JP7122309B2 - Flexible and Conformable Cable Alkaline Metal Battery - Google Patents

Description

CROSS REFERENCES TO RELATED APPLICATIONS This application is part of U.S. Patent Application Serial No. 15/384,749, filed December 20, 2016, and U.S. Patent Application Serial No. 15/384, filed December 20, 2016. , 781, both of which are incorporated herein by reference.

Lithium batteries, including primary (non-rechargeable) and secondary (rechargeable) alkaline metal and alkaline ion batteries of cable type, which are flexible, compatible and flame retardant. It relates to the field of sodium batteries and potassium batteries.

Conventional batteries (e.g., 18650-type cylindrical cells and rectangular pouch or prismatic cells) are mechanically rigid, and this inflexible feature allows them to be implemented in confined spaces or in wearable devices. is severely constrained in its suitability or feasibility. Flexible and conformable power sources can be used to overcome these design limitations. This new power source will enable the development of next-generation electronic devices such as smart mobile gadgets, rollable displays, wearable devices, and biomedical sensors. A flexible and adaptable power supply also saves weight and space in an electric vehicle.

Lithium-ion batteries are the primary candidate energy storage devices for electric vehicle (EV) and mobile device applications. The last two decades have seen continuous improvements in energy density, rate performance, and safety in lithium-ion batteries, but somehow little attention has been paid to Li-metal batteries with significantly higher energy densities. it wasn't directed. However, the use of graphite-based anodes in Li-ion batteries has some major drawbacks, such as: Low specific capacity (372 mAh/g theoretical capacity as opposed to 3,860 mAh/g for Li metal); long Li intercalation requiring long recharge times (e.g. 7 hours for electric vehicle batteries) (e.g., low solid-state diffusion efficiency of Li into and out of graphite and inorganic oxide particles); inability to deliver high pulse power (power density <<1 kW/kg); 2. the need to use a high-quality cathode (eg, lithium cobaltate), which limits the choice of available cathode materials; Additionally, these commonly used cathodes have relatively low specific capacities (typically <200 mAh/g). These factors contribute to the two major drawbacks of today's Li-ion batteries: low gravimetric and volumetric energy densities (typically 150-220 Wh/kg and 450-600 Wh/L), and low power densities (typically (all above values are based on total battery cell weight or volume).

The emerging EV and renewable energy industries require significantly higher gravimetric energy densities (e.g., >>250 Wh/kg, and preferably >>300 Wh/kg) than what current Li-ion battery technology can offer, and Availability of rechargeable batteries with high power density (shorter recharge time) is required. Furthermore, in the microelectronics and power tool industries, consumers are demanding smaller volume, more compact portable devices (e.g., smartphones and tablets) that store more energy, resulting in significantly higher volumetric energy densities (> A battery with 650 Wh/L, preferably >750 Wh/L) is needed. These requirements have led to a great deal of research effort towards developing electrode materials for lithium-ion batteries with higher specific capacity, excellent rate performance, and good cycling stability.

Several elements from groups III, IV, and V of the periodic table can form alloys with Li at certain desired voltages. Therefore, various anode materials and some metal oxides based on such elements have been proposed for lithium-ion batteries. Among them, silicon is recognized as one of the next generation anode materials for high energy lithium ion batteries. Because silicon has about ten times the theoretical gravimetric capacity (3,590 mAh/g based on Li _3.75 Si vs. 372 mAh/g for LiC ₆ ) compared to graphite, and a volumetric capacity of about This is because it is three times. However, the rapid volume change of Si (up to 380%) during lithium-ion alloying and dealloying (cell charge and discharge) often led to severe and rapid battery performance degradation. The performance degradation is mainly due to Si powdering due to volume change and the inability of the binder/conductive additive to maintain electrical contact between the powdered Si particles and the current collector. . Additionally, the inherently low electrical conductivity of silicon is another issue that needs to be addressed.

Although some high capacity anode active materials (eg Si) have been found, there is no corresponding high capacity cathode material available. Current cathode active materials commonly used in Li-ion batteries have significant drawbacks:
(1) practical capacities achievable with current cathode materials (e.g., lithium iron phosphate and lithium transition metal oxides) are limited to the range of 150-250 mAh/g, often less than 200 mAh/g; It is
( ² ) insertion and extraction of lithium into and out of these commonly used ^{cathodes requires} solid-state It relies on the very slow solid-state diffusion of Li in the particles, which leads to very low power densities, another long-standing problem of today's lithium-ion batteries.
(3) Current cathode materials are electrically and thermally insulating, unable to effectively and efficiently transport electrons and heat. Low conductivity means high internal resistance and the need to add large amounts of conductive additives, substantially reducing the proportion of electrochemically active material in the already low capacity cathode. Low thermal conductivity also means a higher tendency to undergo thermal runaway, which is a major safety issue in the lithium battery industry.

As a completely separate class of energy storage device, sodium batteries are viewed as an attractive alternative to lithium batteries because sodium is abundant and its production is much more environmentally friendly than that of lithium. . Furthermore, the high cost of lithium is a major concern, and Na batteries can be much cheaper in some cases.

At least two sodium ions (Na ⁺ ) are shuttled between the anode and cathode of a sodium metal battery having Na metal or alloy as the anode active material and a sodium ion battery having Na intercalation compound as the anode active material. There are types of batteries. Sodium-ion batteries using a hard carbon-based anode active material (Na intercalation compound) and sodium transition metal phosphate as the cathode have been described by several research groups, eg, J. Am. Barker, et al. "Sodium Ion Batteries", US Pat. No. 7,759,008 (July 20, 2010).

However, these sodium-based devices exhibit much lower specific energy and rate characteristics than Li-ion batteries. The anode active material for Na intercalation and the cathode active material for Na intercalation have lower Na storage capacities than their Li storage capacities. For example, hard carbon particles can store up to 300-360 mAh/g of Li ions, whereas the same material can store up to 150-250 mAh/g of Na ions and 100 mAh/g for storage of K ions. can be less than g.

Instead of hard carbon or another carbonaceous intercalation compound, sodium metal can be used as the anode active material in sodium metal cells. However, the use of metallic sodium as an anode active material is generally considered undesirable and dangerous due to problems with dendrite formation, interfacial aging, and electrolyte incompatibility.

Low capacity anode or cathode active materials are not the only problem facing the alkali metal ion battery industry. There are significant design and manufacturing issues that the lithium-ion battery industry seems to be unaware of or largely ignores. For example, despite the high gravimetric capacity at the electrode level (based solely on the weight of the anode or cathode active material) as frequently claimed in the published literature and patent literature, these electrodes are disappointingly However, batteries cannot be provided with high capacity at the battery cell or pack level (based on total battery cell weight or pack weight). This is due to the observation that the actual active material mass loading of the electrodes is too low in these reports. In most cases, the active material mass loading (area density) of the anode is much lower than 15 mg/cm ² and is often <8 mg/cm ² (area density = per electrode cross-sectional area along the thickness of the electrode). amount of active material). The amount of cathode active material is typically 1.5 to 2.5 times the amount of anode active material. As a result, the weight ratio of anode active material (eg, graphite or carbon) in lithium ion batteries is typically 12% to 17%, and the weight ratio of cathode active material (eg, LiMn ₂ O ₄ ) is: 17% to 35% (mostly <30%). The combined weight fraction of cathode active material and anode active material is typically 30% to 45% of the cell weight.

The low active material mass loading is primarily due to the inability to obtain relatively thick electrodes (greater than 100-200 μm) using conventional slurry coating procedures. This is not as easy a task as one might think, and in reality, electrode thickness is not a design parameter that can be arbitrarily and freely varied to optimize cell performance. This is the manufacturing limit. In addition, thicker samples tend to be very brittle or have poor structural integrity and require the use of large amounts of binder resin. Due to the low areal density and low volumetric density (associated with thin electrodes and low packing density), the battery cell has a relatively low volumetric capacity and a low volumetric energy density. Sodium-ion and potassium-ion batteries have similar problems.

In addition, thick electrodes are also mechanically rigid, not flexible, cannot be bent, and do not conform to desired shapes. Therefore, for conventional alkali metal batteries, high volumetric/gravitational energy density and mechanical flexibility appear to be mutually exclusive.

With the growing demand for more compact and portable energy storage systems, there is a strong interest in increasing battery volume utilization. To achieve improved cell volumetric capacity and energy density in alkali metal batteries, new electrode materials and designs that enable high volumetric capacity and high mass loading are essential.

Therefore, high apparent density (high tap density), high electrode thickness without significantly reducing electron and ion transport rates (e.g. high electron transport resistance or long lithium-ion or sodium-ion diffusion paths), high The need for alkali metal batteries with high active material mass loading (high areal density) active materials with volumetric capacity and high volumetric energy density is clear and urgent.

Accomplishment of these properties along with flexibility, conformability, and safety of the resulting battery is necessary.

The present invention provides a cable type alkali metal battery in which the alkali metal is selected from Li, Na, K, or combinations thereof. In other words, the battery is a Li metal battery, Li ion battery, sodium metal battery, Na ion battery, potassium metal battery, potassium ion battery, hybrid Li/Na, Li/K, Na/K, and Li/Na/K It can be a battery.

The battery comprises: (a) an electrically conductive porous rod having pores, a first electrode active material (a conductive additive or binder is optional, not required or desired) and a first (b) a porous separator encasing the first electrode; (c) a second electrode comprising an electrically conductive porous layer enveloping or covering a porous separator, wherein the conductive porous layer comprises pores and a second electrode active material (a conductive additive or binder is (optional and not required) and a second electrolyte, wherein the second mixture resides in the pores of the porous layer; (d) a second electrode; a protective casing or packing tube (cable sheath) that encloses or covers the The first electrolyte can be the same or different than the second electrolyte.

In this alkali metal battery, the first electrode is the negative electrode (or anode) and the second electrode is the positive electrode (or cathode). In some other embodiments, the second electrode is the negative electrode or anode and the first electrode is the positive electrode or cathode.

In some embodiments, the first electrode comprises Li, Na, and/or K metals (not intercalation compounds) as anode active materials. Thus, a cable-type alkali metal battery comprises: (A) an electrically conductive porous rod having pores and a first electrode active material and an optional first electrolyte (preferred but not necessary); wherein the first electrode active material is lithium, sodium, or a combination thereof, and the first mixture resides in the pores of the porous rod (B) a porous separator enveloping the first electrode; and (C) an electrically conductive porous layer enclosing or covering the porous separator, wherein the electrically conductive porous layer is , pores, and a second mixture of a second electrode active material and a second electrolyte, the second mixture being present in the pores of the porous layer; (D) a second electrode; and a protective casing or packing tube enclosing or covering the two electrodes. Alternatively, in (A) the first electrode comprises a conductive rod (not porous foam) and the first mixture is coated or deposited on the surface of the conductive rod. The rod can be as simple as a metal wire, a conductive polymer fiber or yarn, a carbon or graphite fiber or yarn, or a plurality of wires, fibers, or yarns.

In some embodiments, the second electrode comprises Li, Na, and/or K metals as anode active materials. Thus, a cable-type alkali metal battery includes: (a) a first electrode comprising an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte; (b) a porous separator enclosing the first electrode; and (c) an electrically conductive porous layer enclosing or covering the porous separator. wherein the conductive porous layer comprises pores and a second mixture of a second electrode active material and an optional second electrolyte, the second electrode active material comprising: (d) a protective casing or packing tube enclosing or covering the second electrode; include. Alternatively, in (c) the second electrode is a layer of Li, Na, and/or K metal disposed between the separator layer and the cable sheath, or deposited with Li, Na, and/or K metal. a layer of coated current collector (eg, Cu foil, Ni foil, metal foil such as stainless steel foil, or carbon cloth).

In some embodiments, the cable-type battery has a first end and a second end, and the first electrode is embedded in, connected to, or connected to the first electrode. a first terminal connector comprising at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber integral with the electrode of the . In certain preferred embodiments, at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber extends approximately from the first end to the second end. The wire or fiber preferably protrudes from a first end or a second end to provide terminal tabs for connection to an electronic device or external circuit or load.

Alternatively or additionally, the cable type battery has a first end and a second end, the second electrode being connected to the second electrode embedded in the second electrode. a second terminal connector including at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber attached to or integral with the second electrode. In some embodiments, at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber extends approximately from the first end to the second end. The wire or fiber preferably protrudes from a first end or a second end to provide terminal tabs for connection to an electronic device or external circuit or load.

The electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode may be metal foam, metal web, metal fiber mat, metal nanowire mat, conductive polymer fiber mat, conductive conductive polymer foam, conductive polymer coated fiber foam, carbon foam, graphite foam, carbon aerogel, graphene aerogel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, A porous foam selected from graphite fiber foam, exfoliated graphite foam, or combinations thereof may be included. Highly deformable and conformable structures can be obtained from these foams.

These foam structures are easily brought to porosity levels of >70%, more typically preferably >80%, even more typically preferably >90%, and most preferably >95%. (graphene airgel can exceed 99% porosity level). The skeletal structure (pore walls) in these foams forms a 3D network of electronic conducting pathways, while the pores provide a large proportion of the electrode active material ( large proportions of anode active material in the anode, or cathode active material in the cathode).

Foams can have circular, oval, rectangular, square, hexagonal, hollow, or irregularly shaped cross-sections. There are no particular restrictions on the cross-sectional shape of the foam structure. The battery has a certain length and diameter or thickness and an aspect ratio (long It has a cable shape with a thickness/thickness or length/diameter ratio). There is no particular limit to the length or diameter (or thickness) of the cable cell. The thickness or diameter is typically and preferably between 100 nm and 10 cm, more preferably between 1 μm and 1 cm, most typically between 10 μm and 1 mm. Lengths can range from 1 μm to tens of meters, or even hundreds of meters (if so desired).

In some embodiments, the first electrode or the second electrode includes particles, foils, or coatings of Li, Na, K, or combinations thereof as electrode active materials.

In some embodiments of the invention, the alkali metal battery is a lithium ion battery and the first or second electrode active materials are: (a) natural graphite, synthetic graphite, mesocarbon microbeads (MCMB), and particles of carbon. (b) Silicon (Si), Germanium (Ge), Tin (Sn), Lead (Pb), Antimony (Sb), Bismuth (Bi), Zinc (Zn), Aluminum (Al), Nickel (Ni), Cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd); (c) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd and another element (d) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides, and mixtures or composites thereof; ) prelithiated graphene sheets; and combinations thereof.

Prelithiated graphene sheets include pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, graphene doped with boron, and graphene doped with nitrogen. One can choose from doped graphene, chemically functionalized graphene, physically or chemically activated or etched versions thereof, or prelithiated versions of combinations thereof.

In some embodiments, the alkali metal battery is a sodium ion battery and the first or second electrode active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon, templated carbon, Hollow carbon nanowires, hollow carbon spheres, titanates, NaTi ₂ (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Na ₂ C ₈ H ₄ O ₄ , Na ₂ TP, Na _x TiO ₂ (x=0.2-1 _{.0 ) , Na2C8H4O4 , carboxylate - based materials , C8H4Na2O4 , C8H6O4 , C8H5NaO4 , C8Na2F4O4 , Contains} an _{alkaline intercalation compound selected} from _C10H2Na4O8 , _{C14H4O6 , C14H4Na4O8} , or _{combinations thereof} .

In some embodiments, the alkali metal battery is a sodium ion battery and the first or second electrode active material is: (a) sodium or potassium doped silicon (Si), germanium (Ge), tin ( Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium ( Cd), and mixtures thereof; (b) alloys containing sodium or potassium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof, or (c) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof containing sodium or potassium (d) sodium or potassium salts; and (e) sodium or potassium; and combinations thereof. containing an alkaline intercalation compound selected from the group of materials: graphene sheets;

In some preferred embodiments, the first or second electrode active material is lithium cobaltate, doped lithium cobaltate, lithium nickelate, doped lithium nickelate, lithium manganate, doped manganate Lithium, lithium vanadate, doped lithium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, metal sulfide, lithium selenide, lithium polysulfide and combinations thereof.

In some embodiments, the first or second electrode active material is _NaFePO4 , _{Na ( 1-x) KxPO4 , KFePO4 , Na0.7FePO4} , _{Na1.5VOPO4F0 .5} , _{Na3V2 (} PO4) _{3 , Na3V2 ( PO4} ) _2F3 , _Na2FePO4F , _{NaFeF3 , NaVPO4F} , _{KVPO4F , Na3V2 ( PO4} ) _2F3 , _{Na1.5VOPO4F0.5 , Na3V2 ( PO4 ) 3 , NaV6O15 , NaxVO2 , Na0.33V2O5 , NaxCoO2 , Na 2/3} [Ni _1/3 Mn _2/3 ]O ₂ , Na _x (Fe _1/2 Mn _1/2 )O ₂ , Na _x MnO ₂ , λ-MnO ₂ , Na _x K _(1-x) MnO ₂ , Na _0.44 MnO ₂ , Na ₀ . _44MnO2 / _C , _Na4Mn9O18 , _{NaFe2Mn ( PO4} ) _{3 , Na2Ti3O7 , Ni1} / _{3Mn1 / 3Co1 / 3O2} , _Cu0.56Ni0 . _44HCF , _NiHCF , _NaxMnO2 , _{NaCrO2, KCrO2, Na3Ti2(PO4)3 , NiCo2O4 , Ni3S2 / FeS2 , Sb2O4 , Na4Fe ( CN ) 6} /C, NaV _1−x Cr _x PO ₄ F, S _z S _y , y/z=0.01-100, Se, sodium polysulfide, sulfur, aluordite, or combinations thereof (where x is 0 .1 to 1.0).

The first electrolyte and/or the second electrolyte can comprise a lithium salt or sodium salt dissolved in a liquid solvent, the liquid solvent being water, an organic solvent, an ionic liquid, or an organic solvent and an ionic liquid. is a mixture of A liquid solvent can be mixed with the polymer to form a polymer gel.

The first electrolyte and/or the second electrolyte are preferably dissolved in the liquid solvent to greater than 2.5M (preferably >3.0M, more preferably >3.5M, even more preferably >5.5M). 0M, even more preferably >7.0M, most preferably >10M).

In an alkali metal battery, the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode has at least 90 vol. has a diameter or thickness of 200 μm or greater, or has an active mass loading that accounts for at least 30% by weight or volume of the entire battery cell, or the sum of the first and second electrode active materials is Occupying at least 50% by weight or volume.

In some preferred embodiments, the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode has at least 95 vol. The two electrodes have a diameter or thickness of 300 μm or greater, or have an active mass loading that accounts for at least 35% by weight or mass of the entire battery cell, or the sum of the first and second electrode active materials is Occupying at least 60% by weight or volume of the entire cell.

In some preferred embodiments, the first or second electrode active material is an alkali metal intercalate selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides, or combinations thereof. containing an ion compound or an alkali metal absorbing compound.

Preferably, the metal oxide/phosphate/sulfide is lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, vanadium phosphate selected from lithium, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof.

The inorganic material may be selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. Preferably, the inorganic material is selected from _TiS2 , _TaS2 , MoS2, _NbSe3 , _{MnO2 , CoO2} , iron oxide, vanadium oxide, or combinations thereof.

_Preferably , the metal oxide/ _phosphate / _sulfide is _VO2 , _{LixVO2 , V2O5 , LixV2O5 , V3O8} , _{LixV3O8 , LixV 3O7} , _{V4O9 , LixV4O9 , V6O13} , _LixV6O13 , _{doped versions thereof} , _{derivatives thereof} , and combinations thereof Including vanadium oxide, where 0.1<x<5.

Preferably, the metal oxides/phosphates/sulfides are layered compounds _LiMO2 , _spinel compounds _LiM2O4 , olivine compounds _LiMPO4 , silicate compounds _Li2MSiO4 , _taborite compounds _LiMPO4F , borates compound LiMBO ₃ , or combinations thereof, wherein M is a transition metal or a mixture of transition metals.

