KR102565802B1 - Shape adaptable cable type flexible alkali metal battery - Google Patents

Abstract

(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, the first mixture present in the pores of the porous rod; (b) a porous separator surrounding the first electrode; (c) an electrically conductive porous layer surrounding or surrounding the porous separator, the conductive porous layer containing pores and a second mixture of a second electrode active material and a second electrolyte, the second mixture present in the pores of the porous layer a second electrode; and (d) a protective casing or packing tube surrounding or surrounding the second electrode.

Description

Shape adaptable cable type flexible alkali metal battery

CROSS REFERENCES TO RELATED APPLICATIONS

This application claims priority to U.S. Patent Application No. 15/384,749, filed on December 20, 2016, and U.S. Patent Application No. 15/384,781, filed on December 20, 2016, both of which are incorporated herein by reference. .

technology field

The present invention relates generally to the field of lithium, sodium, and potassium batteries, including flexible, shape-adaptable, non-flammable, cable-type primary (non-rechargeable) and secondary (rechargeable) alkali metal batteries and alkali ion batteries.

Conventional batteries (e.g., 18650 type cylindrical cells and rectangular pouches or prismatic cells) are mechanically rigid, and this inflexible feature severely limits their adaptability or potential for implementation in limited space or use in wearable devices. did To overcome these design limitations, a shape adaptable flexible power source may be used. These new power sources will enable the development of next-generation electronic devices such as smart mobile devices, roll-up displays, wearable devices, and biomedical sensors. A shape-adaptable flexible power source will also save weight and space in an electric vehicle.

Lithium ion batteries are a prime candidate energy storage device for electric vehicle (EV) and mobile device applications. Over the past 20 years, Li-ion batteries have continued to improve in terms of energy density, rate capability, and safety, but Li metal batteries with much higher energy densities have been largely overlooked. However, the use of graphite-based anodes in Li-ion cells has several significant drawbacks: low specific capacity (theoretical capacity of 372 mAh/g as opposed to 3,860 mAh/g for Li metal ), long Li intercalation times (eg, low solid-state diffusion coefficients of Li into and out of graphite and inorganic oxide particles) requiring long recharge times (eg, 7 hours in electric vehicle batteries), high pulse Limitation of available cathode material choices due to inability to deliver power (power density << 1 kW/kg), and need to use pre-lithiated cathodes (eg, lithium cobalt oxide). In addition, these commonly used cathodes have relatively low specific capacities (typically less than 200 mAh/g). These factors account for two major drawbacks of current Li-ion batteries: low gravimetric and volumetric energy densities (typically 150-220 Wh/kg and 450-600 Wh/L) and low power densities (typically 0.5 kW). /kg and less than 1.0 kW/L) (all based on total battery cell weight or volume).

The emerging EV and renewable energy industries require significantly higher gravimetric energy densities than current Li-ion cell technologies can provide (e.g., >> 250 Wh/kg, preferably >> 300 Wh/kg). ) and the availability of rechargeable batteries with high power densities (shorter recharge times). Also, as consumers demand smaller portable devices (e.g., smartphones and tablets) with smaller volumes that store more energy, the microelectronics industry is pushing for even greater volumetric energy densities (>650 Wh/L, preferably greater than 750 Wh/L). From these requirements, considerable research has been attempted on the development of electrode materials with higher specific capacity, excellent discharge capacity, and excellent cycle stability for lithium ion batteries.

Several elements from groups III, IV, and V of the periodic table can form alloys with Li at certain desired voltages. Accordingly, various anode materials based on these elements and some metal oxides have been proposed for lithium ion batteries. Of these, silicon has an almost 10-fold higher theoretical gravimetric capacity compared to graphite (372 mAh/g for LiC ₆ versus 3,5950 mAh/g for Li _3.75 Si) and about 3-fold larger volumetric capacity compared to graphite. Therefore, it has been recognized as one of the next-generation anode materials for high-energy lithium-ion batteries. However, rapid volume changes (up to 380%) of Si during lithium ion alloying and de-alloying (cell charging and discharging) often result in severe and rapid cell performance degradation. The performance degradation is mainly due to the powdering due to the change in the volume of Si and the inability of the binder/conductive additive to maintain electrical contact between the powdered Si particles and the current collector. In addition, silicon's inherently low electrical conductivity is another challenge to be addressed.

Although some high capacity anode active materials (e.g. Si) have been found, there are no correspondingly available high capacity cathode materials. Current cathode active materials commonly used in Li-ion batteries have the following serious drawbacks. (1) Actual capacities achievable with current cathode materials (e.g., lithium iron phosphate and lithium transition metal oxide) are limited to the range of 150 to 250 mAh/g, and in most cases less than 200 mAh/g; . (2) Intercalation and extraction of lithium into and out of these commonly used cathodes is a very slow solid phase of Li in solid particles with very low diffusion coefficients (typically 10 ⁻⁸ to 10 ⁻¹⁴ cm ² /s). Depending on diffusion, it results in very low power densities (another long-standing problem with current lithium-ion batteries). (3) Current cathode materials are electrically and thermally insulative and cannot effectively and efficiently transfer electrons and heat. Low electrical conductivity means a high internal resistance and the need to add large amounts of conductive additives, substantially reducing the proportion of electrochemically active material in an already low capacity cathode. Low thermal conductivity also means they are more prone to thermal runaway, a major safety issue in the lithium battery industry.

Since sodium is plentiful and production of sodium is much more environmentally friendly than production of lithium, sodium batteries have been considered as an attractive alternative to lithium batteries as an entirely different type of energy storage device. Also, the high cost of lithium is a significant issue, and Na cells could potentially have much lower costs.

There are two types of cells that operate on sodium ions (Na ⁺ ) bouncing back and forth between the anode and cathode: sodium metal cells with Na metal or alloy as the anode active material, and sodium-metal cells with Na intercalating compounds as the anode active material. Ionic cells exist. Sodium ion batteries using hard carbon-based anode active materials (Na intercalating compounds) and sodium transition metal phosphate as cathode have been described by several research groups (see, for example, US Patent 7,759,008 to J. Barker et al. (July 20, 2010) 1) "Sodium Ion Batteries").

However, these sodium-based devices exhibit much lower specific energy and discharge capacity than Li-ion cells. The anode active material for Na insertion and the cathode active material for Na insertion have a lower Na storage capacity compared to the Li storage capacity. For example, hard carbon particles can store Li ions up to 300-360 mAh/g, but the same material can store Na ions up to 150-250 mAh/g, and less than 100 mAh/g for K ion storage. can be saved as

As the anode active material of the sodium metal cell, sodium metal may be used instead of hard carbon or other carbonaceous intercalating compounds. However, the use of metallic sodium as an anode active material is generally considered undesirable and risky due to problems with dendrite formation, interfacial aging, and electrolyte incompatibility.

Low capacity anode or cathode active materials are not the only problems facing the alkali metal-ion battery industry. There are serious design and manufacturing issues that the lithium-ion battery industry seems to be unaware of or has largely ignored. For example, despite the high gravimetric capacities at the electrode level (based only on anode or cathode active material weight), as often claimed in the published literature and patent literature, these electrodes are unfortunately (in terms of total battery cell weight or pack weight) standard) does not provide a battery having a high capacity at the level of a battery cell or pack. This is due to the notion that, in this report, the actual active material mass loading of the electrode is too low. In most cases, the mass supply of active material (area density) in the anode is much lower than 15 mg/cm ² and in most cases is less than 8 mg/cm ² (area density = amount of active material per electrode cross-sectional area along the electrode thickness direction). The amount of cathode active material is usually 1.5 to 2.5 times greater than that of anode active material. As a result, the weight proportion of the anode active material (eg graphite or carbon) in a lithium-ion battery is typically 12% to 17% and the weight proportion of the cathode active material (eg LiMn ₂ O ₄ ) is 17% to 17%. 35% (mostly less than 30%). The combined weight fraction of the cathode active material and the anode active material is usually 30% to 45% of the cell weight.

The low active material mass supply is mainly because thicker electrodes (thicker than 100-200 μm) cannot be obtained using the conventional slurry coating method. This is not as trivial as one might think, and in practice, electrode thickness is not a design parameter that can be arbitrarily changed freely to optimize cell performance. This is a manufacturing limit. Also, thicker samples tend to be extremely brittle or have poor structural integrity, and will also require the use of large amounts of binder resin. Low areal densities (related to thin electrodes and low packing densities) and low volume densities result in relatively low volumetric capacities and low volumetric energy densities of battery cells. Sodium-ion batteries and potassium-ion batteries have similar problems.

Besides this, thick electrodes are also mechanically rigid, inflexible, inflexible, and do not conform to a desired shape. Thus, in conventional alkali metal batteries, high volume/weight energy density and mechanical flexibility appear to be mutually exclusive.

As the demand for more compact and portable energy storage systems increases, there is a growing interest in increasing the utilization rate of the volume of the battery. Novel electrode materials and designs that enable high volumetric capacities and high mass feeds are essential to achieving improved cell volumetric capacities and energy densities of alkali metal batteries.

Thus, high active material supply (high areal density), active material with high apparent density (tap density), without significantly reducing electron and ion transport rates (e.g., without high electron transfer resistance or long lithium or sodium ion diffusion paths). ) There is a clear and urgent need for alkali metal batteries with thick electrode thickness, high volumetric capacity, and high volumetric energy density.

These attributes must be achieved along with flexibility, shape adaptability, and safety of the resulting battery.

The present invention provides a cable-shaped alkali metal battery, wherein the alkali metal is selected from Li, Na, K, or a combination thereof. In other words, the battery can be 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/ It may be a K cell.

The cell includes (a) an electrically conductive porous rod having pores and a first mixture of a first electrode active material (a conductive additive or binder is optional, not required and not preferred) and a first electrolyte, the first mixture a first electrode present in the pores of the silver porous rod; (b) a porous separator surrounding the first electrode; (c) an electrically conductive porous layer surrounding or enclosing the porous separator, the conductive porous layer comprising pores and a second mixture of a second electrode active material (a conductive additive or binder is optional but not required) and a second electrolyte. and wherein the second mixture is present in the pores of the porous layer; and (d) a protective casing or packing tube (cable sheath) surrounding or surrounding the second electrode. The first electrolyte may be the same as or different from the second electrolyte.

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

In certain embodiments, the first electrode contains Li, Na, and/or K metals (other than intercalating compounds) as active anode materials. Accordingly, a cable-shaped alkali metal cell includes (A) an electrically conductive porous rod having pores and a first mixture of a first electrode active material and an optional first electrolyte (preferred, but not always necessary), the first electrode active material comprising: a first electrode (in this case, an anode) of lithium, sodium, or a combination thereof and the first mixture being within the pores of the porous rod; (B) a porous separator surrounding the first electrode; (C) an electrically conductive porous layer surrounding or surrounding the porous separator, the conductive porous layer containing pores and a second mixture of a second electrode active material and a second electrolyte, the second mixture present in the pores of the porous layer a second electrode; and (D) a protective casing or packing tube surrounding or surrounding the second electrode. Alternatively, in (A), the first electrode comprises a conductive rod (not a porous foam) and the first mixture is coated or deposited on the surface of the conductive rod. This rod can be as simple as a metal wire, a conductive polymer fiber or yarn, a carbon or graphite fiber or yarn, or multiple wires, fibers, or yarns.

In certain embodiments, the second electrode contains Li, Na, and/or K metal as an active anode material. As such, the cable-shaped alkali metal battery includes (a) 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 is present in the pores of the porous rod; electrode; (b) a porous separator surrounding the first electrode; (c) an electrically conductive porous layer surrounding or surrounding the porous separator, the conductive porous layer containing pores and a second mixture of a second electrode active material and an optional second electrolyte, wherein the second electrode active material is lithium, sodium, or a combination thereof, and the second mixture is a second electrode present in the pores of the porous layer; and (d) a protective casing or packing tube surrounding or surrounding the second electrode. 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 a current collector deposited with Li, Na, and/or K metal ( For example, Cu foil, Ni foil, metal foil such as stainless steel foil, or carbon cloth).

