MULTI-FUNCTIONAL ELASTIC POLYMER LAYER FOR A LITHIUM SECONDARY BATTERY AND MANUFACTURING METHOD
20220200094 · 2022-06-23
Inventors
Cpc classification
H01M4/485
ELECTRICITY
H01M4/583
ELECTRICITY
H01M50/46
ELECTRICITY
H01M50/414
ELECTRICITY
H01M10/0525
ELECTRICITY
H01M4/0445
ELECTRICITY
H01M10/4235
ELECTRICITY
International classification
H01M10/0525
ELECTRICITY
H01M4/485
ELECTRICITY
H01M4/583
ELECTRICITY
Abstract
A lithium secondary battery comprising a cathode, an anode, an elastic polymer protective layer disposed between the cathode and the anode, and a working electrolyte, wherein the elastic polymer protective layer comprises a high-elasticity polymer having a thickness from 2 nm to 100 μm, a lithium ion conductivity from 10.sup.−8 S/cm to 5×10.sup.−2 S/cm at room temperature, and a fully recoverable tensile elastic strain from 2% to 1,000% when measured without any additive dispersed therein and wherein the high-elasticity polymer comprises at least a crosslinked polymer network of chains from at least one polymer containing carboxylic and/or hydroxyl groups or from at least one polymer that is water-soluble prior to crosslinking.
Claims
1. A lithium secondary battery comprising a cathode, an anode, an elastic polymer protective layer disposed between the cathode and the anode, and a working electrolyte through which lithium ions are transported between the anode and the cathode during a battery charge or discharge, wherein said elastic polymer protective layer comprises a high-elasticity polymer having a thickness from 2 nm to 100 μm, a lithium ion conductivity from 10.sup.−8 S/cm to 5×10.sup.−2 S/cm at room temperature, and a fully recoverable tensile elastic strain from 2% to 1,000% when measured without any additive dispersed therein and wherein said high-elasticity polymer comprises at least a crosslinked polymer network of chains from at least one polymer containing carboxylic and/or hydroxyl groups or from at least one polymer that is water-soluble prior to crosslinking.
2. The lithium secondary battery of claim 1, wherein said high-elasticity polymer further comprises from 0.1% to 95% by weight of a flame retardant additive dispersed in, dissolved in, or chemically bonded to the high-elasticity polymer.
3. The lithium secondary battery of claim 1, wherein said high-elasticity polymer further comprises from 0.01% to 95% by weight of an inorganic filler dispersed therein.
4. The lithium secondary battery of claim 1, wherein the battery is a lithium metal battery and the anode has an anode current collector but initially the anode has no lithium or lithium alloy as an anode active material supported by said anode current collector when the battery is made and prior to a charge or discharge operation of the battery.
5. The lithium secondary battery of claim 1, wherein the battery is a lithium metal battery and the anode has an anode current collector and an amount of lithium or lithium alloy as an anode active material supported by said anode current collector.
6. The lithium secondary battery of claim 1, wherein the battery is a lithium-ion battery and the anode has an anode current collector and a layer of an anode active material supported by said anode current collector, wherein the anode active materials is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium titanium niobium oxide, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo.sub.2O.sub.4; (f) carbon or graphite particles (g) prelithiated versions thereof; and (h) combinations thereof.
7. The lithium secondary battery of claim 1, wherein said elastic polymer protective layer is in physical contact with an anode current collector or an anode active material layer of the anode to protect said anode current collector or anode active material layer.
8. The lithium secondary battery of claim 1, wherein said elastic polymer protective layer is a separator that electrically isolates the anode and the cathode and in ionic communication with an anode current collector or an anode active material layer and a cathode active material layer.
9. The lithium secondary battery of claim 1, wherein said high-elasticity polymer comprises a cross-linked network of poly (acrylic acid) chains and chains from poly(vinyl alcohol), polyethylene glycol, carboxymethyl cellulose, or a combination thereof.
10. The lithium secondary battery of claim 1, wherein said high-elasticity polymer comprises a crosslinked network of polymer chains from at least one or two compounds selected from poly(acrylic acid), poly(vinyl alcohol), carboxymethyl cellulose, citric acid, glycerol, a derivative of carboxymethyl cellulose, a derivative of poly(vinyl alcohol), a derivative of poly(acrylic acid), a carboxymethyl cellulose substituted with an alkali cation, a poly(acrylic acid) substituted with an alkali cation, or a combination thereof, wherein the alkali cation is selected from Li.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+, or a combination thereof.
11. The lithium secondary battery of claim 1, wherein said high-elasticity polymer comprises a crosslinked polymer network of chains from carboxymethyl cellulose (CMC), a substituted version thereof, or a derivative thereof.
12. The lithium secondary battery of claim 1, wherein said high-elasticity polymer comprises a cross-linked network of carboxymethyl cellulose crosslinked by a crosslinking agent to a degree of crosslinking that imparts an elastic tensile strain from 5% to 500%.
13. The composite particulate of claim 12, wherein said crosslinking agent is selected from N,N-methylene bisacrylamide, epichlorohydrin, 1,4-butanediol diglycidyl ether, tetrabutylammonium hydroxide, cinnamic acid, ferric chloride, aluminum sulfate octadecahydrate, diepoxy, dicarboxylic acid compound, poly(potassium 1-hydroxy acrylate) (MBA), glycerol diglycidyl ether (GDE), ethylene glycol, polyethylene glycol, polyethylene glycol diglycidyl ether (PEGDE), citric acid, acrylic acid, methacrylic acid, a derivative compound of acrylic acid, a derivative compound of methacrylic acid, glycidyl functions, N,N′-Methylenebisacrylamide (MBAAm), Ethylene glycol dimethacrylate (EGDMAAm), isobomyl methacrylate, poly (acrylic acid) (PAA), methyl methacrylate, isobomyl acrylate, ethyl methacrylate, isobutyl methacrylate, n-Butyl methacrylate, ethyl acrylate, 2-Ethyl hexyl acrylate, n-Butyl acrylate, a diisocyanate, an urethane chain, a chemical derivative thereof, or a combination thereof.
14. The lithium secondary battery of claim 2, wherein said flame retardant additive is selected from a halogenated flame retardant, phosphorus-based flame retardant, melamine flame retardant, metal hydroxide flame retardant, silicon-based flame retardant, phosphate flame retardant, biomolecular flame retardant, or a combination thereof.
15. The lithium secondary battery of claim 2, wherein said flame retardant additive is in a form of encapsulated particles comprising the additive encapsulated by a shell of a substantially lithium ion-impermeable and liquid electrolyte-impermeable coating material, wherein said shell is breakable when exposed to a temperature higher than a threshold temperature.
16. The lithium secondary battery of claim 1, wherein said working electrolyte is selected from an organic liquid electrolyte, ionic liquid electrolyte, polymer gel electrolyte, solid-state electrolyte, quasi-solid electrolyte having a lithium salt dissolved in an organic or ionic liquid with a lithium salt concentration higher than 2.0 M, hybrid or composite electrolyte, or a combination thereof.
17. The lithium secondary battery of claim 3, wherein said inorganic filler is selected from an oxide, carbide, boride, nitride, sulfide, phosphide, halogen compound, or selenide of a transition metal, Al, Ga, In, Sn, Pb, Sb, B, Si, Ge, Sb, or Bi, a lithiated version thereof, or a combination thereof.
18. The lithium secondary battery of claim 17, wherein said transition metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, Cd, La, Ta, W, Pt, Au, Hg, a combination thereof.
19. The lithium secondary battery of claim 1, wherein said inorganic filler is selected from an inorganic solid electrolyte material in a fine powder form having a particle size from 2 nm to 30 μm.
20. The lithium secondary battery of claim 19, wherein said particles of an inorganic solid electrolyte material selected from an oxide type, sulfide type, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (LiPON), garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof.
21.-38. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0067]
[0068]
[0069]
[0070]
[0071]
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0072] This disclosure is related to a lithium secondary battery, which is preferably based on an organic electrolyte, a polymer gel electrolyte, an ionic liquid electrolyte, a quasi-solid electrolyte, or a solid-state electrolyte. The shape of a lithium secondary battery can be cylindrical, square, button-like, etc. The present invention is not limited to any battery shape or configuration or any type of electrolyte.
