increase the surface area of the substrate, and, in the case of aluminum sheets, can remove the less reactive aluminum oxide surface layers for expose a more reactive aluminum surface, thus increasing the deposition of the pretreatment coating.
    [00026] As previously indicated, certain embodiments of the present invention relate to methods for treating a conductive substrate 12 which comprises contacting the conductive substrate with a pretreatment composition comprising a group IIIB and/or IVB metal. In embodiments, Group IIIB and/or Group IVB metal is deposited onto the conductive substrate. Often, the pretreatment composition comprises a carrier, often an aqueous medium, such that the composition is in the form of a solution or dispersion of a Group IIIB or IVB metal in the carrier. In these embodiments, the solution or dispersion can be contacted with the substrate by any of a variety of known techniques, such as dipping or dipping, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing or coating. with roller. In certain embodiments, the solution or dispersion, when applied to the conductive substrate, is at a temperature ranging from 60 to 150°F (15 to 65°C). Contact time is often 10 seconds to five minutes, such as 30 seconds to 2 minutes.
    [00027] As used herein, the term "pretreatment composition" refers to a composition that, upon contact with the conductive substrate, reacts with and chemically alters the substrate surface, binding to it to form a protective layer .
    [00028] As used herein, the term "group IIIB metal and/or group IVB metal" refers to an element that is included in group IIIB or group IVB of the CAS Periodic Table of Elements, as shown, for example, in the Handbook of Chemistry and Physics, 63rd edition (1983). Where applicable, the metal itself can be used. In certain embodiments, a group IIIB and/or IVB metal compound is used. As used herein, the term "group IIIB and/or IVB metal compound" refers to compounds that include at least one element that is in group IIIB or group IVB of the Periodic Table of Elements CAS.
    [00029] In certain embodiments, the group IIIB and/or IVB metal compound used in the pretreatment composition may be a zirconium, titanium, hafnium, yttrium, cerium, praseodymium compound, or a mixture thereof. Suitable zirconium compounds include, but are not limited to hexafluorozirconic acid, alkali metal and its ammonium salts, zirconium ammonium carbonate, zirconyl nitrate, zirconium carboxylates and zirconium hydroxy carboxylates such as hydrofluorozirconic acid, zirconium acetate, oxalate of zirconium, ammonium zirconium glycolate, zirconium ammonium lactate, zirconium ammonium citrate, and mixtures thereof. Suitable titanium compounds include, but are not limited to, fluorotitanic acid and its salts. A suitable hafnium compound includes, but is not limited to, hafnium nitrate. A suitable compound of yttrium includes, but is not limited to, yttrium nitrate. A suitable cerium compound includes, but is not limited to, waxy nitrate. A suitable praseodymium compound includes, but is not limited to praseodymium nitrate.
    [00030] In certain embodiments, the group IIIB and/or IVB metal compound is present in the pretreatment composition in an amount of at least 20 ppm, such as at least 50 ppm metal, or, in some cases, at least 180 ppm metal (measured as elemental metal). In certain embodiments, the Group IIIB and/or IVB metal compound is present in the pretreatment composition in an amount of at most 5000 ppm metal, such as at most 1000 metal, or, in some cases, at most. maximum 300 ppm metal (measured as elemental metal). The amount of Group IIIB and/or IVB metal in the pretreatment composition can vary between any combination of the quoted values, including the quoted values.
    [00031] In certain embodiments, the pretreatment composition also comprises an electropositive metal. As used herein, the term "electropositive metal" refers to metals that are more electropositive than the metallic substrate. This means that, for the purposes of the present invention, the term "electropositive metal" encompasses metals that are less easily oxidized than the metal of the metallic substrate being treated. As will be appreciated by the person skilled in the art, the tendency of a metal to be oxidized is called an oxidation potential, being expressed in volts, and measured relative to a standard hydrogen electrode, which is arbitrarily assigned a zero oxidation potential. The oxidation potential for various elements is shown in the table below. One element is considered to be less easily oxidized than another if that element has a voltage value, E*, in the table below, greater than the element to which it is being compared.