In certain embodiments, a cable-shaped battery has a first end and a second end, and the first electrode is at least one metal wire, conductive carbon/graphite fiber, or conductive that is embedded in, connected to, or integrated with the first electrode. and a first terminal connector comprising a polymer fiber. In certain preferred embodiments, at least one metal wire, conductive carbon/graphite fiber, or conductive polymeric fiber runs from approximately the first end to the second end. Preferably, this wire or fiber protrudes from either the first end or the second end to be a terminal tab for connection to an electronic device or an external circuit or load.

Alternatively or additionally, the cable-shaped battery has a first end and a second end, and the second electrode is at least one metal wire embedded in, connected to, or integrated with the second electrode, a conductive carbon/graphite fiber. , or a second terminal connector including a conductive polymer fiber. In certain embodiments, at least one metal wire, conductive carbon/graphite fiber, or conductive polymeric fiber runs from approximately the first end to the second end. Preferably, this wire or fiber protrudes from either the first end or the second end to be a terminal tab for connection to an electronic device or an external circuit or load.

The electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode may be metal foam, metal web, metal fiber mat, metal nanowire mat, conductive polymer fiber mat, conductive polymer foam, conductive polymer-coated fiber foam, carbon selected from foam, graphite foam, carbon airgel, graphene airgel, carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or combinations thereof It may contain a porous foam. These foams can be made into conformable structures that deform very well.

These foam structures can be readily manufactured with porosity levels of greater than 70%, more typically preferably greater than 80%, even more commonly and preferably greater than 90% and most preferably greater than 95% (graphene aerogels). may exceed the 99% porosity level). The skeletal structure (pore walls) of these foams forms a 3D network of electron conduction pathways, while the pores can accommodate a large portion of the electrode active material (anode active material in the anode or cathode active material in the cathode) without the use of conductive additives or binder resins. can

The foam may have a cross section of round, oval, rectangular, square, hexagonal, hollow, or irregular shape. There are no particular restrictions on the cross-sectional shape of the foam structure. The cell has a length and diameter or thickness and aspect ratio (length/thickness or length/diameter ratio) greater than 10, preferably greater than 15, more preferably greater than 20, even more preferably greater than 30, even more preferably It has a cable shape that exceeds 50 or 100. There are no restrictions on the length or diameter (or thickness) of the cable battery. The thickness or diameter is usually preferably between 100 nm and 10 cm, more preferably between 1 μm and 1 cm, most typically between 10 μm and 1 mm. The length can be from 1 μm to tens of meters or (if desired) even to hundreds of meters.

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

In certain embodiments of the present invention, the alkali metal cell is a lithium-ion cell, and the first or second electrode active material is (a) particles of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), and 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 intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements; (d) oxides, carbides, nitrides, sulfides, phosphides, selenium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof. cargo, and tellurium cargo; (e) their pre-lithiated form; (f) a pre-lithiated graphene sheet; and combinations thereof.

Pre-lithiated graphene sheets include pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, and nitrated graphene. , boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physically or chemically activated or etched forms thereof, or pre-lithiated forms of combinations thereof. .

In some embodiments, the alkali metal cell is a sodium-ion cell, and the 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 sphere, titanate, 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 to 1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate material, 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 ₄ O ₄ , C ₁₀ H _{2 Na 4} O ₈ , an alkali intercalating compound selected from C ₁₄ H ₄ O ₆ , C ₁₄ H ₄ Na ₄ O ₈ , or a combination thereof.

In some embodiments, the alkali metal cell is a sodium-ion cell, and the first or second active electrode 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 these a mixture of; (b) sodium- or potassium-containing alloys or intermetallics of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof; (c) sodium- or potassium-containing oxides, carbides, nitrides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof; sulfide, phosphide, selenide, telluride, or antimonide; (d) sodium or potassium salts; and (e) a graphene sheet pre-supplied with sodium or potassium; and an alkali intercalating compound selected from the group of substances of combinations thereof.

In some preferred embodiments, the second or first electrode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, doped A lithium intercalating compound selected from the group consisting of lithium vanadium 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; or Contains a lithium absorbing compound.

In certain embodiments, the second or first electrode active material is NaFePO ₄ , Na _(1-x) K _x PO ₄ , KFePO ₄ , Na _0.7 FePO ₄ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na ₂ FePO ₄ F, NaFeF ₃ , NaVPO ₄ F, KVPO ₄ F, Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , NaV ₆ O ₁₅ , Na _x VO ₂ , Na _0.33 V ₂ O ₅ , 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 . ₄₄ MnO ₂ /C, Na ₄ Mn ₉ O ₁₈ , NaFe ₂ Mn(PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Ni _1/3 Mn _1/3 Co _1/3 O ₂ , Cu _0.56 Ni ₀ . ₄₄ HCF, NiHCF, Na _x MnO ₂ , NaCrO ₂ , KCrO ₂ , Na ₃ Ti ₂ (PO ₄ ) ₃ , NiCo ₂ O ₄ , Ni ₃ S ₂ /FeS ₂ , Sb ₂ O ₄ , Na ₄ Fe(CN) ₆ /C, NaV _1-x Cr _x PO ₄ F, Se _z S _y , (y/z = 0.01 to 100), a sodium intercalating compound selected from Se, sodium polysulfide, sulfur, aluoselite, or combinations thereof or a potassium intercalating compound ( x is from 0.1 to 1.0).

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

Preferably, the first electrolyte and/or the second electrolyte has a concentration greater than 2.5 M (preferably greater than 3.0 M, more preferably greater than 3.5 M, even more preferably greater than 5.0 M, even more preferably greater than 7.0 M, most preferably contains a lithium or sodium salt dissolved in a liquid solvent having a salt concentration of greater than 10 M).

In the alkali metal battery of the present invention, the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode has pores of at least 90% by volume, and the first or second electrode has a diameter or thickness of 200 μm or more. or has an active mass supply amount of at least 30% by weight or vol% of the total battery cell, or the sum of the first electrode active material and the second electrode active material accounts for at least 50% by weight or vol% of the total battery cell.

In some preferred embodiments, the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode has at least 95% porosity by volume, and the first or second electrode has a diameter or thickness greater than or equal to 300 μm, or the entire The active mass supply accounts for at least 35% by weight or vol% of the battery cell, or the sum of the first electrode active material and the second electrode active material accounts for at least 60% by weight or vol% of the total battery cell.

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

Preferably, the metal oxide/phosphate/sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, transition metal sulfides, or 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 TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or combinations thereof.

Preferably, the metal oxide/phosphate/sulfide is VO ₂ , Li _x VO ₂ , V ₂ O ₅ , Li _x V ₂ O ₅ , V ₃ O ₈ , Li _x V ₃ O ₈ , Li _x V ₃ O ₇ , V ₄ O ₉ , Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped forms thereof, derivatives thereof, and combinations thereof (0.1 < x < 5).

Preferably, the metal oxide/phosphate/sulfide is a layered compound LiMO ₂ , a spinel compound LiM ₂ O ₄ , an olivine compound LiMPO ₄ , a silicate compound Li ₂ MSiO ₄ , a taborite compound LiMPO ₄ F, a borate compound LiMBO ₃ , or any of these are selected from combinations (M is a transition metal or a mixture of several transition metals).

In some preferred embodiments, 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 a sulfide, selenide, or telluride of a transition metal, (d) boron nitride, or (e) combinations thereof.

In certain 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 substance, tetracyanoquino-dimethane (TCNQ), tetracyano Ethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxy anthraquinone) (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 polymer, quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetron (PT), 5-amino-2,3 -Dihydro-1,4-dihydroxy anthraquinone (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 , or a cathode containing an organic or polymeric material selected from combinations thereof.

Thioether polymers are poly[methanetetril-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), poly(ethene-1,1,2,2-tetrathiol) Polymers containing (PETT) as main chain thioether polymers, side chain thioether polymers having main chains composed of conjugated aromatic moieties and having thioether side chains as pendants, 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(ethyrendithio)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, aluminum phthalocyanine chloride. , cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or combinations thereof.

Preferably, the cathode contains an alkali metal intercalating 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, nanodisks, nanoribbons, or nanoplatelets. , alkali metal intercalating compounds or alkali metal absorbing compounds selected from dichalcogenides, trichalcogenides, sulfides, selenides, and tellurides.

In some embodiments, the cathode active material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, nanodiscs, nanoplatelets, nanocoatings of an inorganic material selected from sulfides, selenides, or tellurides of cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof; or nanosheets, wherein the disks, platelets, or sheets have a thickness of less than 100 nm.

1A is a prior art lithium (as an example of an alkali metal battery) composed of an anode current collector, an anode electrode (eg, a thin Si coating layer), a porous separator, a cathode electrode (eg, a sulfur layer), and a cathode current collector. -Schematic diagram of an ion battery cell.
1B is a schematic diagram of a prior art lithium-ion cell in which the electrode layer consists of discrete particles of an active material (eg, graphite or tin oxide particles in an anode layer or LiCoO ₂ in a cathode layer).
Figure 1c is a schematic diagram of a process for manufacturing a flexible alkali metal battery in the shape of a shape adaptable cable.
Figure 1d shows four examples of methods for manufacturing electrodes (anode or cathode) in a continuous automated manner.
1E is a schematic diagram of the process of the present invention for continuously producing alkali metal-ion battery electrodes.
2 is an electron microscope image of an isolated graphene sheet.
3A is an example of a conductive porous layer (metal grid/mesh and carbon nanofiber mat).
3B is an example of a conductive porous layer (graphene foam and carbon foam).
3C is an example of a conductive porous layer (graphite foam and Ni foam).
3D is an example of a conductive porous layer (Cu foam and stainless steel foam).
Figure 4a shows a process commonly used for the manufacture of exfoliated graphite, expanded graphite flakes (thickness greater than 100 nm) and graphene sheets (thickness less than 100 nm, more typically less than 10 nm, and may be as thin as 0.34 nm). it is a schematic
4B is a schematic diagram for explaining a manufacturing process of exfoliated graphite, expanded graphite flakes, and isolated graphene sheets.
5 is a Ragone plot (weight and volumetric power density versus energy density) of a lithium-ion battery cell containing graphite particles as anode active material and carbon-coated LFP particles as cathode active material. Two of the four data curves are for cable-shaped cells made according to an embodiment of the present invention and the other two are for cells made by conventional electrode slurry coating (roll-coating).
6 is a Ragone plot (both gravimetric and volumetric power densities versus gravimetric and volumetric energy densities) of two cells containing graphene-containing Si nanoparticles as anode active material and LiCoO ₂ nanoparticles as cathode active material. Experimental data were obtained from a cable-shaped Li-ion battery cell prepared by the method of the present invention and a Li-ion battery cell prepared by conventional electrode slurry coating.
7 is a Ragon diagram of a lithium metal battery containing lithium foil as an anode active material, dilithium rhodizonate (Li ₂ C ₆ O ₆ ) as a cathode active material, and lithium salt (LiPF ₆ )-PC/DEC as an organic liquid electrolyte. . Data are for both cable-shaped lithium metal cells prepared by the method of the present invention and lithium metal cells prepared by conventional electrode slurry coating.
8 is a cell-level gravimetric energy density (Wh/kg) and volume energy density (Wh /L) is plotted over the achievable cathode thickness range of the MnO ₂ /RGO cathode.
9 is the cell-level weight and volumetric energy density of a cable-shaped graphite/NMC cell prepared by the method of the present invention and a graphite/NMC cell prepared by a conventional roll-coating method.
10 is a Ragone plot (weight and volumetric power density versus energy 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. . Two of the four data curves are for cable cells made according to an embodiment of the present invention and the other two are for cells made by conventional electrode slurry coating (roll-coating).
11 is a Ragone plot (both gravimetric and volumetric power densities versus gravimetric and volumetric energy densities) of two cells containing graphene-containing Sn nanoparticles as anode active material and NaFePO ₄ nanoparticles as cathode active material. Data are for both cabled sodium-ion cells made by the method of the present invention and sodium-ion cells made by conventional electrode slurry coating.
12 is a sodium metal battery containing graphene-supported sodium foil as an anode active material, disodium rhodizonate (Na ₂ C ₆ O ₆ ) as a cathode active material, and sodium salt (NaPF ₆ )-PC/DEC as an organic liquid electrolyte. is the Ragone diagram of Data are for both cable shaped sodium metal cells made by the method of the present invention and sodium metal cells made by conventional electrode slurry coating.
Figure 13 is a Ragone plot of a series of K-ion cells prepared by a conventional slurry coating process and a corresponding K-ion cell manufactured by the process of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention may be more readily understood by reference to the following detailed description of the invention in conjunction with the accompanying drawings, which form a part of this disclosure. The present invention is not limited to the specific devices, methods, conditions or parameters described and/or shown herein, and the terminology used herein is for the purpose of describing specific implementations by way of example only and is not intended to limit the claimed invention. You have to understand that no

The present invention relates to a shape-adaptable cable-type flexible alkali metal battery exhibiting very high volumetric energy density and gravimetric energy density. Such an alkali metal battery may be a primary battery, but is preferably a lithium-ion battery or a lithium metal secondary battery (eg, using lithium metal as an anode active material), a sodium-ion battery, a sodium metal battery, a potassium-ion battery batteries, or secondary batteries selected from potassium metal batteries. Cells are based on aqueous electrolytes, non-aqueous or organic electrolytes, gel electrolytes, ionic liquid electrolytes, or mixtures of organic and ionic liquids.