In some preferred embodiments, the inorganic material is: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenides or trichalcogenides, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium. , cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides; (d) boron nitride, or (e) combinations thereof.

In some embodiments, the first or second electrode is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly( anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino (triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE) ), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PDAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5-benzylidene hydantoin , isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi ₄ ), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N '-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone compound, 1,4 -benzoquinone, 5,7,12,14-pentacentetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxy anthraquinone (ADDAQ), 5-amino-1,4-dihydroxy ( _dyhydroxy ) _{anthraquinone} ( _ADAQ ), _calixquinone , _Li4C6O6 , _Li2C6O6 , _Li6C6O6 , or a _{combination thereof} .

Thioether polymers include poly[methantetriyl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), poly(ethene-1,1,2,2-tetrathiol as backbone thioether polymer ) (PETT), a side-chain thioether polymer with a backbone composed of conjugated aromatic moieties and pendant thioether side chains, poly(2-phenyl-1,3-dithiolane) (PPDT), poly( 1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4,5-tetrakis(propylthio)benzene] ( PTKPTB, or poly[3,4(ethylenedithio)thiophene] (PEDTT).

In some alternative embodiments, the organic material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, phthalocyanine chloro A phthalocyanine compound selected from aluminum, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or combinations thereof.

Preferably, the cathode comprises an alkali metal intercalation compound or an alkali metal absorbing compound selected from metal carbides, metal nitrides, metal borides, metal dichalcogenides, or combinations thereof. More preferably, the cathode is an oxide of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in the form of nanowires, nanodiscs, nanoribbons, or nanoplatelets. an alkali metal intercalating compound or an alkali metal absorbing compound selected from monochalcogenides, dichalcogenides, trichalcogenides, sulfides, selenides, or tellurides.

In some embodiments, the cathode active material is: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenides or trichalcogenides, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium. , cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides; (d) boron nitride, or (e) combinations thereof. , nanocoatings, or nanosheets; said discs, platelets, or sheets having a thickness of less than 100 nm.

FIG. 1(A) shows a prior art lithium battery composed of an anode current collector, an anode electrode (e.g. a thin Si coating layer), a porous separator, a cathode electrode (e.g. a sulfur layer), and a cathode current collector. 1 is a schematic diagram of an ion battery cell (as an example of an alkali metal battery); FIG. FIG. 1(B) is a schematic diagram of a prior art lithium-ion battery in which the electrode layers are composed of discrete particles of active material (eg, graphite or tin oxide particles in the anode layer or LiCoO ₂ in the cathode layer). be. FIG. 1(C) is a schematic illustration of a method for fabricating a cable-type, flexible and conformable alkali metal battery. FIG. 1(D) shows four examples of procedures for manufacturing electrodes (anode or cathode) in a continuous and automated manner. FIG. 1(E) is a schematic diagram of the method of the present invention for continuously producing an alkali metal ion battery electrode. FIG. 2 is an electron microscope image of an isolated graphene sheet. FIG. 3(A) is a metal grid/mesh and a carbon nanofiber mat as examples of conductive porous layers. FIG. 3B is graphene foam and carbon foam as examples of conductive porous layers. FIG. 3C is graphite foam and Ni foam as examples of conductive porous layers. FIG. 3(D) is Cu foam and stainless steel foam as examples of conductive porous layers. FIG. 4(A) produces exfoliated graphite, expanded graphite flakes (thickness >100 nm), and graphene sheets (thickness <100 nm, more typically <10 nm, and can be as thin as 0.34 nm). 1 is a schematic diagram of a commonly used method for doing; FIG. 4(B) is a schematic diagram showing a method for producing exfoliated graphite, expanded graphite flakes, and isolated graphene sheets. FIG. 5 is a Ragone plot (weight and volumetric power density versus energy density) of a lithium-ion battery cell containing graphite particles as the anode active material and carbon-coated LFP particles as the cathode active material. Two of the four data curves are for cabled cells prepared according to embodiments of the present invention and the other two are from conventional slurry coating (roll coating) of the electrodes. FIG. 6 shows Ragone plots (weight and volumetric power density versus weight and volumetric energy density) of _two cells containing graphene-encapsulated Si nanoparticles as anode active materials and LiCoO2 nanoparticles as cathode active materials. be. Experimental data were obtained from cable-type Li-ion battery cells prepared by the method according to the present invention and cable-type Li-ion battery cells prepared by conventional slurry coating of electrodes. FIG. 7 is a Ragone lithium metal battery containing lithium foil as the anode active material, dilithium rhodizonate (Li ₂ C ₆ O ₆ ) as the cathode active material, and lithium salt (LiPF ₆ )-PC/DEC as the organic liquid electrolyte. FIG. 10 shows a plot; The data relate both to cable-type lithium metal cells prepared by the method according to the invention and to cable-type lithium metal cells prepared by conventional slurry coating of electrodes. FIG. 8 is a lithium metal cell plotted over the achievable cathode thickness range for MnO ₂ /RGO cathodes made by conventional methods without delamination and cracking, and a cable cell cell by the method according to the present invention. Weight (Wh/kg) and volumetric energy density (Wh/L) of the level. FIG. 9 shows the cell-level gravimetric and volumetric energy densities of a cable-type graphite/NMC cell prepared by the method according to the invention and a cell prepared by a conventional roll-coating method. FIG. 10 is a Ragone plot (weight and volumetric power density) of a Na-ion battery cell containing hard carbon particles as anode active material and carbon-coated Na ₃ V ₂ (PO ₄ ) ₂ F ₃ particles as cathode active material. versus energy density). Two of the four data curves are for cable cells made according to one embodiment of the present invention and the other two are for conventional slurry coating (roll coating) of electrodes. FIG. 11 shows Ragone plots of two cells containing both graphene-encapsulated Sn nanoparticles as anode active material and _NaFePO4 nanoparticles as cathode active material (weight and volumetric power density vs. weight and volumetric energy density). both). The data are for both cable type sodium ion cells made by the method according to the invention and for sodium ion cells made by conventional slurry coating of electrodes. FIG. 12 shows graphene-supported sodium foil as anode active material, disodium rhodizonate (Na ₂ C ₆ O ₆ ) as cathode active material, and sodium salt (NaPF ₆ )-PC/DEC as organic liquid electrolyte. 1 is a Ragone plot of a sodium metal battery containing The data are for both cabled sodium metal cells made by the method according to the invention and for cabled sodium metal cells made by conventional slurry coating of electrodes. FIG. 13 is a Ragone plot of a series of K-ion cells made by a conventional slurry coating method and a corresponding Ragone plot of a cable K-ion cell made by a method according to the invention.

The present invention can be more readily understood by reference to the following detailed description of the invention taken in conjunction with the accompanying drawings which form a part of this disclosure. The present invention is not limited to the particular devices, methods, conditions or parameters described and/or illustrated herein, and the terminology used herein describes particular embodiments by way of example only. is intended as a limitation of the claimed invention.

The present invention is directed to flexible, conformable, cable-like alkali metal batteries that exhibit very high volumetric and gravimetric energy densities. The alkali metal battery may be a primary battery, but is preferably a lithium ion battery or a lithium metal secondary battery (e.g. using lithium metal as the anode active material), a sodium ion battery, a sodium metal battery, a potassium ion battery. , or potassium metal batteries. The batteries are based on aqueous electrolytes, non-aqueous or organic electrolytes, gel electrolytes, ionic liquid electrolytes, or mixtures of organic and ionic liquids.

For convenience, we use lithium iron phosphate (LFP), vanadium oxide (V _x O _y ), lithium nickel manganese cobalt oxide (NMC), dilithium rhodizonate (Li ₂ C ₆ O ₆ ), and copper phthalocyanine (CuPc), and selected materials such as graphite, SnO, Co ₃ O ₄ , and Si particles as examples of anode active materials. For sodium batteries, we use _NaFePO4 and λ- _MnO2 particles as illustrative examples of cathode active materials, and hard carbon and _{NaTi2 (PO4)3 particles} as examples of anode active materials for Na-ion cells. Using selected materials such as A similar method can be applied to K-ion batteries. Nickel foam, graphite foam, graphene foam, and stainless steel fiber webs are used as examples of conductive porous layers as contemplated current collectors. They should not be construed as limiting the scope of the invention.

As shown in FIGS. 1(A) and 1(B), a lithium-ion battery cell typically consists of an anode current collector (e.g., Cu foil), an anode electrode (anode active material layer), a porous It consists of a separator and/or electrolyte component, a cathode electrode (cathode active material layer), and a cathode current collector (eg, Al foil). In the more commonly used cell configuration (FIG. 1(B)), the anode layer consists of an anode active material (e.g. graphite or Si), a conductive additive (e.g. carbon black particles), and a resin binder. (eg SBR or PVDF) particles. The cathode layer is composed of particles of cathode active material (eg, LFP particles), conductive additive (eg, carbon black particles), and resin binder (eg, PVDF). Both the anode and cathode layers are typically up to 100-200 μm thick and are likely to produce a sufficient amount of current per unit electrode area. This thickness range is considered an industry accepted constraint with which battery designers routinely work. This thickness limitation is due to several reasons: (a) existing battery electrode coating machines are not equipped to coat very thin or very thick electrode layers; (b) thinner layers are preferred given the reduced lithium-ion diffusion path length; (c) thicker electrodes are prone to delamination or cracking during drying or handling after roll coating, requiring coating lines of >100 meters in length to produce thicker electrodes. (expensive and impractical); and (d) to obtain minimum overhead weight and maximum lithium storage capacity and thus maximum energy density (Wk/kg or Wh/L of cell), all in the battery cell of non-active material layers (eg, current collectors and separators) should be kept to a minimum.

Also notably, the shape and dimensions of conventional lithium-ion batteries render them rigid (inflexible) and incapable of being bent or twisted. It is also difficult to integrate these conventional batteries into the bodywork of electric vehicles (eg, e-bikes and battery powered vehicles). For example, some confined spaces inside a car door structure are not conductive to a suitable rigid rectangular or cylindrical battery.

In a less commonly used cell configuration, the anode active material (e.g. Si) or cathode active material (e.g. lithium transition metal oxide) is a copper foil or Al It is deposited in thin film form directly onto a current collector such as a foil. However, such thin film structures with very small thickness dimensions (typically much less than 500 nm, and often less than 100 nm if desired) do not allow for the same electrode or current collector surface area. (assuming ) that only a small amount of active material can be incorporated into the electrode, reducing the total lithium storage capacity and reducing the lithium storage capacity per unit electrode surface area. Such thin films should be less than 100 nm thick in order to be more resistant to cycling-induced cracking (for the anode) or to facilitate full utilization of the cathode active material. Such constraints further reduce the total lithium storage capacity and the lithium storage capacity per unit electrode surface area. Such thin film batteries have a very limited range of applications.

On the anode side, Si layers thicker than 100 nm have been found to be less crack resistant during charge-discharge cycling of the battery. It will be crushed in just a few cycles. On the cathode side, a sputtered layer of lithium metal oxide thicker than 100 nm does not allow the lithium ions to fully penetrate and reach the entire cathode layer, resulting in low cathode active material utilization. Desirable electrode thickness is at least 100 μm, and individual active material coatings or particles desirably have dimensions less than 100 nm. Therefore, these thin film electrodes (with thickness <100 nm) deposited directly on the current collector are three orders of magnitude short of the required thickness. As a further problem, not all cathode active materials are conductive to both electrons and lithium ions. A large layer thickness implies a very high internal resistance and a low active material utilization.

That is, material type, size, electrode layer thickness, and active material mass loading, as well as electrode or cell geometry and dimensions, must be considered simultaneously in the design and selection of cathode or anode active materials. There are several conflicting factors that do not. So far, there have been no effective solutions provided by any prior art teachings to these often-conflicting problems. As disclosed herein, the inventors have addressed these challenges that have plagued battery designers and also electrochemists for over 30 years by developing a novel method of manufacturing lithium batteries. resolved.

Prior art lithium battery cells are typically manufactured by a method that includes the following steps: (a) the first step is to prepare an anode active material (e.g., Si nanoparticles or mesocarbon microbeads, MCMB); , a conductive filler (eg, graphite flakes), and particles of a resin binder (eg, PVDF) in a solvent (eg, NMP) to form an anode slurry. Separately, particles of cathode active material (e.g., LFP particles), conductive filler (e.g., acetylene black), and resin binder (e.g., PVDF) are mixed and dispersed in a solvent (e.g., NMP). to form a cathode slurry. (b) the second step is to coat one or both major surfaces of the anode current collector (e.g. Cu foil) with the anode slurry and dry the coated layer by evaporating the solvent (e.g. NMP); to form a dry anode electrode coated on Cu foil. Similarly, the cathode slurry is coated and dried to form a dry cathode electrode coated on Al foil. In practical manufacturing situations, slurry coating is usually done in a roll-to-roll manner; (c) the third step is to laminate the anode/Cu foil sheet, porous separator layer and cathode/Al foil sheet together to , to form a 3- or 5-layer assembly, which is cut or slit to the desired size and laminated to form a rectangular structure (as an example shape) or rolled into a cylindrical cellular structure. including doing (d) The rectangular or cylindrical laminated structure is then encased in an aluminum plastic laminated envelope or steel casing. (e) then injecting a liquid electrolyte into the laminate structure to fabricate a lithium battery cell;

There are several significant problems associated with conventional methods and the resulting lithium-ion or sodium-ion battery cells.
1) It is very difficult to manufacture electrode layers (anode or cathode layers) thicker than 200 μm (100 μm on each side of a solid current collector such as Al foil). There are several reasons. Electrodes with a thickness of 100-200 μm typically require heating zones of 30-50 meters in length in slurry coating facilities, which are too time consuming, too energy consuming and cost effective. do not have. For some electrode active materials, such as metal oxide particles, it has not been possible to continuously produce electrodes thicker than 100 μm with good structural integrity in a practical manufacturing environment. The resulting electrodes are very fragile and brittle. Thicker electrodes are more prone to delamination and cracking.
2) In the conventional method as shown in FIG. 1(A), the actual mass loading of the electrodes and the apparent density for the active material are too low to achieve gravimetric energy densities above 200 Wh/kg. Most of the time, even for relatively large graphite particles, the anode active material mass loading (area density) of the electrode is well below 25 mg/cm ² and the apparent volume or tap density of the active material is typically 1.2 g. / ^cm3 . The cathode active material mass loading (area density) of the electrode is substantially lower than 45 mg/cm ² for inorganic materials based on lithium metal oxides and substantially lower than 15 mg/cm ² for organic or polymeric materials. . In addition, there are numerous other non-active materials (eg, conductive additives and resin binders) that add additional weight and volume to the electrodes without contributing to battery capacity. These low areal densities and low volumetric densities result in relatively low gravimetric and low volumetric energy densities.
3) The conventional method requires the electrode active material (anode active material or cathodic active material) to be dispersed and slurried in a liquid solvent (e.g., NMP), and the liquid solvent is applied after coating the current collector surface. After removal, the electrode layer must be dried. After the anode and cathode layers are laminated together with a separator layer and packaged in a housing to form a battery cell, a liquid electrolyte is injected into the cell. In practice, the two electrodes are wetted, then the electrodes are dried and finally wetted again. Such a wet-dry-wet process does not appear to be a good process.
4) Current lithium-ion batteries still suffer from relatively low gravimetric energy densities and low volumetric energy densities. Commercially available lithium-ion batteries exhibit gravimetric energy densities of about 150-220 Wh/kg and volumetric energy densities of 450-600 Wh/L.

Energy densities for practical battery cells or devices cannot be directly derived from energy density data reported in the literature based on active material weight alone or electrode weight. "Overhead weight", ie the weight of other device components (binders, conductive additives, current collectors, separators, electrolytes, and packaging) must also be taken into account. In conventional manufacturing methods, the weight ratio of anode active material (eg, graphite or carbon) in lithium-ion batteries is typically 12%-17%, and the weight ratio of cathode active material (eg, LiMn ₂ O ₄ ) is typically 12%-17%. The ratio is between 20% and 35%.

The present invention provides flexible, conformable, and flame-retardant alkali metal battery cells with cable geometry, high active material mass loading, low overhead weight and volume, high gravimetric energy density, and high volumetric energy density. A manufacturing method is provided. Moreover, the production cost of alkali metal batteries produced by the method according to the invention is much lower than the cost of conventional methods.

In one embodiment of the invention, as shown in FIG. 1(C), the cable alkali metal battery of the invention is partially or completely filled with a mixture of a first electrode active material and a first electrolyte. It is manufactured by a method comprising a first step of providing a first electrode 11 consisting of an electrically conductive porous rod with pores. Conductive additives or resin binders can optionally be added into this mixture, but this is not necessary or even desirable. This first electrode 11 can optionally include an active material-free, electrolyte-free end portion 13 that can serve as a terminal tab for connection to an external load. This first electrode can assume a cross section of any shape; for example circular 11a, rectangular 11b, oval, square, hexagonal, hollow or irregularly shaped.

Alternatively, in a first step, the first electrode comprises a conductive rod (not porous foam) and the first mixture is coated or deposited on the surface of the conductive rod. The rod can be as simple as a metal wire, a conductive polymer fiber or yarn, a carbon or graphite fiber or yarn, or a plurality of thin wires, fibers or yarns. However, in this situation the second electrode must comprise a porous foam structure.

The second step is to cover the first with a thin layer of a porous separator 15 permeable to Li ⁺ , Na ⁺ , or K ⁺ ions (e.g. porous plastic film, paper, fiber mat, non-woven fabric, glass fiber cloth, etc.). Enveloping or covering the electrode 11 is included. Here the cross-sectional areas of the structure appear to be areas as schematically indicated at 15a, 15b, etc. FIG. This step may be as simple as wrapping a thin porous plastic tape around the first electrode for one or slightly more than one turn, or in a spiral. Its main purpose is to electronically isolate the anode and cathode to prevent internal short circuits. The porous layer can simply be deposited around the first electrode by spraying, printing, coating, dip casting, or the like.

This separator covering or wrapping step is followed by a third step involving wrapping or covering the separator protected structure with a layer of second electrode 17 . The second electrode 17 comprises a mixture of a second active material and a second electrolyte, and optionally a conductive additive or resin binder (but neither necessary nor desirable). This second electrode 17 can optionally include an active material-free and electrolyte-free end portion 21 that can serve as a terminal tab for connection to an external load. Here the cross-sectional areas of the structure appear to be areas as schematically indicated at 17a, 17b, etc. FIG.

As a fourth step, the structure is then wrapped or protected by an electrically insulating cable sheath 19 (eg a plastic sheath or rubbery shell). Before being connected to an external load (e.g. light bulb, LED light, electronic device), the cross-sectional area of the resulting cable cell structure looks like the area schematically indicated at 19a, 19b, etc. FIG.

Alternatively, the second electrode is a layer of Li, Na, and/or K metal placed between the separator layer and the cable sheath, or a current collector deposited with Li, Na, and/or K metal ( For example, Cu foil, Ni foil, stainless steel foil, or metal foil such as carbon cloth). However, in this case the first electrode must comprise a conductive porous foam structure.

There are several means of manufacturing the first electrode or the second electrode. One preferred method is to use one or more electrically conductive porous foam layers ( 304, 310, 322, or 330; only one foam layer is shown, but there can be multiple layers in each case) from a feeder roller (not shown) to the active material/ continuously feeding into an electrolyte impregnation zone, wherein a wet active material mixture (e.g., slurry, suspension, or gel mass, e.g., 306a) of electrode active material, electrolyte, and optional conductive additive; , 306b, 312a, 312b) are delivered to at least the porous surface of the porous layer (eg, 304 or 310 in schematics A and B, respectively, of FIG. 1(D)). Using schematic A as an example, one or two sets of rollers (302a, 302b, 302c, and 302d) are used to impregnate the wet active material/electrolyte mixture (306a, 306b) into the porous layer from both sides. This forms an impregnated active electrode 308 (anode or cathode). The conductive porous foam layer has an interconnected network of electronically conducting pathways and at least 70% (preferably >80%, more preferably >90%, even more preferably >95%) pores by volume. including.