    [00032] Thus, as will be evident, when a cathode substrate 12 comprises one of the materials listed above, such as aluminum, the electropositive metals suitable for inclusion in the pretreatment composition will include, for example, tin, indium, gallium, cobalt, nickel, copper, silver, and gold, as well as mixtures thereof.
    [00033] In certain embodiments, the source of electropositive metal in the pretreatment composition is a water-soluble metal salt. In certain embodiments of the present invention, the water-soluble metal salt is a water-soluble copper compound. Specific examples of water-soluble copper compounds suitable for use in the present invention include, but are not limited to, copper cyanide, potassium copper cyanide, copper sulfate, copper nitrate, copper pyrophosphate, copper thiocyanate, ethylenediaminetetraacetate. disodium copper tetrahydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride, copper gluconate, copper citrate, copper lauroyl sarcosinate, copper formate, copper acetate, copper propionate, butyrate copper, copper lactate, copper oxalate, copper phytate, copper tartrate, copper malate, copper succinate, copper malonate, copper maleate, copper benzoate, copper salicylate, copper aspartate, copper glutamate , copper fumarate, copper glycerophosphate, sodium copper chlorophyllin, copper fluorosilicate, copper fluoroborate, and copper iodate, as well as copper salts of carboxylic acids in the acid homolog series. ormic to decanoic acid, copper salts of polybasic acids in the oxalic acid to suberic acid series, and copper salts of hydroxycarboxylic acids, including glycolic, lactic, tartaric, malic and citric acids.
    [00034] When copper ions supplied by such a water-soluble copper compound are precipitated as impurity in the form of copper sulfate, copper oxide, etc., it may be preferable to add a complexing agent that suppresses the precipitation of copper ions , thus stabilizing them as a copper complex in the solution.
    [00035] In certain embodiments, the copper compound is added as a copper complex salt, such as K3Cu(CN)4 or Cu-EDTA, which may be stably present in the composition by itself, but which is also possible form a copper complex which can be stably present in the composition by combining a complexing agent with a poorly soluble compound on its own. Examples thereof include a copper cyanide complex through a combination of CuCN and KCN or a combination of CuSCN and KSCN or KCN, and a Cu-EDTA complex formed through a combination of CuSO4 and EDTA.2Na.
    [00036] In relation to the complexing agent, one can use a compound that can form a complex with copper ions; examples thereof include inorganic compounds, such cyanide compounds and thiocyanate compounds, and polycarboxylic acids, and specific examples thereof include ethylenediaminetetraacetic acid, salts of ethylenediaminetetraacetic acid, such as dihydrogen ethylenediaminetetraacetic acid dihydrate, aminocarboxylic acids, such as nitrilodiacetic acid, and imimyloxyacetic acid , such as citric acid and tartaric acid, succinic acid, oxalic acid, ethylenediaminetetramethylenephosphonic acid and glycine.
    [00037] In certain embodiments, electropositive metal, such as copper, is included in the pretreatment compositions in an amount of at least 2 ppm, such as at least 60 ppm, or in some cases, at least 60 ppm total metal (measured as elemental metal). In certain embodiments, electropositive metal is included in such pretreatment compositions in an amount of at most 20 ppm, such as at most 100 ppm, or in some cases, at most 80 ppm total metal (measured as elemental metal ). The amount of electropositive metal in the pretreatment composition can vary between any combination of quoted values, including quoted values.
    [00038] The pretreatment compositions of the present invention may also comprise free fluoride. As will be appreciated, the source of free fluoride in the pretreatment compositions of the present invention can vary. For example, in some cases, the free fluoride may be derived from the group IIIB and/or IVB metal compound used in the pretreatment composition, as is the case, for example, with hexafluorozirconic acid. As the group IIIB and/or IVB metal is deposited onto the metal substrate during the pretreatment process, the fluorine in the hexafluorozirconic acid becomes free fluoride and, as will be appreciated, the level of free fluoride in the pretreatment, if uncontrolled, will increase over time as the metal is pretreated with the pretreatment composition of the present invention.