For convenience, in the present invention, 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 the anode active material are used. In the case of a sodium battery, selected materials such as hard carbon and NaTi ₂ (PO ₄ ) ₃ particles as examples of anode active materials in Na-ion cells, and NaFePO ₄ and λ-MnO ₂ particles as illustrative examples of cathode active materials are used. . A similar approach can be applied to K-ion cells. Nickel foam, graphite foam, graphene foam, and stainless fiber web are used as examples of the conductive porous layer as a target current collector. They should not be construed as limiting the scope of the present invention.

As shown in FIGS. 1A and 1B, a lithium-ion battery cell typically includes an anode current collector (eg, Cu foil), an anode electrode (anode active material layer), a porous separator and/or electrolyte component, a cathode electrode ( cathode active material layer), and a cathode current collector (eg, Al foil). In a more commonly used cell configuration (FIG. 1B), the anode layer consists of anode active material particles (e.g. graphite or Si), a conductive additive (e.g. carbon black particles), and a resin binder (e.g. SBR or PVDF). The cathode layer is composed of cathode active material particles (eg, LFP particles), conductive additives (eg, carbon black particles), and a resin binder (eg, PVDF). Both the anode and cathode layers typically have a thickness of at most 100-200 μm in order to generate a presumably sufficient amount of current per unit electrode area. These thickness ranges are considered industry-accepted constraints within which cell designers typically work. This thickness limitation is due to several reasons: (a) existing battery electrode coaters are not equipped to coat very thin or very thick electrode layers; (b) a thinner layer is preferred given the reduced lithium ion diffusion path length, but a layer that is too thin (e.g., less than 100 μm) does not contain a sufficient amount of active lithium storage material (and thus reduces the current output); insufficient); (c) thicker electrodes are prone to peeling or cracking upon drying or handling after roll-coating, and manufacturing of thicker electrodes requires a coating line longer than 100 meters (expensive and impractical); (d) all inert material layers of the battery cell (e.g., current collector and separator) should be kept to a minimum.

Also importantly, the shape and dimensions of conventional lithium-ion cells are such that the cells are rigid (inflexible) and cannot be bent or twisted. It is also difficult to implement such a conventional battery into a body of an electric vehicle (eg, an electric bicycle and a battery-powered car). For example, some limited space inside car door structures cannot accommodate rigid rectangular or cylindrical cells.

In a less commonly used cell configuration as shown in FIG. 1A, an active anode material (eg Si) or cathode active material (eg lithium transition metal oxide) is placed on a current collector such as a sheet of copper foil or Al foil. It is directly deposited in the form of a thin film. However, such thin-film structures with extremely small thickness-direction dimensions (typically much smaller than 500 nm, and often inevitably thinner than 100 nm) allow only a small amount of active material to be incorporated into the electrode (for the same electrode or current collector surface area). This means that it can provide a low total lithium storage capacity and a low lithium storage capacity per unit electrode surface area. In order to be more resistant to cracking by cycling (in the case of the anode) or to facilitate full utilization of the cathode active material, such a thin film should have a thickness of less than 100 nm. These constraints further reduce the total lithium storage capacity and the lithium storage capacity per unit electrode surface area. These thin-film batteries have a very limited application range.

On the anode side, Si layers thicker than 100 nm were found to exhibit low crack resistance during cell charge/discharge cycles. It fragments in a few cycles. On the cathode side, if the sputtered layer of lithium metal oxide is thicker than 100 nm, lithium ions cannot completely permeate and reach the entire cathode layer, resulting in poor cathode active material utilization. A preferred electrode thickness is at least 100 μm, and the individual active material coatings or particles preferably have dimensions less than 100 nm. Thus, these thin film electrodes (less than 100 nm thick) deposited directly on the current collector are 1000 times thinner than the required thickness. As a further matter, all active cathode materials are non-conductive to both electrons and lithium ions. When the layer thickness is thick, the internal resistance becomes excessively high and the utilization rate of the active material deteriorates.

In other words, there are several conflicting factors that must be considered simultaneously in terms of material type, size, electrode layer thickness and active material mass supply, and in terms of electrode or cell shape and dimensions, in terms of design and selection of cathode or anode active materials. Hitherto, no effective solution to these often conflicting problems has been provided in any prior art teaching. The present inventors have solved this difficult problem that has plagued both battery designers and electrochemists for over 30 years by developing a novel manufacturing process for lithium batteries as described herein.

Prior art lithium battery cells are typically prepared by a process comprising the following steps: (a) a first step is anode active material particles (e.g., Si nanoparticles or mesocarbon microbeads, MCMB), a conductive filler ( eg, graphite flakes) and a resin binder (eg, PVDF) in a solvent (eg, NMP) to form an anode slurry. On a separate basis, cathode active material particles (e.g. LFP particles), conductive filler (e.g. acetylene black), 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 the anode slurry on one or both of the primary surfaces of the anode current collector (eg, Cu foil) and vaporize the solvent (eg, NMP) to remove the coated layer. and drying 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. Slurry coating is generally carried out in a roll-to-roll manner in practical manufacturing situations. (c) The third step is to laminate the anode/Cu foil sheet, the porous separator layer, and the cathode/Al foil sheet together to form a three-layer or five-layer assembly, and cut or cut and laminate them to the desired size (one of the shapes As an example of) forming a rectangular structure or winding into a cylindrical cell structure. (d) The rectangular or cylindrical laminate structure is then placed in an aluminum-plastic laminate enclosure or steel casing. (e) Subsequently, a lithium battery cell is manufactured by injecting a liquid electrolyte into the laminate structure.

There are several serious problems associated with conventional processes and resulting lithium-ion battery cells or sodium-ion cells:

1) It is very difficult to manufacture an electrode layer (anode layer or cathode layer) thicker than 200 μm (100 μm on each side of a solid current collector such as Al foil). There are several reasons for this. 100-200 μm thick electrodes typically require a 30-50 meter long heating zone in a slurry coating plant, which is too time consuming, too energy intensive and not cost effective Some active electrode materials such as metal oxide particles In the case of , it was not possible to continuously fabricate electrodes with excellent structural integrity thicker than 100 μm in a real manufacturing environment. The resulting electrode is very brittle and brittle. Thicker electrodes are more prone to delamination and cracking.

2) The actual mass supply of the electrode and the apparent density for the active material are too low to achieve energy densities greater than 200 Wh/kg with conventional processes as shown in FIG. 1A. In most cases, the mass supply (area density) of the anode active material of the electrode is well below 25 mg/cm ² and the apparent volume density or tap density of the active material is typically less than 1.2 g/cm ³ even for relatively large graphite particles. . The cathode active material mass supply (area density) of the electrode is much lower than 45 mg/cm ² for lithium metal oxide type inorganic materials and lower than 15 mg/cm ² for organic or polymeric materials. In addition, there are many other inactive materials (e.g., conductive additives and resin binders) that add additional weight and volume to the electrodes without contributing to cell capacity. These low areal densities and low volume densities result in relatively low gravimetric energy densities and low volumetric energy densities.

3) The conventional process requires a step of preparing a slurry by dispersing an electrode active material (anode active material or cathode active material) in a liquid solvent (eg, NMP), and when coated on the surface of the current collector, the liquid solvent dries the electrode layer must be removed in order to When a battery cell is manufactured by laminating an anode layer and a cathode layer together with a separator layer and packaging in a housing, a liquid electrolyte is injected into the cell. In practice, the two electrodes are wetted, then the electrodes are dried, and finally wetted again. This wet-dry-wet process does not seem to be a good process at all.

4) Current lithium-ion batteries still suffer from relatively low gravimetric energy density and low volumetric energy density. Commercially available lithium-ion batteries exhibit gravimetric energy densities of about 150-220 Wh/kg and volumetric energy densities of 450-600 Wh/L.

In the literature, energy density data reported based on active material weight alone or electrode weight cannot be directly converted to energy density of actual battery cells or devices. The "overhead weight" or weight of other device components (binders, conductive additives, current collectors, separators, electrolytes, and packaging) should also be considered. According to the conventional manufacturing process, the weight ratio of the anode active material (eg graphite or carbon) in a lithium-ion battery is typically 12% to 17% and the weight ratio of the cathode active material (eg LiMn ₂ O ₄ ) is 20% to 35%.

The present invention provides a method for manufacturing a cable-shaped, shape-adaptable, incombustible flexible alkali metal battery cell having a high active material mass supply, low overhead weight and volume, high gravimetric energy density, and high volumetric energy density. In addition, the manufacturing cost of alkali metal cells produced by the method of the present invention is much lower than that by conventional processes.

In one embodiment of the present invention, as shown in FIG. 1C, the cable-shaped alkali metal battery of the present invention is an electrically conductive porous rod having pores partially or completely filled with a mixture of a first electrode active material and a first electrolyte. It can be manufactured by a process including the first step of supplying the first electrode 11 made of. A conductive additive or resin binder may optionally be added to the mixture, but this is not necessary or even desirable. This first electrode 11 can optionally include an end 13 of an active material member electrolyte member that can serve as a terminal tab for connection to an external load. This first electrode can have 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 a porous foam) and the first mixture is coated or deposited on the surface of the conductive rod. This rod can be as simple as a metal wire, a conductive polymer fiber or yarn, a carbon or graphite fiber or yarn, or a number of thin wires, fibers, or yarns. However, in this state, the second electrode must include a porous foam structure.

In the second step, a thin porous separator ( 15 ) permeable to Li ⁺ , Na ⁺ , or K ⁺ ions (eg, porous plastic film, paper, fiber mat, non-woven fabric, glass fiber fabric, etc.) is used as the first electrode ( 11 ) enclosing or enclosing. The cross-sectional area of this structure is now schematically shown at 15a , 15b, etc. This step can be as simple as wrapping the first electrode completely or slightly more than one turn, or spirally, with a thin porous plastic tape. The main purpose is to electrically separate the anode and cathode to prevent internal short circuits. A porous layer may simply be deposited around the entire first electrode by spraying, printing, coating, dip casting, or the like.

This separator covering or lapping step is followed by a third step comprising the step of enclosing or wrapping the separator-protecting structure with a layer of second electrode 17 . The second electrode 17 includes a mixture of a second active material and a second electrolyte and, optionally (although not necessary or preferred) a conductive additive or resin binder. This second electrode 17 can optionally include an end 21 of an active material member electrolyte member that can serve as a terminal tab for connection to an external load. The cross-sectional area of this structure is now schematically shown at 17a , 17b, etc.

As a fourth step, this structure is then wrapped or protected by an electrically insulative cable sheath 19 (eg a plastic sheath or rubber shell). The cross-sectional area of the resulting cable cell structure is now as shown schematically at 19a , 19b , etc. before being connected to an external load (eg light bulb, LED light, electronic device).