[0073] The present disclosure provides a lithium secondary battery comprising a cathode, an anode, and an elastic polymer protective layer disposed between the cathode and the anode, and a working electrolyte through which lithium ions are transported between the anode and the cathode during a battery charge or discharge, wherein the elastic polymer protective layer comprises a high-elasticity polymer having a thickness from 2 nm to 100 μm (preferably 5-100 nm if used as an anode-protecting layer; or preferably from 1 to 20 μm if used as a primary separator), a lithium ion conductivity from 10.sup.−8 S/cm to 5×10.sup.−2 S/cm at room temperature, and a fully recoverable tensile elastic strain from 2% to 1,000% (preferably greater than 10% and further preferably from 30% to 300%) when measured without any additive dispersed therein and wherein the high-elasticity polymer comprises at least a crosslinked polymer network of chains from at least one polymer containing carboxylic and/or hydroxyl groups or from at least one polymer that is water-soluble prior to crosslinking.
[0074] The high-elasticity polymer preferably comprises a cross-linked network of poly (acrylic acid) chains and chains from poly(vinyl alcohol), polyethylene glycol, carboxymethyl cellulose, or a combination thereof.
[0075] In certain embodiments, the high-elasticity polymer comprises a crosslinked network of polymer chains from at least one or two compounds selected from poly(acrylic acid), poly(vinyl alcohol), carboxymethyl cellulose, citric acid, glycerol, a derivative of carboxymethyl cellulose, a derivative of poly(vinyl alcohol), a derivative of poly(acrylic acid), a carboxymethyl cellulose substituted with an alkali cation, a poly(acrylic acid) substituted with an alkali cation, or a combination thereof, wherein the alkali cation is selected from Li.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+, or a combination thereof.
[0076] In certain desired embodiments, the high-elasticity polymer contains a cross-linked network of polymer chains. This high-elasticity polymer has a carboxylic group (—COOH), a hydroxyl group (—OH), a derivative thereof, or a combination thereof. For example, the high-elasticity polymer comprises a cross-linked network of poly (acrylic acid) (PAA, Chemical formula 1) and poly (vinyl alcohol) (PVA, Chemical formula 2) chains. The PAA polymer, oligomer (low-molecular weight polymer), or monomer bears one or multiple —COOH groups prior to being polymerized or crosslinked.
##STR00001##
[0077] At a temperature of typically from 100° C. to 200° C., PAA and PVA chains can react to form a crosslinked polymer network, typically through the etherification between the carboxylic functional group (—COOH) of PAA and the hydroxyl functional group (—OH) of PVA.
[0078] The high-elasticity polymer may be obtained from a wide variety of polymer chains, oligomers, or monomers having a carboxylic functional group (—COOH or a derivative thereof). Examples of the high-elasticity polymer can include at least two compounds selected from poly(acrylic acid), poly(vinyl alcohol), citric acid, glycerol, CMC, a derivative of poly(vinyl alcohol), a derivative of poly(acrylic acid), poly(acrylic acid) substituted with an alkali cation, or a combination thereof, wherein the alkali cation is selected from Li.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+, or a combination thereof. These network or cross-linked polymers exhibit a unique combination of a high elasticity (high elastic deformation strain) and high lithium-ion conductivity.
[0079] In some embodiments, the high-elasticity polymer comprises a crosslinked polymer network of chains from carboxymethyl cellulose (CMC), a substituted version thereof, or a derivative thereof.
[0080] The high-elasticity polymer may comprise a cross-linked network of carboxymethyl cellulose crosslinked by a crosslinking agent to a degree of crosslinking that imparts an elastic tensile strain from 5% to 500%.
[0081] In certain desired embodiments, the high-elasticity polymer contains a cross-linked network of polymer chains from carboxymethyl cellulose. Carboxymethyl cellulose (CMC; Formula 3) is a water-soluble material and it is soluble in either hot or cold water. The CMC may have some of its —H substituted by an alkali ion, such as Li.sup.+, Na.sup.+, K.sup.+, and NH.sub.4.sup.+).
##STR00002##
[0082] The crosslinking agent for CMC is preferably selected from N,N-methylene bisacrylamide, epichlorohydrin, 1,4-butanediol diglycidyl ether, tetrabutylammonium hydroxide, cinnamic acid, ferric chloride, aluminum sulfate octadecahydrate, diepoxy, dicarboxylic acid compound, poly(potassium 1-hydroxy acrylate) (PKHA), glycerol diglycidyl ether (GDE), ethylene glycol, polyethylene glycol, polyethylene glycol diglycidyl ether (PEGDE), citric acid (Formula 4 below), acrylic acid, methacrylic acid, a derivative compound of acrylic acid, a derivative compound of methacrylic acid (e.g. polyhydroxyethylmethacrylate), glycidyl functions, N,N′-Methylenebisacrylamide (MBAAm), Ethylene glycol dimethacrylate (EGDMAAm), isobomyl methacrylate, poly (acrylic acid) (PAA; Chemical Formula 1 and Formula 5), methyl methacrylate, isobomyl acrylate, ethyl methacrylate, isobutyl methacrylate, n-Butyl methacrylate, ethyl acrylate, 2-Ethyl hexyl acrylate, n-Butyl acrylate, a diisocyanate (e.g. methylene diphenyl diisocyanate, MDI), an urethane chain, a chemical derivative thereof, or a combination thereof.
##STR00003##
[0083] Particularly desirable crosslinking agents for CMC are acrylic acid and poly(acrylic acid) (PAA). At a temperature of typically from 50° C. to 200° C., PAA and CMC chains can react to form a crosslinked polymer network, typically through the etherification between the carboxylic functional group (—COOH) of PAA and the hydroxyl functional group (—OH) of CMC. Some of the —COOH groups in the PAA chain can form a strong covalent bond with the —OH group commonly found on surfaces of Si, a high-capacity anode active material. This implies that Si particles can be chemically bonded to the crosslinked polymer network.
[0084] For substituted CMC species, the —H groups in the CMC structure (Chemical formula 1) may be replaced by —R, where R is selected from a substituted or unsubstituted C1 to C10 alkyl group, an alkali metal, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 alkoxy group.
[0085] In certain desired embodiments, one can make use of a semi-interpenetrating polymer network (semi-IPN) as an elastic polymer matrix, wherein the semi-IPN includes CIVIC-derived chains and polymer chains from a repeating unit represented by Chemical Formula 6 or a repeating unit represented by Chemical Formula 7, wherein, R.sup.1 and R.sup.2 are the same or different and are independently selected from hydrogen, or a substituted or unsubstituted C1 to C10 alkyl group, and Wand R.sup.4 are an alkali metal, and wherein, R.sup.5 to R.sup.8 are the same or different, and are independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 alkoxy group.
##STR00004##
[0086] In a typical configuration, the elastic polymer protective layer is in ionic contact with both the anode and the cathode and typically in physical contact with an anode active material layer (or an anode current collector) and with a cathode active material layer.
[0087] In certain embodiments, the anode in the lithium secondary battery has an amount of lithium or lithium alloy as an anode active material supported by an anode current collector. In certain other embodiments, initially the anode has no lithium or lithium alloy as an anode active material supported by an anode current collector when the battery is made and prior to a charge or discharge operation of the battery. This latter configuration is referred to as an anode-less lithium battery.
[0088] In certain embodiments, the battery is a lithium-ion battery and the anode has an anode current collector and a layer of an anode active material supported by the anode current collector, which is in physical contact with the elastic flame-retardant composite separator. The anode active materials is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium titanium niobium oxide, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo.sub.2O.sub.4; (f) carbon or graphite particles (g) prelithiated versions thereof; and (h) combinations thereof.
[0089] The current collector may be a Cu foil, a layer of Ni foam, a porous layer of nano-filaments, such as graphene sheets, carbon nanofibers, carbon nano-tubes, etc. forming a 3D interconnected network of electron-conducting pathways.
[0090] Preferably and most typically, this elastic polymer protective layer is different in composition than the working electrolyte used in the lithium battery and the elastic polymer protective layer maintains as a discrete layer (not to be dissolved in the electrolyte).