In schematic B, two feeder rollers 316a, 316b are used to continuously unwind two protective films 314a, 314b supporting wet active material/electrolyte mixture layers 312a, 312b. These wet active material/electrolyte mixture layers 312a, 312b are coated with protective (support) films 314a, 314a, 314b using a wide variety of procedures (e.g., printing, spraying, casting, coating, etc., well known in the art). 314b. As the conductive porous foam layer 110 moves through the gap between the two sets of rollers (318a, 318b, 318c, 318d), the wet active mixture material/electrolyte enters the pores of the porous layer 310. Impregnation forms an active material electrode 320 (anode or cathode electrode layer) covered with two protective films 314a, 314b. These protective films can be removed later.

Using schematic C as another example, two atomizers 324a, 324b was used. Impregnated active electrode 326 (anode or cathode) is formed by impregnating the wet active material mixture into the porous layer from both sides using one or two sets of rollers. Similarly, in Schematic D, two spray devices 332a, 332b are provided for supplying wet active material mixtures (333a, 333b) to two opposite porous foam layer surfaces of the electrically conductive porous layer 330. used. Impregnated active electrode 338 (anode or cathode) is formed by impregnating the wet active material-electrolyte mixture into the porous layer from both sides using one or two sets of rollers.

In another example, as shown in schematic view E of FIG. Start. Roller 342 immerses porous layer 356 into wet active material mixture 346 (slurry, suspension, gel, etc.) in container 344 . As it moves toward roller 342b, the active material mixture begins to impregnate into the pores of porous layer 356 and exits the container into the gap between the two rollers 348a, 348b. Two protective films 350a, 350b are simultaneously fed from two respective rollers 352a, 352b to cover the impregnated porous layer 354, which is continuously collected on a rotating drum (take-up roller 355). can be done. This process is applicable to both anode and cathode electrodes.

The resulting electrode layer (anode or cathode electrode) can have a thickness or diameter of 100 nm to several centimeters (or larger if desired) after solidification. In the case of microcables (eg, as flexible power sources for microelectronic devices), the thickness or diameter of the electrodes is between 100 nm and 100 μm, more typically between 1 μm and 50 μm, most typically between 10 μm and 30 μm. For flexible and conformable cable cells of visible size (e.g. for use in confined spaces in electric vehicle EVs), the electrodes typically and desirably have a thickness of 100 μm or more. (preferably >200 μm, more preferably >300 μm, more preferably >400 μm; even more preferably >500 μm, 600 μm, or even >1,000 μm; there is no theoretical limit to electrode thickness.

These are just a few examples of how a flexible, conformable, cable-like alkaline metal battery according to the present invention can be manufactured. These examples should not be used to limit the scope of the invention.

The conductive porous layer can be a metal foam, a metal web or screen, a structure based on a perforated metal sheet, a metal fiber mat, a metal nanowire mat, a conductive polymer nanofiber mat, a conductive polymer foam, a conductive polymer coated fiber. foam, carbon foam, graphite foam, carbon aerogel, carbon xerox gel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam , or combinations thereof. The porous layer may be a conductive material such as carbon, graphite, metal, metal-coated fiber, conductive polymer, or conductive polymer-coated fiber in the form of highly porous mats, screens/grids, nonwovens, foams, and the like. It must be done. Examples of conductive porous layers are shown in FIGS. 3(A), 3(B), 3(C) and 3(D). The porosity level should be at least 70% by volume, preferably above 80% by volume, more preferably above 90% by volume and most preferably above 95% by volume. The backbone or foam wall forms a network of electronically conducting pathways.

These foam structures can be easily made into any cross-sectional shape. They are also very flexible; typically non-metallic foams are more flexible than metallic foams. Because the electrolyte is either in a liquid or gel state, the resulting cable battery can be very flexible and conformable to virtually any special shape. Even at high salt concentrations in the liquid solvent (eg, 2.5M to 12M), foams containing electrolyte in the pores are still deformable, bendable, twistable, and special. It remains adaptable even to tight shapes.

Preferably, substantially all pores in the original conductive porous layer contain the electrode active material (anode or cathode), electrolyte, and optional conductive additives (no binder resin required). be filled. Since there is a large amount of pores (70-99%) to pore walls or conductive pathways (1-30%), there is very little wasted space (“wasted” refers to the electrode active material and electrolyte), resulting in a high electrode active material-electrolyte mixture ratio (high active material loading mass).

In such a battery electrode configuration (e.g., FIG. 1(C)), pore walls are everywhere throughout the electrode structure (the conductive foam acts as a current collector), so electrons It only needs to travel a short distance (on average half the pore size; eg a few nanometers or micrometers) before being collected by the wall. These pore walls form a 3D network of interconnected electron transport pathways with minimal resistance. Furthermore, in each anode or cathode electrode, all electrode active material particles are pre-dispersed in liquid electrolyte (no wetting problems) and prepared by conventional methods of wet coating, drying, packing, and electrolyte infusion. There are no dry pockets that are commonly present in the electrode. Thus, the method according to the invention yields completely unexpected advantages over conventional battery cell manufacturing methods.

In preferred embodiments, the anode active material is pure graphene (eg, FIG. 2), graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitrogen, chemical Prelithiated or presodiumated versions of graphene sheets selected from functionalized graphene, or combinations thereof. Starting graphene materials for making any one of the above graphene materials include natural graphite, synthetic graphite, mesophase carbon, mesophase pitch, mesocarbon microbeads, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber , carbon nanotubes, or combinations thereof. Graphene materials are also good conductive additives for both anode and cathode active materials in alkali metal batteries.

Assuming that interplanar van der Waals forces can be overcome, the constituent graphene planes of graphite crystals in natural or artificial graphite particles can be exfoliated and extracted or isolated to form individual graphenes of hexagonal carbon atoms. Sheets can be obtained and these sheets are a single atom thick. An isolated individual graphene plane of carbon atoms is commonly referred to as monolayer graphene. A stack of multiple graphene planes joined by van der Waals forces with a graphene plane spacing of about 0.3354 nm in the thickness direction is commonly referred to as multi-layer graphene. Multilayer graphene platelets have up to 300 graphene planes (thickness less than 100 nm), but more typically up to 30 graphene planes (thickness less than 10 nm), even more typically up to 20 layers. It has graphene planes (thickness less than 7 nm), and most typically up to 10 layers of graphene planes (commonly referred to in the scientific community as few-layer graphene). Single-layer graphene and multi-layer graphene sheets are collectively referred to as “nanographene platelets” (NGP). Graphene sheets/platelets (collectively NGPs) are a new class of carbon nanomaterials (2D nanocarbons) distinct from 0D fullerenes, 1D CNTs or CNFs, and 3D graphite. For the purposes of defining the claims, and as commonly understood in the art, graphene materials (isolated graphene sheets) are not carbon nanotubes (CNT) or carbon nanofibers (CNF). ).

In one method, as shown in FIGS. 4(A) and 4(B) (schematic diagrams), graphene materials are prepared by intercalating natural graphite particles with strong acids and/or oxidizing agents to produce graphite intercalation. Obtained by obtaining a compound (GIC) or graphite oxide (GO). The presence of chemical species or functional groups in the interstitial space between graphene planes in GIC or GO serves to increase the graphene spacing ( _d002 ; determined by X-ray diffraction), thereby This greatly reduces the van der Waals forces that hold the graphene planes together along the c-axis direction. GIC or GO is prepared by adding natural graphite powder (reference number 100 in FIG. 4(B)) in a mixture of sulfuric acid, nitric acid (an oxidizing agent), and another oxidizing agent (e.g., potassium permanganate or sodium perchlorate). is most often produced by soaking When an oxidizing agent is present during the intercalation procedure, the resulting GIC (102) is actually a type of graphite oxide (GO) particles. The GIC or GO is then repeatedly washed and rinsed in water to remove excess acid, resulting in a graphite oxide suspension or dispersion that is dispersed in water in discrete, visually distinguishable containing graphite oxide particles. To produce graphene material, one of two processing routes can be followed after this rinsing step, briefly described below.

Route 1 involves removing water from the suspension to obtain "expanded graphite" which is essentially a mass of dry GIC or dry graphite oxide particles. When exfoliated graphite is exposed to temperatures typically in the range of 800-1,050° C. for about 30 seconds to 2 minutes, the GIC undergoes a rapid volume expansion of 30-300 times to form a “graphite worm” (104). to form Each graphite worm (104) is a collection of flakes of graphite that have been exfoliated, but are largely unseparated and remain interconnected.

In Route 1A, these graphite worms (exfoliated graphite or "network of interconnected/unseparated graphite flakes") are recompressed to typically 0.1 mm (100 μm) to 0.5 mm A flexible graphite sheet or foil (106) with a thickness in the range of (500 μm) can be obtained. Alternatively, low intensity air mills or shears are used to produce so-called "expanded graphite flakes" (108) which mainly contain graphite flakes or platelets thicker than 100 nm (thus not nanomaterials by definition). You can also choose to simply crush the worms.

In Route 1B, exfoliated graphite is treated with (e.g., ultrasonic equipment, high subjected to high-intensity mechanical shearing (using a shear mixer, high-intensity air-jet mill, or high-energy ball mill) to form separated monolayer and multi-layer graphene sheets (collectively referred to as NGP112). Single-layer graphene can be as thin as 0.34 nm, while multi-layer graphene can have a thickness of up to 100 nm, but more typically less than 10 nm (commonly referred to as few-layer graphene). Multiple graphene sheets or platelets may be formed as a sheet of NGP paper using a papermaking process. This NGP paper is an example of a porous graphene structured layer utilized in the method according to the present invention.

Route 2 involves sonicating a graphite oxide suspension (eg, graphite oxide particles dispersed in water) for the purpose of separating/isolating individual graphene oxide sheets from the graphite oxide particles. This shows that the separation of the graphene planes has been increased from 0.3354 nm in natural graphite to 0.6-1.1 nm in highly oxidized graphite oxide, a van der Waals separation that holds adjacent planes together. It is based on the view that it greatly weakens power. The ultrasonic power may be sufficient to further separate the graphene plane sheets to form fully separated, isolated, or discrete graphene oxide (GO) sheets. These graphene oxide sheets can then be chemically or thermally reduced to yield “reduced graphene oxide” (RGO), which typically contains 0.001 wt % to 10 wt %, More typically it has an oxygen content of 0.01% to 5% by weight, and most typically and preferably contains less than 2% by weight oxygen.

For the purposes of defining the claims of this application, NGP or graphene materials include single and multilayer (typically less than 10 layers) pure graphene, graphene oxide, reduced graphene oxide (RGO), graphene fluoride , graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitrogen, chemically functionalized graphene, discrete sheets/platelets of doped (eg, B or N doped) graphene. Pure graphene has essentially 0% oxygen. RGO typically has an oxygen content of 0.001% to 5% by weight. Graphene oxide (including RGO) can have between 0.001% and 50% oxygen by weight. Except for pure graphene, all graphene materials contain 0.001% to 50% by weight of non-carbon elements (eg, O, H, N, B, F, Cl, Br, I, etc.). These materials are referred to herein as impure graphene materials.

Pure graphene is produced as smaller, discrete graphene sheets (typically 0.3 μm to 10 μm) by direct sonication (also known as liquid phase exfoliation or generation) or supercritical fluid exfoliation of graphite particles. can do. These methods are well known in the art.

Graphene oxide (GO) is added to the starting graphite material in a reaction vessel at a desired temperature for a period of time (typically 0.5-96 hours depending on the nature of the starting material and the type of oxidant used). can be obtained by immersing a powder or filament of (eg, natural graphite powder) in an oxidizing liquid medium (eg, a mixture of sulfuric acid, nitric acid, and potassium permanganate). As described above, the resulting graphite oxide particles can then be subjected to thermal exfoliation or ultrasonically induced exfoliation to produce isolated GO sheets. These GO sheets can then be transformed into various graphene materials by replacing the OH groups with other chemical groups (such as Br and _NH2 ).

Fluorinated graphene or graphene fluoride is used herein as an example of a group of halogenated graphene materials. There are two different approaches that have been taken to produce fluorinated graphene. (1) Fluorination of pre-synthesized graphene: This approach requires treating graphene prepared by mechanical exfoliation or CVD growth with a fluorinating agent such as XeF2 or F _- based plasma. (2) Exfoliation of multilayer graphite fluoride: Both mechanical exfoliation and liquid phase exfoliation of graphite fluoride can be easily achieved.

Graphite intercalation compound (GIC) CxF ( ₂ ≤ _x ≤ 24) is produced at low temperature, whereas the interaction of F2 with graphite at high temperature is covalent graphite fluoride (CF) _n or ( _{C2F)n .} In (CF) _n , the carbon atoms are sp3-hybridized, so the fluorocarbon layers are corrugated and consist of trans-linked cyclohexane chair conformations. In (C ₂ F) _n , only half of the C atoms are fluorinated and any pair of adjacent carbon sheets are linked by C—C covalent bonds. Systematic studies on fluorination reactions show that the obtained F/C ratio depends on the fluorination temperature, the partial pressure of fluorine in the fluorination gas, and the physical properties of the graphite precursor, such as the degree of graphitization, grain size, and ratio. It was shown to strongly depend on the surface area. _In addition to fluorine ₍ F2), other fluorinating agents can be used, but most of the available literature involves fluorination with F2 gas, sometimes in the presence of fluoride.

In order to exfoliate the layered precursor material into individual layers or several layers, it is necessary to overcome the attractive forces between adjacent layers and further stabilize the layers. This may be achieved by covalent modification of the graphene surface with functional groups or by non-covalent modification using specific solvents, surfactants, polymers, or donor-acceptor aromatic molecules. The process of liquid phase exfoliation involves sonication of graphite fluoride in a liquid medium.

Nitridation of graphene can be performed by exposing graphene materials, such as graphene oxide, to ammonia at elevated temperatures (200-400° C.). Nitrogenated graphene can also be produced at lower temperatures by hydrothermal methods. This is done, for example, by sealing the GO and ammonia in an autoclave and then increasing the temperature to 150-250°C. Other methods to synthesize nitrogen-doped graphene include nitrogen plasma treatment on graphene, arc discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and graphene oxide at various temperatures. and hydrothermal treatment of urea.

The above features are described and explained in more detail as follows. As shown in FIG. 4B, graphite particles (eg, 100) are typically composed of a plurality of graphite crystals or microparticles. Graphite crystals are composed of layered planes of a hexagonal network of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered to be substantially parallel and equidistant from each other in a particular crystal. These layers of carbon atoms in a hexagonal structure, commonly called graphene layers or basal planes, are weakly bonded in their thickness direction (crystallographic c-axis direction) by weak van der Waals forces, and the group of these graphene layers are arranged as crystals. Graphite crystal structure is usually characterized with respect to two axes or directions. That is, the c-axis direction and the a-axis (or b-axis) direction. The c-axis is the direction perpendicular to the basal plane. The a-axis or b-axis is a direction parallel to the basal plane (perpendicular to the c-axis direction).

Weak van der Waals forces that hold parallel graphene layers treat natural graphite to significantly open the spacing between the graphene layers, thereby allowing significant expansion in the c-axis direction and thus enhancing the layered character of the carbon layers. A substantially retained expanded graphite structure can be formed. Methods for making flexible graphite are well known in the art. Generally, flakes of natural graphite (eg, reference number 100 in FIG. 4B) are intercalated in an acid solution to produce a graphite intercalation compound (GIC, 102). The GIC is washed, dried and then exfoliated by brief exposure to elevated temperature. This causes the flakes to expand or exfoliate along the c-axis of the graphite to 80-300 times their original dimensions. The exfoliated graphite flakes are worm-like in appearance and are therefore commonly referred to as graphite worms 104 . These worms of highly expanded graphite flakes are cohesive of expanded graphite with typical densities of about 0.04-2.0 g/cm ³ without the use of binders for most applications. Or it can be formed as a monolithic sheet, such as a web, paper, strip, tape, foil, mat, etc. (typically referred to as "flexible graphite" 106).

Acids such as sulfuric acid are not the only type of intercalant that penetrates the space between graphene planes to obtain GIC. Many other types of intercalating agents such as alkali metals (Li, K, Na, Cs, and their alloys or eutectics) are used to intercalate graphite into stage 1, stage 2, stage 3, etc. can be used. Stage n implies one intercalant layer for every n graphene planes. For example, a stage 1 potassium-intercalated GIC implies one K layer per graphene plane. That is, we can find one K atomic layer inserted between two adjacent graphene planes in the order G/K/G/K/G/KG . . . Here, G is the graphene plane and K is the potassium atom plane. A stage 2 GIC has the permutation GG/K/GG/K/GG/K/GG . . . A stage 3 GIC has the permutation GGG/K/GGG/K/GGG . . . The same applies hereinafter. These GICs can then be contacted with water or water-alcohol mixtures to produce exfoliated graphite and/or separated/isolated graphene sheets.

Subjecting exfoliated graphite worms to high intensity mechanical shearing/separation treatment using high intensity air jet mill, high intensity ball mill, or ultrasonic device to produce separated nanographene platelets (NGP). , and the graphene platelets are all thinner than 100 nm, mostly thinner than 10 nm, and often monolayer graphene (also shown as reference number 112 in FIG. 4(B)). NGP is composed of a graphene sheet or multiple graphene sheets, each sheet being a two-dimensional hexagonal structure of carbon atoms. A film-forming method was used to form a plurality of NGP clumps containing discrete sheets/platelets of single-layer and/or few-layer graphene or graphene oxide into a porous graphene film (reference numeral 114 in FIG. 4(B)). can be formed. Alternatively, at low intensity shear, graphite worms tend to separate into so-called expanded graphite flakes (reference number 108 in FIG. 4B) with a thickness greater than 100 nm. From these flakes, a mat manufacturing process can be used with or without a resin binder to form a graphite mat or nonwoven 106 to form an expanded graphite foam. Graphite foam can also be produced by graphitization of carbon foam.

There is no limit to the type of anode active material or cathode active material that can be used in the practice of the invention. ^Preferably , in the method according ^to the invention, when the battery is charged, it is less than ^{1.0 Volt} ( At high electrochemical potentials (preferably less than 0.7 volts), the anode active material absorbs alkali ions (eg, lithium ions). In one preferred embodiment, the anode active material is: (a) particles of natural graphite, synthetic graphite, mesocarbon microbeads (MCMB), and carbon (including soft carbon, hard carbon, carbon nanofibers, and carbon nanotubes); (b) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt ( Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd) (Si, Ge, Al, and Sn are most desirable due to their high specific capacities); (c) Si , Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with another element, stoichiometric or non-stoichiometric. SiAl, SiSn); (d) oxides, carbides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or composites thereof , nitrides, sulfides, phosphides, selenides, and tellurides ₍ e.g. SnO, _TiO2 , Co3O4 _, etc.); (f) _prelithiated graphene sheets; and combinations thereof.

In some embodiments, the first electrode or the second electrode includes particles, foils, or coatings of Li, Na, K, or combinations thereof as electrode active materials.

In another preferred embodiment, the anode active material is pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, graphene chemically functionalized , or combinations thereof. Starting graphite materials for making any one of the above graphene materials include natural graphite, synthetic graphite, mesophase carbon, mesophase pitch, mesocarbon microbeads, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, It can be selected from carbon nanotubes, or combinations thereof. Graphene materials are also good conductive additives for both anode and cathode active materials in alkali metal batteries.