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

There are several means of manufacturing either the first electrode or the second electrode. Taking a square or rectangular foam layer cross-section as an example, as schematically shown in FIG . 322, or 330 (only one foam layer is shown, but there may be multiple layers in each case) to the active material/electrolyte impregnation zone, wherein the electrode active material, electrolyte and optional A wet active material mixture (eg, a slurry, suspension, or gel-like material such as 306a, 306b, 312a, 312b ) of a conductive additive is added to a porous layer (eg, 304 or 310 in Schematic A and Schematic B in FIG. 1D, respectively). of is transferred to at least the porous surface. Taking Schematic A as an example, the wet active material/electrolyte mixture 306a, 306b is forcibly impregnated into the porous layer from both sides using one or two pairs of rollers 302a, 302b, 302c, and 302d using a pair of rollers 302a, 302b, 302c, and 302d to form an impregnated active electrode ( 308 ) (anode or cathode). The conductive porous foam layer comprises an interconnected network of electron conduction pathways and at least 70% by volume (preferably greater than 80%, more preferably greater than 90%, even more preferably greater than 95%) pores.

In Schematic B, two supply rollers 316a and 316b are used to continuously unroll the two protective films 314a and 314b supporting the wet active material/electrolyte mixture layers 312a and 312b . These wet active material/electrolyte mixture layers 312a , 312b can be transferred to the protective (support) films 314a , 314b using a variety of methods (eg, printing, spraying, casting, coating, etc. well known in the art). there is. As the conductive porous foam layer 110 moves through the gaps between the two sets of rollers 318a, 318b, 318c, and 318d , the wet active mixture material/electrolyte impregnates the pores of the porous layer 310 , forming two An active material electrode 320 (anode or cathode electrode layer) covered with protective films 314a and 314b is formed. These protective films can be removed later.

Taking Schematic C as another example, two spray devices 324a and 324b were used to dispense wet active material/electrolyte mixtures 325a and 325b onto two opposing porous surfaces of conductive porous layer 322 . The wet active material/electrolyte mixture is forcibly impregnated into the porous layer from both sides using one or two pairs of rollers to form an impregnated active electrode 326 (anode or cathode). Similarly, in Schematic D, two spray devices 332a, 332b were used to dispense the wet active material mixture 333a, 333b onto the surfaces of the two opposing porous foam layers of the conductive porous layer 330 . The wet active material-electrolyte mixture is forcibly impregnated into the porous layer from both sides using one or two pairs of rollers to form an impregnated active electrode 338 (anode or cathode).

As another example, as shown in schematic E of FIG. 1E , the electrode manufacturing process starts by continuously supplying a conductive porous foam layer 356 of an arbitrary cross-sectional shape from a supply roller 340 . Porous layer 356 is guided by roller 342 to be dipped into wet active material mixture material 346 (slurry, suspension, gel, etc.) in vessel 344 . As the active material mixture moves toward the roller 342b , it begins to impregnate the pores of the porous layer 356 , and is supplied from the container to the gap between the two rollers 348a and 348b . The two protective films 350a, 350b are simultaneously supplied from the two respective rollers 352a, 352b to cover the impregnated porous layer 354 , which is continuously recovered on a rotary drum (winding roller 355 ). It can be. This process can be applied to both anode and cathode electrodes.

The resulting electrode layer (anode or cathode electrode) may have a thickness or diameter after compaction from 100 nm to several centimeters (or more if desired). For a microcable (e.g., as a flexible power source for a microelectronic device), the thickness or diameter of the electrode is between 100 nm and 100 μm, more typically between 1 μm and 50 μm, most typically between 10 μm and 30 μm. am. In the case of a macroscopic shape-adaptive flexible cable battery (for example, for use in the limited space of an electric vehicle (EV)), the electrode is typically and preferably 100 μm or more (preferably greater than 200 μm, more preferably greater than 300 μm, more preferably greater than 400 μm, even more preferably greater than 500 μm, greater than 600 μm, or even greater than 1,000 μm), and there is no theoretical limit to the thickness of the electrode.

The above are just a few examples to illustrate how the shape adaptable cable type flexible alkali metal battery of the present invention can be manufactured. These examples should not be used to limit the scope of the invention.

The electrically conductive porous layer may be a metal foam, a metal web or screen, a perforated metal sheet-based structure, a metal fiber mat, a metal nanowire mat, a conductive polymer nanofiber mat, a conductive polymer foam, a conductive polymer-coated fiber foam, a carbon foam, graphite foam, carbon airgel, carbon xerogel, graphene airgel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or combinations thereof. there is. The porous layer must be made of an electrically conductive material (in the form of a highly porous mat, screen/grid, non-woven fabric, foam, etc.) such as carbon, graphite, metal, metal-coated fibers, conductive polymers, or conductive polymer-coated fibers. Examples of conductive porous layers are shown in FIGS. 3A, 3B, 3C, and 3D. The porosity level should be at least 70% by volume, preferably greater than 80% by volume, more preferably greater than 90% by volume and most preferably greater than 95% by volume. The backbone or foam wall forms a network of electron conduction pathways.

These foam structures can be easily manufactured into any cross-sectional shape. They can also be very flexible, and usually non-metallic foams are more flexible than metal foams. Since the electrolyte is in a liquid or gel state, the resulting cable cell can be highly flexible and can be made to conform to essentially any unusual shape. Even when the salt concentration in the liquid solvent is high (e.g., 2.5 M to 12 M), the foam containing the electrolyte inside the pores can still be deformed, bent, twisted, and conformed to unusual shapes. there is.

Preferably, substantially all of the pores of the original conductive porous layer are filled with an active electrode material (anode or cathode), an electrolyte, and an optional conductive additive (no binder resin required). Since the amount of pores (70-99%) is high compared to the pore walls or conductive pathways (1-30%), very little space is wasted ("wasted" means not occupied by active electrode material and electrolyte). ), a high proportion of the electrode active material-electrolyte mixture (high active material supply mass) occurs.

In such cell electrode configurations (e.g., FIG. 1C), since the pore walls are ubiquitous throughout the entire electrode structure, electrons can pass short distances (on average half the pore size, e.g., nanometers) before being collected by the pore walls. meters or a few micrometers) (conductive foam acts as a current collector). These pore walls form a 3D network of interconnected electron transport pathways with minimal resistance. In addition, in each anode electrode or cathode electrode, all electrode active material particles are pre-dispersed in a liquid electrolyte (no wettability problem), and generally in electrodes prepared by conventional processes of wet coating, drying, packing, and electrolyte injection Eliminate the presence of any existing dry pockets. Thus, the process of the present invention brings completely unexpected advantages over conventional battery cell manufacturing processes.

In a preferred embodiment, the anode active material is pure graphene (eg, FIG. 2), graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene It is a pre-lithiated or pre-sodium form of a graphene sheet selected from pin, nitride graphene, chemically functionalized graphene, or combinations thereof. The starting graphite material for preparing any one of the graphene materials is natural graphite, artificial 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 excellent conductive additives for both anode and cathode active materials in alkali metal cells.

If interplanar van der Waals forces can be overcome, graphene planes, which are constituents of graphite microcrystals within natural or artificial graphite grains, can be exfoliated and extracted or isolated to yield discrete graphene sheets of monoatomic thickness, hexagonal carbon atoms. can Isolated, individual graphene facets of carbon atoms are commonly referred to as monolayer graphene. A stack consisting of several graphene facets bonded through van der Waals forces in the thickness direction with an interplanar spacing of about 0.3354 nm is generally referred to as multilayer graphene. A multilayer graphene sheet has up to 300 graphene planes (less than 100 nm thick), but typically less than 30 graphene planes (less than 10 nm thick), and even more typically up to 20 graphene planes. It has fin facets (less than 7 nm thick), most commonly fewer than 10 graphene facets (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 sheets" (NGP). Graphene sheets/plates (collectively, NGPs) are a new class of carbon nanomaterials (2-D nanocarbons) distinct from 0-D fullerenes, 1-D CNTs or CNFs, and 3-D graphite. For purposes of defining the claims and as is generally understood in the art, the graphene material (isolated graphene sheet) is not (and does not include) carbon nanotubes (CNTs) or carbon nanofibers (CNFs). .

In one process, graphene materials are prepared by intercalating natural graphite particles with strong acids and/or oxidizing agents to obtain graphite intercalating compounds (GICs) or graphite oxides (GOs), as shown in FIGS. 4A and 4B (schematic). obtained by obtaining In GIC or GO, the presence of chemical species or functional groups in the interstitial space between the graphene planes serves to increase the intergraphe spacing ( d ₀₀₂ measured by X-ray diffraction), otherwise along the c- axis direction It significantly reduces the van der Waals forces that bind the graphene facets together. GIC or GO is in most cases produced by immersing natural graphite powder ( 100 in Fig. 4b) in a mixture of sulfuric acid, nitric acid (oxidizing agent), and another oxidizing agent (e.g., potassium permanganate or sodium perchlorate). If an oxidizing agent is present during the intercalation process, the resulting GIC ( 102 ) is actually some type of graphite oxide (GO) particle. This GIC or GO is then repeatedly washed and rinsed in water to remove excess acid, resulting in a graphite oxide suspension or dispersion containing visually discernible discrete graphite oxide particles dispersed in water. To prepare the graphene material, after this cleaning step, one of two processing routes outlined below can be followed.

Route 1 involves removing water from the suspension to obtain "expandable graphite" which is essentially a large amount of dried GIC or dried graphite oxide particles. When expandable graphite is exposed to temperatures typically in the range of 800 to 1,050 °C for about 30 seconds to 2 minutes, the GIC undergoes a rapid volume expansion of 30 to 300 times, resulting in a collection of exfoliated but largely unseparated, interconnected graphite flakes. form a "graphite worm" ( 104 ).

In path 1A, these graphite worms (exfoliated graphite or "networks of interconnected/unseparated graphite flakes") are recompressed into a flexible material with a thickness typically ranging from 0.1 mm (100 μm) to 0.5 mm (500 μm). A graphite sheet or foil 106 can be obtained. Alternatively, using low-intensity air mills or shears for the purpose of producing so-called “expanded graphite flakes” ( 108 ) containing primarily graphite flakes or platelets thicker than 100 nm (and therefore not nanomaterials by definition) You can choose to simply destroy the graphite worm.

In Route 1B, as disclosed in Applicant's U.S. Application Serial No. 10/858,814 (June 3, 2004), exfoliated graphite is prepared (e.g., by a sonicator, high shear mixer, high intensity air jet mill, or high energy ball mill). are subjected to high-intensity mechanical shearing) to form isolated monolayer and multilayer graphene sheets (collectively referred to as NGPs, 112 ). Single-layer graphene can be as thin as 0.34 nm, while multi-layer graphene can have a thickness of less than 100 nm, but more typically less than 10 nm (commonly referred to as few-layer graphene). Several graphene sheets or plates can be made into NGP paper sheets using papermaking processes. This NGP paper sheet is an example of a porous graphene structure layer used in the process of the present invention.

Route 2 involves sonicating a graphite oxide suspension (eg graphite oxide particles dispersed in water) for the purpose of separating/isolating the individual graphene oxide sheets from the graphite oxide particles. This is based on the concept that interplanar separation between graphenes increased from 0.3354 nm in natural graphite to 0.6–1.1 nm in highly oxidized graphite oxide, significantly weakening the van der Waals forces binding adjacent planes together. The ultrasonic power may be sufficient to further separate the graphene face sheets to form fully separated, isolated, or discrete graphene oxide (GO) sheets. These graphene oxide sheets are then chemically or thermally reduced to an oxygen content of typically 0.001% to 10% by weight, more typically 0.01% to 5% by weight, most typically preferably less than 2% by weight. "Reduced graphene oxide" (RGO) with oxygen can be obtained.

For purposes of defining the claims of this application, NGPs or graphene materials are monolayer and multilayer (typically less than 10 layers) pure graphene, graphene oxide, reduced graphene oxide (RGO), graphene fluoride. , graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrated graphene, chemically functionalized graphene, discrete sheets of doped (e.g., doped with B or N) graphene. /include plate Pure graphene has essentially 0% oxygen. RGO typically has an oxygen content of 0.001% to 5% by weight. Graphene oxide (including RGO) may have 0.001% to 50% oxygen by weight. Other than pure graphene, all graphene materials have from 0.001% to 50% by weight of non-carbon elements (eg, O, H, N, B, F, Cl, Br, I, etc.). Such materials are referred to herein as impure graphene materials.

Pure graphene in smaller discrete graphene sheets (typically 0.3 μm to 10 μm) can be produced by supercritical fluid exfoliation or direct sonication (also known as liquid phase exfoliation or preparation) of graphite particles. Such processes are well known in the art.