[0091] We have discovered that this elastic polymer protective layer provides several unexpected benefits: (a) the formation and penetration of dendrite can be essentially eliminated; (b) uniform deposition of lithium back to the anode side is readily achieved during battery charging; (c) the layer ensures smooth and uninterrupted transport of lithium ions from/to the anode current collector surface (or the lithium film deposited thereon during the battery operations) and through the interface between the current collector (or the lithium film deposited thereon) and the elastic polymer protective layer with minimal interfacial resistance; (d) flame and fire-fighting capability is intrinsically built into the battery if a desired amount of flame-retardant additive is added into the high-elasticity layer; (e) reduced/eliminated electrolyte/lithium metal reactions; (e) reduced interfacial resistance at both the anode side and the cathode side; and (f) cycle stability can be significantly improved and cycle life increased. No additional protective layer for the lithium metal anode is required. The separator itself also plays the role as an anode protective layer.
[0092] In a conventional lithium metal cell, as illustrated in
[0093] We have solved these challenging issues that have troubled battery designers and electrochemists alike for more than 30 years by developing and implementing a new elastic polymer protective layer disposed between the anode (an anode current collector or an anode active material layer) and a cathode active material layer. This elastic polymer protective layer comprises a high-elasticity polymer having a recoverable (elastic) tensile strain no less than 2% (preferably no less than 5%, and further preferably from 10% to 500%) under uniaxial tension and a lithium ion conductivity no less than 10.sup.−8 S/cm at room temperature (preferably and more typically from 1×10.sup.−5 S/cm to 5×10.sup.−2 S/cm).
[0094] As schematically shown in
[0095] The high-elasticity polymer material refers to a material (polymer or polymer composite) that exhibits an elastic deformation of at least 2% when measured under uniaxial tension. In the field of materials science and engineering, the “elastic deformation” is defined as a deformation of a material (when being mechanically stressed) that is essentially fully recoverable and the recovery is essentially instantaneous upon release of the load. The elastic deformation is preferably greater than 5%, more preferably greater than 10%, furthermore preferably greater than 30%, and still more preferably greater than 100% (up to 500%).
[0096] It may be noted that
[0097] As the charging procedure continues, more lithium ions get to deposit onto the anode current collector, forming a lithium metal film or coating. During the subsequent discharge procedure, this lithium film or coating layer decreases in thickness due to dissolution of lithium into the electrolyte to become lithium ions, possibly creating a gap between the current collector and the separator layer if the separator layer were not elastic (e.g. a ceramic separator). Such a gap would make the re-deposition of lithium ions back to the anode impossible during a subsequent recharge procedure. We have observed that the presently invented elastic polymer protective layer is capable of expanding or shrinking congruently or conformably with the anode active layer (i.e. lithium metal layer). This capability helps to maintain a good contact between the current collector (or the lithium film subsequently or initially deposited on the current collector surface) and the protective layer, enabling the re-deposition of lithium ions without interruption.
[0098]
[0099] Flame-retardant additives are intended to inhibit or stop polymer pyrolysis and combustion processes by interfering with the various mechanisms involved—heating, ignition, and propagation of thermal degradation.
[0100] The flame retardant additive may be selected from a halogenated flame retardant, phosphorus-based flame retardant, melamine flame retardant, metal hydroxide flame retardant, silicon-based flame retardant, phosphate flame retardant, biomolecular flame retardant, or a combination thereof.
[0101] There is no limitation on the type of flame retardant that can be physically or chemically incorporated into the elastic polymer. The main families of flame retardants are based on compounds containing: Halogens (Bromine and Chlorine), Phosphorus, Nitrogen, Intumescent Systems, Minerals (based on aluminum and magnesium), and others (e.g. Borax, Sb.sub.2O.sub.3, and nanocomposites). Antimony trioxide is a good choice, but other forms of antimony such as the pentoxide and sodium antimonate may also be used.
[0102] One may use the reactive types (being chemically bonded to or becoming part of the polymer structure) and additive types (simply dispersed in the polymer matrix). For instance, reactive polysiloxane can chemically react with EPDM type elastic polymer and become part of the crosslinked network polymer. It may be noted that flame-retarding group modified polysiloxane itself is an elastic polymer composite containing a flame reatardant according to an embodiment of instant disclosure. Both reactive and additive types of flame retardants can be further separated into several different classes: [0103] 1) Minerals: Examples include aluminum hydroxide (ATH), magnesium hydroxide (MDH), huntite and hydromagnesite, various hydrates, red phosphorus and boron compounds (e.g. borates). [0104] 2) Organo-halogen compounds: This class includes organochlorines such as chlorendic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a replacement for decaBDE), polymeric brominated compounds such as brominated polystyrenes, brominated carbonate oligomers (BCOs), brominated epoxy oligomers (BEOs), tetrabromophthalic anyhydride, tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCD). [0105] 3) Organophosphorus compounds: This class includes organophosphates such as triphenyl phosphate (TPP), resorcinol bis(diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonates such as dimethyl methylphosphonate (DMMP); and phosphinates such as aluminum diethyl phosphinate. In one important class of flame retardants, compounds contain both phosphorus and a halogen. Such compounds include tris(2,3-dibromopropyl) phosphate (brominated tris) and chlorinated organophosphates such as tris(1,3-dichloro-2-propyl)phosphate (chlorinated tris or TDCPP) and tetrakis(2-chlorethyl) dichloroisopentyldiphosphate (V6). [0106] 4) Organic compounds such as carboxylic acid and dicarboxylic acid
[0107] The mineral flame retardants mainly act as additive flame retardants and do not become chemically attached to the surrounding system (the polymer). Most of the organohalogen and organophosphate compounds also do not react permanently to attach themselves into the polymer. Certain new non halogenated products, with reactive and non-emissive characteristics have been commercially available as well.
[0108] In certain embodiments, the flame retardant additive is in a form of encapsulated particles comprising the additive encapsulated by a shell of coating material that is breakable or meltable when exposed to a temperature higher than a threshold temperature (e.g., flame or fire temperature induced by internal shorting). The encapsulating material is a substantially lithium ion-impermeable and liquid electrolyte-impermeable coating material. The encapsulating or micro-droplet formation processes that can be used to produce protected flame-retardant particles are briefly described below.
[0109] Several encapsulated composite droplet forming processes require the encapsulating polymer or its precursor (monomer or oligomer) to be dissolvable in a solvent. Fortunately, there are a wide variety of polymers or their precursors used herein are soluble in some common solvents or water; water being the preferred liquid solvent. The un-cured polymer or its precursor can be readily dissolved in a common organic solvent or water to form a solution. This solution can then be used to embed, immerse, engulf or encapsulate the solid particles (e.g. flame retardant aluminum hydroxide particles and magnesium hydroxide particles) via several of the micro-droplet-forming methods to be discussed in what follows. Upon formation of the droplets, the polymer matrix is then polymerized and cross-linked.
[0110] There are three broad categories of micro-encapsulation methods that can be implemented to produce polymer-encapsulated flame retardant: physical methods, physico-chemical methods, and chemical methods. The physical methods include extrusion and pelletizing, solution dipping and drying, suspension coating or casting on a solid substrate (e.g. slot-die coating, Comma coating, spray-coating) followed by drying and scratching off particles from the substrate, pan-coating, air-suspension coating, centrifugal extrusion, vibration nozzle, and spray-drying methods. The physico-chemical methods include ionotropic gelation and coacervation-phase separation methods. The chemical methods include interfacial polycondensation, interfacial cross-linking, in-situ polymerization, and matrix polymerization.
[0111] It may be noted that some of these methods (e.g. pan-coating, air-suspension coating, and spray-drying) may be used to coat or encapsulate particles by adjusting the solid content, degree of dispersion, spraying and drying conditions, etc.
[0112] Pan-coating method: The pan coating process involves tumbling the flame retardant particles in a pan or a similar device while the matrix material (e.g. monomer/oligomer liquid or uncured polymer/solvent solution; possibly containing a lithium salt dispersed or dissolved therein) is applied slowly until a desired amount of matrix is attained.