In rechargeable alkali metal batteries, the anode comprises an alkali ion source selected from alkali metals, alkali metal alloys, mixtures of alkali metals or alkali metal alloys with alkali intercalation compounds, compounds containing alkali elements, or combinations thereof. can contain. Petroleum coke, carbon black, amorphous carbon, hard carbon, template carbon, hollow carbon nanowires, hollow carbon spheres, titanate, _{NaTi2 (} PO4) _{3 , Na2Ti3O7 (} sodium titanate), _{Na2C 8} H ₄ O ₄ (disodium terephthalate), Na ₂ TP (sodium terephthalate), TiO ₂ , Na _x TiO ₂ (x=0.2-1.0), carboxylate-based material, C ₈ H ₄ Na _{2O4 , C8H6O4 , C8H5NaO4 , C8Na2F4O4 , C10H2Na4O8 , C14H4O6 , C14H4Na4O _ _ _ _ _ _ _ _ _} Particularly desirable are anode active materials containing alkali intercalation compounds selected from ₈ , or combinations thereof.

In one embodiment, the anode can contain a mixture of two or three anode active materials (eg mixed particles of activated carbon + NaTi ₂ (PO ₄ ) ₃ ) and the cathode is a sodium intercalation compound alone (eg Na _x MnO ₂ ), an electric double layer capacitive cathode active material alone (eg, activated carbon), or a redox couple of λ-MnO ₂ /activated carbon for pseudocapacitance.

A wide variety of cathode active materials can be used to carry out the method according to the invention. Cathode active materials are typically alkali metal intercalation compounds or alkali metal absorbers capable of storing alkali metal ions when the battery is discharged and releasing the alkali metal ions to the electrolyte when the battery is recharged. is a compound. Cathode active materials can be selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides (the most desirable type of inorganic cathode materials), or combinations thereof such as:

lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium transition metal oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, The group of metal oxides, metal phosphates and metal sulfides consisting of transition metal sulfides and combinations thereof. _{In particular} , _{lithium vanadate is VO2 , LixVO2 , V2O5 , LixV2O5 , V3O8} , _LixV3O8 , _{LixV3O7 , V4O9} , Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped versions thereof, derivatives thereof, and combinations thereof, where 0 .1<x<5). The lithium transition metal oxide is a layered compound _LiMO2 , a _spinel compound _LiM2O4 , an olivine compound _LiMPO4 , a silicate compound _Li2MSiO4 , a taborite compound _LiMPO4F , a borate compound _{LiMBO3 ,} or combinations thereof. where M is a transition metal or a mixture of transition metals.

In alkali metal or alkali metal ion cells, the cathode active materials are _{NaFePO4 (} sodium iron phosphate) _{, Na0.7FePO4} , _{Na1.5VOPO4F0.5 , Na3V2 ( PO4} ) ₃ . , _{Na3V2 ( PO4} ) _2F3 , _Na2FePO4F , _{NaFeF3 , NaVPO4F , Na3V2 ( PO4} ) _{2F3 , Na1.5VOPO4F0.5 , Na3} V2 ₍ PO4) ₃ , _NaV6O15 , _NaxVO2 , _Na0.33V2O5 , _{NaxCoO2 (} sodium cobaltate), _{Na2 /3 [ Ni1 / 3Mn2 / 3} ]O ₂ , Na _x (Fe _1/2 Mn _1/2 )O ₂ , Na _x MnO ₂ (sodium manganese bronze), λ-MnO ₂ , Na _0.44 MnO ₂ , Na ₀ . _44MnO2 / _C , _Na4Mn9O18 , _{NaFe2Mn ( PO4} ) _{3 , Na2Ti3O7 , Ni1} / _{3Mn1 / 3Co1 / 3O2} , _Cu0.56Ni0 . ₄₄ HCF (copper and nickel hexacyanoferrate), _NiHCF (nickel hexacyanoferrate), _NaxCoO2 , _{NaCrO2 , Na3Ti2 (} PO4) _{3 , NiCo2O4 , Ni3S2} /FeS ₂ , Sb ₂ O ₄ , Na ₄ Fe(CN) ₆ /C, NaV _1-x Cr _x PO ₄ F, Se _y S _z (selenium and selenium/sulphur, z/y is 0.01-100), Se (no S), aluordite, or a combination thereof (or their potassium counterparts) selected from sodium intercalation compounds.

Other inorganic materials for use as cathode active materials may be selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. In particular, the inorganic material is selected from _TiS2 , _TaS2 , MoS2, _NbSe3 , _{MnO2 , CoO2} , iron oxide, vanadium oxide, or combinations thereof. These are discussed further below.

In particular, the inorganic materials are (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenides or trichalcogenides, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron , nickel, or transition metal sulfides, selenides, or tellurides, (d) boron nitride, or (e) combinations thereof.

Alternatively, the cathode active material can be selected from functional or nanostructured materials having alkali metal ion trapping functional groups or alkali metal ion storage surfaces in direct contact with the electrolyte. Preferably, the functional group reacts reversibly with alkali metal ions, forms redox pairs with alkali metal ions, or forms chemical complexes with alkali metal ions. The functional or nanostructured material is selected from (a) soft carbon, hard carbon, polymeric carbon or carbonized resin, mesophase carbon, coke, carbonized pitch, carbon black, activated carbon, nanocellular carbon foam, or partially graphitized carbon. (b) nanographene platelets selected from single-walled graphene sheets or multi-walled graphene platelets; (c) carbon nanotubes selected from single-walled carbon nanotubes or multi-walled carbon nanotubes. (d) carbon nanofibers, nanowires, metal oxide nanowires or fibers, conductive polymer nanofibers, or combinations thereof; (e) carbonyl-containing organic or polymeric molecules; (f) carbonyl, carboxyl, or amine groups. and combinations thereof.

Functional or nanostructured materials include poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene), Na _x C ₆ O ₆ (x=1-3), Na ₂ (C ₆ H ₂ O ₄ ), Na ₂ C ₈ H ₄ O ₄ (sodium terephthalate), Na ₂ C ₆ H ₄ O ₄ (trans-trans-muconic acid Li), 3,4,9,10-perylenetetracarboxylic acid di anhydride (PTCDA) sulfide polymer, PTCDA, 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4 , 5,8-tetrahydroxyanthraquinones, tetrahydroxy-p-benzoquinones, and combinations thereof. Desirably the functional or nanostructured material has functional groups selected from -COOH, =O, _-NH2 , -OR, or -COOR, where R is a hydrocarbon group.

Organic or polymeric materials include poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbons, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene -4,5,9,10-tetraone (PYT), polymer-bound PYT, quino (triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6 ,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PDAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ]n), lithiated 1 , 4,5,8-naphthalene tetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5-benzylidenehydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi ₄ ), N,N'-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N'-diallyl-2,3,5,6 - tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone compound, 1,4-benzoquinone, 5,7,12,14- pentcentetron (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDQ), 5-amino-1,4-dihydroxyanthraquinone (ADAQ), calixquinone, Li ₄ C ₆ O ₆ , It may be _selected from _Li2C6O6 , _{Li6C6O6 ,} or _{combinations thereof} .

Thioether polymers include poly[methantetriyl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), poly(ethene-1,1,2,2-tetrathiol as backbone thioether polymer ) (PETT), a side-chain thioether polymer with a backbone composed of conjugated aromatic moieties and pendant thioether side chains, poly(2-phenyl-1,3-dithiolane) (PPDT), poly( 1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4,5-tetrakis(propylthio)benzene] ( PTKPTB, or poly[3,4(ethylenedithio)thiophene] (PEDTT).

Organic materials include copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, phthalocyanine chloroaluminum, cadmium phthalocyanine, chlorogallium phthalocyanine, Phthalocyanine compounds selected from cobalt phthalocyanines, silver phthalocyanines, metal-free phthalocyanines, chemical derivatives thereof, or combinations thereof.

The lithium intercalating compound or lithium absorbing compound may be selected from metal carbides, metal nitrides, metal borides, metal dichalcogenides, or combinations thereof. Preferably, the lithium intercalating compound or lithium absorbing compound comprises niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, in the form of nanowires, nanodiscs, nanoribbons, or nanoplatelets. It is selected from manganese, iron or nickel oxides, dichalcogenides, trichalcogenides, sulfides, selenides or tellurides.

The inventors have discovered that a wide variety of two-dimensional (2D) inorganic materials can be used as cathode active materials in lithium batteries according to the invention prepared by the direct active material-electrolyte injection method according to the invention. Layered materials provide a variety of sources for 2D systems that can exhibit unexpected electronic properties and good affinity for lithium ions. Graphite is the best-known layered material, but transition metal dichalcogenides (TMDs), transition metal oxides (TMOs), and a wide range of other compounds such as BN _{, Bi2Te3 ,} and _Bi2Se3 can also be a source of 2D material.

Preferably, the lithium intercalating compound or lithium absorbing compound is (a) bismuth selenide or bismuth telluride, (b) a transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten , titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides; (d) boron nitride; or (e) combinations thereof. Selected from platelets, nanocoatings or nanosheets, wherein the discs, platelets or sheets have a thickness of less than 100 nm. Lithium intercalating compounds or lithium absorbing compounds include (i) bismuth selenide or bismuth telluride, (ii) transition metal dichalcogenides or trichalcogenides, (iii) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, nanodiscs, nanoplatelets, nanodiscs of compounds selected from sulfides, selenides, or tellurides of cobalt, manganese, iron, nickel, or transition metals, (iv) boron nitride, or (v) combinations thereof Coatings, or nanosheets, may be included, where the discs, platelets, coatings, or sheets have a thickness of less than 100 nm.

Single-layer or few-layer (up to 20 layers) non-graphene 2D nanomaterials can be fabricated by several methods as follows. Mechanical ablation, laser ablation (e.g., using laser pulses to ablate the TMD to a monolayer), liquid phase exfoliation, and synthesis of thin film techniques, e.g., PVD (e.g., sputtering), vapor deposition, vapor phase epitaxy, liquid phase epitaxy, chemical vapor deposition epitaxy, molecular beam epitaxy (MBE), atomic layer epitaxy (ALE), and plasma versions thereof.

A wide variety of electrolytes can be used in the practice of the invention. Non-aqueous organic and/or ionic liquid electrolytes are most preferred. Non-aqueous electrolytes employed herein may be produced by dissolving an electrolyte salt in a non-aqueous solvent. Any known nonaqueous solvent that is employed as a solvent for lithium secondary batteries can be employed. A non-aqueous solvent (hereinafter referred to as a second (referred to as the solvent of ) can preferably be employed. The non-aqueous solvent is (a) stable to negative electrodes containing well-formed carbonaceous materials in a graphite structure, (b) effective in inhibiting reduction or oxidative decomposition of the electrolyte, and ( c) It has the advantage of high electrical conductivity. A non-aqueous electrolyte composed only of ethylene carbonate (EC) has the advantage of being relatively stable against decomposition due to reduction by a graphitized carbonaceous material. However, the melting point of EC is relatively high at 39 to 40° C., and the viscosity of EC is relatively high, so the conductivity of EC is low. Therefore, EC alone is used as an electrolyte for secondary batteries that operate below room temperature is inappropriate for The second solvent used in the mixture with EC serves to make the solvent mixture less viscous than EC alone, thereby increasing the ionic conductivity of the mixed solvent. Furthermore, the use of a second solvent having a donor number of 18 or less (ethylene carbonate has a donor number of 16.4) allows the ethylene carbonate to be easily and selectively solvated with lithium ions, thus sufficiently It is hypothesized that the reduction reaction of the second solvent with the carbonaceous material produced by graphitization of 1 is inhibited. Furthermore, when the number of donors in the second solvent is controlled to 18 or less, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, thereby producing a high voltage lithium secondary battery. becomes possible.

Preferred second solvents are dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), γ-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, and methyl acetate (MA). These second solvents may be employed alone or in combination of two or more. More desirably, this second solvent should be selected from those having a donor number of 16.5 or less. The viscosity of this second solvent should preferably be no greater than 28 cps at 25°C.

The mixing ratio of the ethylene carbonate in the mixed solvent should preferably be 10-80% by volume. If the mixing ratio of ethylene carbonate is out of this range, the conductivity of the solvent may be lowered, or the solvent tends to decompose more easily, thereby deteriorating the charge-discharge efficiency. A more preferable mixing ratio of ethylene carbonate is 20 to 75% by volume. When the mixing ratio of ethylene carbonate in the non-aqueous solvent is increased to 20% by volume or more, the solvation effect of ethylene carbonate on lithium ions is promoted, and the effect of inhibiting solvent decomposition can be improved.

Examples of preferred mixed solvents are compositions comprising EC and MEC; compositions comprising EC, PC and MEC; compositions comprising EC, MEC and DEC; compositions comprising EC, MEC and DMC; , MEC, PC and DEC, and the volume ratio of MEC is controlled within the range of 30-80%. By selecting the volume ratio of MEC from the range of 30-80%, more preferably 40-70%, the conductivity of the solvent can be improved. For the purpose of suppressing the decomposition reaction of the solvent, the electrolyte with dissolved carbon dioxide can be employed, thereby effectively improving both the capacity and the cycle life of the battery. Electrolyte salts incorporated into the non-aqueous electrolyte include lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), trifluoro -lithium metasulfonate (LiCF ₃ SO ₃ ), and lithium salts such as lithium bis-trifluoromethylsulfonylimide [LiN(CF ₃ SO ₂ ) ₂ ]. Among them, LiPF ₆ , LiBF ₄ and LiN(CF ₃ SO ₂ ) ₂ are preferred.

The content of said electrolyte salt in the non-aqueous solvent is preferably above 2.5M (mol/l), more preferably >3.0M, even more preferably >5.0M, even more preferably >7 .0M, and most preferably >10M. Electrolytes containing higher concentrations of alkali metal salts make it easier to form cable cells that are not prone to leakage during manufacture or while the cable cells are flexed or twisted. Even more surprisingly, the inventors have determined that most electrolytes become flame retardant when the salt concentration exceeds 3.5M. Some become flame retardant at salt concentrations above 3.0M or only >2.5M. Battery scientists and engineers would expect higher concentrations to mean higher viscosities and lower ionic mobilities, and thus lower alkali ion conductivity. We have found that this trend is generally true for the salt concentration range of 0.01M to 2.0M. However, quite unexpectedly, alkali ion conductivity (Li ⁺ , Na ⁺ , and K ⁺ ions) begin to increase.

Ionic liquids are composed only of ions. Ionic liquids are salts with low melting temperatures that become molten or liquid when a desired temperature is exceeded. For example, a salt is considered an ionic liquid if its melting point is below 100°C. If the melting temperature is below room temperature (25° C.), the salt is called a room temperature ionic liquid (RTIL). IL salts are characterized by weak interactions in combination with large cations and charge-delocalized anions. This reduces the propensity for crystallization due to flexibility (anions) and asymmetry (cations).

A typical well-known ionic liquid is formed by combining the 1-ethyl-3-methylimidazolium (EMI) cation with the N,N-bis(trifluoromethane)sulfonamide (TFSI) anion. This combination results in a fluid with ionic conductivity comparable to many organic electrolyte solutions up to about 300-400° C., as well as low degradability and low vapor pressure. This suggests electrolytes with generally lower volatility and non-flammability, and thus much safer for batteries.

Ionic liquids are basically composed of organic ions that undergo an essentially unlimited number of structural changes due to the ease of preparing a wide variety of components. Therefore, different types of salts can be used to design ionic liquids with desired properties for a given application. These include, inter alia, imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl)imide and hexafluorophosphate as anions. Based on their composition, ionic liquids basically fall into different classes, including aprotic, protic, and zwitterionic forms, each suitable for specific applications.

Common cations of room temperature ionic liquids (RTILs) include, but are not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkylpyrrolidinium, dialkylpiperidinium, tetra Alkylphosphoniums, as well as trialkylsulfoniums are mentioned. Common anions of RTIL include, but are not limited to, BF ₄ ⁻ , B(CN) ₄ ⁻ , CH ₃ BF ₃ ⁻ , CH2CHBF ₃ ⁻ , CF ₃ BF ₃ ⁻ , C ₂ F ₅ BF ₃ ⁻ , n _-C3F7BF3- ^, _{n - C4F9BF3- , PF6-} ^, _{CF3CO2- , CF3SO3-} ^, N _{( SO2CF3} ^{) 2- ,} _{N ( COCF3 )} (SO ₂ CF ₃ ) ⁻ , N(SO ₂ F) ₂ ⁻ , N(CN) ₂ ⁻ , C(CN) ₃ ⁻ , SCN ⁻ , SeCN ⁻ , CuCl ₂ ⁻ , AlCl ₄ ⁻ , F(HF) _{2 .3} ^- and the like. Relatively speaking, imidazolium or sulfonium-based cations and AlCl ₄ ⁻ , BF ₄ ⁻ , CF ₃ CO ₂ ⁻ , CF ₃ SO ₃ ⁻ , NTf ₂ ⁻ , N(SO ₂ F) ₂ ⁻ , or F Combinations with complex halide anions such as (HF) _2.3 ^- lead to RTILs with good operational conductivity.

RTILs have high intrinsic ionic conductivity, high thermal stability, low volatility, low (substantially zero) vapor pressure, non-flammability, and the ability to remain liquid over a wide temperature range above and below room temperature. , high polarity, high viscosity, and a wide electrochemical window. These properties, with the exception of high viscosity, are desirable properties when using RTILs as electrolyte components (salts and/or solvents) in supercapacitors.

A cable-type battery according to the present invention has many unique features, some of these features and advantages are summarized below:
By definition, cable geometry means a geometry having a length and diameter or thickness with an aspect ratio (ratio of length to diameter or length to thickness) of at least 10, preferably at least 20. A cabled alkali metal battery can have a length of over 1 m, or even over 100 m. This length can be as short as 1 μm, but typically between 10 μm and 10 m, more typically between a few micrometers and a few meters. In fact, there is no theoretical limit to the length of this type of cable battery.

Because the cabled alkali metal battery according to the invention is flexible, the battery can be easily bent to have a radius of curvature greater than 10 cm. The battery can be bent to substantially conform to the shape of a void or interior compartment within the vehicle. This gap or interior compartment may be the trunk, door, hatch, spare tire compartment, area under the seat, or area under the dashboard. The battery is removable from the vehicle and can be bent to fit different gap or interior compartment shapes.

One or more units of the cable type battery of the present invention may be used in clothing, belts, luggage straps, weapon straps, musical instrument straps, helmets, hats, boots, foot covers, gloves, wrist covers, watch bands, jewelry, It can be incorporated into an animal collar or animal harness.

One or more units of the cable type battery of the present invention may be used in removably incorporated clothing, belts, luggage straps, weapon straps, musical instrument straps, helmets, hats, boots, foot covers, gloves, wrist covers, It may be a watch band, jewelry, animal collar, or animal harness.

Furthermore, the battery according to the invention fits the inner radius of the hollow bicycle frame.

A number of different types of anode active materials, cathode active materials, and electrically conductive porous layers (e.g., graphite foams, graphene foams, and metal foams) are described below to illustrate the best mode of practicing the invention. ). These illustrative examples, as well as the rest of the specification and drawings, individually or in combination, are more than sufficient to enable those skilled in the art to practice the invention. However, these examples should not be construed as limiting the scope of the invention.

Example 1: Illustrative Examples of Electronically Conducting Porous Rods or Layers as Current Collectors Various types of metal foams, carbon foams and fine metal webs/screens can be used as conductive porous rods in anodes or cathodes. Commercially available for use as rods or layers (to act as current collectors); e.g. Ni foam, Cu foam, Al foam, Ti foam, Ni mesh/web, stainless steel fiber mesh, etc. . Metal-coated polymer foams and carbon foams are also used as current collectors. The most desirable thickness of these conductive porous layers is between 50 and 1000 μm, preferably between 100 and 800 μm, for the production of cable-type, flexible, conformable batteries of visible size, More preferably 200 to 600 μm. For the fabrication of microscopic cable cells (eg, with diameters of 100 nm to 100 μm), graphene foams, graphene airgel foams, porous carbon fibers (eg, electrospinning of polymer fibers, carbonization of the polymer fibers, and (manufactured by the activation of sintered carbon fibers), and porous graphite fibers can be used to accommodate mixtures of electrode active materials and electrolytes.