    [00039] In addition, the source of free fluoride in the treatment compositions of the present invention may include a compound other than the group IIIB and/or IVB compound. Non-limiting examples of such sources include HF, NH4HF2, NaF, and NaHF2. Ammonium fluorides or bifluorides, phosphonium, Group IA metals, Group IIA metals, Group IIIA metals, or a combination thereof.
    [00040] As used herein, the term "free fluoride" refers to isolated fluoride and its concentration in the pretreatment compositions of the present invention can be determined by measuring a pretreatment composition through a meter with a fluoride-electrode. selective.
    [00041] In certain embodiments, free fluoride is included in the pretreatment compositions in an amount of at least 2 ppm, such as at least 25 ppm, or in some cases, at least 250 ppm total metal (measured as elemental metal). In certain embodiments, electropositive metal is included in such pretreatment compositions in an amount of at most 1000 ppm, such as at most 500 ppm, or in some cases, at most 100 ppm total metal (measured as elemental metal ). The amount of electropositive metal in the treatment composition can vary between any combination of quoted values, including quoted values.
    [00042] In certain embodiments, the pH of the pretreatment composition ranges from 2 to 6, such as from 4.5 to 5.5. The pH of the pretreatment composition can be adjusted using, for example, any acid or base as needed. In certain embodiments, the pH of the solution is maintained by including a base material, including water-soluble and/or dispersible bases, such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and/or amines , such as triethylamine, methylethylamine or mixtures thereof.
    [00043] In certain embodiments, the pretreatment composition comprises a resinous binder. Suitable resins include reaction products of one or more alkanolamines and an epoxy-functional material containing at least two epoxy groups, such as those described in U.S. Patent No. 5,653,823. In some cases, such resins contain beta hydroxy ester, imide, or sulfide functionality incorporated through the use of dimethylolpropionic acid, phthalimide, or mercaptoglycerin as an additional reagent in preparing the resin. Alternatively, the reaction product is that of bisphenol A diglycidyl ether (commercially available from Shell Chemical Company as EPON 880), dimethylol propionic acid, and diethanolamine in a molar ratio of 0.6 to 5.0:0.05 to 5 .5:1. Other suitable resin binders include water-soluble and water-dispersible polyacrylic acids as described in US Pat. 3,912,548 and 5,328,525; phenol formaldehyde resins as described in U.S. Patent No. 5,662,746; water-soluble polyamides such as those described in WO 95/33869; copolymers of maleic acid or acrylic with allyl ether, as described in Canadian patent application 2,087,352; and water-soluble and water-dispersible resins, including epoxy resins, aminoplastics, phenol-formaldehyde resins, tannins, and polyvinyl phenols, as discussed in US Patent No. 5,449,415. Other suitable resin binders include conductive and semiconductor binders, including polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepone, and/or polyaniline, or resin binders that contain an additive conductive, such as electrically conductive particles, such as electrically conductive carbon particles, including, but not limited to, electrically conductive carbon blacks, carbon nanotubes, carbon fibers, fullerenes and the like, electrically conductive silica, metallic powders including aluminum, copper , steel, molybdenum disulfide, iron oxide, iron oxide, black steel oxide, antimony-doped titanium dioxide, and nickel-doped titanium dioxide, as well as particles of alumina, aluminum, aromatic polyester, boron nitride, chromium, graphite, iron, molybdenum, neodymium/iron/boron, samarium cobalt, silicon carbide , stainless steel, titanium diboride, tungsten, tungsten carbide, zirconia, ceramic microballoons, cut glass fibers, lamellar and powdered graphite, boron nitride, lamellar mica, lamellar and powdered copper, powdered nickel, lamellar nickel coated with metals such as cobalt, copper, nickel, iron, tin, zinc, palladium, silicon, silver, titanium, and combinations thereof.
    [00044] In those embodiments of the present invention, the resinous binder is present in the pretreatment composition in an amount of from 0.005 percent to 30 percent by weight, such as from 0.5 to 3 percent by weight, based on weight. total ingredients of the composition.