[0113] Air-suspension coating method: In the air suspension coating process, the solid particles are dispersed into the supporting air stream in an embedding chamber. A controlled stream of a reactive precursor solution (e.g. polymer or its monomer or oligomer dissolved in a solvent; or its monomer or oligomer alone in a liquid state) is concurrently introduced into this chamber, allowing the solution to hit and embed the suspended particles. These suspended particles are embedded in the reactive precursor (monomer, oligomer, etc. which is polymerized/cured concurrently or subsequently) while the volatile solvent is removed, leaving behind a composite comprising a matrix of conducting network polymer and anode active material particles. This process may be repeated several times until the required parameters, such as full embedding, are achieved. The air stream which supports the anode particles also helps to dry them, and the rate of drying is directly proportional to the temperature of the air stream, which can be adjusted for optimized polymer network amount.
[0114] In a preferred mode, the particles in the embedding zone portion may be subjected to re-circulation for repeated embedding. Preferably, the chamber is arranged such that the particles pass upwards through the embedding zone, then are dispersed into slower moving air and sink back to the base of the encapsulating chamber, enabling repeated passes of the particles through the embedding zone until the desired matrix amount is achieved.
[0115] Centrifugal extrusion: Additive particles may be embedded in a polymer network or precursor material using a rotating extrusion head containing concentric nozzles. In this process, a stream of core fluid (slurry containing additive particles dispersed in a solvent) is surrounded by a sheath of shell solution or melt containing the polymer or precursor. As the device rotates and the stream moves through the air it breaks, due to Rayleigh instability, into droplets of core, each coated with the shell solution. While the droplets are in flight, the molten shell may be hardened or the solvent may be evaporated from the shell solution. If needed, the capsules can be hardened after formation by catching them in a hardening bath. Since the drops are formed by the breakup of a liquid stream, the process is only suitable for liquid or slurry. A high production rate can be achieved. Up to 22.5 kg of microcapsules can be produced per nozzle per hour and extrusion heads containing 16 nozzles are readily available.
[0116] Vibrational nozzle encapsulation method: matrix-encapsulation of particles can be conducted using a laminar flow through a nozzle and vibration of the nozzle or the liquid. The vibration has to be done in resonance with the Rayleigh instability, leading to very uniform droplets. The liquid can include any liquids with limited viscosities (1-50,000 mPa.Math.s): emulsions, suspensions or slurry containing the anode active material particles and the polymer or precursor.
[0117] Spray-drying: Spray drying may be used to encapsulate and embed particles when the particles are suspended in a melt or polymer/precursor solution to form a suspension. In spray drying, the liquid feed (solution or suspension) is atomized to form droplets which, upon contacts with hot gas, allow solvent to get vaporized and a polymer matrix to fully embed the particles.
[0118] In-situ polymerization: In some micro-encapsulation processes, particles are fully embedded in a monomer or oligomer first. Then, direct polymerization of the monomer or oligomer is carried out with the presence of these material particles dispersed therein.
[0119] Matrix polymerization: This method involves dispersing and embedding solid particles in a polymeric matrix during formation of the particles. This can be accomplished via spray-drying, in which the particles are formed by evaporation of the solvent from the matrix material. Another possible route is the notion that the solidification of the matrix is caused by a chemical change.
[0120] The elastic polymer protective layer may comprise an inorganic filler dispersed in the high-elasticity polymer matrix wherein the inorganic filler is preferably selected from an oxide, carbide, boride, nitride, sulfide, phosphide, halogen compound, or selenide of a transition metal, Al, Ga, In, Sn, Pb, Sb, B, Si, Ge, Sb, or Bi, a lithiated version thereof, or a combination thereof. The transition metal is preferably selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Pd, Ag, Cd, La, Ta, W, Pt, Au, Hg, a combination thereof. Particularly desired metal oxide particles include Al.sub.2O.sub.3 and SiO.sub.2.
[0121] In certain preferred embodiments, the inorganic filler comprises fine particles of a solid-state electrolyte made into a powder form. Preferably, the inorganic solid electrolyte material (to be added into the elastic polymer protective layer as a lithium ion conductivity enhancer and a lithium dendrite stopper) is in a fine powder form having a particle size preferably from 10 nm to 30 μm (more preferably from 50 nm to 1 μm). The inorganic solid electrolyte material may be selected from an oxide type (e.g., perovskite-type), sulfide type, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (UPON), Garnet-type. lithium superionic conductor (LISICON) sodium superionic conductor (NASICON), or a combination thereof.
[0122] The inorganic solid electrolytes that can be incorporated into an elastic polymer protective layer include, but are not limited to, perovskite-type, NASICON-type, garnet-type and sulfide-type materials. A representative and well-known perovskite solid electrolyte is Li.sub.3xLa.sub.2/3−xTiO.sub.3, which exhibits a lithium-ion conductivity exceeding 10.sup.−3 S/cm at room temperature. This material has been deemed unsuitable in lithium batteries because of the reduction of Ti.sup.4+ on contact with lithium metal. However, we have found that this material, when dispersed in an elastic polymer, does not suffer from this problem.
[0123] The sodium superionic conductor (NASICON)-type compounds include a well-known Na.sub.1+xZr.sub.2Si.sub.xP.sub.3−xO.sub.12. These materials generally have an AM.sub.2(PO.sub.4).sub.3 formula with the A site occupied by Li, Na or K. The M site is usually occupied by Ge, Zr or Ti. In particular, the LiTi.sub.2(PO.sub.4).sub.3 system has been widely studied as a solid state electrolyte for the lithium-ion battery. The ionic conductivity of LiZr.sub.2(PO.sub.4).sub.3 is very low, but can be improved by the substitution of Hf or Sn. This can be further enhanced with substitution to form Li.sub.1+xM.sub.xTi.sub.2−x(PO.sub.4).sub.3 (M=Al, Cr, Ga, Fe, Sc, In, Lu, Y or La). Al substitution has been demonstrated to be the most effective solid state electrolyte. The Li.sub.1+xAl.sub.xGe.sub.2−x(PO.sub.4).sub.3 system is also an effective solid state due to its relatively wide electrochemical stability window. NASICON-type materials are considered as suitable solid electrolytes for high-voltage solid electrolyte batteries.
[0124] Garnet-type materials have the general formula A.sub.3B.sub.2Si.sub.3O.sub.12, in which the A and B cations have eightfold and sixfold coordination, respectively. In addition to Li.sub.3M.sub.2Ln.sub.3O.sub.12 (M=W or Te), a braod series of garnet-type materials may be used as an additive, including Li.sub.5La.sub.3M.sub.2O.sub.12 (M=Nb or Ta), Li.sub.6ALa.sub.2M.sub.2O.sub.12 (A=Ca, Sr or Ba; M=Nb or Ta), Li.sub.5.5La.sub.3M.sub.1.75B.sub.0.25O.sub.12 (M=Nb or Ta; B=In or Zr) and the cubic systems Li.sub.7La.sub.3Zr.sub.2O.sub.12 and Li.sub.7.06M.sub.3Y.sub.0.06Zr.sub.1.94O.sub.12 (M=La, Nb or Ta). The Li.sub.6.5La.sub.3Zr.sub.1.75Te.sub.0.25O.sub.12 compounds have a high ionic conductivity of 1.02×10.sup.−3 S/cm at room temperature.
[0125] The sulfide-type solid electrolytes include the Li.sub.2S—SiS.sub.2 system. The highest reported conductivity in this type of material is 6.9×10.sup.−4 S/cm, which was achieved by doping the Li.sub.2S—SiS.sub.2 system with Li.sub.3PO.sub.4. The sulfide type also includes a class of thio-LISICON (lithium superionic conductor) crystalline material represented by the Li.sub.2S—P.sub.2S.sub.5 system. The chemical stability of the Li.sub.2S—P.sub.2S.sub.5 system is considered as poor, and the material is sensitive to moisture (generating gaseous H.sub.2S). The stability can be improved by the addition of metal oxides. The stability is also significantly improved if the Li.sub.2S—P.sub.2S.sub.5 material is dispersed in an elastic polymer.