Example 2: Ni-foam supported on Ni-foam template and porous layer based on CVD graphene foam Procedures for making CVD graphene foam are disclosed in the following published literature Adapted from: Chen, Z.; et al. "Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapor deposition," Nature Materials, 10, 424-428 (2011). Nickel foam, a porous structure with interconnected 3D scaffolds of nickel, was selected as a template for the growth of graphene foam. Briefly, carbon was introduced into the nickel foam by decomposing CH4 at 1000 °C under ambient pressure, and then a graphene film was deposited _on the surface of the nickel foam. Due to the difference in thermal expansion coefficient between nickel and graphene, the graphene film was wavy and wrinkled. The four types of foams formed in this example: Ni foams, CVD graphene-coated Ni foams, CVD graphene foams (where the Ni is etched away), and conductive polymer-bonded CVD graphene foams. It was used as a current collector in a lithium battery according to the present invention.

The Ni frame was etched away to recover (separate) the graphene foam from the supporting Ni foam. In the procedure proposed by Chen et al., a thin layer of poly(methyl methacrylate) (PMMA) is deposited on the surface of the graphene film as a support before etching away the nickel framework by hot HCl (or FeCl) solution, It prevented the graphene network from collapsing during nickel etching. After careful removal of the PMMA layer with hot acetone, brittle graphene foam samples were obtained. The use of PMMA support layers was thought to be important for making free-standing films of graphene foam. Instead, a conductive polymer was used as the binder resin to hold the graphene together while etching away the Ni. The thickness range of graphene foam or Ni foam was 35 μm to 600 μm.

The layer of Ni foam or CVD graphene foam used in the present invention is used to house the anode and/or cathode components (active material of anode or cathode + optional conductive additive + liquid electrolyte). is intended as a conductive porous layer (CPL) of. For example, a gel-like material is formed from Si nanoparticles dispersed in an organic liquid electrolyte (eg, 1-5.5 M LiPF ₆ dissolved in PC-EC), which is continuously fed from a feeder roller. was delivered to the porous surface of the Ni foam to form an anode electrode roller (shown in schematic A of FIG. 1(C)).

A cathode slurry was formed from graphene-supported LFP nanoparticles dispersed in the same liquid electrolyte and sprayed onto the two porous surfaces of the continuous Ni foam layer to form the cathode electrode. A porous foam rod (first electrode) containing a Si nanoparticle electrolyte mixture impregnated in the foam pores was wrapped with a porous separator layer (porous PE-PP copolymer), which was then subjected to LFP wrapped with a system cathode layer. This cylindrical structure is then encased in a thin polymer sheath, resulting in a cable-style lithium-ion battery.

Example 3: Graphite Foam-Based Conductive Porous Layer from Pitch-Based Carbon Foam Pitch powder, granules, or pellets are placed in an aluminum mold having the desired final shape of the foam. Mitsubishi ARA-24 mesophase pitch was utilized. The sample is evacuated to less than 1 Torr and then heated to a temperature of approximately 300°C. At this point the vacuum was released to a nitrogen blanket and then pressure was applied to 1,000 psi. The temperature of the system was then raised to 800°C. This was done at a rate of 2°C/min. The temperature was held for at least 15 minutes to achieve immersion, then the furnace power was turned off and allowed to cool to room temperature at a rate of about 1.5° C./min while releasing pressure at a rate of about 2 psi/min. The final foam temperatures were 630°C and 800°C. During the cooling cycle the pressure is gradually released to atmospheric conditions. The foam was then heat treated under a nitrogen blanket to 1050° C. (carbonization) and then separately heat treated in argon to 2500° C. and 2800° C. (graphitization) in graphite crucibles. Graphite foam layers are available in a thickness range of 75-500 μm.

Example 4: Preparation of Graphene Oxide (GO) and Reduced Graphene Oxide (RGO) Nanosheets from Natural Graphite Powder Huadong Graphite Co.; (Qingdao, China) was used as the starting material. GO was obtained by following the well-known modified Hummers method. This method involved two oxidation stages. In a typical procedure, the first oxidation was achieved under the following conditions. 1100 mg of graphite was placed in a 1000 mL boiling flask. K ₂ S ₂ O ₈ , 20 g of P ₂ O ₅ and 400 mL of concentrated aqueous H ₂ SO ₄ (96%) were then added to the flask. The mixture was heated under reflux for 6 hours and then left at room temperature for 20 hours. The graphite oxide was filtered and rinsed with copious amounts of distilled water to neutral pH. At the end of this first oxidation, a wet cake material was collected.

_In the second oxidation process, the previously collected wet cake was placed in a boiling flask containing 69 mL of concentrated aqueous H2SO4 ₍ 96%). The flask was kept in an ice bath while 9 g of KMnO ₄ was added slowly. Care was taken to avoid overheating. The resulting mixture was stirred at 35° C. for 2 hours (sample color turned dark green) followed by the addition of 140 mL of water. After 15 minutes, the reaction was quenched by adding 420 mL of water and 15 mL of 30 wt % H ₂ O ₂ aqueous solution. The color of the sample at this stage turned bright yellow. The mixture was filtered and rinsed with 1:10 aqueous HCl to remove metal ions. Collected material was gently centrifuged at 2700 g and rinsed with deionized water. The final product was a wet cake containing 1.4 wt% GO as estimated from the dry extract. A liquid dispersion of GO platelets was then obtained by lightly sonicating the wet cake material diluted with deionized water.

Surfactant-stabilized RGO (RGO-BS) was obtained by diluting the wet cake with an aqueous surfactant solution instead of pure water. A commercial mixture of salts of sodium cholate (50 wt%) and sodium deoxycholate (50 wt%) provided by Sigma Aldrich was used. The weight fraction of surfactant was 0.5 wt%. This fraction was kept constant for all samples. Sonication was performed using a Branson Sonifier S-250A equipped with a 13 mm step distractor horn and a 3 mm tapered microtip operating at a frequency of 20 kHz. For example, 10 mL of an aqueous solution containing 0.1 wt % GO was sonicated for 10 minutes and then centrifuged at 2700 g for 30 minutes to remove undissolved large particles, aggregates, and impurities. Chemical reduction of GO obtained as described above was carried out to produce RGO by following a method comprising placing 10 mL of 0.1 wt % GO aqueous solution in a 50 mL boiling flask. To the surfactant-stabilized mixture was then added 10 μL of 35 wt % aqueous N ₂ H ₄ (hydrazine) and 70 mL of 28 wt % aqueous NH ₄ OH (ammonia). The solution was heated to 90° C. and refluxed for 1 hour. The pH value measured after the reaction was about 9. The color of the sample turned dark black during the reduction reaction.

Some lithium batteries according to the present invention used RGO as a conductive additive in either or both of the anode and cathode active materials. Prelithiated RGO (e.g., RGO + lithium particles, or RGO pre-deposited with a lithium coating) was also used as an anode active material mixed with a liquid electrolyte to form a wet anode active material mixture for use in selected lithium ion cells. . Selected cathode active materials (TiS ₂ nanoparticles and LiCoO ₂ particles, respectively) and non-lithiated RGO sheets were dispersed in liquid electrolyte to prepare wet cathode active material mixtures. A wet anode active mixture and a wet cathode active mixture were separately delivered to the surface of the graphite foam to form the anode layer and the cathode layer, respectively. Cable type cells were then fabricated where the core structure (first electrode) was either the anode or cathode and the second electrode was the corresponding counter electrode (either cathode or anode).

For comparison, a slurry coating and drying procedure was performed to produce a conventional electrode. The electrodes and a separator disposed between two dry electrodes were then assembled into an Al-plastic laminated packaging envelope followed by injection of a liquid electrolyte to form a conventional lithium battery cell. .

Example 5 Preparation of Sheets of Pure Graphene (0% Oxygen) Recognizing the possibility that high defect populations in GO sheets act to reduce the conductivity of individual graphene planes, we , by using sheets of pure graphene (e.g., non-oxidized, oxygen-free, non-halogenated, halogen-free) conductive additive with high electrical and thermal conductivity I decided to research if I could get the drug. Prelithiated pure graphene and presodiumated pure graphene were also used as anode active materials for lithium-ion and sodium-ion batteries, respectively. Sheets of pure graphene were fabricated by using direct sonication or liquid-phase fabrication methods.

In a typical procedure, 5 grams of graphite flakes, ground to a size of about 20 μm or less, were mixed with 1,000 mL of deionized water (containing 0.1 wt % dispersant, Zonyl® FSO from DuPont). to obtain a suspension. An ultrasonic energy level of 85 W (Branson S450 Ultrasonicator) was used for exfoliation, separation, and size reduction of graphene sheets over a period of 15 minutes to 2 hours. The resulting graphene sheets are pure graphene that has never been oxidized, does not contain oxygen, and is relatively defect-free. Pure graphene is essentially free of non-carbon elements.

Sheets of pure graphene are then used as the conductive additive to form the anode active material (or cathode active material for the cathode) using both procedures according to the present invention and conventional slurry coating, drying and lamination procedures. ) in the battery. Both lithium ion and lithium metal batteries (impregnation on cathode only) were investigated. A sodium ion cell was also prepared and investigated.

Example 6 Lithium Iron Phosphate (LFP) Cathodes for Lithium Metal Batteries Uncoated or carbon-coated LFP powders are commercially available from several sources. LFP targets for sputtering were prepared by compacting and sintering LFP powder. Sputtering of LFPs was carried out on graphene films and separately on carbon nanofiber (CNF) mats. The LFP-coated graphene films were then crushed and pulverized to form LFP-coated graphene sheets.

Both carbon-coated LFP powders and graphene-supported LFPs were then separately coated with a liquid electrolyte using both the cable-type structure fabrication procedure according to the present invention and conventional slurry coating, drying, and lamination procedures. , built into the battery.

Example 7: Preparation of disodium terephthalate (Na ₂ C ₈ H ₄ O ₄ ) as anode active material for sodium ion batteries Pure disodium terephthalate was obtained by recrystallization method. Terephthalic acid was added to aqueous NaOH to prepare an aqueous solution, then ethanol (EtOH) was added to the mixture to precipitate disodium terephthalate into the water/EtOH mixture. Due to resonance stabilization, terephthalic acid has a relatively low pKa value, so it can be easily deprotonated by NaOH to give disodium terephthalate (Na ₂ TP) by acid-base chemistry. . In a typical procedure, terephthalic acid (3.00 g, 18.06 mmol) was treated with sodium hydroxide (1.517 g, 37.93 mmol) in EtOH (60 mL) at room temperature. After 24 hours, the suspended reaction mixture was centrifuged and the supernatant solution was decanted. The resulting precipitate was re-dispersed in EtOH and then centrifuged again. This procedure was repeated twice to give a white solid. The product was dried in vacuum at 150° C. for 1 hour. In another sample, GO was added to an aqueous NaOH solution (5 wt% GO sheets) to produce graphene-supported disodium terephthalate sheets under similar reaction conditions.

Both the carbon-disodium terephthalate mixed powder and the graphene-supported disodium terephthalate were then separately, respectively, using both the procedure according to the invention and the conventional slurry coating, drying, and lamination procedure. It was incorporated into a battery together with a liquid electrolyte.

Example ₈ : _V2O5 as an example of a transition metal oxide cathode active material for lithium batteries
V ₂ O ₅ powder is commercially available separately. In a typical experiment, for the preparation of graphene-supported V ₂ O ₅ powder samples, vanadium pentoxide gels were obtained by mixing V ₂ O ₅ into LiCl aqueous solutions. The Li ⁺ exchanged gel obtained by interaction with a LiCl solution (li:V molar ratio was kept at 1:1) was mixed with the GO suspension and then placed in a Teflon-lined stainless steel 35 ml autoclave. Sealed and heated to 180° C. for 12 hours. After such hydrothermal treatment, the raw solids were collected, washed thoroughly, sonicated for 2 minutes, dried at 70° C. for 12 hours, then mixed with additional 0.1% GO in water, The nanobelt size was crushed by sonication and then spray-dried at 200° C. to obtain graphene-encapsulated composite particles.

V ₂ O ₅ powder (including carbon black powder as a conductive additive) and graphene-supported V ₂ O were then coated using both the procedure according to the invention and the conventional slurry coating, drying and lamination procedure. ₅ powders were separately incorporated into the battery together with the liquid electrolyte.

Example ₉ : LiCoO2 as an example of a lithium transition metal oxide cathode active material for lithium ion batteries
Commercially available LiCoO ₂ powder and carbon black powder were dispersed in the liquid electrolyte to form a cathode active material mixture, which was impregnated into the Ni foam-based cathode current collector layer to form the cathode electrode. A graphite particle-liquid electrolyte (ie, anode active mixture) was impregnated into the pores of the Cu foam layer to form the anode electrode. Furthermore, a mixture of graphene-encapsulated Si nanoparticles and a liquid electrolyte was impregnated into the pores of the Cu foam to obtain an anode electrode. The anode electrode, porous separator layer, and cathode electrode were assembled, compressed and encased in a plastic Al envelope to make a battery cell. The cell was then hermetically sealed.

LiCoO2 powder, carbon black powder, and PVDF resin binder _were separately dispersed in NMP solvent to form a slurry, which was applied to both sides of the AL foil current collector, and then vacuum dried to form the cathode layer. formed. Graphite particles and PVDF resin binder were dispersed in NMP solvent to form a slurry, which was coated on both sides of a Cu foil current collector and then vacuum dried to form an anode layer. The anode layer, separator and cathode layers were then laminated and encased in an Al-plastic housing into which a liquid electrolyte was injected to form a conventional lithium ion battery.

Example 10: Mixed Transition Metal _Oxide Based _Cathode Active Materials Examples include _{Na1.0Li0.2Ni0.25Mn0.75O [ delta ]} , _{Ni0.25Mn0.75CO3 ,} or _Ni0 For the synthesis of the cathode active material of _{.25Mn0.75 (} OH) _{2 , Na2CO3} and _{Li2CO3 were} used as starting compounds. Appropriate molar ratios of materials were ground together and heat treated first at 500° C. for 8 hours in air and then finally at 800° C. for 8 hours in air and cooled in a furnace.

Sheets of aluminum foil were coated with an N-methylpyrrolidinone (NMP) slurry of the cathode mixture for electrode fabrication using conventional procedures. The electrode mixture consisted of 82 wt% active oxide material, 8 wt% conductive carbon black (Timcal Super-P), and 10 wt% PVDF binder (Kynar). After casting, the electrodes were first dried at 70° C. for 2 hours followed by dynamic vacuum drying at 80° C. for at least 6 hours. Hexane was used to remove the oil and then the sodium metal foil was cut from a rolled and stamped sodium chunk (Aldrich, 99%). For the preparation of the slurry according to the invention, NMP was replaced by liquid electrolyte (propylene carbonate with 1 M NaClO ₄ ). Such slurry was impregnated directly into the pores of the cathode current collector.

_{Na1.0Li0.2Ni0.25Mn0.75O [ delta ]} powder ₍ conductive additive Both the graphene-supported Na _1.0 Li _0.2 Ni _0.25 Mn _0.75 O _δ powders, with carbon black powder as the agent, were separately incorporated into the battery together with the liquid electrolyte.

The electrolyte was propylene carbonate with 1M _NaClO4 electrolyte salt (Aldrich, 99%). The pouch cells were cycled under galvanostatic conditions (15 mA/g) to a cutoff of 4.2V vs. Na/Na ⁺ and then discharged at various current rates to a cutoff voltage of 2.0V.

Charge storage capacity was measured periodically and recorded as a function of cycle number for all fabricated battery cells. The specific discharge capacities referred to herein take into account the unit mass of the composite cathode (the combined weight of cathode active material, conductive additive or support, binding agent, and any optional additives). , excluding the current collector) is the total charge inserted into the cathode during discharge. Specific charge capacity means the amount of charge per unit mass of the composite cathode. The specific energy and specific power values given in this section are based on total cell weight for all pouch cells. Morphological or microstructural changes in selected samples after a desired number of repeated charging and recharging cycles are observed using both transmission electron microscopy (TEM) and scanning electron microscopy (SEM). did.

Example ₁₁ : Cathode of _{Na3V2 (} PO4) ₃ /C and _{Na3V2 (} PO4) ₃ /graphene _A sample of _{Na3V2 ( PO4)3 /} C was prepared by a solid state reaction according to the following procedure. Synthesized: A stoichiometric mixture of _{NaH2PO4.2H2O (} 99.9%, Alpha) and _{V2O3 (} 99.9% _, Alpha) powders was put into an agate jar as a precursor, and then The precursor was ball milled for 8 hours at 400 rpm in a planetary ball mill in a stainless steel vessel. During ball milling, sugar (99.9%, Alpha) was also added as a carbon precursor and reducing agent to prevent oxidation of ^V3+ for the carbon-coated samples. After ball milling, the mixture was pressed into pellets and then heated at 900° C. for 24 hours in an Ar atmosphere. Separately, a Na ₃ V ₂ (PO ₄ ) ₃ /graphene cathode was made with a similar procedure using graphene oxide instead of sugar.

These cathode active materials were used in several Na metal cells containing 1-7.5 M NaPF ₆ salt in PC+DOL as electrolyte. Na metal cells were fabricated using both a conventional NMP slurry coating process and the procedure according to the present invention.

カソード活性材料（Ｌｉ_２Ｃ_６Ｏ_６）と導電性添加剤（カーボンブラック、１５％）との混合物を１０分間ボールミル加工し、得られたブレンドを研磨して複合物粒子を製造した。電解質は、ＰＣ－ＥＣ中で１Ｍのヘキサフルオロリン酸リチウム（ＬｉＰＦ_６）であった。 Example ₁₂ : Organic Material ( _Li2C6O6 ) as _Cathode Active Material in Lithium Metal Batteries
To synthesize dilithium rhodizonate (Li ₂ C ₆ O ₆ ), rhodizonate dihydrate (species 1 in the formula below) was used as a precursor. A basic lithium salt Li ₂ CO ₃ can be used in aqueous media to neutralize both enediolic acid functions. Strict stoichiometric amounts of both reactants, rhodizonic acid and lithium carbonate, were reacted for 10 hours to achieve a yield of 90%. Dilithium rhodizonate (species 2) is readily soluble in even small amounts of water, suggesting that water molecules are present in species 2. Water was removed in vacuo at 180° C. for 3 hours to give the anhydrous form (species 3).

A mixture of cathode active material (Li ₂ C ₆ O ₆ ) and conductive additive (carbon black, 15%) was ball milled for 10 minutes and the resulting blend was ground to produce composite particles. The electrolyte was 1 M lithium hexafluorophosphate (LiPF ₆ ) in PC-EC.

Note that the two Li atoms in the formula Li ₂ C ₆ O ₆ are part of a fixed structure and do not participate in the reversible storage and release of lithium ions. This suggests that lithium ions must come from the anode side. Therefore, a lithium source (eg, lithium metal or lithium metal alloy) must be present at the anode. A layer of lithium is deposited (eg, by sputtering or electrochemical plating) on the anode current collector (graphene airgel foam rod). This can be done prior to assembling the lithium coating layer (or simply lithium rod), porous separator, and impregnated cathode layer into a casing. For comparison, a corresponding conventional Li metal cell was also fabricated by conventional slurry coating, drying, lamination, packaging, and electrolyte injection procedures.