    [00045] In other embodiments, however, the pretreatment composition is substantially free or, in some cases, completely free of any resinous binder. As used herein, the term "substantially free", when used with reference to the absence of resinous binder in the pretreatment composition, means that any resinous binder is present in the pretreatment composition in an amount of less than 0.005 percent by weight. As used herein, the term "completely free" means that there is no resinous binder in the pretreatment composition.
    [00046] The pretreatment composition may optionally contain other materials, such as nonionic surfactants and auxiliaries conventionally used in the pretreatment state of the art. In an aqueous medium, water-dispersible or water-soluble solvents, for example, alcohols with up to about 8 carbon atoms, such as methanol, isopropanol and the like, may be present; or glycol ethers, such as ethylene glycol monoalkyl ethers, diethylene glycol or propylene glycol and the like, primary amines with about up to 8 carbon atoms, such as propylamine and butylamine, secondary and tertiary amines, such as triethylamine, and diisopropyl ethylamine, alkanolamines such as diisopropylethanolamine, polymeric amines such as Jeffamine, aromatic/cyclic amines such as pyridines and pyrrolidines or sulfonamides. When present, water-dispersible organic solvents are typically used in amounts of about up to ten percent by volume, based on the total volume of aqueous medium.
    [00047] Other optional materials include surfactants that function as defoamers or substrate wetting agents.
    [00048] In certain embodiments, the pretreatment composition also comprises a reaction accelerator, such as nitrite ions, nitrate ions, compounds containing nitro group, hydroxylamine sulfate, persulfate ions, sulfite ions, hyposulfite ions, peroxides, ions iron(III), iron compounds, citric acid, molybdate ions, bromate ions, perchlorate ions, chlorate ions, chlorite ions, as well as ascorbic acid, citric acid, tartaric acid, malonic acid, succinic acid and their salts. Specific examples of suitable materials and their quantities are described in U.S. Patent Application Publication No. 2004/0163736 A1 at [0032] to [0041], the cited portion of which is incorporated herein by reference.
    [00049] In certain embodiments, the pretreatment composition also comprises a filler, such as a siliceous filler. Non-limiting examples of suitable fillers include silica, mica, montmorillonite, kaolinite, asbestos, talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, cement, calcium silicate, aluminum silicate, sodium aluminum silicate, aluminum polysilicate, silica gel alumina, and glass particles. In addition to siliceous fillers, other finely divided and substantially water-soluble particulate fillers can also be employed. Examples of such optional fillers include carbon black, carbon, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, zinc sulfide, zinc sulfate. barium, strontium sulfate, calcium carbonate, and magnesium carbonate. In certain other embodiments, the pretreatment composition can also comprise a conductive charge, or a charge that contains a conductive additive, such as the electrically conductive particles described above.
    [00050] In certain embodiments, the pretreatment composition comprises phosphate ions. In certain embodiments, phosphate ions are present in an amount of from 10 to 500 ppm of phosphate ions, such as from 25 to 200 ppm of phosphate ions. Representative sources of phosphate ions include H3PO4, NaH2PO4, and/or (NH4)H2PO4. In certain embodiments, however, the pretreatment composition of the present invention is substantially or, in some cases, completely free of phosphate ion. As used herein, the term "substantially free", when used in reference to the absence of phosphate ion in the pretreatment composition, means that the phosphate ion is present in the composition in an amount of less than 10 ppm. As used herein, the term "completely free", when used in reference to the absence of phosphate ions, means that there are no phosphate ions in the composition.
    [00051] In certain embodiments, the pretreatment composition is substantially or, in some cases, completely free of chromate and/or heavy metal phosphate, such as zinc phosphate. As used herein, the term "substantially free", when used with reference to the absence of heavy metal chromate and/or phosphate in the pretreatment composition, means that these substances are not present in the composition to the point of causing harm to the environment. environment. That is, they are substantially not used and the formation of sludge, such as zinc phosphate, formed by using a treatment agent based on zinc phosphate, is eliminated. As used herein, the term "completely free", when used in reference to the absence of a heavy metal phosphate and/or chromate, means that there is no heavy metal phosphate and/or chromate in the composition.