[0126] These solid electrolyte particles dispersed in an elastic polymer can help stop the penetration of lithium dendrites (if present) and enhance the lithium ion conductivity of certain elastic polymers having an intrinsically low ion conductivity.
[0127] Preferably and typically, the high-elasticity polymer has a lithium ion conductivity no less than 10.sup.−5 S/cm, more preferably no less than 10.sup.−4 S/cm, further preferably no less than 10.sup.−3 S/cm, and most preferably no less than 10.sup.−2 S/cm. The high-elasticity composite separator is a polymer matrix composite containing from 1% to 95% (preferably 10% to 85%) by weight of lithium ion-conducting solid electrolyte particles dispersed in or bonded by a high-elasticity polymer matrix material.
[0128] The high-elasticity polymer should have a high elasticity (elastic deformation strain value >2%). An elastic deformation is a deformation that is fully recoverable and the recovery process is essentially instantaneous (no significant time delay). The high-elasticity polymer can exhibit an elastic deformation from 5% up to 1,000% (10 times of its original length), more typically from 10% to 800%, and furthermore typically from 50% to 500%, and most typically and desirably from 70% to 300%. It may be noted that although a metal typically has a high ductility (i.e. can be extended to a large extent without breakage), the majority of the deformation is plastic deformation (non-recoverable) and only a small amount of elastic deformation (typically <1% and more typically <0.2%).
[0129] Typically, a high-elasticity polymer is originally in a monomer or oligomer states that can be cured to form a cross-linked polymer that is highly elastic. Prior to curing, these polymers or oligomers are soluble in an organic solvent to form a polymer solution. An ion-conducting or flame retardant additive may be added to this solution to form a suspension. This solution or suspension can then be formed into a thin layer of polymer precursor on a surface of an anode current collector. The polymer precursor (monomer or oligomer and initiator) is then polymerized and cured to form a lightly cross-linked polymer. This thin layer of polymer may be tentatively deposited on a solid substrate (e.g. surface of a polymer or glass), dried, and separated from the substrate to become a free-standing polymer layer. This free-standing layer is then laid on a lithium foil/coating or implemented between a lithium film/coating and electrolyte or separator. Polymer layer formation can be accomplished by using one of several procedures well-known in the art; e.g. spraying, spray-painting, printing, coating, extrusion-based film-forming, casting, etc.
[0130] It is essential for these materials to form a lightly cross-linked network of polymer chains. In other words, the network polymer or cross-linked polymer should have a relatively low degree of cross-linking or low cross-link density to impart a high elastic deformation.
[0131] The cross-link density of a cross-linked network of polymer chains may be defined as the inverse of the molecular weight between cross-links (Mc). The cross-link density can be determined by the equation, Mc=ρRT/Ge, where Ge is the equilibrium modulus as determined by a temperature sweep in dynamic mechanical analysis, ρ is the physical density, R is the universal gas constant in J/mol*K and T is absolute temperature in K. Once Ge and p are determined experimentally, then Mc and the cross-link density can be calculated.
[0132] The magnitude of Mc may be normalized by dividing the Mc value by the molecular weight of the characteristic repeat unit in the cross-link chain or chain linkage to obtain a number, Nc, which is the number of repeating units between two cross-link points. We have found that the elastic deformation strain correlates very well with Mc and Nc. The elasticity of a cross-linked polymer derives from a large number of repeating units (large Nc) between cross-links. The repeating units can assume a more relaxed conformation (e.g. random coil) when the polymer is not stressed. However, when the polymer is mechanically stressed, the linkage chain uncoils or gets stretched to provide a large deformation. A long chain linkage between cross-link points (larger Nc) enables a larger elastic deformation. Upon release of the load, the linkage chain returns to the more relaxed or coiled state. During mechanical loading of a polymer, the cross-links prevent slippage of chains that otherwise form plastic deformation (non-recoverable).
[0133] Preferably, the Nc value in a high-elasticity polymer is greater than 5, more preferably greater than 10, furthermore preferably greater than 100, and even more preferably greater than 200. These Nc values can be readily controlled and varied to achieve different elastic deformation values by using different cross-linking agents with different functionalities, and by designing the polymerization and cross-linking reactions to proceed at different temperatures for different periods of time.
[0134] Alternatively, Mooney-Rilvin method may be used to determine the degree of cross-linking. Crosslinking also can be measured by swelling experiments. In a swelling experiment, the crosslinked sample is placed into a good solvent for the corresponding linear polymer at a specific temperature, and either the change in mass or the change in volume is measured. The higher the degree of crosslinking, the less swelling is attainable. Based on the degree of swelling, the Flory Interaction Parameter (which relates the solvent interaction with the sample, Flory Huggins Eq.), and the density of the solvent, the theoretical degree of crosslinking can be calculated according to Flory's Network Theory. The Flory-Rehner Equation can be useful in the determination of cross-linking.
[0135] The high-elasticity polymer may contain a simultaneous interpenetrating network (SIPN) polymer, wherein two cross-linking chains intertwine with each other, or a semi-interpenetrating network polymer (semi-IPN), which contains a cross-linked polymer and a linear polymer.
[0136] The aforementioned high-elasticity polymers may be used alone to protect the lithium foil/coating layer at the anode. Alternatively, the high-elasticity polymer can be mixed with a broad array of elastomers, electrically conducting polymers, lithium ion-conducting materials, and/or strengthening materials (e.g., carbon nanotube, carbon nano-fiber, or graphene sheets).
[0137] A broad array of elastomers can be mixed with a high-elasticity polymer to form a blend, co-polymer, or interpenetrating network. The elastomeric material may be selected from natural polyisoprene (e.g. cis-1,4-polyisoprene natural rubber (NR) and trans-1,4-polyisoprene gutta-percha), synthetic polyisoprene (IR for isoprene rubber), polybutadiene (BR for butadiene rubber), chloroprene rubber (CR), polychloroprene (e.g. Neoprene, Baypren etc.), butyl rubber (copolymer of isobutylene and isoprene, IIR), including halogenated butyl rubbers (chloro butyl rubber (CIIR) and bromo butyl rubber (BIIR), styrene-butadiene rubber (copolymer of styrene and butadiene, SBR), nitrile rubber (copolymer of butadiene and acrylonitrile, NBR), EPM (ethylene propylene rubber, a copolymer of ethylene and propylene), EPDM rubber (ethylene propylene diene rubber, a terpolymer of ethylene, propylene and a diene-component), epichlorohydrin rubber (ECO), polyacrylic rubber (ACM, ABR), silicone rubber (SI, Q, VMQ), fluorosilicone rubber (FVMQ), fluoroelastomers (FKM, and FEPM; such as Viton, Tecnoflon, Fluorel, Aflas and Dai-El), perfluoroelastomers (FFKM: Tecnoflon PFR, Kalrez, Chemraz, Perlast), polyether block amides (PEBA), chlorosulfonated polyethylene (CSM; e.g. Hypalon), and ethylene-vinyl acetate (EVA), thermoplastic elastomers (TPE), protein resilin, protein elastin, ethylene oxide-epichlorohydrin copolymer, polyurethane, urethane-urea copolymer, and combinations thereof.
[0138] The urethane-urea copolymer film usually includes two types of domains, soft domains and hard ones. Entangled linear backbone chains including poly (tetramethylene ether) glycol (PTMEG) units constitute the soft domains, while repeated methylene diphenyl diisocyanate (MDI) and ethylene diamine (EDA) units constitute the hard domains. The lithium ion-conducting additive can be incorporated in the soft domains or other more amorphous zones.
[0139] In some embodiments, a high-elasticity polymer can form a polymer matrix composite containing a lithium ion-conducting additive dispersed in the high-elasticity polymer matrix material, wherein the lithium ion-conducting additive is selected from Li.sub.2CO.sub.3, Li.sub.2O, Li.sub.2C.sub.2O.sub.4, LiOH, LiX, ROCO.sub.2Li, HCOLi, ROLi, (ROCO.sub.2Li).sub.2, (CH.sub.2OCO.sub.2Li).sub.2, Li.sub.2S, Li.sub.xSO.sub.y, or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, 1≤y≤4.