Graphene oxide (GO) is prepared by dissolving a powder or filaments of a starting graphite material (eg, natural graphite powder) in an oxidizing liquid medium (eg, a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel at a desired temperature. for a period of time (typically 0.5 to 96 hours depending on the nature of the starting material and the type of oxidizing agent used). 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 converted into various graphene materials by replacing the -OH groups with other chemical groups (eg -Br, NH ₂ , etc.).

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

At high temperatures, interaction of F ₂ with graphite results in the formation of covalent graphite fluorides (CF) _n or (C ₂ F) _n , whereas at low temperatures, graphite intercalation compounds (GIC) C _x F (2 ≤ x ≤ 24) are formed. . (CF) Since the carbon atom at _n is sp3-hybridized, the fluorocarbon layer is a wavy structure composed of trans-linked cyclohexane chains. In (C ₂ F) _n , only half of the C atoms are fluorinated, and all pairs of adjacent carbon sheets are linked to each other by C-C covalent bonds. A systematic study of the fluorination reaction showed that the resulting F/C ratio was highly dependent on the fluorination temperature, the partial pressure of fluorine in the fluorination gas, and the physical properties of the graphite precursor (including the degree of graphitization, particle size and specific surface area). appear. Most of the available literature involves fluorination with F ₂ gas (sometimes in the presence of fluoride), but other fluorination agents besides fluorine (F ₂ ) may be used.

In order to exfoliate the layered precursor material in the state of individual layers or few layers, it is necessary to overcome the attractive forces between adjacent layers and to further stabilize these layers. This can be achieved by covalent modification of the graphene surface by functional groups or by non-covalent modification using certain solvents, surfactants, polymers, or donor-acceptor aromatic molecules. The liquid phase exfoliation process involves the ultrasonication of graphitic fluoride in a liquid medium.

Nitriding of graphene may be performed by exposing a graphene material such as graphene oxide to ammonia at a high temperature (200 to 400° C.). Nitride graphene can also be formed by hydrothermal methods at low temperatures, for example, by sealing GO and ammonia in an autoclave and then increasing the temperature to 150-250 °C. Other methods for the synthesis of nitrogen-doped graphene include nitrogen plasma treatment of graphene, arc-discharge between graphite electrodes in the presence of ammonia, ammonia decomposition of graphene oxide under CVD conditions, and graphene oxide and Include sequence processing of elements.

The foregoing features are further described and explained in detail as follows. As shown in FIG. 4B, graphite particles (eg, 100 ) are typically composed of many graphite microcrystals or grains. Graphite crystallites consist of layered planes of a hexagonal network of carbon atoms. These layered planes of hexagonally arranged carbon atoms are substantially flat and, in certain crystallites, are oriented or aligned to be substantially parallel and equidistant from each other. These hexagonal carbon atom layers, which are generally referred to as graphene layers or basal planes, are weakly bonded to each other in the thickness direction (crystallographic c- axis direction) by weak van der Waals forces, and these groups of graphene layers form microcrystals. are arranged Graphite crystallite structure is generally characterized in terms of two axes or directions: the c-axis direction and the a- axis (or b- axis) direction. The c axis is the direction normal to the base plane. The a- axis or b- axis is the direction parallel to the base plane (perpendicular to the direction of the c-axis).

Due to the weak van der Waals force binding the parallel graphene layers, natural graphite can be treated to significantly widen the graphene interlayer spacing to provide significant expansion in the c- axis direction, substantially maintaining the layered nature of the carbon layers. An expanded graphite structure can be formed. Processes for making flexible graphite are well known in the art. In general, a graphite intercalation compound (GIC, 102 ) is prepared by intercalating flakes of natural graphite (eg, 100 in FIG. 4B ) in an acidic solution. GIC is washed, dried and then exfoliated by exposure to high temperatures for a short period of time. This causes the flakes to expand or exfoliate up to 80 to 300 times their original dimension in the c- axis direction of the graphite. Exfoliated graphite flakes are generally referred to as graphite worms 104 because they have a worm-like appearance. These highly expanded graphite flake worms form agglomerated or consolidated sheets of expanded graphite, such as webs, papers, strips, tapes, foils, typically having a density of about 0.04 to 2.0 g/cm ³ for most applications. , a mat or the like (commonly referred to as “flexible graphite” 106 ) without using a binder.

Acids such as sulfuric acid are not the only type of intercalating agent (intercalating agent) that penetrates into the space between graphene planes to obtain GIC. Many different types of intercalation agents such as alkali metals (Li, K, Na, Cs, and their alloys or eutectics) can be used to intercalate graphite with Stage 1, Stage 2, Stage 3, etc. . Stage n means that there is one intercalator layer for every n graphene facets. For example, a stage-1 potassium-intercalated GIC means that there is one K layer for every graphene facet, or the order G/K/G/K/G/KG... where G is the graphene facet and K is the potassium atomic plane), which means that one can find one K atomic layer inserted between two adjacent graphene planes. Stage-2 GICs will have the order GG/K/GG/K/GG/K/GG..., Stage-3 GICs will have the order GGG/K/GGG/K/GGG... etc. . These GICs can then be contacted with water or a water-alcohol mixture to produce exfoliated graphite and/or separated/isolated graphene sheets.

Exfoliated graphite worms are subjected to high-intensity mechanical shearing/separation using high-intensity air jet mills, high-intensity ball mills, or ultrasonic devices, so that all graphene plates are thinner than 100 nm, most of which are thinner than 10 nm, and many are single-layer graphene. nanographene platelets (NGP) (also shown as 112 in FIG. 4B). NGPs are composed of a graphene sheet or a plurality of graphene sheets, each sheet having a two-dimensional hexagonal structure of carbon atoms. (Volumes of several NGPs comprising single- and/or few-layer graphene or discrete sheets/platelets of graphene oxide can be fabricated into porous graphene films ( 114 in FIG. 4B ) using film fabrication processes. Alternatively, , using low-intensity shear, the graphite worms tend to separate into so-called expanded graphite flakes ( 108 in Fig. 4b) having a thickness greater than 100 nm These flakes, with or without the use of a resin binder, can be used to produce mats. A process can be used to form expanded graphite foam that is formed into a graphite mat or nonwoven fabric 106. Graphite foam can also be made by graphitization of carbon foam.

There are no limitations on the type of anode active material or cathode active material that can be used in the practice of the present invention. Preferably, in the process of the present invention, when the battery is being charged, the anode active material is less than 1.0 volts (preferably, Li/Li ⁺ (i.e., Li as standard potential → Li ⁺ + e ^- vs.) Na/Na ⁺ reference) absorbs alkali ions (eg, lithium ions) at high electrochemical potentials (less than 0.7 volts). In a preferred embodiment, the active anode material comprises (a) particles of natural graphite, artificial 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 preferred due to their high specific capacities); (c) stoichiometric or non-stoichiometric alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements (eg, SiAl, SiSn); (d) oxides, carbides, nitrides, sulfides, phosphides, selenium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof. cargoes, and tellurides (eg, SnO, TiO ₂ , Co ₃ O ₄ , etc.); (e) their pre-lithiated form (eg, pre-lithiated TiO ₂ , which is lithium titanate); (f) a pre-lithiated graphene sheet; 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 the active electrode material.

In another embodiment, the active anode material is chemically selected from pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrated graphene, It is a pre-sodium or pre-potassium form of a graphene sheet selected from functionalized graphene, or combinations thereof. The starting graphite material for preparing any one of the graphene materials is natural graphite, artificial 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 excellent conductive additives for both anode and cathode active materials in alkali metal cells.

In a rechargeable alkali metal cell, the anode may contain an alkali ion source selected from alkali metals, alkali metal alloys, mixtures of alkali metals or alkali metal alloys with alkali intercalating compounds, alkali element-containing compounds, or combinations thereof. . Petroleum coke, carbon black, amorphous carbon, hard carbon, template carbon, hollow carbon nanowires, hollow carbon spheres, titanate, NaTi ₂ (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ (sodium titanate), Na ₂ C ₈ H ₄ O ₄ (disodium terephthalate), Na ₂ TP (sodium terephthalate), TiO ₂ , Na _x TiO ₂ (x is 0.2 to 1.0), carboxylate-based material, 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 ₄ O ₄ , C ₁₀ H ₂ Na ₄ O ₈ , C ₁₄ H ₄ O ₆ , C ₁₄ H ₄ Na ₄ O ₈ , or these An anode active material containing an alkali intercalating compound selected from combinations of

In one embodiment, the anode may contain a mixture of two or three types of anode active materials (eg activated carbon + mixed particles of NaTi ₂ (PO ₄ ) ₃ ) and the cathode may contain a sodium intercalating compound alone (eg For example, Na _x MnO ₂ ), an electric double layer capacitor type cathode active material alone (eg, activated carbon), or a redox pair of λ-MnO ₂ /activated carbon for pseudo-capacitance.

A variety of active cathode materials may be used in the practice of the process of this invention. The cathode active material is usually an alkali metal intercalating compound or an alkali metal absorbing compound capable of storing alkali metal ions when the battery is discharged and releasing the alkali metal ions into the electrolyte when it is recharged. Active cathode materials can be selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides (the most preferred types of inorganic cathode materials), or combinations thereof.

The group of metal oxides, metal phosphates, and metal sulfides includes lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium transition metal oxides, lithium mixed metal oxides, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof. In particular, lithium vanadium oxide is VO ₂ , Li _x VO ₂ , V ₂ O ₅ , Li _x V ₂ O ₅ , V 3 O _{8 , Li x V 3 O 8 , Li x V 3 O 7 , V 4 O 9 ,} Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped forms thereof, derivatives thereof, and combinations thereof (0.1 < x < 5). The lithium transition metal oxide may be selected from layered compounds LiMO ₂ , spinel compounds LiM ₂ O ₄ , olivine compounds LiMPO ₄ , silicate compounds Li ₂ MSiO ₄ , taborite compounds LiMPO ₄ F, borate compounds LiMBO ₃ , or combinations thereof. (M is a transition metal or a mixture of several transition metals).

In an alkali metal cell or alkali metal-ion cell, the cathode active material is NaFePO ₄ (sodium iron phosphate), Na _0.7 FePO ₄ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , Na ₃ V2 (PO ₄ ) ₂ F ₃ , Na ₂ FePO ₄ F, NaFeF ₃ , NaVPO ₄ F, Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , NaV ₆ O ₁₅ , Na _x VO ₂ , Na _0.33 V ₂ O ₅ , Na _x CoO ₂ (sodium cobalt oxide), 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 (sodium manganese bronze), λ-MnO ₂ , Na _0.44 MnO ₂ , Na ₀ . ₄₄ MnO ₂ /C, Na ₄ Mn ₉ O ₁₈ , NaFe ₂ Mn(PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Ni _1/3 Mn _1/3 Co _1/3 O ₂ , Cu _0.56 Ni ₀ . ₄₄ HCF (copper and nickel hexacyanoferrate), NiHCF (nickel hexacyanoferrate), Na _x CoO ₂ , NaCrO ₂ , Na ₃ Ti ₂ (PO ₄ ) ₃ , NiCo ₂ O ₄ , Ni ₃ S ₂ /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/sulfur, z/y is from 0.01 to 100), Se (without S), aluoselite, or combinations thereof (or their potassium counterparts).

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 TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or combinations thereof. This is further explained later.

In particular, 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 a sulfide, selenide, or telluride of a transition metal, (d) boron nitride, or (e) a combination thereof.

Alternatively, the cathode active material may be selected from functional materials or nanostructured materials having alkali metal ion-storing surfaces or alkali metal ion-trapping functional groups in direct contact with the electrolyte. Preferably, the functional groups react reversibly with alkali metal ions, form redox pairs with alkali metal ions, or form chemical complexes with alkali metal ions. The functional material or nanostructured material is (a) selected from 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. nanostructured or porous irregular carbon materials; (b) a nano-graphene sheet selected from a single-layer graphene sheet or a multi-layer graphene sheet; (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) functional materials containing carbonyl, carboxyl, or amine groups; And it may be selected from the group consisting of combinations thereof.