カソード活性材料（Ｎａ_２Ｃ_６Ｏ_６）と導電性添加剤（カーボンブラック、１５％）との混合物を１０分間ボールミル粉砕し、得られたブレンドを粉砕して複合粒子を形成した。電解質は、ＰＣ－ＥＣ中の１Ｍのヘキサフルオロリン酸ナトリウム（ＮａＰＦ_６）であった。 Example ₁₃ : Organic Material ( _Na2C6O6 ) as _Cathode Active Material in Sodium Metal Batteries
To synthesize disodium rhodizonate (Na ₂ C ₆ O ₆ ), rhodizonate dihydrate (species 1 in the formula below) was used as a precursor. The basic sodium salt Na ₂ CO ₃ can be used in aqueous media to neutralize both enediolic acid functional groups. Strict stoichiometric amounts of both rhodizonic acid and sodium carbonate reactants could be reacted for 10 hours to achieve an 80% yield. Disodium rhodizonate (species 2) is readily soluble in even small amounts of water, suggesting that water molecules are present in species 2. Water was removed in vacuo at 180° C. for 3 hours to give the anhydrous form (species 3).

A mixture of cathode active material (Na ₂ C ₆ O ₆ ) and conductive additive (carbon black, 15%) was ball milled for 10 minutes and the resulting blend was ground to form composite particles. The electrolyte was 1M sodium hexafluorophosphate (NaPF ₆ ) in PC-EC.

The two Na atoms in the formula Na ₂ C ₆ O ₆ are part of a fixed structure and they do not participate in reversible lithium ion storage and release. Sodium ions must be obtained from the anode side. Therefore, a sodium source (eg, sodium metal or sodium metal alloy) must be present at the anode. A layer of sodium (eg, by electrochemical plating) is deposited on the anode current collector (carbon foam rod or thin Cu wire). This can be done prior to assembling the cable from the sodium coated layer or simply sodium rods, the porous separator and the foam impregnated with the cathode active material/electrolyte. The pores of the cathode current collector are pre-infiltrated with a suspension of cathode active material and conductive additive (Na ₂ C ₆ O ₆ /C composite particles) dispersed in a liquid electrolyte. For comparison, a corresponding conventional Na metal cell was also fabricated by conventional slurry coating, drying, lamination, packaging, and electrolyte injection procedures.

Example 14 Metal Naphthalocyanine-RGO Hybrid Cathodes for Lithium Metal Batteries CuPc-coated graphene sheets were obtained by vaporizing CuPc in a chamber with graphene films (5 nm) prepared from spin-coating of RGO-water suspensions. rice field. The resulting coated film was cut and pulverized to produce CuPc-coated graphene sheets, which had lithium metal rods as anode active material and were subjected to 1-3. in propylene carbonate (PC) solution as electrolyte. It was used as a cathode active material in a lithium metal battery with 7M _LiClO4 .

Example 15 Preparation of MoS2/RGO Hybrid Materials as Cathode Active Materials for Lithium Metal Batteries _In this example, a variety of inorganic materials were investigated. For example, the one-step solvothermal reaction of (NH ) ₂ MoS ₄ with hydrazine in N,N-dimethylformamide (DMF) solution of oxidized graphene oxide (GO) at 200 °C _yields ultrathin MoS ₂ /RGO hybrids were synthesized. In a typical procedure, 22 mg (NH ₄ ) ₂ MoS ₄ was added to 10 mg DMF dispersed in 10 ml DMF. The mixture was sonicated at room temperature for about 10 minutes until a clear, homogeneous solution was obtained. Then _{0.1 ml} of _N2H4.H2O was added. The reaction solution was sonicated for an additional 30 minutes before being transferred to a Teflon-lined 40 mL autoclave. The system was heated at 200° C. for 10 hours in an oven. The product was collected by centrifugation at 8000 rpm for 5 minutes, washed with DI water and recollected by centrifugation. The washing step was repeated at least 5 times to ensure most of the DMF was removed. Finally, the product was dried and mixed with liquid electrolyte to form a mixture slurry for active cathode impregnation.

Example 16 Preparation of Two-Dimensional (2D) Layered Bi ₂ Se ₃ Chalcogenide Nanoribbons The preparation of (2D) layered Bi ₂ Se ₃ chalcogenide nanoribbons is well known in the art. For example, a vapor-liquid-solid (VLS) method was used to grow Bi ₂ Se ₃ nanoribbons. The nanoribbons produced herein have an average thickness of 30-55 nm and range in width and length from hundreds of nanometers to several micrometers. Larger nanoribbons were ball milled to reduce lateral dimensions (length and width) to less than 200 nm. Nanoribbons prepared by these procedures (with or without graphene sheets or exfoliated graphite flakes) were used as cathode active materials in lithium metal batteries.

Example 17: Preparation of graphene-supported _MnO2 cathode active materials MnO2 powders were synthesized by _two methods (with or without graphene sheets, respectively). In one method, a 0.1 mol/L KMnO ₄ aqueous solution was prepared by dissolving potassium permanganate in deionized water. Meanwhile, 13.32 g of high purity sodium bis(2-ethylhexyl) sulfosuccinate surfactant was added to 300 mL of isooctane (oil) and stirred well to obtain an optically clear solution. Then, 32.4 mL of 0.1 mol/L KMnO ₄ solution and selected amount of GO solution were added into the solution, which was sonicated for 30 min to prepare a dark brown precipitate. . The product was isolated, washed several times with distilled water and ethanol, and dried at 80° C. for 12 hours. The sample was graphene-supported _MnO2 in powder form, which was mixed in the liquid electrolyte to form a cathode active material mixture slurry.

Example 18: Graphene Reinforced Nanosilicon Fabricated from TEOS as Anode Active Material for Lithium Ion Batteries In one of the experiments, 1 wt% N002-PS (GO-water suspension) was added to 0.2 wt% in DI water. % N002-PS. This diluted PS solution was placed in an ultrasonic bath and sonicated for 30 minutes. Following this, TEOS (0.2 wt% N002-PS:TEOS=5:2) was slowly added into the solution while stirring the PS solution. Stirring was then maintained for 24 hours in order to fully hydrolyze the TEOS. Subsequently, ₁₀ % _NH3.H2O was added dropwise to the solution until it reached a gel state, referred to herein as TP gel. The TP gel was ground to small particles and oven dried at 120° C. for 2 hours and 150° C. for 4 hours. The dried TP particles were mixed with Mg at a ratio of 10:7. Twenty times as many 7 mm SS balls were added into the grinding chamber and the samples were ball milled under argon protection. The rotation speed was gradually increased to 250 rpm. A sample of TPM powder was placed in a nickel crucible and heat treated at 680°C. A volume of 2M HCl solution was also prepared. The heat treated TPM powder was then slowly added to the acid solution. The reaction was maintained for 2-24 hours, then the cloudy liquid was placed in an ultrasonic bath and sonicated for 1 hour. The suspension was poured through a filtration system and large particles at the bottom were discarded. The sample was washed three times with DI water. The resulting yellow paste was dried and ground into powder using a blender. Nanoparticle samples as prepared exhibited specific surface area (SSA) values in the range of 30 m ² /g to 200 m ² /g for different graphene contents.

A sample of the dried TPM particles is placed in a muffle furnace and calcined at 400° C.-600° C. for 2 hours under an air purge to remove the carbon content from the nanocomposite and produce graphene-free yellow silicon nanopowder. . Both Si nanopowder and graphene-wrapped Si nanoparticles were used as high-capacity anode active materials.

Example 19 Cobalt Oxide ₍ Co3O4) Fine Particles as Anode Active Material LiCoO2 is the cathode active material in lithium _- ion _{batteries ,} while _Co3O4 is the anode active material. Because LiCoO ₂ has an electrochemical potential of about +4.0 volts vs. Li/Li ⁺ and Co ₃ O ₄ has an electrochemical potential of about +0.8 volts vs. Li/Li ⁺ . is.

Appropriate amount of inorganic salt Co(NO ₃ ) _{2.6H 2 O followed by ammonia solution (NH 3.H 2 O , 25} wt %) was slowly added to the GO suspension. The resulting precursor suspension was stirred under a stream of argon for several hours to ensure complete reaction. The resulting Co(OH) ₂ /graphene precursor suspension was divided into two portions. One portion was filtered and vacuum dried at 70° C. to obtain a Co(OH) ₂ /graphene composite precursor. The precursor was calcined in air at 450° C. for 2 hours to form a layered Co ₃ O ₄ /graphene composite. It is characterized by having Co ₃ O ₄ -coated graphene sheets on top of each other. These _Co3O4 coated graphene sheets _are another high capacity anode active material.

Example 20: Graphene Reinforced Tin Oxide Microparticles as Anode Active Materials Tin oxide ₍ SnO2) nanoparticles, an anode active material, _were prepared by controlled hydrolysis of _SnCl4.5H2O and NaOH using the following procedure. Obtained: SnCl ₄ .5H ₂ O (0.95 g, 2.7 m-mol) and NaOH (0.212 g, 5.3 m-mol) were each dissolved in 50 mL of distilled water. The NaOH solution was added dropwise at a rate of 1 mL/min to the tin chloride solution with vigorous stirring. The solution was homogenized by sonication for 5 minutes. The resulting hydrosol was then reacted with the GO dispersion for 3 hours. A few drops of 0.1 M H ₂ SO ₄ were added to the mixed solution to aggregate the product. The precipitated solid was collected by centrifugation, washed with water and ethanol and dried in vacuum. The dried product was heat treated at 400° C. for 2 hours under Ar atmosphere.

Example 21: Preparation of graphene-supported _MnO2 and _NaMnO2 cathodic active materials MnO2 powders were synthesized in _two ways (with or without graphene sheets, respectively). In one method, a 0.1 mol/L KMnO ₄ aqueous solution was prepared by dissolving potassium permanganate in deionized water. Meanwhile, 13.32 g of surfactant high purity sodium bis(2-ethylhexyl)sulfosuccinate was added in 300 mL of isooctane (oil) and stirred well to obtain an optically clear solution. Then, 32.4 mL of 0.1 mol/L KMnO ₄ solution and selected amount of GO solution were added into the solution, which was sonicated for 30 min to prepare a dark brown precipitate. . The product was isolated, washed several times with distilled water and ethanol, and dried at 80° C. for 12 hours. The sample was graphene-supported MnO ₂ in powder form, which was dispersed in a liquid electrolyte to form a slurry and impregnated into the pores of the foamed current collector.

Furthermore, by ball milling a mixture of Na ₂ CO ₃ and MnO ₂ (1:2 molar ratio) with or without graphene sheets for 12 hours followed by heating at 870° C. for 10 hours, NaMnO ₂ and NaMnO ₂ /graphene composites were synthesized.

Example 22 Preparation of Electrodes for Potassium Metal Cells Sheets of potassium-coated graphene films were used as the anode active material, while Angstron Materials, Inc. PVDF-bonded reduced graphene oxide (RGO) sheets supplied by (Dayton, Ohio) were used as the cathode active material. The electrolyte used was 1 M KClO ₄ salt dissolved in a mixture of propylene carbonate and DOL (1/1 ratio). Charge-discharge curves were determined for several current densities (50 mA/g to 50 A/g) corresponding to different C-rates, and the resulting energy density and power density data were measured and calculated.

Example 23 Preparation and Electrochemical Testing of Various Alkali Metal Battery Cells For most of the anode and cathode active materials investigated, using both the method according to the invention and conventional methods, alkali metal ion cells or alkali metal prepared the cell.

In conventional methods, a typical anode composition comprises 85 wt % active material (eg, Si or Co ₃ O ₄ coated graphene sheets) dissolved in N-methyl-2-pyrrolidinone (NMP) and 7 wt % acetylene black (Super-P) and 8 wt % polyvinylidene fluoride binder (PVDF, 5 wt % solids). After coating the slurry on the Cu foil, the electrode was vacuum dried at 120° C. for 2 hours to remove the solvent. By this method, typically no binder resin is required or used, saving 8% by weight (reducing the amount of non-active materials). The cathode layer is similarly formed (using Al foil as the cathode current collector) using conventional slurry coating and drying procedures. The anode layer, separator layer (eg Celgard 2400 membrane), and cathode layer are then laminated together and housed within a plastic Al envelope. A 1 M LiPF ₆ electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v) is then injected into the cell. Some cells used ionic liquids as liquid electrolytes. A cell assembly was formed in an argon-filled glove box.

Cyclic voltammetry (CV) measurements were performed using an Arbin electrochemical workstation with a typical scan rate of 1 mV/s. Furthermore, the electrochemical performance of various cells was evaluated at current densities from 50 mA/g to 10 A/g by galvanostatic charge/discharge cycling. A LAND multi-channel battery tester was used for long-term cycling tests.

In the lithium-ion battery industry, it is common practice to define the cycle life of a battery as the number of charge-discharge cycles at which the battery undergoes a 20% capacity fade based on the initial capacity measured after the required electrochemical formation. be.

Example 24: Typical Test Results for Lithium Cells For each sample, several current densities (representing charge/discharge rates) were imposed to determine the electrochemical response and Ragone plots (power density versus energy It enabled the calculation of the energy density and power density values required to build the density). Shown in FIG. 5 is a Ragone plot (weight and volumetric power density versus energy density) of a lithium-ion battery cell containing graphite particles as the anode active material and carbon-coated LFP particles as the cathode active material. Two of the four data curves are for cable-type cells prepared according to embodiments of the present invention, and the other two are for conventional slurry coating (roll coating) of the electrodes. cell. Several important observations can be made from these data:

The gravimetric and volumetric energy densities and power densities of the lithium-ion battery cells prepared by the method according to the invention (denoted as "invention" in the figure legend) were compared with the conventional roll coating method (denoted as "conventional"). significantly higher than those of the counterparts provided by 160 μm anode thickness (coated on flat solid Cu foil) to 160 μm diameter foam rods (all contained within the pores of Ni foam with 85% porosity), and A corresponding change in the cathode to maintain a balanced capacity ratio results in an increase in gravimetric energy density from 165 Wh/kg to 282 Wh/kg. More surprisingly, the volumetric energy density is increased from 412.5 Wh/L to 733 Wh/L. This latter value of 733 Wh/L has not previously been achieved in a lithium-ion battery using a graphite anode and a lithium iron phosphate cathode.

These large differences are not solely due to increased electrode thickness and mass loading. This difference is probably due to the much higher active material mass loading (not just mass loading) associated with cable cells according to the invention, the reduced ratio of overhead (inactive) components to active material weight/volume, caking Lack of agent resin, surprisingly good utilization of electrode active materials (most, if not all, graphite particles and LFP particles contribute to lithium ion storage capacity; especially under high charge/discharge rate conditions, electrode no dry pockets or ineffective spots inside) and the surprising results of the method according to the present invention for more efficient packing of the active material particles into the pores of the porous conductive layer (foamed current collector). because of ability. They are not taught, suggested or even implied in the slightest in the field of lithium ion batteries. Furthermore, the maximum power density increases from 621 W/kg to 1356 W/kg. This is likely due to the very low internal resistance to electron transport and lithium ion transport.

Figure 6 shows Ragone plots (weight and volumetric power density versus weight and volumetric energy density) of _two cells containing graphene-encapsulated Si nanoparticles as anode active materials and LiCoO2 nanoparticles as cathode active materials. Experimental data were obtained from a (cable type) Li-ion battery cell prepared by the method according to the invention and a Li-ion battery cell prepared by conventional slurry coating of electrodes.

These data show that the gravimetric and volumetric energy densities and power densities of battery cells prepared by the method according to the invention are significantly higher than their counterparts prepared by conventional methods. The difference is big here too. A conventionally formed cell exhibits a gravimetric energy density of 265 Wh/kg and a volumetric energy density of 689 Wh/L, while a cell according to the invention delivers 423 Wh/kg and 1,227 Wh/L respectively. A cell-level energy density of 1,227 Wh/L has not previously been achieved in a rechargeable lithium battery. The high power densities of 2213 W/kg and 6,417 W/L are also unprecedented for lithium-ion batteries. The power density of cells made by the method according to the invention is always much higher than that of corresponding cells made by conventional methods.

These energy density and power density differences are primarily due to the following. High active material mass loading (>25 mg/cm ² for anode and >45 mg/cm ² for cathode) associated with cells according to the present invention; reduced ratio of overhead (non-active) components to active material weight/volume; No need to have a binder resin; better utilization of the active material particles (all particles are accessible to the liquid electrolyte, high ionic and The ability of the method according to the invention to allow more effective filling of the active material particles in the pores.

FIG. 7 shows the Ragone lithium metal battery comprising lithium foil as the anode active material, dilithium rhodizonate (Li ₂ C ₆ O ₆ ) as the cathode active material, and lithium salt (LiPF ₆ )-PC/DEC as the organic liquid electrolyte. A plot is shown. The data relate both to lithium metal cells prepared by the method according to the invention and to lithium metal cells prepared by conventional slurry coating of electrodes. These data show that the gravimetric and volumetric energy densities and power densities of lithium metal cells prepared by the method according to the invention are significantly higher than their counterparts prepared by conventional methods. Again, the differences are large, probably due to the following. Significantly higher active material mass loading (rather than just mass loading) associated with cells according to the present invention; reduced ratio of overhead (non-active) components to active material weight/volume; no need to have binder resins surprisingly good utilization of electrode active materials (most, if not all, active materials contribute to lithium-ion storage capacity; especially under conditions of high charge/discharge rates, no dry pockets or ineffective spots); and the surprising ability of the method according to the present invention to more effectively pack the active material particles into the pores of the foamable current collector.

The gravimetric energy density of the lithium metal-organic cathode cell according to the present invention is as high as 503 Wh/kg, which is the gravimetric energy density of all rechargeable lithium metal or lithium ion batteries reported so far (current lithium ion batteries have a total cell The observation of higher than 150-220 Wh/kg based on weight) is quite remarkable and surprising. The observation that the volumetric energy density of such an organic cathode-based battery is as high as 1006 Wh/L, an unprecedentedly high value that exceeds the volumetric energy densities of all lithium-ion and lithium-metal batteries reported to date. The results are also very surprising. Furthermore, a gravimetric power density of 1,753 W/kg and a maximum volumetric power density of 5,080 W/L were unthinkable for lithium batteries based on organic cathode active materials.

Reporting energy and power densities per weight of the active material alone on Ragone plots, as many researchers do, may not give a realistic picture of the performance of the assembled supercapacitor cells. It would be important to point out The weight of other device components must also be taken into account. These overhead components, including current collectors, electrolytes, separators, binders, connectors, and packaging, are inactive materials and do not contribute to charge storage mass. These components only add weight and volume to the device. Therefore, it is desirable to reduce the relative proportions of weight of overhead components and increase the percentage of active material. However, it has not been possible to achieve this goal using conventional battery manufacturing methods. The present invention overcomes this longstanding and most serious problem in the lithium battery art.

In commercial lithium-ion batteries with an electrode thickness of 100-200 μm, the weight ratio of anode active material (e.g., graphite or carbon) in lithium-ion batteries is typically 12-17%, and that of the cathode active material. The weight ratio (for inorganic materials such as LiMn ₂ O ₄ ) is 22%-41%, or 10%-15% for organic or polymeric materials. Therefore, a factor of 3-4 is frequently used to extrapolate the energy or power density of a device (cell) from properties based on active material weight alone. In most scientific papers, reported properties are typically based on active material weight only, and electrodes are typically very thin (<<100 μm, and often <<50 μm). The active material weight is typically 5%-10% of the total device weight, which is the actual cell (device) energy or power density by dividing the corresponding active material weight base value by a factor of 10-20. suggests that we can obtain After this factor is taken into account, the properties reported in these papers are unlikely to be better than those of commercial batteries. Therefore, great caution must be exercised in reading and interpreting battery performance data reported in scientific papers and patent applications.