[0140] In some embodiments, the high-elasticity polymer can be mixed with a lithium ion-conducting additive, which contains a lithium salt selected from lithium perchlorate (LiClO.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6), lithium trifluoro-methanesulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3), Li-fluoroalkyl-phosphate (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof
[0141] In some embodiments, the high-elasticity polymer may form a mixture, co-polymer, semi-interpenetrating network, or simultaneous interpenetrating network with a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a derivative thereof (e.g. sulfonated versions), or a combination thereof.
[0142] The presently invented lithium secondary batteries can contain a wide variety of cathode active materials. The cathode active material layer may contain a cathode active material selected from an inorganic material, an organic material, a polymeric material, or a combination thereof. The inorganic material may be selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, or a combination thereof.
[0143] The inorganic cathode active material may be selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, lithium metal silicide, or a combination thereof.
[0144] The cathode active material layer may contain a metal oxide containing vanadium oxide selected from the group consisting of Li.sub.xVO.sub.2, Li.sub.xV.sub.2O.sub.5, Li.sub.xV.sub.3O.sub.8, Li.sub.xV.sub.3O.sub.7, Li.sub.xV.sub.4O.sub.9, Li.sub.xV.sub.6O.sub.13, their doped versions, their derivatives, and combinations thereof, wherein 0.1<x<5.
[0145] The cathode active material layer may contain a metal oxide or metal phosphate, selected from a layered compound LiMO.sub.2, spinel compound LiM.sub.2O.sub.4, olivine compound LiMPO.sub.4, silicate compound Li.sub.2MSiO.sub.4, Tavorite compound LiMPO.sub.4F, borate compound LiMBO.sub.3, or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.
[0146] The electrolyte used in the lithium battery may be a liquid electrolyte, polymer gel electrolyte, solid-state electrolyte (including solid polymer electrolyte, inorganic electrolyte, and composite electrolyte), quasi-solid electrolyte, ionic liquid electrolyte.
[0147] The liquid electrolyte or polymer gel electrolyte typically comprises a lithium salt dissolved in an organic solvent or ionic liquid solvent. There is no particular restriction on the types of lithium salt or solvent that can be used in practicing the present inventions.
[0148] Some particularly useful lithium salts are lithium perchlorate (LiClO.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6), lithium trifluoro-methanesulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3), Li-fluoroalkyl-phosphate (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.
[0149] There are a wide variety of processes that can be used to produce layers of elastic polymer protective layers. These include coating, casting, painting, spraying (e.g. ultrasonic spraying), spray coating, printing (screen printing, 3D printing, etc.), tape casting, etc.
[0150] In certain embodiments, the process for manufacturing elastic protective layer may comprise (A) providing a liquid reactive mass comprising a polymer and a crosslinking agent or a mixture of a monomer or oligomer, an optional catalyst, and a crosslinking agent dissolved in a liquid, wherein the liquid reactive mass comprises optional particles of a flame retardant additive and/or an optional inorganic material particles dispersed therein to form a slurry; (B) dispensing and depositing a layer of the liquid reactive mass onto a solid substrate surface; and (C) polymerizing and/or curing the reactive mass to form a layer of elastic polymer protective layer, wherein the high-elasticity polymer comprises at least a crosslinked polymer network of chains from at least one polymer containing carboxylic and/or hydroxyl groups or from at least one polymer that is water-soluble prior to crosslinking.
[0151] The solid substrate may be an anode current collector, an anode active material layer, or a cathode active material layer. In other words, this elastic composite separator can be directly deposited onto a layer of anode active material, an anode current collector, or a layer of cathode active material. This is achievable because curing of the high-elasticity polymer does not require a high temperature; curing temperature typically lower than 200° C. or even lower than 100° C. This is in stark contrast to the typically 900-1,200° C. required of sintering an inorganic solid electrolyte to form a ceramic separator. In addition, the presently disclosed elastic separator is at least as good as a ceramic separator in terms of reducing interfacial impedance and stopping dendrite penetration.
[0152] Preferably, the process is a roll-to-roll process wherein step (B) comprises (i) continuously feeding a layer of the solid substrate (e.g. flexible metal film, plastic film, etc.) from a feeder roller to a dispensing zone where the reactive mass is dispensed and deposited onto the solid substrate to form a continuous layer of the reactive mass; (ii) moving the layer of the reactive mass into a reacting zone where the reactive mass is exposed to heat, ultraviolet (UV) light, or high-energy radiation to polymerize and/or cure the reactive mass to form a continuous layer of elastic composite; and (iii) collecting the elastic composite on a winding roller. This process is conducted in a reel-to-reel manner.
[0153] In certain embodiments, as illustrated in
[0154] The process may further comprise cutting and trimming the layer of elastic composite into one or multiple pieces of elastic composite separators.
[0155] The process may further comprise combining an anode, the elastic composite separator, an electrolyte, and a cathode electrode to form a lithium battery.
[0156] The lithium battery may be a lithium metal battery, lithium-ion battery, lithium-sulfur battery, lithium-selenium battery, lithium-air battery, etc. The cathode active material in the lithium-sulfur battery may comprise sulfur or lithium polysulfide.
EXAMPLE 1
Anode-Less Lithium Battery Containing an Elastic Polymer Protective Layer
[0157] PAA/PVA crosslinked network polymer-based elastic polymer protective layers were prepared by a thermo-induced polymerization approach. The reactive solution or slurry was prepared by mixing a polymer precursor (PAA and PVA aqueous solution, weight ratio of 9:1) and a desired amount of selected flame retardant (e.g. aluminum hydroxide and a phosphorus compound, Chemical Formula 7 below, from Amfine Chemical Corp.).
##STR00005##
[0158] The mixture was stirred for 3 hours, followed by casting onto a glass surface to form a layer. The prepared layer was then thereto-polymerized by heating at 120° C. for 5 hours and then at 150° C. for 2 hours. The etherification reaction took place between the carboxyl functional group (—COOH) of PAA and the hydroxyl functional group (—OH) of PVA.
[0159] On a separate basis, some amount of the PVA/PAA aqueous solution was cast onto a glass surface to form a wet film, which was thermally cured under similar conditions to form a film of cross-linked polymer. In this experiment, the PAA/PVA weight ratio was varied from 1/9 to 9/1 to vary the degree of cross-linking in several different polymer films. Some of the cure polymer samples were subjected to dynamic mechanical testing to obtain the equilibrium dynamic modulus, Ge, for the determination of the number average molecular weight between two cross-link points (Mc) and the corresponding number of repeat units (Nc), as a means of characterizing the degree of cross-linking.
[0160] Several tensile testing specimens were cut from each cross-linked film and tested with a universal testing machine. The representative tensile stress-strain curves indicate that this series of network polymers have an elastic deformation from approximately 55% to 345%. These above are for neat polymers without any additive. The addition of up to 30% by weight of a lithium salt typically reduces this elasticity down to a reversible tensile strain from 10% to 100%.
[0161] For electrochemical testing, the working electrodes (cathode layers) were prepared by mixing 85 wt. % LiV.sub.2O.sub.5 or 88% of graphene-embraced LiV.sub.2O.sub.5 particles, 5-8 wt. % CNTs, and 7 wt. % polyvinylidene fluoride (PVDF) binder dissolved in N-methyl-2-pyrrolidinoe (NMP) to form a slurry of 5 wt. % total solid content. After coating the slurries on Al foil, the electrodes were dried at 120° C. in vacuum for 2 h to remove the solvent before pressing. Then, the electrodes were cut into a disk (ϕ=12 mm) and dried at 100° C. for 24 h in vacuum.
[0162] Electrochemical measurements were carried out using CR2032 (3V) coin-type cells with lithium metal as the counter/reference electrode, an elastic polymer protective layer as a composite separator, and 1 M LiPF.sub.6 electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v). The cell assembly was performed in an argon-filled glove-box. For comparison purposes, cells with the conventional Celgard 2400 membrane as separator were also prepared. The CV measurements were carried out using a CH-6 electrochemical workstation at a scanning rate of 1-100 mV/s. The electrochemical performance of the cell featuring the elastic polymer composite separator and that containing a conventional separator were evaluated by galvanostatic charge/discharge cycling at a current density of 50 mA/g using an Arbin electrochemical workstation.