    [00052] Furthermore, in certain embodiments, the pretreatment composition is substantially free or, in some cases, completely free of any organic materials. As used herein, the term "substantially free", when used with reference to the absence of organic materials in the composition, means that any organic materials are present in the composition, if any, as an incidental impurity. In other words, the presence of any organic material does not affect the composition's properties. As used herein, the term "completely free", when used in reference to the absence of organic material, means that there is no organic material in the composition at all.
    [00053] In certain embodiments, the skin coating of the residue of the pretreatment coating composition generally ranges from 2 to 400 milligrams per square meter (mg/m2), such as from 5 to 150 mg/m2. The thickness of the pretreatment coating can vary, although it is generally very thin, often less than 5 to 500 nanometers thick, such as 10 to 120 nanometers.
    [00054] After contact with the pretreatment solution, the substrate can be rinsed with water and dried.
    [00055] In certain embodiments of the methods of the present invention, after the conductive substrate is contacted with the pretreatment composition, it is contacted with a coating composition comprising a lithium-containing compound. Any appropriate technique can be used to contact the conductive substrate with such a coating composition, including, for example, groove die coating, doctor blade coating, reverse roller coating, direct roller coating, coating by etching, extrusion coating, dipping, brushing, dipping, flow/flow coating, spray/atomization, electrodeposition, and the like, to deposit the lithium-containing compound onto at least a portion of the pretreated conductive substrate.
    [00056] As previously indicated, in certain embodiments, the conductive substrate is contacted with a coating composition comprising a lithium-containing compound.
    [00057] As used herein, the term "lithium-containing compound", when used in association with lithium ion batteries, means any known type of lithium containing compound conventionally used in lithium ion battery electrode coatings. Examples of lithium-containing compounds used in the coating composition can be LiCoO2, LiNiO2, LiFePO4, LiMnO2, LiMnO4, Li(NiMnCO)O2, Li(NiCoAl)O2, LiFePO4 coated with lithium or mixtures thereof.
    [00058] In certain embodiments, the lithium-containing compound may be present in the coating composition in an amount of at least 60 percent by weight, at least 70 percent by weight, at least 80 percent by weight, such as at least 85 percent by weight or, in some cases, at least 90 percent by weight, based on the total weight of solids, in the coating composition.
    [00059] In certain embodiments, the coating composition also comprises electrically conductive particles, such as electrically conductive carbon particles, including, but not limited to, electrically conductive carbon blacks, carbon nanotubes, graphenes, carbon fibers, fullerenes, and the like , electrically conductive silica, metallic powders including aluminum, copper or special steel, molybdenum disulfide, iron oxide, black iron oxide, antimony-doped titanium dioxide, and nickel-doped titanium dioxide, and alumina, aluminum particles, aromatic polyester, boron nitride, chromium, graphite, iron, molybdenum, neodymium/iron/boron, samarium cobalt, silicon carbide, stainless steel, titanium diboride, tungsten, tungsten carbide, zirconia, ceramic microballoons, fiberglass cut, lamellar and powdered graphite, boron nitride, lamellar mica, lamellar and powdered copper, powdered nickel, lamellar nickel coated with metals such as cobalt, copper, nickel, iron, tin, zinc, palladium, silicon, silver, titanium, and combinations thereof.
    [00060] In certain embodiments, electrically conductive particles may have an average particle size, prior to incorporation into the coating composition, of less than 300 nanometers, such as from 1 to 200 nanometers, from 10 to 100 nanometers, or, in some cases, from 30 to 50 nanometers.
    [00061] In certain embodiments, electrically conductive particles may be present in the composition in an amount such that the relative weight ratio of lithium-containing compound to electrically conductive particles in the composition is at least 3:1, at least 4:1, at least 5:1, at least 8:1, at least 10:1, or, in some cases, at least 15:1.
    [00062] In certain embodiments, such electrically conductive particles may be present in an amount of at most 20 percent by weight, at most 10 percent by weight, such as 1 to 10 percent by weight, or 1 to 5 percent by weight, based on the total weight of solids in the coating composition.