Functional materials 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 (Na terephthalate), Na ₂ C ₆ H ₄ O ₄ (Li trans-trans muconate), 3,4,9,10-perylenetetracarboxylic acid- dianhydride (PTCDA) sulfide polymer, PTCDA, 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5, 8-tetrahydroxy anthraquinone, tetrahydroxy- p- benzoquinone, and combinations thereof. Preferably, the functional material or nanostructured material has a functional group selected from -COOH, = O, -NH ₂ , -OR, or -COOR (where R is a hydrocarbon radical).

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-linked PYT, quino(triazene), redox active organic substance, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2 ,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxy anthraquinone) (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-tetraquet Topiperazine (PHP), N,N'-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraquet Topiperazine (PRP), thioether polymer, quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetron (PT), 5-amino-2,3-dihydro-1, 4-dihydroxy anthraquinone (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 , or combinations thereof.

Thioether polymers are poly[methanetetril-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), poly(ethene-1,1,2,2-tetrathiol) Polymers containing (PETT) as main chain thioether polymers, side chain thioether polymers having main chains composed of conjugated aromatic moieties and having thioether side chains as pendants, 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(ethyrendithio)thiophene] (PEDTT).

Organic substances are copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine , cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or phthalocyanine compounds selected from 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 is niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron in the form of nanowires, nanodiscs, nanoribbons, or nanoplatelets. , or an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of nickel.

The present inventors have found that a wide variety of two-dimensional (2D) inorganic materials can be used as cathode materials in the lithium battery of the present invention manufactured by the direct active material-electrolyte injection process of the present invention. Layered materials represent a versatile source of 2D systems that can exhibit unexpected electrical properties and good lithium ion affinity. Graphite is the best known layered material, but transition metal dichalcogenides (TMDs), transition metal oxides (TMOs), and various other compounds such as BN, Bi ₂ Te ₃ , and Bi ₂ Se ₃ are also possible sources of 2D materials. .

Preferably, the lithium intercalating compound or lithium absorbing compound is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten , nanodiscs, nanoplatelets of an inorganic material selected from titanium, cobalt, manganese, iron, nickel, or a sulfide, selenide, or telluride of a transition metal, (d) boron nitride, or (e) combinations thereof; selected from nanocoatings, or nanosheets, wherein the disks, platelets, or sheets have a thickness of less than 100 nm. The lithium intercalating compound or lithium absorbing compound is (i) bismuth selenide or bismuth telluride, (ii) transition metal dichalcogenide or trichalcogenide, (iii) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, nanodisks, nanoplatelets, nanocoatings, or of a compound selected from sulfides, selenides, or tellurides of cobalt, manganese, iron, nickel, or transition metals, (iv) boron nitride, or (v) combinations thereof; may contain nanosheets, and the disks, platelets, coatings, or sheets have a thickness of less than 100 nm.

Non-graphenic 2D nanomaterials, monolayers or few layers (up to 20 layers) can be fabricated by several methods: mechanical cutting, laser ablation (e.g. using laser pulses to ablate a TMD down to a monolayer), liquid phase Exfoliation, and thin film techniques such as PVD (eg sputtering), evaporation, vapor phase epitaxy, liquid phase epitaxy, chemical vapor phase epitaxy, molecular beam epitaxy (MBE), atomic layer epitaxy (ALE), and plasmas thereof -Synthesis by auxiliary forms.

A variety of electrolytes may be used in the practice of the present invention. Non-aqueous organic and/or ionic liquid electrolytes are most preferred. The non-aqueous electrolyte used herein can be prepared by dissolving an electrolyte salt in a non-aqueous solvent. Any known non-aqueous solvent that has been used as a solvent for lithium secondary batteries can be used. A non-aqueous solvent mainly composed of ethylene carbonate (EC) and a mixed solvent including at least one non-aqueous solvent (hereinafter referred to as a second solvent) having a melting point lower than that of ethylene carbonate and a donor number of 18 or less may be preferably used. These non-aqueous solvents are (a) stable to negative electrodes containing carbonaceous materials with well-developed graphitic structures; (b) is effective in inhibiting reduction or oxidative degradation of the electrolyte; (c) It is advantageous in that it has high conductivity. A non-aqueous electrolyte consisting only of ethylene carbonate (EC) is advantageous in that it is relatively stable against decomposition through reduction by a graphitized carbonaceous material. However, since EC has a relatively high melting point of 39 to 40° C. and relatively high viscosity and low conductivity, EC alone is not suitable for use as a secondary battery electrolyte operating at room temperature or lower. The second solvent used in the mixture with EC serves to improve the ionic conductivity of the mixed solvent by making the viscosity of the solvent mixture lower than that of EC alone. In addition, when a second solvent having a donor number of 18 or less (the donor number of ethylene carbonate is 16.4) is used, the ethylene carbonate can be easily and selectively solvated with lithium ions, so that the carbonaceous material with well-initiated graphitization It is estimated that the reduction reaction of the second solvent and the second solvent is suppressed. In addition, when the donor number of the second solvent is controlled to be 18 or less, the oxidation decomposition potential of the lithium electrode can be easily increased to 4 V or more, so that a high-voltage lithium secondary battery can be manufactured.

Preferred second solvents are dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (gamma-BL ), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA). These second solvents may be used alone or in combination of two or more. More preferably, this second solvent should be selected from solvents having a donor number of 16.5 or less. Preferably, the viscosity of this second solvent should be less than or equal to 28 cps at 25°C.

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

Examples of preferred mixed solvents include compositions containing EC and MEC, in which the volume ratio of MEC is controlled within the range of 30 to 80%; compositions comprising EC, PC and MEC; compositions comprising EC, MEC and DEC; compositions comprising EC, MEC and DMC; and compositions comprising EC, MEC, PC and DEC. By selecting the volume ratio of MEC in the range of 30 to 80%, more preferably 40 to 70%, the conductivity of the solvent can be improved. In order to suppress the decomposition reaction of the solvent, an electrolyte in which carbon dioxide is dissolved can be used, thereby effectively improving both the capacity and cycle life of the battery. The electrolyte salt incorporated into the nonaqueous electrolyte is lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium hexafluoroarsenide (LiAsF ₆ ), lithium trifluoro-meta lithium salts such as sulfonates (LiCF ₃ SO ₃ ) and bis-trifluoromethyl sulfonylimide lithium [LiN(CF ₃ SO ₂ ) ₂ ]. Among these, LiPF ₆ , LiBF ₄ and LiN(CF ₃ SO ₂ ) ₂ are preferred.

The content of the electrolyte salt in the non-aqueous solvent is preferably greater than 2.5 M (mol/l), more preferably greater than 3.0 M, even more preferably greater than 5.0 M, still more preferably greater than 7.0 M, and most preferably greater than 10 M. is greater than M. The use of an electrolyte containing a higher concentration of an alkali metal salt makes it easier to form a cable-shaped cell that does not tend to leak during manufacture or during bending or twisting of the cable cell. Also surprisingly, the inventors observed that most electrolytes become non-flammable when the salt concentration exceeds 3.5 M. Some electrolytes become non-flammable at salt concentrations greater than 3.0 M or only greater than 2.5 M. Cell scientists and engineers would expect higher concentrations to mean higher viscosities and lower ion mobilities, and therefore lower alkali ion conductivities. We found that this trend generally corresponds to a salt concentration range of 0.01 M to 2.0 M. Quite unexpectedly, however, alkali ion conductivities (Li ⁺ , Na ⁺ , and K ⁺ ions) start to increase after the concentration increases to greater than a critical level (typically 2.1 to 3.0 M).

Ionic liquids are composed of only ions. An ionic liquid is a low-melting salt that is in a molten or liquid state above a certain temperature. For example, a salt is considered an ionic liquid if its melting point is less than 100 °C. If the melting point is below room temperature (25° C.), the salt is referred to as a room temperature ionic liquid (RTIL). IL salts are characterized by weak interactions due to the combination of large cations and charge-delocalizing anions. The result is a lower crystallization tendency due to flexibility (anion) and asymmetry (cation).

A common well-known ionic liquid is formed by the combination of 1-ethyl-3-methylimidazolium (EMI) cations and N , N -bis(trifluoromethane)sulfonamide (TFSI) anions. This combination provides a fluid with ionic conductivity comparable to many organic electrolyte solutions and low vapor pressure and low decomposition tendency up to about 300-400°C. This generally means low volatility and non-flammability, and therefore a much safer electrolyte for batteries.

Essentially, ionic liquids are composed of organic ions subjected to an essentially unlimited number of structural transformations due to the ease of manufacture of a wide variety of components. Thus, a wide variety 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. do. Based on composition, ionic liquids are basically divided into different classes including aprotic, protic and zwitterionic types, each of which is suitable for a particular application.

Common cations of room temperature ionic liquids (RTIL) are tetraalkylammonium, di-, tri-, and tetra-alkylimidazoliums, alkylpyridiniums, dialkylpyrrolidiniums, dialkylpiperidiniums, tetraalkylphosphoniums, and trialkylsulfonium, but is not limited thereto. Common anions of RTIL are BF ₄ ^- , B(CN) ₄ ^- , CH ₃ BF ₃ ^- , CH ₂ CHBF ₃ ^- , CF ₃ BF ₃ ^- , C ₂ F ₅ BF ₃ ^- , n -C ₃ F ₇ BF ₃ ^- , n -C ₄ F ₉ BF ₃ ^- , PF ₆ ^- , CF ₃ CO ₂ ^- , CF ₃ SO ₃ ^- , N(SO ₂ CF ₃ ) ₂ ^- , N(COCF ₃ )(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 ^{- ,} etc., but It is not limited. Relatively speaking, imidazolium-based or sulfonium-based cations and complex halide anions such as AlCl ₄ ^- , BF ₄ ^- , CF ₃ CO ₂ ^- , CF ₃ SO ₃ ^- , NTf ₂ ^- , N(SO ₂ F) ₂ ^- , or F(HF) _2.3 ⁻ to produce RTILs with good working conductivity.

RTILs have high intrinsic ionic conductivity, high thermal stability, low volatility, low (practically zero) vapor pressure, non-flammability, ability to remain liquid over a wide temperature range above and below room temperature, high polarity, high viscosity, and a wide range of electrical properties. It may have typical properties such as chemical windows. Aside from high viscosity, these properties are desirable when using RTIL as an electrolyte component (salt and/or solvent) in supercapacitors.

The cable-shaped cell of the present invention has many unique features, some of which are summarized as follows.

By definition, a cable shape means a shape having a length and diameter or thickness with an aspect ratio (ratio of length to diameter or length to thickness) greater than or equal to 10, preferably greater than or equal to 20. An alkali metal cell in the form of a cable may have a length greater than 1 m, or even greater than 100 m. The length can be as short as 1 μm, but is typically 10 μm to 10 m, more typically micrometers to several meters. In practice, there is no theoretical limit to the length of this type of cable battery.

The cable-shaped alkali metal battery of the present invention is very flexible and can be easily bent to have a radius of curvature greater than 10 cm. The battery may be bent to substantially conform to the shape of the vehicle's void or interior compartment. The void or interior compartment may be a trunk, a door, a hatch, a spare tire compartment, an area under a seat or an area under a dashboard. The battery is removable from the vehicle and can be bent to conform to the shape of other voids or interior compartments.

One or more units of the cable-shaped battery of the present invention may be used for clothing, belts, luggage straps, weapon straps, instrument straps, helmets, hats, boots, foot covers, gloves, wrist covers, watch bands, jewelry items, animal collars or animal harnesses. can be incorporated into

One or more units of the cable-shaped battery of the present invention may be used for clothing, belts, luggage straps, weapon straps, instrument straps, helmets, hats, boots, foot covers, gloves, wrist covers, watch bands, jewelry items, animal collars or animal harnesses. It can be detachably integrated into

Additionally, the battery of the present invention conforms to the inner radius of a hollow bicycle frame.

Hereinafter, examples of several different types of anode active materials, cathode active materials, and conductive porous layers (e.g., graphite foam, graphene foam, and metal foam) are provided to illustrate the best embodiment of the present invention. . These exemplary embodiments and other portions and drawings of this specification, individually or in combination, are sufficiently relevant to enable one skilled in the art to practice the present invention. However, these examples should not be construed as limiting the scope of the present invention.