[0163] The specific intercalation capacity curves of two lithium cells each having a cathode containing LiV.sub.2O.sub.5 particles (one cell having a flame retardant-filled cross-linked polymer-based separator and the other having no protection, just a conventional separator) were obtained and compared. As the number of cycles increases, the specific capacity of the un-protected cells drops at a very fast rate. In contrast, the presently invented cross-linked polymer-based composite separator (also serving as an anode protection layer) provides the battery cell with a significantly more stable and high specific capacity for a large number of cycles. These data have demonstrated the surprising and superior performance of the presently invented cross-linked polymer protection approach.
[0164] The high-elasticity cross-linked polymer protective layer appears to be capable of reversibly deforming to a great extent without breakage when the lithium foil decreases in thickness during battery discharge. The elastic polymer protective layer also prevents the continued reaction between liquid electrolyte and lithium metal at the anode, reducing the problem of continuing loss in lithium and electrolyte. This also enables a significantly more uniform deposition of lithium ions upon returning from the cathode during a battery re-charge; hence, no lithium dendrite.
EXAMPLE 2
High-Elasticity Polymer Protective Layer Implemented as a Composite Separator in a Lithium-LiCoO.SUB.2 .Cell (Initially the Cell Being Lithium-Free)
[0165] The high-elasticity polymer was based on 18 wt % of a polyacrylic acid aqueous solution (10 wt % concentration), and 8 wt % of NaOH, and 74 wt % of polyvinyl alcohol. Upon casting on a glass surface, the resulting reactive mass was heated at 200° C. for 60 minutes to produce a film of cross-linked compound of Na.sup.+-substituted polyacrylic acid and polyvinyl alcohol.
[0166] Separately, the reacting mass was cast onto a glass surface to form several films which were cured to obtain cross-linked polymers having different degrees of cross-linking. Tensile testing was also conducted on these films. This series of cross-linked polymers can be elastically stretched up to approximately 43% (higher degree of cross-linking) to 445% (lower degree of cross-linking).
[0167] In some samples, a desired amount of a flame retardant (e.g. decabromodiphenyl ethane (DBDPE), brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO), and melamine-based flame retardant, separately; the latter from Italmatch Chemicals) was then added into the solution.
[0168] In several samples, a garnet-type solid electrolyte (Li7La3Zr2O12 (LLZO) powder) was also added into the solution. Subsequently, these solutions were separately cast to form a thin layer of precursor reactive mass onto a Cu foil. The precursor reactive mass was then heated at a temperature from 75 to 100° C. for 2 to 8 hours to obtain a layer of high-elasticity polymer composite adhered to the Cu foil surface.
[0169] Electrochemical testing results show that the cell having an anode-protecting polymer composite layer offers a significantly more stable cycling behavior. The high-elasticity polymer appears to act to isolate the liquid electrolyte from the subsequently deposited lithium coating, preventing continued reaction between the liquid electrolyte and lithium metal.
EXAMPLE 3
Li Metal Cells Containing a Semi-Interpenetrating Network Polymer-Based Protective Layer
[0170] Several elastic polymer protective layers were obtained from a semi-interpenetrating network polymer including (a) a copolymer containing a repeating unit represented by the following Chemical Formula 8 and a repeating unit represented by the following Chemical Formula 9 and (ii) polyacrylamide polyalkylene glycol.
##STR00006##
[0171] In an example, 390 g of deionized water, 25 g of isobutylene-co-maleic anhydride, and 10 g of polyethylene glycol were introduced into a 2 L reactor having a heater, a cooler, and an agitator. An aqueous solution prepared by dissolving 8.0 g of lithium hydroxide in 80 g of deionized water at room temperature was slowly added into this reactor, and the mixture was agitated for 10 minutes. The reactor was heated up to 80° C. under nitrogen atmosphere and maintained for 3 hours, Subsequently, a solution prepared by dissolving 0.125 g of ammonium persulfate in 10 g of deionized water was added to the mixture. which was maintained for 20 minutes, and an aqueous solution prepared by dissolving 65 g of acrylamide in 180 g of deionized water was added thereto in a dropwise fashion for 2 hours. The mixture was reacted for 1 hour and cooled down to lower than 40° C. An aqueous solution prepared by dissolving lithium 2.9 g of hydroxide in 20 g of deionized water was added thereto in a dropwise fashion for 10 minutes. The slurry was coated onto a PEI film. Upon curing, the high-elasticity polymer layer included a semi-interpenetrating polymer network including a copolymer including a repeating unit represented by Chemical Formula 8 and a repeating unit represented by Chemical Formula 9 and polyacrylamide, and polyalkylene glycol, and included free lithium ion.
[0172] In this example, in the above Chemical Formula 8, R.sup.1 and R.sup.2 are hydrogen, and R.sup.3 and R.sup.4 are Li. In the above Chemical Formula 9, R.sup.5 and R.sup.7 are hydrogen, and R.sup.6 and R.sup.8 are CH.sub.3. The repeating unit represented by the above Chemical Formula 8 was included in an amount of 40 mol % based on the total amount of the copolymer, and the repeating unit represented by the above Chemical Formula. 9 was included in an amount of 60 mol % based on the total amount of the copolymer. Furthermore, in the semi-interpenetrating polymer network, a mole ratio of the copolymer to the polyacrylamide was 3:7. The amount of the send-interpenetrating polymer was 90 mol % and that of polyalkylene glycol was 10 mole % in the elastic polymer composition. The weight-average molecular weight of the polyalkylene glycol was 3000 g/mol, and the amount of free lithium ion was 6.6 mol %.
[0173] In some samples, a flame retardant (e.g. triphenylphosphate (TPP) and “Phoslite”, a phosphorus compound from Italmatch Chemicals) was dispersed in the elastic polymer, prior to being cast onto a lithium metal layer pre-deposited on a Cu foil surface to form a precursor film, which was polymerized and cured at 70° C. for half an hour to obtain a lightly cross-linked polymer.
[0174] Additionally, the reacting mass, the reactive mass (without any additive), was cast onto a glass surface to form several films that were polymerized and cured to obtain cross-linked polymers having different degrees of cross-linking. Tensile testing was also conducted on these films and this series of cross-linked polymers can be elastically stretched up to approximately 25% (higher degree of cross-linking) to 80% (lower degree of cross-linking)
[0175] Commercially available NCM-532 powder (well-known lithium nickel cobalt manganese oxide), along with graphene sheets (as a conductive additive), was then added into an NMP and PVDF binder suspension to form a multiple-component slurry. The slurry was then slurry-coated on Al foil and dried to form cathode layers.
[0176] An Al foil-supported cathode active layer, an elastic protective layer (essentially a flame retardant polymer composite separator), and a Cu foil-supported lithium metal foil were then assembled into a lithium metal cell, followed by an electrolyte injection procedure.
EXAMPLE 4
Li Metal Cells Containing a Crosslinked CMC/PAA Network-Based Elastic Polymer Protective Layer
[0177] A crosslinked polymer network of CMC/PAA chains was prepared according to the following procedure: The PAA crosslinked CMC network polymer was prepared by a thermo-induced polymerization and crosslinking approach. The reactive slurry was prepared by mixing 100 mg CMC, 400 mg acrylic acid monomer (AA), 40 mg (NH.sub.4).sub.2S.sub.2O.sub.8, and 12 mg NaHSO.sub.3 in 12 mL water. The solution was heated at 45-50° C. for 2-3 hours, and was neutralized by NaOH to a pH value of 6.2. Approximately 3 g of silicon powder (approximately 1 μm in average diameter) was added into the solution. The resulting slurry was stirred for 2 hours and then cast to form layers of reactive mass, which were then heat treated at 115° C. for 5 hours and then at 150° C. for 2 hours. The etherification reaction presumably took place between the carboxyl functional group (—COOH) of PAA and the hydroxyl functional group (—OH) of CMC.