Example 25: Feasible Electrode Diameter or Thickness and its Impact on Electrochemical Performance of Lithium Battery Cells Electrode thickness in lithium batteries is believed to be a design parameter that can be adjusted at will for optimization of device performance. It is easy to think. In practice, contrary to this perception, the thickness of lithium battery electrodes is subject to manufacturing limitations, and in a real-world industrial manufacturing environment (e.g., a roll-to-roll slurry coating facility), a specific thickness level is required. It is not possible to fabricate electrodes with good structural integrity beyond that. Conventional battery electrode designs are based on the coating of electrode layers onto flat metal current collectors, which have several major problems as follows. (a) Thick coatings on Cu or Al foils require long drying times (requiring heating zones of 30-100 meters in length). (b) Thick electrodes are prone to delamination or cracking during drying and subsequent handling, and even at 15-20% resin binder ratios, which are expected to improve electrode integrity, this problem is significant. remains a limiting factor. Therefore, such industry practice of roll coating slurries onto solid flat current collectors does not allow for high active mass loadings. (c) thick electrodes prepared by coating, drying, and pressing make it difficult for the electrolyte (which is injected into the cell after it is formed) to penetrate through the electrode; means many dry pockets or spots that are not wetted by This suggests a low utilization of active material. The present invention solves these long-standing and very important problems associated with lithium batteries.

In FIG. 8, a lithium metal cell plotted over the feasible cathode thickness range for MnO ₂ /RGO cathodes prepared by conventional methods without delamination and cracking and cathodes prepared by methods according to the present invention. cell-level gravimetric energy density (Wh/kg) and volumetric energy density (Wh/L) are shown.

Electrodes can be manufactured in thicknesses up to 100-200 μm using conventional slurry coating methods. However, in contrast, there is no theoretical limit to the electrode thickness or diameter that can be achieved with the method according to the invention. Typically, practical electrode thicknesses range from 1 μm to 1000 μm, more typically from 10 μm to 800 μm, and most typically from 100 μm to 600 μm.

These data further confirm the surprising effectiveness of the method according to the present invention in fabricating ultra-thick lithium battery electrodes, which has heretofore been unfeasible. These ultra-thick electrodes in lithium metal batteries are typically substantially >25 mg/cm ² (more typically >30 mg/cm ² , still more typically >40 mg/cm 2 with respect to the inorganic cathode active material). cm ² , often >50 mg/cm ² and even >60 mg/cm ² ). These high active mass loadings have not been possible with conventional lithium batteries formed by slurry coating methods. These high active mass loadings lead to very high gravimetric and volumetric energy densities hitherto unachievable, given the same battery system (e.g. 503 Wh/kg and 956 Wh/L for lithium metal batteries according to the present invention). brought

Example 26: Active Material Weight Percentages Realizable in Cells and Their Impact on Electrochemical Performance of Lithium Battery Cells The combined weight of anode and cathode active materials is the total mass of a packaged commercial lithium battery. , a factor of 30% to 50% must be used to extrapolate device energy or power density from performance data for the active materials alone. Therefore, an energy density of 500 Wh/kg of the combined weight of graphite and NMC (lithium nickel manganese cobalt oxide) translates to about 150-250 Wh/kg of the packaged cell. However, this extrapolation is valid only for electrodes with thicknesses and densities similar to those of commercial electrodes (150 μm or about 15 mg/cm ² for graphite anodes and 30 mg/cm ² for NMC cathodes). . A thinner or lighter electrode of the same active material means lower energy or power density based on cell weight. Therefore, it is desirable to produce lithium-ion battery cells with high active material ratios. Unfortunately, in most commercial lithium-ion batteries, it has not previously been possible to achieve total active material percentages greater than 45% by weight.

The method according to the invention enables lithium batteries to well exceed these limits for all investigated active materials. In fact, the present invention makes it possible to increase the active material proportion above 85% if desired. However, it is typically 45% to 80%, more typically 40% to 70%, most typically 40% to 65%.

FIG. 9 shows the cell-level gravimetric and volumetric energy densities of graphite/NMC cells prepared by the method according to the invention and by the conventional roll coating method. These data further suggest that greater than 50% total active material mass can be obtained, an unexpectedly high weight and volume that was not previously possible given the same lithium battery system. Enable energy densities to be achieved (eg increased from 189 Wh/kg to 305 Wh/kg and from 510 Wh/L to 793 Wh/L).

Example 26: Representative Test Results for Sodium and Potassium Metal Cells Na _- Ion Battery Containing Hard Carbon Particles as Anode Active Material and Carbon _- Coated _{Na3V2 (} PO4) _2F3 Particles as Cathode Active Material A Ragone plot (weight and volume power density versus energy density) of the cell is shown in FIG. Two of the four data curves are for cells made according to one embodiment of the present invention and the other two are for conventional slurry coating (roll coating) of electrodes. Several important observations can be made from these data:

Both the weight and volumetric energy densities and power densities of the sodium ion battery cells made by the method according to the invention (denoted as "invention" in the figure legend) were compared with the conventional roll coating method (denoted as "conventional"). are considerably higher than those of counterparts made by The change from 150 μm anode thickness (coated on flat solid Cu foil) to 200 μm diameter (all contained within the pores of carbon foam with 85% porosity) and balanced A corresponding change in the cathode to maintain the capacity ratio increases the gravimetric energy density from 115 Wh/kg to 157 Wh/kg. Even more surprisingly, the volumetric energy density increases from 241 Wh/L to 502 Wh/L. This latter value of 502 Wh/L is exceptional for a sodium ion battery with a hard carbon anode and a sodium transition metal phosphate type cathode.

These major differences are probably due to the much higher active material mass loading (relative to other materials) associated with cells according to the invention, the reduced ratio of overhead (inactive) components to active material weight/volume, No need to have a binder resin, surprisingly good utilization of the electrode active material ₍ most if not all hard carbon particles and _{Na3V2 (} PO4) _2F3 particles _are sodium ion storage contributes to capacity; no dry pockets or ineffective spots in the electrode, especially under conditions of high charge/discharge rate), and active material in the pores of the porous conductive layer (foamed current collector) This is due to the surprising ability of the method according to the invention to pack particles more efficiently.

The sodium ion cell according to the invention also delivers much higher energy densities than conventional cells. This is also unexpected.

FIG. 11 shows Ragone plots of two cells containing both graphene-encapsulated Sn nanoparticles as anode active material and _NaFePO4 nanoparticles as cathode active material (weight and volumetric power density vs. weight and volumetric energy density). ) are shown. Experimental data was obtained from Na-ion battery cells made by the method according to the present invention and Na-ion battery cells made by slurry coating of conventional electrodes.

These data show that both the gravimetric and volumetric energy densities and power densities of sodium battery cells made by the method according to the invention are much higher than their counterparts made by conventional methods. The difference is big here too. Conventionally fabricated cells exhibit gravimetric energy densities of 185 Wh/kg and volumetric energy densities of 388 Wh/L, while cabled cells according to the invention deliver 311 Wh/kg and 777 Wh/L, respectively. A cell-level volumetric energy density of 777 Wh/L has not previously been achieved in any rechargeable sodium battery. In fact, even state-of-the-art lithium-ion batteries rarely exhibit volumetric energy densities above 750 Wh/L. The high power densities of 1236 W/kg and 3,585 W/L are unprecedented for typical high energy lithium ion batteries, let alone for sodium ion batteries.

These energy and power density differences are primarily due to high active material mass loading, reduced ratio of overhead (non-active) components to active material weight/volume, lack of binder resin, and more active material particles. The ability of the method of the present invention to take full advantage (all particles are accessible to the liquid electrolyte, fast ion and electron velocity), and the more efficient delivery of the active material particles into the pores of the foamed current collector. for proper filling.

A sodium metal battery containing sodium foil as anode active material, disodium rhodizonate (Na ₂ C ₆ O ₆ ) as cathode active material, and lithium salt (NaPF ₆ )-PC/DEC as organic liquid electrolyte. A Ragone plot of is shown in FIG. These data are for both sodium metal cells made by the method according to the invention and for sodium metal cells made by conventional slurry coating of electrodes. These data show that both the gravimetric and volumetric energy densities and power densities of sodium metal cells made by the method according to the invention are much higher than their counterparts made by conventional methods. Again the differences are significant, probably due to the much higher active material mass loading associated with the cells according to the invention, the reduced ratio of overhead (non-active) components to the weight/volume of active material, and the binder resin. Surprisingly good utilization of the electrode active materials (most, if not all, of the active materials contribute to the sodium ion storage capacity; especially under conditions of high charge/discharge rate, no drying in the electrode) no pockets or ineffective spots) and the surprising ability of the method according to the invention to more efficiently pack the active material particles into the pores of the foamed current collector.

The gravimetric energy density of the sodium metal-organic cathode cell according to the present invention is as high as 325 Wh/kg, which is higher than that of all rechargeable sodium metal or sodium-ion batteries reported so far (current Na-ion batteries are The observation of higher than 100-150 Wh/kg based on cell weight) is quite remarkable and unexpected. Furthermore, for organic cathode active material-based sodium batteries (and for corresponding lithium batteries), a gravimetric power density of 1,289 W/kg and a volumetric power density of 3,738 W/L were unthinkable.

We note that reporting energy and power densities per weight of active materials alone on Ragone plots, as many researchers do, may not give a realistic picture of the performance of the assembled battery cells. It is important to point out The weight of other device components must also be taken into account. These overhead components, including current collectors, electrolytes, separators, binders, connectors, and packaging, are inactive materials and do not contribute to charge storage mass. These only add weight and volume to the device. Therefore, it is desirable to reduce the relative proportions of weight of overhead components and increase the percentage of active material. However, this goal could not be achieved using conventional battery manufacturing methods. The present invention overcomes this longstanding and most serious problem in the lithium battery art.

In commercial lithium-ion batteries with an electrode thickness of 150 μm, the weight ratio of anode active material (eg, graphite or carbon) in the lithium-ion battery is typically 12% to 17%, and that of cathode active material. The weight ratio (for inorganic materials such as LiMn ₂ O ₄ ) is between 22% and 41% and for organic or polymeric materials between 10% and 15%. Since both the anode and cathode active materials have similar physical densities between the two types of batteries, and the ratio of cathode specific capacity to anode specific capacity is also similar, the corresponding Weight fractions are expected to be very similar. Therefore, a factor of 3-4 can be used to extrapolate the energy or power density of a sodium cell from properties based on active material weight alone. In most scientific papers, reported properties are typically based on active material weight only, and electrodes are typically very thin (<<100 μm, and often <<50 μm). The active material weight is typically 5% to 10% of the total device weight, which is the actual cell (device) energy or power by dividing the corresponding active material weight-based value by a factor of 10-20. It suggests that the density can be obtained. After this factor is taken into account, the properties reported in these papers are unlikely to be better than those of commercial batteries. Therefore, great caution must be exercised in reading and interpreting battery performance data reported in scientific papers and patent applications.

Ragone plots of a series of K-ion cells made by the conventional slurry coating method and Ragone plots of corresponding cable K-ion cells made by the method according to the invention are summarized and contrasted in FIG. These data also confirm that the method according to the invention is effective in producing both Na and K metal batteries with ultra-high energy and power densities.

Claims (82)