    [00063] In certain embodiments, the coating composition comprises a binder. Suitable binders include polyvinylidene difluoride (PVDF), sodium carboxymethylcellulose, polyvinyl alcohol, styrene-butadiene rubber, polytetrafluoroethylene, acrylonitrile-butadiene rubber, ethylene propylene diene monomer rubber, polyurethane, polyacrylate, polyacrylic acid, polyvinyl ether, polyimide, including copolymers and their mixtures. In certain embodiments, the coating composition can comprise a conductive or semiconductor binder, including polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepone, and/or polyaniline.
    [00064] In certain embodiments, the binder may be present in an amount of at most 20 percent by weight, at most 10 percent by weight, such as 1 to 10 percent by weight or 1 to 5 percent by weight. weight, based on the total weight of solids in the coating composition. In certain embodiments, the binder may be present in the coating composition in a percentage by weight that is equal to the percentage by weight of the electrically conductive particles.
    [00065] In certain embodiments, the coating composition may optionally contain other materials such as corrosion inhibitors, antioxidants, flow control agents, and surfactants conventionally used in prior art coatings.
    [00066] In embodiments, after the conductive substrate is contacted with the coating composition comprising a lithium-containing compound, the coating is often heated to cure the deposited composition. Any suitable technique can be used to heat or cure the deposited coating composition, including, for example, warm air drying, hot air drying, low humidity air drying, infrared drying, remote infrared drying, and drying by electron radiation. The heating or curing operation is often conducted at a temperature in the range of ambient temperature to 250 °C, such as 120 to 190 °C, for a period ranging from 1 to 60 minutes. In certain embodiments, the resulting film thickness is 40 to 150 microns, such as 80 to 90 microns.
    [00067] As will be appreciated by the aforementioned report, the present invention relates to compositions for treating a conductive substrate. In certain embodiments, such compositions comprise a Group IIIB and/or IV metal. The composition, in certain embodiments, is substantially free of heavy metal phosphate, such as zinc phosphate and zinc chromate.
    [00068] In still other aspects, the present invention relates to compositions for treating a conductive substrate comprising a group IIIB and/or IVB metal. These compositions of the present invention are substantially free of phosphate and chromate ions.
    [00069] The following examples illustrate the invention, which should not be considered as restricting it in its details. All parts and percentages in the examples, as well as throughout the report, are by weight unless otherwise noted. Examples Example 1
    [00070] 1g Kynar® HSV900 PVDF binder (commercially available from Arkema Inc., King of Prussia, PA) and 25.5g n-methyl-2-pyrrolidone solvent (commercially available from International Specialty Products, Inc., Wayne , NJ) were placed in a 100 ml DAC mixing vessel (FlackTek, Inc., Landrum, SC) and shaken until complete dissolution of the PVDF polymer. Then, 1g of C-EnergyTM Super C65 conductive carbon (commercially available from Timcal) and 18g of Lithium Dioxide Nickel Cobalt Manganese TX 10 (commercially available from Umicore) were added to the container. After screwing the lid on, the container was placed in the Speedmixer DAC 600 FVZ mixer (FlackTek, Inc.) and the mixing conducted at 2350 rpm for 5 minutes. The cathode slurry from the lithium ion battery was then deposited onto the ethanol-cleaned aluminum foil (commercially available from Targray Technology International Inc., Rancho Dominguez, CA) using a doctor blade fitted to a 400 micron span and an automatic table ( MTI Corporation, Richmond, CA). The coating was then dried at 120°C for 20 minutes. The coated sheet was quickly passed through a calender press with an opening set to 0.030 mm, compressing the coating to a thickness of 93 to 65 microns.
    [00071] This coated sample was tested for peel strength adhesion using an Instron tensiometer and a method very similar to ASTM D903-98, "Standard Test Method for Peel Resistance and Stripping of Adhesive Bonds", except that a fee 2 inch per minute traction was used, with no further sample conditioning.