Example 1 : Exemplary Example of an Electrically Conductive Porous Rod or Layer as a Current Collector

Various types of metal foams (acting as current collectors), carbon foams, and fine metal webs/screens, such as Ni foams, Cu foams, Al foams, for use as conductive porous rods or layers in anodes or cathodes; Ti foam, Ni mesh/web, stainless steel fiber mesh, and the like are commercially available. Metal-coated polymer foams and carbon foams are also used as current collectors. In producing a macroscopic shape adaptable cable-shaped flexible battery, the most preferred thickness range of such a conductive porous layer is 50 to 1000 μm, preferably 100 to 800 μm, more preferably 200 to 600 μm. In manufacturing a microscopic cable-shaped battery (eg, having a diameter of 100 nm to 100 μm), graphene foam, graphene airgel foam, porous carbon fiber (eg, For example, produced by electrospinning of polymer fibers, carbonization of polymer fibers, and activation of the resulting carbon fibers), and porous graphite fibers may be used.

Example 2 : Ni foam and CVD graphene foam-based porous layer supported on a Ni foam mold

Methods for preparing CVD graphene foams are described in publications [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 nickel scaffolds, was chosen as a template for the growth of graphene foams. Briefly, carbon was introduced into the nickel foam by decomposing CH ₄ at 1,000° C. under atmospheric 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, ripples and wrinkles were formed on the graphene film. The four types of foams prepared in this example, namely Ni foams, CVD graphene-coated Ni foams, CVD graphene foams (Ni is etched away), and CVD graphene foams bonded with conductive polymers, were used as lithium batteries of the present invention. was used as a collector in

To recover (separate) the graphene foam from the supporting Ni foam, the Ni frame was etched away. In the method proposed by Chen et al., prior to etching away the nickel framework with a high-temperature HCl (or FeCl ₃ ) solution, poly(methyl metamethoxide) was applied to the surface of a graphene film as a support to prevent the graphene network from collapsing during nickel etching. acrylate) (PMMA) was deposited. After carefully removing the PMMA layer with hot acetone, brittle graphene foam samples were obtained. The use of a PMMA support layer was considered important for fabricating free-standing films of graphene foams. Instead, graphene was bonded to each other using a conductive polymer as a binder resin while Ni was etched away. The thickness range of the graphene foam or Ni foam was 35 μm to 600 μm.

The layer of Ni foam or CVD graphene foam as used herein is intended as a conductive porous layer (CPL) to contain the components for the anode or cathode or both (anode or cathode active material + optional conductive additives + liquid electrolyte). For example, Si nanoparticles dispersed in an organic liquid electrolyte (eg, 1 to 5.5 M LiPF ₆ dissolved in PC-EC) are made into a gel-like material, and the porous material of Ni foam continuously supplied from a supply roller. The anode electrode roller was prepared by transferring to a surface (as shown in schematic A in FIG. 1C).

Graphene-supported LFP nanoparticles dispersed in the same liquid electrolyte were made into a cathode slurry, which was sprayed onto two porous surfaces of a continuous Ni foam layer to form a cathode electrode. A porous foam rod (first electrode) containing a Si nanoparticle-electrolyte mixture impregnated in foam pores was surrounded by a porous separator layer (porous PE-PP copolymer), which was in turn surrounded by an LFP-based cathode layer. Subsequently, a cable-shaped lithium-ion battery was obtained by wrapping the cylindrical structure with a thin polymer shell.

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 final desired foam shape. Mitsubishi ARA-24 mesophase pitch was used. After evacuating the sample to less than 1 torr, it was heated to a temperature of about 300°C. At this point, the vacuum was broken with a nitrogen blanket and then a pressure of up to 1,000 psi was applied. Then, the temperature of the system was raised to 800 °C. This was done at a rate of 2°C/min. After holding the temperature for at least 15 minutes to achieve a soak, the furnace was turned off and cooled to room temperature at a rate of about 1.5° C./min while releasing the 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 standby. The foam was then heat treated (carbonized) at 1050° C. under a nitrogen blanket and then separately heat treated (graphitized) at 2500° C. and 2800° C. under argon in a graphite crucible. Graphite foam layers are available in a thickness range of 75 to 500 μm.

Example 4 : Preparation of graphene oxide (GO) and reduced graphene oxide (RGO) nanosheets from natural graphite powder

Natural graphite from Huadong Graphite Co. (Qingdao, China) was used as a starting material. GO was obtained according to the well-known modified Hummers method involving two oxidation steps. In the general procedure, the first oxidation was achieved under the following conditions: 1100 mg of graphite was placed in a 1000 ml boiling flask. Then, 20 g of K ₂ S ₂ O ₈ , 20 g of P ₂ O ₅ , and 400 mL of a concentrated aqueous solution of H ₂ SO ₄ (96%) were added to the flask. The mixture was heated under reflux for 6 hours and then left undisturbed for 20 hours at room temperature. The oxidized graphite was filtered off and washed with plenty of distilled water until neutral pH. At the end of this first oxidation a wet cake-like material was recovered.

For the second oxidation step, the previously recovered wet cake was placed in a boiling flask containing 69 mL of a concentrated aqueous solution of H ₂ SO ₄ (96%). The flask was placed in an ice bath while 9 g of KMnO ₄ was slowly added. Care was taken to prevent overheating. The resulting mixture was stirred at 35° C. for 2 hours (sample color turned dark green), then 140 mL of water was added. After 15 minutes, the reaction was stopped by adding 420 mL of water and 15 mL of an aqueous solution of 30 wt % H ₂ O ₂ . At this stage, the color of the sample changed to bright yellow. To remove metal ions, the mixture was filtered and washed with 1:10 HCl aqueous solution. The recovered material was gently centrifuged at 2700 g and washed with deionized water. The final product was a wet cake containing 1.4 wt% of GO, as estimated from the dry extract. The wet cake material was then gently sonicated to obtain a liquid dispersion of the GO platelets, which was diluted in deionized water.

Surfactant-stabilized RGO (RGO-BS) was obtained by diluting the wet cake in an aqueous solution of surfactant instead of pure water. A commercially available mixture of sodium cholate (50 wt%) and sodium deoxycholate (50 wt%) salts provided by Sigma Aldrich was used. The weight fraction of surfactant was 0.5 wt%. This fraction was kept constant in all samples. Sonication was performed using a Branson Sonifier S-250A operating at a frequency of 20 kHz equipped with a 13 mm step disruptor horn and a 3 mm tapered microtip. For example, 10 mL of an aqueous solution containing 0.1 wt% of GO was sonicated for 10 min, followed by centrifugation at 2700 g for 30 min to remove undissolved large particles, aggregates, and impurities. The obtained GO was chemically reduced to obtain RGO by a method comprising adding 10 mL of 0.1 wt% GO aqueous solution to a 50 mL boiling flask. Then, 10 μL of a 35 wt % aqueous solution of N ₂ H ₄ (hydrazine) and 70 mL of a 28 wt % aqueous solution of NH ₄ OH (ammonia) were added to the mixture, which was stabilized by a surfactant. The solution was heated to 90° C. and refluxed for 1 hour. The pH value measured after the reaction was about 9. During the reduction reaction, the color of the sample changed to dark black.

RGO was used as a conductive additive in the anode active material and/or cathode active material of certain lithium batteries of the present invention. Pre-lithiated RGO (e.g., RGO + lithium particles, or RGO pre-deposited with a lithium coating) was also used as an anode active material, which was mixed with a liquid electrolyte to form a wet anode active material for use in selected Li-ion cells. A mixture was formed. Wet cathode active material mixtures were prepared by dispersing selected cathode active materials (TiS ₂ nanoparticles and LiCoO ₂ particles, respectively) and unlithiated RGO sheets in a liquid electrolyte. The wet anode active mixture and cathode active mixture were separately delivered to the surface of the graphite foam for forming the anode layer and cathode layer, respectively. Subsequently, a cable-shaped battery was fabricated in which the core structure (first electrode) was an anode or cathode and the second electrode was a corresponding counter electrode (cathode or anode).

For comparison, a conventional electrode was prepared by performing a slurry coating and drying procedure. Then, the electrodes and the separator disposed between the two dried electrodes were assembled, placed in an Al-plastic laminate packaging enclosure, and then liquid electrolyte was injected to form a conventional lithium battery cell.

Example 5 : Preparation of pure graphene sheet (0% oxygen)

Recognizing the possibility of a large number of defects in the GO sheet that act to reduce the conductivity of the individual graphene facets, and recognizing the possibility of a pure (non-oxidized, oxygen-free, non-halogenated, halogen-free, etc.) graphene sheet It was decided to investigate whether using can lead to conductive additives with high electrical and thermal conductivity. Pre-lithiated pristine graphene and pre-sodium pristine graphene were also used as anode active materials for lithium-ion batteries and sodium-ion batteries, respectively. Pure graphene sheets were prepared using direct sonication or liquid-phase preparation processes.

In a general procedure, 5 g of graphite flakes ground to a size of about 20 μm or less were dispersed in 1,000 mL of deionized water (containing 0.1% by weight dispersant (Zonyl® FSO from DuPont)) to obtain a suspension. The graphene sheets were exfoliated, separated, and size reduced using an ultrasonic energy level of 85 W (Branson S450 sonicator) for 15 minutes to 2 hours. The resulting graphene sheets are pristine graphene that has never been oxidized, does not contain oxygen, and is relatively defect-free. Pure graphene contains essentially no non-carbon elements.

Then, using both the method of the present invention and the conventional methods of slurry coating, drying, and layer lamination, the pristine graphene sheet as a conductive additive was incorporated into the cell along with an anode active material (or cathode active material in the case of a cathode). Both lithium-ion cells and lithium metal cells (impregnated cathode only) were investigated. Sodium-ion cells were also fabricated and studied.

Example 6 : Lithium Iron Phosphate (LFP) Cathode of Lithium Metal Battery

Uncoated or carbon-coated LFP powders are commercially available from several sources. The LFP powders were pressed together and sintered to prepare an LFP target for sputtering. Sputtering of LFP was performed separately on the graphene film and carbon nanofiber (CNF) mat. Then, the LFP-coated graphene film was broken and pulverized to form an LFP-coated graphene sheet.

Subsequently, both the carbon-coated LFP powder and the graphene-supported LFP were individually and together with a liquid electrolyte, using both the inventive method of making a cable-like structure and the conventional method of slurry coating, drying and layer lamination, integrated into.

Example 7 : Preparation of disodium terephthalate (Na ₂ C ₈ H ₄ O ₄ ) as anode active material of sodium-ion battery

Pure disodium terephthalate was obtained by the recrystallization method. After preparing an aqueous solution by adding terephthalic acid to an aqueous NaOH solution, ethanol (EtOH) was added to the mixture to precipitate disodium terephthalate in the water/EtOH mixture. Because of resonance stabilization, terephthalic acid has a relatively low pKa value, which facilitates deprotonation by NaOH to give disodium terephthalate (Na ₂ TP) via acid-base chemistry. In the general 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 was decanted. The precipitate was redispersed in EtOH and centrifuged again. This process was repeated twice to obtain a white solid. The product was dried under vacuum at 150° C. for 1 hour. As a separate sample, graphene-supported disodium terephthalate sheets were prepared by adding GO to aqueous NaOH solution (5 wt% GO sheets) under similar reaction conditions.

Subsequently, both the carbon-disodium terephthalate mixture powder and the graphene-supported disodium terephthalate were individually, each together with a liquid electrolyte, using both the method of the present invention and the conventional methods of slurry coating, drying, and layer lamination. integrated into the battery.

Example 8 : V ₂ O ₅ as an Example of Transition Metal Oxide Cathode Active Material for Lithium Battery

Only V ₂ O ₅ powder is commercially available. For the preparation of graphene-supported V ₂ O ₅ powder samples, in a typical experiment, V ₂ O ₅ was mixed with an aqueous LiCl solution to obtain a vanadium pentoxide gel. The Li ⁺ -exchanged gel obtained by interaction with LiCl solution (li:V molar ratio maintained at 1:1) was mixed with the GO suspension, then placed in a Teflon-lined stainless steel 35 ml autoclave, sealed, and 12 It was heated to 180 °C for an hour. After this hydrothermal treatment, the raw solid was recovered, washed thoroughly, sonicated for 2 min, dried at 70 °C for 12 h, mixed with another 0.1% GO in water, and sonicated to break down to nanobelt size. and then spray-dried at 200° C. to obtain graphene-containing composite fine particles.