[0178] On a separate basis, some amount of the CMC/PAA aqueous solution was cast onto a glass surface to form a wet film, which was thermally cured under similar conditions to form films of cross-linked polymer. In this experiment, the PAA/CMC weight ratio was varied from 1/9 to 9/1 to vary the degree of cross-linking in several different polymer films. Some of the cure polymer samples were subjected to dynamic mechanical testing to obtain the equilibrium dynamic modulus, Ge, for the determination of the number average molecular weight between two cross-link points (Mc) and the corresponding number of repeat units (Nc), as a means of characterizing the degree of cross-linking.
[0179] Several tensile testing specimens were cut from each cross-linked film and tested with a universal testing machine. The representative tensile stress-strain curves indicate that this series of network polymers have an elastic deformation from approximately 22% to 310%.
[0180] Desired amounts of a flame retardant (aluminum hydroxide and magnesium hydroxide), along with some desired particles of a solid inorganic electrolyte, were then added into the solution to form slurry samples. The slurry samples were slot-die coated on a PET plastic substrate to form layers of elastic polymer protective polymer. These flame retardants were found to have insignificant impact on the lithium ion conductivity.
EXAMPLE 5
Elastic Polymer Protective Layer from Crosslinked Polyacrylic Acid and CMC
[0181] The high-elasticity polymer layer for protecting a lithium metal anode was based on 18 wt % of a polyacrylic acid aqueous solution (10 wt % concentration) and 8 wt % of NaOH, and 74 wt % of CMC. Upon casting onto a Cu foil surface, the reactive polymer layer was heated at 125° C. for 2 hours to produce a layer of cross-linked compound of Na.sup.+-substituted polyacrylic acid and CMC.
[0182] Separately, the reacting mass was cast onto a glass surface to form several films which were cured to obtain cross-linked polymers having different degrees of cross-linking. Tensile testing was also conducted on these films. This series of cross-linked polymers can be elastically stretched up to approximately 33% (higher degree of cross-linking) to 420% (lower degree of cross-linking).
[0183] In several samples, a desired amount of a selected flame retardant additive (aluminum hydroxide) was added into the reactive mass to produce flame-retardant protective layers.
EXAMPLE 6
Citric Acid-Crosslinked CMC as an Elastic Polymer Shell/Matrix
[0184] CMC solution (2% w/v) was prepared by adding sodium carboxymethyl cellulose powder (2.0 g) to 100 mL of DI water and stirring at room temperature until complete solubilization occurred. After dissolution, the crosslinking agent, citric acid (CA), was added under stirring at concentrations of 10% (CMC/CA10), 15% (CMC/CA15), 20% (CMC/CA20), and 25% (CMC/CA25) m/m of CMC polymer and homogenized for 20 min to form several different reactive suspensions (slurry samples). The reactive slurries were subsequently coated onto a solid substrate, which were cured at 80±2° C. for 24 h to complete the crosslinking reaction.
EXAMPLE 7
PEGDE-Crosslinked CMC as an Elastic Polymer Shell/Matrix
[0185] A series of CMC-based network polymers crosslinked by polyethylene glycol diglycidyl ether (PEGDE) was prepared. A typical procedure was performed as follows: 5.0 g of CMC (23 mmol for monomeric unit) was completely dissolved in 100 mL of 1.5 mol L.sup.−1 aqueous NaOH solution, and 0.50 g of PEGDE (1.1 mmol) was subsequently added to the solution with stirring at 300 rpm using a Teflon impeller at 25° C. The crosslinking reaction was initiated at 60° C. with stirring at 300 rpm for 30 minutes and then the slurry was then cast onto a stainless steel surface to obtain reactive layers. These layers were maintained at 60° C. for another 2 hours to complete the crosslinking reaction.
EXAMPLE 8
Preparation of Solid Electrolyte Powder, Lithium Nitride Phosphate Compound (LIPON) for Use as a Solid Filler or Additive
[0186] Particles of Li.sub.3PO.sub.4 (average particle size 4 μm) and urea were prepared as raw materials; 5 g each of Li.sub.3PO.sub.4 and urea was weighed and mixed in a mortar to obtain a raw material composition. Subsequently, the raw material composition was molded into 1 cm×1 cm×10 cm rod with a molding machine, and the obtained rod was put into a glass tube and evacuated. The glass tube was then subjected to heating at 500° C. for 3 hours in a tubular furnace to obtain a lithium nitride phosphate compound (LIPON). The compound was ground in a mortar into a powder form. These particles can be added into an elastic polymer matrix.
EXAMPLE 9
Preparation of Solid Electrolyte Powder, Lithium Superionic Conductors with the Li.SUB.10.GeP.SUB.2.S.SUB.12 .(LGPS)-Type Structure
[0187] The starting materials, Li.sub.2S and SiO.sub.2 powders, were milled to obtain fine particles using a ball-milling apparatus. These starting materials were then mixed together with P.sub.2S.sub.5 in the appropriate molar ratios in an Ar-filled glove box. The mixture was then placed in a stainless steel pot, and milled for 90 min using a high-intensity ball mill. The specimens were then pressed into pellets, placed into a graphite crucible, and then sealed at 10 Pa in a carbon-coated quartz tube. After being heated at a reaction temperature of 1,000° C. for 5 h, the tube was quenched into ice water. The resulting solid electrolyte material was then subjected to grinding in a mortar to form a powder sample to be later added as an inorganic solid electrolyte particles dispersed in an intended elastic polymer matrix.
EXAMPLE 10
Preparation of Garnet-Type Solid Electrolyte Powder
[0188] The synthesis of the c-Li.sub.6.25Al.sub.0.25La.sub.3Zr.sub.2O.sub.12 was based on a modified sol-gel synthesis-combustion method, resulting in sub-micron-sized particles after calcination at a temperature of 650° C. (J. van den Broek, S. Afyon and J. L. M. Rupp, Adv. Energy Mater., 2016, 6, 1600736).
[0189] For the synthesis of cubic garnet particles of the composition c-Li.sub.6.25Al.sub.0.25La.sub.3Zr.sub.2O.sub.12, stoichiometric amounts of LiNO.sub.3, Al(NO.sub.3).sub.3-9H.sub.2O, La(NO.sub.3).sub.3-6(H.sub.2O), and zirconium (IV) acetylacetonate were dissolved in a water/ethanol mixture at temperatures of 70° C. To avoid possible Li-loss during calcination and sintering, the lithium precursor was taken in a slight excess of 10 wt % relative to the other precursors. The solvent was left to evaporate overnight at 95° C. to obtain a dry xerogel, which was ground in a mortar and calcined in a vertical tube furnace at 650° C. for 15 h in alumina crucibles under a constant synthetic airflow. Calcination directly yielded the cubic phase c-Li.sub.6.25Al.sub.0.25La.sub.3Zr.sub.2O.sub.12, which was ground to a fine powder in a mortar for further processing.
[0190] The c-Li.sub.6.25Al.sub.0.25La.sub.3Zr.sub.2O.sub.12 solid electrolyte pellets with relative densities of ˜87±3% made from this powder (sintered in a horizontal tube furnace at 1070° C. for 10 h under O.sub.2 atmosphere) exhibited an ionic conductivity of ˜0.5×10.sup.−3 S cm.sup.−1 (RT). The garnet-type solid electrolyte with a composition of c-Li.sub.6.25Al.sub.0.25La.sub.3Zr.sub.2O.sub.12 (LLZO) in a powder form was dispersed in several electric, ion-conducting polymers discussed earlier.
EXAMPLE 11
Preparation of Sodium Superionic Conductor (NASICON) Type Solid Electrolyte Powder
[0191] The Na.sub.3.1Zr.sub.1.95M.sub.0.05Si.sub.2PO.sub.12 (M=Mg, Ca, Sr, Ba) materials were synthesized by doping with alkaline earth ions at octahedral 6-coordination Zr sites. The procedure employed includes two sequential steps. Firstly, solid solutions of alkaline earth metal oxides (MO) and ZrO.sub.2 were synthesized by high energy ball milling at 875 rpm for 2 h. Then NASICON Zr.sub.3.1Zr.sub.1.95M.sub.0.05Si.sub.2PO.sub.12 structures were synthesized through solid-state reaction of Na.sub.2CO.sub.3, Zr.sub.1.95M.sub.0.05O.sub.3.95, SiO.sub.2, and NH.sub.4H.sub.2PO.sub.4 at 1260° C.