A cable type alkali metal battery, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, and the cable geometry is such that the length-to-diameter or length-to-thickness aspect ratio is at least 10. having a thickness and a diameter or thickness; the battery:
(a) a first electrode comprising an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, wherein said first mixture comprises said porous rod; a first electrode present in said pores of
(b) a porous separator encasing the first electrode;
(c) a second electrode comprising an electrically conductive porous layer enveloping or covering said porous separator, said conductive porous layer comprising pores and a second electrode active material and a second electrolyte; 2, wherein said second mixture resides in said pores of said porous layer;
(d) a protective casing or sheath enclosing or covering said second electrode;
including
The electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode comprises a conductive polymer fiber mat, a conductive polymer foam, a conductive polymer coated fiber foam. body, carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or An alkali metal battery comprising a porous foam selected from combinations thereof . 2. An alkali metal battery according to claim 1, wherein said first electrode is a negative electrode or anode and said second electrode is a positive electrode or cathode. 2. An alkali metal battery according to claim 1, wherein said second electrode is a negative electrode or anode and said first electrode is a positive electrode or cathode. A cable type alkali metal battery, wherein said alkali metal is selected from Li, Na, K, or combinations thereof; said battery:
(a) a first electrode comprising an electrically conductive rod and a first mixture of a first electrode active material and an optional first electrolyte coated on the surface of said conductive rod;
(b) a porous separator encasing the first electrode;
(c) a second electrode comprising an electrically conductive porous layer enveloping or covering said porous separator, wherein said conductive porous layer comprises pores and a second electrode active material and a second electrolyte; 2, wherein said second mixture resides in said pores of said porous layer;
(d) a protective casing or sheath enclosing or covering said second electrode;
including
wherein said electrically conductive rod in said first electrode or said electrically conductive porous layer in said second electrode comprises a conductive polymer fiber mat, a conductive polymer foam, a conductive polymer-coated fiber foam; carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or An alkali metal battery comprising a porous foam selected from combinations . A cable type alkali metal battery, wherein said alkali metal is selected from Li, Na, K, or combinations thereof; said battery:
(a) a first electrode comprising an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, wherein said first mixture comprises said porous rod; a first electrode present in said pores of
(b) a porous separator encasing the first electrode;
(c) a second electrode comprising an electrically conductive layer enveloping or covering said porous separator, said conductive layer comprising a second mixture of a second electrode active material and an optional second electrolyte; a second electrode;
(d) a protective casing or sheath enclosing or covering said second electrode;
including
wherein the electrically conductive porous rod in the first electrode or the electrically conductive layer in the second electrode comprises a conductive polymer fiber mat, a conductive polymer foam, a conductive polymer coated fiber foam; carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or An alkali metal battery comprising a porous foam selected from combinations . 2. The alkali metal battery of claim 1, wherein said cable-type cell has a first end and a second end, and said first electrode is embedded within said first electrode. An alkali comprising a first terminal connector connected to or integral with an electrode and comprising at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber. metal battery. 7. The alkali metal battery of claim 6 , wherein said at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber extends from said first end to said second end. alkaline metal battery. 2. The alkali metal battery of claim 1, wherein said cable-type cell has a first end and a second end, and wherein said second electrode is embedded in said second electrode. An alkali comprising a second terminal connector connected to or integral with an electrode and comprising at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber. metal battery. 7. The alkali metal battery of claim 6, wherein said at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber extends approximately from said first end to said second end. alkaline metal batteries. The alkali metal battery of claim 1 , wherein said porous foam has a circular, elliptical, rectangular, square, hexagonal, hollow, or irregularly shaped cross-section. . 2. The alkali metal battery of claim 1, wherein the battery has a cable shape having a length and a diameter or thickness and an aspect ratio that is the ratio of length/thickness or length/diameter. and wherein said aspect ratio is greater than 10. 2. The alkali metal battery of claim 1, wherein said first electrode or second electrode comprises particles, foils, or coatings of Li, Na, K, or combinations thereof as electrode active material. alkaline metal batteries. 5. The alkali metal battery of claim 4, wherein said first electrode or second electrode comprises particles, foils, or coatings of Li, Na, K, or combinations thereof as electrode active material. alkaline metal batteries. 6. The alkali metal battery of claim 5, wherein the first or second electrode comprises Li, Na, K, or combinations thereof particles, foils, or coatings as electrode active materials. alkaline metal batteries. 2. The alkali metal battery of claim 1, wherein said alkali metal battery is a lithium ion battery and said first or second electrode active material comprises:
(a) natural graphite, synthetic graphite, mesocarbon microbeads (MCMB), and particles of carbon;
(b) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt ( Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd);
(c) stoichiometric or non-stoichiometric alloys or compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with another element or intermetallic compound;
(d) oxides, carbides, nitrides, sulfides, phosphides, selenides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and tellurides, and mixtures or composites thereof;
(e) prelithiated versions thereof;
(f) prelithiated graphene sheets;
and combinations thereof. 16. The alkali metal battery of claim 15, wherein the prelithiated graphene sheets are pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride. , nitrided graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physically or chemically activated or etched versions thereof, and combinations thereof. An alkali metal battery, characterized in that it is selected from the group consisting of versions. 2. The alkali metal battery of claim 1, wherein the alkali metal battery is a sodium ion battery and the first or second electrode active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, Soft carbon, templating carbon, hollow carbon nanowires, hollow carbon spheres, _titanates , _{NaTi2 ( PO4 ) 3} , _{Na2Ti3O7 , Na2C8H4O4} , _Na2TP , _{NaxTiO2 ( x} = 0.2-1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate-based materials, C ₈ H ₄ Na ₂ O ₄ , C ₈ H ₆ O ₄ , C ₈ H ₅ NaO ₄ , C ₈ Na _{2F4O4 , C10H2Na4O8 , C14H4O6 , C14H4Na4O8 , and combinations thereof . _ _} An alkali metal battery characterized by: 2. The alkali metal battery of claim 1, wherein said alkali metal battery is a sodium ion battery and said first or second electrode active material comprises:
(a) sodium or potassium doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al); Titanium (Ti), Cobalt (Co), Nickel (Ni), Manganese (Mn), Cadmium (Cd), and mixtures thereof;
(b) alloys or intermetallic compounds containing sodium or potassium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
(c) oxides and carbides containing sodium or potassium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof; , nitrides, sulfides, phosphides, selenides, tellurides, or antimonides;
(d) sodium or potassium salts;
(e) sodium or potassium prefilled graphene sheets; and (f) an alkali intercalation compound selected from the group consisting of combinations thereof. 2. The alkali metal battery of claim 1, wherein the second or first electrode active material is lithium cobaltate, doped lithium cobaltate, lithium nickelate, doped lithium nickelate, lithium manganate, doped doped lithium manganate, lithium vanadate, doped lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, non-lithium metal sulfide , lithium selenide, and combinations thereof. 2. The alkali metal battery of claim 1, wherein the second or first electrode active material is _NaFePO4 , Na _{(1-x) KxPO4 , KFePO4 , Na0.7FePO4} , Na1 _{. 5VOPO4F0.5 , Na3V2 ( PO4} ) ₃ , _{Na3V2 ( PO4} ) _{2F3 , Na2FePO4F} , _{NaFeF3 , NaVPO4F} , _{KVPO4F , Na3V 2 ( PO4} ) _{2F3 , Na1.5VOPO4F0.5} , _{Na3V2 ( PO4 ) 3} , _{NaV6O15 , NaxVO2 , Na0.33V2O5 , Na x} CoO ₂ , Na _2/3 [Ni _1/3 Mn _2/3 ]O ₂ , Na _x (Fe _1/2 Mn _1/2 )O ₂ , Na _x MnO ₂ , λ-MnO ₂ , Na _x K _{( 1-x)} MnO ₂ , Na _0.44 MnO ₂ , Na ₀ . _44MnO2 / _C , _Na4Mn9O18 , _{NaFe2Mn ( PO4} ) _{3 , Na2Ti3O7 , Ni1} / _{3Mn1 / 3Co1 / 3O2} , _Cu0.56Ni0 . _44HCF , _NiHCF , _NaxMnO2 , _{NaCrO2, KCrO2, Na3Ti2(PO4)3 , NiCo2O4 , Ni3S2 / FeS2 , Sb2O4 , Na4Fe ( CN ) 6} /C, NaV _1-x Cr _x PO ₄ F, Se zS _y (y/ _z =0.01-100), Se, alodite, and combinations thereof. An alkali metal battery comprising a compound or a potassium intercalation compound, wherein x is between 0.1 and 1.0. 2. The alkali metal battery of claim 1, wherein said first electrolyte and/or said second electrolyte comprises a lithium or sodium salt dissolved in a liquid solvent, said liquid solvent being water, an organic solvent, An alkali metal battery characterized by being an ionic liquid, a mixture of an organic solvent and an ionic liquid, or a liquid solvent polymer gel. The alkali metal battery of claim 1, wherein said first electrolyte and/or said second electrolyte contains a lithium or sodium salt dissolved in a liquid solvent having a salt concentration greater than 2.5M. An alkali metal battery characterized by: The alkali metal battery of claim 1, wherein said first electrolyte and/or said second electrolyte contains a lithium or sodium salt dissolved in a liquid solvent having a salt concentration greater than 5.0M. An alkali metal battery characterized by: The alkali metal battery of claim 1, wherein said first electrolyte and/or said second electrolyte contains a lithium or sodium salt dissolved in a liquid solvent having a salt concentration greater than 7.0M. An alkali metal battery characterized by: 2. The alkali metal battery of claim 1, wherein the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode comprises at least 85 vol. and wherein said first or second electrode has a diameter or thickness of 100 μm or greater, or has an active mass loading that accounts for at least 25% by weight or volume of the total battery cell, or said first and second electrodes An alkali metal battery characterized in that the two electrode active materials together constitute at least 40% by weight or volume of the total battery cell. 2. The alkali metal battery of claim 1, wherein the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode comprises at least 90 vol. and wherein said first or second electrode has a diameter or thickness of 200 μm or greater, or has an active mass loading that accounts for at least 30% by weight or volume of the entire battery cell, or said first and second electrodes An alkali metal battery characterized in that the two electrode active materials together comprise at least 50% by weight or volume of the total battery cell. 2. The alkali metal battery of claim 1, wherein the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode comprises at least 95 vol. and said first or second electrode has a diameter or thickness of 300 μm or greater, or has an active mass loading that accounts for at least 35% by weight or volume of the total battery cell, or said first and second electrodes An alkali metal battery characterized in that the two electrode active materials together constitute at least 60% by weight or volume of the total battery cell. 2. The alkali metal battery of claim 1, wherein said first or second electrode active material is selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides, or combinations thereof. An alkali metal battery comprising an alkali metal intercalation compound or an alkali metal absorbing compound. 29. The alkali metal battery of claim 28, wherein the metal oxide/phosphate/sulfide is lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium mixed metal oxide, lithium iron phosphate , lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof. 29. The alkali metal battery of claim 28, wherein the inorganic material is selected from transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. 29. The alkali metal battery of claim 28, wherein said inorganic material is selected from _TiS2 , _TaS2 , MoS2, _NbSe3 , _{MnO2 , CoO2} , iron oxide, vanadium oxide, or combinations thereof. An alkaline metal battery characterized by: 29. The alkali metal battery of claim ₂₈ , wherein said metal oxides/phosphates/ _{sulfides are VO2} , _LixVO2 , _{V2O5 , LixV2O5} , _V3O8 , _{Li xV3O8 , LixV3O7 , V4O9 , LixV4O9 , V6O13 , LixV6O13} , _{doped versions thereof} , _{derivatives thereof} , and their An alkali metal battery comprising vanadium oxide selected from the group consisting of combinations of: wherein 0.1<x<5. 29. The alkali metal battery of claim 28, wherein said metal oxide/phosphate/sulfide is layered compound _LiMO2 , _spinel compound _LiM2O4 , _olivine compound _LiMPO4 , silicate compound _Li2MSiO4 , An alkali metal battery selected from the group consisting of taborite compound _LiMPO4F , borate compound _LiMBO3 , and combinations thereof, wherein M is a transition metal or a mixture of transition metals. 29. The alkali metal battery of claim 28, wherein the inorganic material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum. , tungsten, titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides; (d) boron nitride, and (e) combinations thereof. and alkaline metal batteries. 29. The alkali metal battery of claim 28, wherein the organic or polymeric material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride ( PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino (triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), Tetracyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymer ( [(NPS ₂ ) ₃ ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ) , 5-benzylidenehydantoin, isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi ₄ ), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP ), N,N'-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymers, quinones Compounds 1,4-benzoquinone, 5,7,12,14-pentacentetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDAQ), 5-amino-1 ,4-dihydroxyanthraquinone (ADAQ), calixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , and combinations thereof. and alkaline metal batteries. 36. The alkali metal battery of claim 35, wherein the thioether polymer is poly[methanetetriyl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), poly(ethene-1,1 Poly(2-phenyl -1,3-dithiolane) (PPDT), poly(1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1, 2,4,5-tetrakis(propylthio)benzene](PTKPTB ) , poly[3,4(ethylenedithio)thiophene](PEDTT), and combinations thereof. . 29. The alkali metal battery of claim 28, wherein the organic material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine , phthalocyanine chloroaluminum, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, and combinations thereof. battery. 3. The alkali metal battery of claim 2, wherein the cathode is an alkali metal intercalation compound or alkali metal selected from the group consisting of metal carbides, metal nitrides, metal borides, metal dichalcogenides, and combinations thereof. An alkali metal battery comprising an absorbing compound. 4. The alkali metal battery of claim 3, wherein the cathode comprises niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, in the form of nanowires, nanodiscs, nanoribbons, or nanoplatelets. characterized by comprising an alkali metal intercalation compound or an alkali metal absorbing compound selected from the group consisting of manganese, iron and nickel oxides, dichalcogenides, trichalcogenides, sulfides, selenides, or tellurides. alkaline metal batteries. 3. The alkali metal battery of claim 2, wherein the cathode active material is (a) bismuth selenide or bismuth telluride, (b) a transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, sulfides, selenides, or tellurides of tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metals; (d) boron nitride, and (e) combinations thereof. wherein said discs, platelets or sheets have a thickness of less than 100 nm. 2. An alkali metal battery according to claim 1, characterized in that the length of the battery is greater than 1 m. 2. The alkali metal battery of claim 1, wherein said battery is bendable with a radius of curvature greater than 10 cm. 2. The alkali metal battery of claim 1, wherein the battery is bendable to substantially conform to the shape of a void or interior compartment within a vehicle, wherein the void or interior compartment includes a trunk, door, hatch, An alkali metal battery comprising a spare tire compartment, an area inside the seat, an area inside the seat back, an area under the seat, or an area under the dashboard. 44. The alkali metal battery of claim 43, wherein the battery is removable from the vehicle and can be bent to conform to different gap or internal compartment shapes. 2. The alkali metal battery of claim 1, wherein one or more units of the battery include clothing, belts, support straps, carrying straps, luggage straps, weapon straps, musical instrument straps, helmets, hats, boots, Alkaline metal batteries characterized by being incorporated into foot covers, gloves, wrist covers, watch bands, jewelry, animal collars or animal harnesses. The alkali metal battery of claim 1, wherein one or more units of the battery are removably incorporated into clothing, belts, support straps, carrying straps, luggage straps, weapon straps, musical instrument straps, Alkaline metal batteries characterized in that they are helmets, hats, boots, foot covers, gloves, wrist covers, watch bands, jewelry, animal collars or animal harnesses. 2. An alkali metal battery according to claim 1, wherein said battery fits into the internal cavity of a hollow bicycle frame. A method for manufacturing a cable-type alkali metal battery, wherein the alkali metal is selected from Li, Na, K, or combinations thereof, and the shape of the cable has a length-to-thickness or length-to-diameter ratio of 10 or more. and wherein said method:
(a) providing a first electrode comprising an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, wherein the first mixture comprises residing in said pores of said porous rod;
(b) wrapping or covering the first electrode with a porous separator to form a porous separator protected structure;
(c) wrapping or covering the porous separator-protected structure with a second electrode comprising an electrically conductive porous layer, wherein the conductive porous layer comprises pores and a second electrode active layer; a second mixture of a material and a second electrolyte, said second mixture being present in said pores of said porous layer;
(d) enclosing or covering the second electrode with a protective casing or sheath to form the battery;
including
The electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode comprises a conductive polymer fiber mat, a conductive polymer foam, a conductive polymer coated fiber foam. body, carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or A method comprising a porous foam selected from combinations thereof . A method of making a cabled alkali metal battery, wherein said alkali metal is selected from Li, Na, K, or combinations thereof; said method comprising:
(a) providing a first electrode comprising an electrically conductive rod and a first mixture of a first electrode active material and an optional first electrolyte coated on the surface of said conductive rod; When;
(b) wrapping or covering the first electrode with a porous separator to form a porous separator protected structure;
(c) wrapping or covering the porous separator-protected structure with a second electrode comprising an electrically conductive porous layer, wherein the conductive porous layer comprises pores and a second electrode active layer; a second mixture of a material and a second electrolyte, said second mixture being present in said pores of said porous layer;
(d) enclosing or covering the second electrode with a protective casing or sheath to form the battery;
including
wherein said electrically conductive rod in said first electrode or said electrically conductive porous layer in said second electrode comprises a conductive polymer fiber mat, a conductive polymer foam, a conductive polymer-coated fiber foam; carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or A method comprising a porous foam selected from a combination . A method of making a cabled alkali metal battery, wherein said alkali metal is selected from Li, Na, K, or combinations thereof; said method comprising:
(a) providing a first electrode comprising an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, wherein the first mixture comprises residing in said pores of said porous rod;
(b) wrapping or covering the first electrode with a porous separator to form a porous separator protected structure;
(c) wrapping or covering the porous separator-protected structure with a second electrode comprising an electrically conductive layer, wherein the electrically conductive layer comprises a second electrode active material and an optional second electrode active material; comprising a second mixture of electrolytes;
(d) enclosing or covering the second electrode with a protective casing or sheath to form the battery;
including
wherein the electrically conductive porous rod in the first electrode or the electrically conductive layer in the second electrode comprises a conductive polymer fiber mat, a conductive polymer foam, a conductive polymer coated fiber foam; carbon foam, graphite foam, carbon aerogel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or A method comprising a porous foam selected from a combination . 49. The method of claim 48, wherein step (a) further comprises introducing at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber into the conductive porous rod. A method characterized by 49. The method of claim 48, wherein the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode is a metal foam, metal web, metal fiber mat, metal nanowire mat, conductive polymer fiber mat, conductive polymer foam, conductive polymer coated fiber foam, carbon foam, graphite foam, carbon airgel, carbon xerogel, graphene aerogel, graphene foam, graphene oxide foam a porous foam selected from a body, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or combinations thereof. 53. The method of claim 52 , wherein the porous foam has a circular, oval, rectangular, square, hexagonal, hollow, or irregularly shaped cross-section. 49. The method of claim 48, wherein step (a) or step (c) comprises using particles, foils, or coatings of Li, Na, K, or combinations thereof as an electrode active material in the first electrode or the A method comprising introducing into a second electrode. 50. The method of claim 49, wherein step (a) or step (c) comprises using particles, foils, or coatings of Li, Na, K, or combinations thereof as an electrode active material in the first electrode or the A method comprising introducing into a second electrode. 50. The method of claim 49, wherein step (a) or step (c) comprises using particles, foils, or coatings of Li, Na, K, or combinations thereof as an electrode active material in the first electrode or the A method comprising introducing into a second electrode. 49. The method of claim 48, wherein in step (a), in the operation of (i) continuously feeding the electrically conductive porous rod into the first electrode active material impregnation zone, the electrically conductive porous (ii) said first mixture from said at least one porous surface into said electrically conductive porous rod; to form the first electrode. 58. The method of claim 57, wherein step (a) applies the first mixture to the at least one porous substrate by spraying, printing, coating, casting, conveyor film feeding, and/or roller surface feeding. A method comprising the step of continuously or intermittently delivering on demand to a surface. 49. The method of claim 48, wherein step (c) comprises: (i) continuously feeding the electrically conductive porous layer to the impregnation zone of the second electrode active material, wherein the conductive porous layer (ii) said second porous layer from said at least one porous surface into said electrically conductive porous layer; and impregnating the mixture to form the second electrode. 60. The method of claim 59, wherein step (c) applies the second mixture to the at least one porous substrate by spraying, printing, coating, casting, conveyor film feeding, and/or roller surface feeding. A method comprising the step of continuously or intermittently delivering on demand to a surface. 49. The method of claim 48, wherein step (b) comprises coiling or spirally wrapping the first electrode with a band of porous separator to form a structure protected by the porous separator. A method comprising: 49. The method of claim 48, wherein said step (b) includes spraying an electrically insulating material to cover said first electrode to form a porous shell structure covering said first electrode, said porous forming a structure protected with a quality separator. 49. The method of claim 48, wherein step (c) comprises linearly or spirally wrapping or covering the porous separator protected structure with the second electrode. . 49. The method of claim 48, wherein said alkali metal battery is a lithium ion battery and said first or second electrode active material comprises:
(g) natural graphite, synthetic graphite, mesocarbon microbeads (MCMB), and particles of carbon;
(h) Silicon (Si), Germanium (Ge), Tin (Sn), Lead (Pb), Antimony (Sb), Bismuth (Bi), Zinc (Zn), Aluminum (Al), Nickel (Ni), Cobalt ( Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd);
(i) stoichiometric or non-stoichiometric alloys or compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with another element or intermetallic;
(j) oxides, carbides, nitrides, sulfides, phosphides, selenides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and tellurides, and mixtures or composites thereof;
(k) prelithiated versions thereof;
(l) prelithiated graphene sheets;
and combinations thereof. 49. The method of claim 48, wherein said alkali metal battery is a sodium ion battery and said first or second electrode active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon. , template carbon, hollow carbon nanowires, hollow carbon spheres, titanates, _{NaTi2 ( PO4} ) ₃ , _{Na2Ti3O7 , Na2C8H4O4} , _Na2TP , _{NaxTiO2 ( x = 0} .2-1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate-based materials, C ₈ H ₄ Na ₂ O ₄ , C ₈ H ₆ O ₄ , C ₈ H ₅ NaO ₄ , C ₈ Na ₂ F _{4O4 , C10H2Na4O8 , C14H4O6 , C14H4Na4O8 , and combinations thereof . _} and how to. 49. The method of claim 48, wherein said alkali metal battery is a sodium ion battery and said first or second electrode active material comprises:
(g) sodium or potassium doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al); Titanium (Ti), Cobalt (Co), Nickel (Ni), Manganese (Mn), Cadmium (Cd), and mixtures thereof;
(h) sodium or potassium containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
(i) oxides and carbides containing sodium or potassium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof; , nitrides, sulfides, phosphides, selenides, tellurides, or antimonides;
(j) sodium or potassium salts;
(k) sodium or potassium prefilled graphene sheets; and (l) an alkaline intercalation compound selected from the group consisting of combinations thereof. 49. The method of claim 48, wherein the second or first electrode active material is lithium cobaltate, doped lithium cobaltate, lithium nickelate, doped lithium nickelate, lithium manganate, doped lithium manganate, lithium vanadate, doped lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, metal sulfide, lithium selenide and combinations thereof. 49. The method of claim 48, wherein the second or first electrode active material is _NaFePO4 , Na _{(1-x) KxPO4 , KFePO4 , Na0.7FePO4} , _{Na1.5VOPO 4F0.5 , Na3V2 ( PO4} ) ₃ , _{Na3V2 ( PO4} ) _2F3 , _Na2FePO4F , _{NaFeF3 , NaVPO4F} , _{KVPO4F , Na3V2 ( PO4 ) 2F3} , _{Na1.5VOPO4F0.5 , Na3V2 ( PO4 ) 3 , NaV6O15 , NaxVO2 , Na0.33V2O5 , NaxCoO 2} , Na _2/3 [Ni _1/3 Mn _2/3 ]O ₂ , Na _x (Fe _1/2 Mn _1/2 )O ₂ , Na _x MnO ₂ , λ-MnO ₂ , Na _x K _{(1- x) MnO2} , _{Na0.44 MnO2} , _Na0 . _44MnO2 / _C , _Na4Mn9O18 , _{NaFe2Mn ( PO4} ) _{3 , Na2Ti3O7 , Ni1} / _{3Mn1 / 3Co1 / 3O2} , _Cu0.56Ni0 . _44HCF , _NiHCF , _NaxMnO2 , _{NaCrO2, KCrO2, Na3Ti2(PO4)3 , NiCo2O4 , Ni3S2 / FeS2 , Sb2O4 , Na4Fe ( CN ) 6} /C, NaV _1-x Cr _x PO ₄ F, Se zS _y (y/ _z =0.01-100), Se, alodite, and combinations thereof. compound or potassium intercalation compound, wherein x is between 0.1 and 1.0. 49. The method of claim 48, wherein the first electrolyte and/or the second electrolyte comprise lithium or sodium salts dissolved in a liquid solvent, the liquid solvent being water, organic solvents, ionic liquids. , a mixture of an organic solvent and an ionic liquid, or a liquid solvent polymer gel. 49. The method of claim 48, wherein said first electrolyte and/or said second electrolyte contains a lithium or sodium salt dissolved in a liquid solvent having a salt concentration of 2.5M to 14M. A method characterized. 49. The method of claim 48, wherein the electrically conductive porous rod in the first electrode or the electrically conductive porous layer in the second electrode is between 70% and 99% by volume fine particles. A method characterized by having a hole. 49. The method of claim 48, wherein the first or second electrode active material is an alkali metal selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides, or combinations thereof. A method comprising an intercalation compound or an alkali metal absorbing compound. 73. The method of claim 72, wherein the metal oxide/phosphate/sulfide is lithium cobaltate, lithium nickelate, lithium manganate, lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, phosphorus selected from the group consisting of lithium manganese oxide, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof. 73. The method of claim 72, wherein the inorganic material is selected from the group consisting of _TiS2 , _TaS2 , MoS2, _NbSe3 , _{MnO2 , CoO2} , iron oxide, vanadium oxide, and combinations thereof. A method characterized by _{73. The} method of claim 72 , wherein the metal oxide/phosphate/ _sulfide is _VO2 , _{LixVO2 , V2O5 , LixV2O5} , _V3O8 , _{LixV 3O8} , _{LixV3O7 , V4O9 , LixV4O9 , V6O13 , LixV6O13} , _{doped versions thereof} , _{derivatives thereof} , and combinations thereof A method comprising vanadium oxide selected from the group consisting of: wherein 0.1<x<5. 73. The method of claim 72, wherein the metal oxides/phosphates/sulfides are layered compounds _LiMO2 , _spinel compounds _LiM2O4 , olivine compounds _LiMPO4 , silicate compounds _Li2MSiO4 , _taborite compounds. A method selected from the group consisting of LiMPO ₄ F, borate compound LiMBO ₃ , and combinations thereof, wherein M is a transition metal or mixture of transition metals. 73. The method of claim 72, wherein the inorganic material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenides or trichalcogenides, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten. , titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides; (d) boron nitride, and (e) combinations thereof. Method. 73. The method of claim 72, wherein the organic or polymeric material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). , poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino (triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyano Ethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymer ([( NPS ₂ ) ₃ ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5 - benzylidene hydantoin, isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi ₄ ), N,N'-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N'-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymers, quinone compounds, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDAQ), 5-amino-1,4 - dihydroxy anthraquinone (ADAQ), calixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , and combinations thereof; Method. 73. The method of claim 72, wherein the organic material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, phthalocyanine a phthalocyanine compound selected from the group consisting of chloroaluminum, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, and combinations thereof. 50. The method of claim 49, wherein the second electrode comprises an alkali metal intercalation compound or an alkali intercalation compound selected from the group consisting of metal carbides, metal nitrides, metal borides, metal dichalcogenides, and combinations thereof. A method comprising a metal-absorbing compound. 51. The method of claim 50, wherein the second electrode is niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt in the form of nanowires, nanodiscs, nanoribbons, or nanoplatelets. , manganese, iron, and nickel oxides, dichalcogenides, trichalcogenides, sulfides, selenides, and tellurides. and how. 50. The method of claim 49, wherein the second electrode active material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenides or trichalcogenides, (c) niobium, zirconium, molybdenum, hafnium. , tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides; (d) boron nitride, and (e) combinations thereof. A method comprising nanodiscs, nanoplatelets, nanocoatings, or nanosheets of material; wherein said discs, platelets, or sheets have a thickness of less than 100 nm.

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