    [00072] The maximum average force or peel strength in Newtons for this coated sample is shown in Table 1 below. Example
    [00073] Bath A was prepared using 30.0 grams of Chemfos AFL (free fluoride liquid additive, commercially available from PPG Industries, Inc., Euclid, OH) and 11.4 liters of deionized water. The pH of Bath A was 3.6 and that of free fluoride 220 ppm.
    [00074] Bath B was prepared using 11.4 liters of deionized water, 10.0g of fluorozirconic acid (45% by weight in water) and 8.4g of Chemfos AFL (PPG Industries). The pH was adjusted to 4.5 with Chemfil buffer (a commercially available alkaline material from PPG Industries, Inc.). The zirconium level was 180 ppm and the free fluoride level was 100 ppm in Bath B.
    [00075] Ethanol-cleaned aluminum foil was fixed to an aluminum holder with four stainless steel paper clips. The sheet was immersed in an acid fluoride pickling bath (Bath A) for two minutes at 70°C. The sheet was immediately placed in a bath containing zirconium and fluoride (Bath B) for two minutes at 80°F. The pretreated sheet was then rinsed with deionized water for thirty seconds and dried with hot air (130°F).
    [00076] The pretreated sheet was then coated as described in Example 1. The maximum average peel strength or peel strength, in Newtons, for this pretreated and coated sample is shown in Table 1 below. Example 3
    [00077] Bath A was prepared as described in Example 2.
    [00078] Bath B was prepared as described in Example 2, except that 12.0 grams of copper nitrate solution (2.0% by weight in deionized water) was added to Bath B. The zirconium level was 180 ppm, free fluoride 100 ppm, and copper 20.0 ppm in Bath B.
    [00079] The sheet was then pretreated, coated, and tested as described in Example 2.
    [00080] The maximum average peel strength or peel strength in Newtons for this pretreated and coated sample is shown in Table 1 below. Example 4
    [00081] Bath A was prepared as described in Example 2.
    [00082] Bath B was prepared as described in Example 2, except that 24.0 grams of copper nitrate solution (2.0% by weight in deionized water) was added to Bath B. The zirconium level was 180 ppm, free fluoride 100 ppm, and copper 40.0 ppm in Bath B.
    [00083] The sheet was then pretreated, coated, and tested, as described in Example 2.
    [00084] The maximum average peel strength or peel strength in Newtons for this pretreated and coated sample is shown in Table 1 below. Example 5
    [00085] Bath A was prepared as described in Example 2.
    [00086] Bath B was prepared as described in Example 2, except that 36.0 grams of copper nitrate solution (2.0% by weight in deionized water) was added to Bath B. The zirconium level was 180 ppm, free fluoride 100 ppm, and copper 60.0 ppm in Bath B.
    [00087] The sheet was then pretreated, coated, and tested, as described in Example 2.
    [00088] The maximum average peel strength or peel strength in Newtons for this pretreated and coated sample is shown in Table 1 below. Example 6
    [00089] Bath A was prepared as described in Example 2.
    [00090] Ethanol-cleaned aluminum foil was fixed to an aluminum holder with four stainless steel paper clips. The sheet was immersed in an acid fluoride pickling bath (Bath A) for two minutes at 70°C. The fluoride pickled sheet was then rinsed with deionized water for thirty seconds, dried with hot air (130°F) and then coated and tested as described in Example 1.
    [00091] The maximum average peel strength or peel strength in Newtons for this pretreated and coated sample is shown in Table 1 below. Table 1

    [00092] Pretreatment Examples 2-5 above exhibit significantly increased maximum average peel strength, demonstrating significantly improved coating adhesion, eg greater than 10 percent, eg greater than 25 to 30 percent, or greater than 40 to 50 percent.
    [00093] It will be appreciated by those skilled in the art that changes may be made in the embodiments described above, without departing from their broad inventive concept. It is, therefore, understood that the present invention is not restricted to the specific embodiments described, although it is intended to encompass modifications within the spirit and scope of the invention as defined in the appended claims.
    权利要求:
    Claims (14)
    [0001]
    1. Cathode of a lithium ion battery, characterized in that it comprises: - a conductive substrate (12); - a first layer (14) coating at least a portion of the conductive substrate (12) deposited from a pretreatment composition comprising a Group IIIB and/or Group IVB metal compound dissolved or dispersed in a carrier in an electropositive metal comprising tin, indium, gallium, cobalt, nickel, copper, silver, gold or a combination thereof; and - a second layer (16) coating at least a portion of the first layer (14), the second layer being deposited from a coating composition comprising a lithium-containing compound.
    [0002]
    2. Cathode according to claim 1, characterized in that the Group IIIB and/or Group IVB metal comprises zirconium.
    [0003]
    3. Cathode according to claim 1, characterized in that the Group IIIB and/or Group IVB metal is present in the pretreatment composition in an amount of 20 ppm metal to 5000 ppm metal based on weight total pretreatment composition.
    [0004]
    4. Cathode according to claim 1, characterized in that the electropositive metal is present in an amount of 2 ppm metal to 200 ppm metal based on the total weight of the pretreatment composition.
    [0005]
    5. Cathode according to claim 1, characterized in that the pretreatment composition further comprises a source of free fluoride present in an amount of 2ppm to 1000ppm metal based on the total weight of the pretreatment composition .
    [0006]
    6. Cathode according to claim 5, characterized in that the free fluoride source comprises ammonium fluorides or bifluorides, phosphonium, Group IA metals, Group IIA metals, Group IIIA metals, or a combination thereof.
    [0007]
    7. Cathode according to claim 1, characterized in that the lithium-containing compound comprises lithium nickel cobalt manganese dioxide, lithium iron phosphate, carbon-coated lithium iron phosphate, or a combination thereof.
    [0008]
    8. Cathode according to claim 1, characterized in that the lithium-containing compound comprises from 80 to 90 percent by weight, based on the total weight of the coating, and wherein the coating composition further comprises a conductive agent comprising from 5 to 10 percent by weight and a binder comprising from 5 to 10 percent by weight, based on the total weight of the coating.
    [0009]
    9. Cathode according to claim 1, characterized in that the cathode (10) has an adhesion resistance to peeling at 180° greater than 1.5N.
    [0010]
    10. Cathode according to claim 1, characterized in that the first layer (14) has a thickness of 5 to 500 nm.
    [0011]
    11. Cathode according to claim 1, characterized in that the cathode (10) comprises aluminum.
    [0012]
    12. Battery, characterized in that it comprises: - a cathode (10), as defined in any one of claims 1 to 8, 11: - an anode (20); - a spacer (40) between the anode (20) and the cathode (10); and - an electrolyte (30) in contact with the anode (20) and the cathode (10).
    [0013]
    13. Method for treating a battery cathode as defined in claim 1, characterized in that it comprises: - contacting a conductive substrate (12) of the battery cathode (10) with a pretreatment composition comprising a Group metal compound IIIB and/or Group IVB dissolved or dispersed in a carrier in an electropositive metal comprising tin, indium, gallium, cobalt, nickel, copper, silver, gold or a combination thereof; and - depositing a coating composition comprising lithium-containing compounds on at least a portion of the pretreated conductive substrate (12).
    [0014]
    14. Method according to claim 13, characterized in that it further comprises contacting the conductive substrate (12) with a fluoride solution before contacting the conductive substrate (12) with the pre-treatment composition.
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    HK1213302A1|2016-06-30|
    MX2015013213A|2016-10-19|
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    AU2014237576A1|2015-10-08|
    AU2014237576B2|2016-06-09|
    KR101735985B1|2017-05-24|
    RU2015144166A|2017-04-24|
    CA2904439C|2017-10-17|
    BR112015023240A8|2019-12-03|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/832,074|US9273399B2|2013-03-15|2013-03-15|Pretreatment compositions and methods for coating a battery electrode|
    US13/832,074|2013-03-15|
    PCT/US2014/022005|WO2014150050A1|2013-03-15|2014-03-07|Pretreatment compositions and methods for coating a battery electrode|
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