Then, using both the method of the present invention and the conventional methods of slurry coating, drying and layer laminating, V ₂ O ₅ powder (containing carbon black powder as conductive additive) and graphene-supported V ₂ O ₅ powder were prepared. All individually and together with the liquid electrolyte were incorporated into the cell.

Example 9 : LiCoO ₂ as an example of a lithium transition metal oxide cathode active material for a lithium-ion battery

Commercially available LiCoO ₂ powder and carbon black powder were dispersed in a liquid electrolyte to form a cathode active material mixture, which was impregnated into a Ni foam-based cathode current collector layer to form a cathode electrode. A graphite particle-liquid electrolyte (i.e., anode active mixture) was impregnated into the pores of the Cu foam layer to form an anode electrode. In addition, a mixture of graphene-containing Si nanoparticles and a liquid electrolyte was impregnated into the pores of the Cu foam to obtain an anode electrode. An anode electrode, a porous separator layer, and a cathode electrode were assembled, compressed, and placed in a plastic-Al enclosure to form a battery cell. The cell was then hermetically sealed.

Separately, LiCoO ₂ powder, carbon black powder, and a PVDF resin binder were dispersed in an NMP solvent to form a slurry, which was coated on both sides of an Al foil current collector and then dried under vacuum to form a cathode layer. Graphite particles and a PVDF resin binder were dispersed in an NMP solvent to form a slurry, which was coated on both sides of a Cu foil current collector and then dried under vacuum to form an anode layer. Subsequently, the anode layer, the separator, and the cathode layer were laminated and placed in an Al-plastic housing, and a liquid electrolyte was injected to form a conventional lithium-ion battery.

Example 10 : Cathode Active Material Based on Mixed Transition Metal Oxide

As examples, for the synthesis of Na _1.0 Li _0.2 Ni _0.25 Mn _0.75 O _δ , Ni _0.25 Mn _0.75 CO ₃ , or Ni _0.25 Mn _0.75 (OH) ₂ cathode active materials, Na ₂ CO ₃ , and Li ₂ CO ₃ are used as starting compounds. was used as Materials in appropriate molar ratios were pulverized together, 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.

For electrode fabrication using a conventional method, a sheet of aluminum foil was coated with an N-methylpyrrolidinone (NMP) slurry of the cathode mixture. The electrode mixture was composed 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 and then dynamized vacuum dried at 80° C. for at least 6 hours. Sodium metal foil was cut, rolled and punched from a sodium block (Aldrich, 99%) that had been cleaned of all oil with hexane. To prepare the slurry of the present invention, NMP was replaced with a liquid electrolyte (propylene carbonate with 1 M NaClO ₄ ). This slurry was directly impregnated into the pores of the cathode current collector.

Then, Na _1.0 Li _0.2 Ni _0.25 Mn _0.75 O _δ powder (containing carbon black powder as conductive additive) and graphene-supported The Na _1.0 Li _0.2 Ni _0.25 Mn _0.75 O _δ powders were all individually and incorporated into the cell together with the liquid electrolyte.

The electrolyte was propylene carbonate with 1 M NaClO ₄ electrolyte salt (Aldrich, 99%). The pouch cell was constant current cycled (15 mA/g) with a cutoff of 4.2 V versus Na/Na ⁺ and then discharged at various current rates to a cutoff voltage of 2.0 V.

In all battery cells manufactured, the charge storage capacity was measured periodically and reported as a function of cycle number. Specific discharge capacity, as referred to herein, is the total charge inserted into the cathode during discharge per unit mass of the composite cathode (including the combined weight of the cathode active material, conductive additives or supports, binders, and any optional additives, but excluding the current collector). Specific charge capacity means the amount of charge per unit mass of the composite cathode. The specific energy and specific power values presented in this section are based on whole cell weight for all pouch cells. After a desired number of repeated charging and recharging cycles, morphological or microstructural changes of selected samples were observed using both transmission electron microscopy (TEM) and scanning electron microscopy (SEM).

Example 11 : Na ₃ V ₂ (PO ₄ ) ₃ /C and Na ₃ V ₂ (PO ₄ ) ₃ /graphene cathode

Na ₃ V ₂ (PO ₄ ) ₃ /C samples were synthesized by solid phase reaction according to the following procedure: NaH ₂ PO ₄ 2H ₂ O (99.9%, Alpha) and V ₂ O ₃ (99.9%, Alpha) powders. A stoichiometric mixture of was put into an agate bottle as a precursor, then the precursor was ball milled in a planetary ball mill at 400 rpm for 8 hours in a stainless steel vessel. During the ball mill, for carbon coated samples, sugar (99.9%, Alpha) was also added as carbon precursor and reducing agent (this prevents oxidation of V ³⁺ ). After ball milling, the mixture was compressed into pellets and then heated at 900° C. for 24 hours under an Ar atmosphere. Separately, a Na ₃ V ₂ (PO ₄ ) ₃ /graphene cathode was prepared in a similar manner (but replacing the sugar with graphene oxide).

This cathode active material was used in several Na metal cells containing 1–7.5 M NaPF ₆ salt in PC+DOL as electrolyte. Na metal cells were prepared according to both the conventional NMP slurry coating process and the method of the present invention.

Example 12 : Organic Material as Cathode Active Material of Lithium Metal Battery (Li ₂ C ₆ O ₆ )

To synthesize dilithium rhodizonate (Li ₂ C ₆ O ₆ ), rhodizonate dihydrate (species 1 in the reaction scheme below) was used as a precursor. A basic lithium salt, Li ₂ CO ₃ , in an aqueous medium can be used to neutralize both functions of endoacid. Accurate stoichiometric amounts of both reactants rhodizoic acid and lithium carbonate were reacted for 10 hours to achieve a yield of 90%. Dilithium rhodizonate (species 2) was readily soluble even in small amounts of water, indicating the presence of water molecules in species 2. Water was removed under vacuum at 180° C. for 3 h to give the anhydrous form (species 3).

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

It can be noted 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 reversible lithium ion storage and release. This means that lithium ions must be provided from the anode side. Therefore, there must be a lithium source (eg, lithium metal or lithium metal alloy) in the anode. An anode current collector (graphene aerosol form rod) is deposited with a layer of lithium (eg via sputtering or electrochemical plating). This may be done prior to assembling the lithium coating layer (or simply lithium rod), porous separator, and impregnated cathode layer into the casing enclosure. For comparison, a corresponding conventional Li metal cell was also fabricated by conventional methods of slurry coating, drying, laminating, packaging, and electrolyte injection.

Example 13 : Organic Material (Na ₂ C ₆ O ₆ ) as Cathode Active Material of Sodium Metal Battery

To synthesize disodium rhodizonic acid (Na ₂ C ₆ O ₆ ), rhodizonic acid dihydrate (species 1 in the reaction scheme below) was used as a precursor. A basic sodium salt, Na ₂ CO ₃ , in an aqueous medium can be used to neutralize both functions of endioic acid. Accurate stoichiometric amounts of both reactants rhodizoic acid and sodium carbonate were reacted for 10 hours to achieve a yield of 80%. Disodium rhodizonate (species 2) was readily soluble even in small amounts of water, indicating the presence of water molecules in species 2. Water was removed under vacuum at 180° C. for 3 h to give the anhydrous form (species 3).

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

The two Na atoms in the formula Na ₂ C ₆ O ₆ are part of the fixed structure and do not participate in the reversible lithium ion storage and release. Sodium ions must be provided from the anode side. Therefore, there must be a sodium source (eg sodium metal or sodium metal alloy) at the anode. The anode current collector (carbon foam rod or thin Cu wire) is deposited with a layer of sodium (eg via electrochemical plating). This can be done prior to assembling the sodium coating layer or simply the sodium rod, porous separator, and cathode active material/electrolyte-impregnated foam into the cable. The pores of the cathode current collector were previously impregnated with a suspension of the 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 methods of slurry coating, drying, laminating, packaging, and electrolyte injection.

Example 14 : Metal Naphthalocyanine-RGO Hybrid Cathode of Lithium Metal Battery

CuPc-coated graphene sheets were obtained by vaporizing CuPc in a chamber together with a graphene film (5 nm) prepared from spin-coating of an RGO-water suspension. The resulting coating film was cut and milled to prepare a CuPc-coated graphene sheet, which was used as a cathode active material for a lithium metal battery. This cell has a lithium metal rod as the anode active material and 1-3.7 M LiClO ₄ in propylene carbonate (PC) as the electrolyte.

Example 15 : Preparation of MoS ₂ /RGO Hybrid Material as Cathode Active Material for Lithium Metal Battery

In this example, various inorganic materials were investigated. For example, ultra-thin MoS ₂ was obtained by single-step solvothermal synthesis of (NH ₄ ) ₂ MoS ₄ and hydrazine at 200 °C in a N , N -dimethylformamide (DMF) solution of oxidized graphene oxide (GO). /RGO hybrid was synthesized. In a general procedure, 22 mg of (NH ₄ ) ₂ MoS ₄ was added to 10 mg of GO dispersed in 10 ml of DMF. The mixture was sonicated for about 10 minutes at room temperature until a clear and homogeneous solution was obtained. Then, 0.1 ml of N ₂ H ₄ .H ₂ O was added. The reaction solution was further sonicated for 30 minutes before being transferred to a 40 mL Teflon-lined autoclave. The system was heated in an oven at 200° C. for 10 hours. The product was recovered by centrifugation at 8000 rpm for 5 minutes, washed with deionized water and recovered again 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 a liquid electrolyte to prepare an active cathode mixture slurry for impregnation.

Example 16 : Preparation of two-dimensional (2D) layered Bi ₂ Se ₃ chalcogenide nanoribbons

(2D) Preparation of layered Bi ₂ Se ₃ chalcogenide nanoribbons is well known in the art. For example, Bi ₂ Se ₃ nanoribbons were grown using a vapor-liquid-solid (VLS) method. On average, the nanoribbons prepared herein have a thickness of 30 to 55 nm and a width and length ranging from hundreds of nanometers to several micrometers. The larger nanoribbons were ball milled to reduce the transverse dimensions (length and width) to less than 200 nm. The nanoribbons prepared by this method (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 MnO ₂ cathode active material

MnO ₂ powder was 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 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 a 0.1 mol/L KMnO ₄ solution and a selected amount of GO solution were added to this solution and sonicated for 30 minutes to produce 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 mixed with a liquid electrolyte to form a cathode active material mixture slurry.

Example 18 : Graphene-reinforced nano-silicon fabricated from TEOS as an anode active material for lithium-ion batteries

In the experiment, 1 wt% of N002-PS (GO-water suspension) was diluted to 0.2 wt% of N002-PS by deionized water. The diluted PS solution was placed in an ultrasonic cleaner and sonicated for 30 minutes. Thereafter, TEOS (0.2 wt% N002-PS : TEOS = 5:2) was slowly added to the solution while stirring the PS solution. Stirring was then maintained for 24 hours to obtain complete hydrolysis of TEOS. Then, 10% NH ₃ •H ₂ O was added dropwise to the solution until it reached a gel state (herein referred to as TP gel). The TP gel was ground into small particles and oven dried at 120°C for 2 hours and 150°C for 4 hours. Dried TP particles were mixed with Mg in a ratio of 10:7. Twenty times as many 7 mm SS balls were added to the milling chamber and the samples were ball milled under argon protection. The rotational speed was gradually increased to 250 rpm. A TPM powder sample was placed in a nickel crucible and heat treated at 680 °C. A small amount of 2 M HCl solution was also prepared. Then, the heat-treated TPM powder was slowly added to the acidic solution. After maintaining the reaction for 2 to 24 hours, the turbid liquid was put into an ultrasonic cleaner and sonicated for 1 hour. The suspension was poured into a filtration system and large particles at the bottom were discarded. The sample was washed 3 times with deionized water. The resulting yellow paste was dried and ground into a powder using a blender. As-prepared nanoparticle samples exhibit specific surface area (SSA) values ranging from 30 m ² /g to 200 m ² /g due to different graphene contents.

Subsequently, the dried TPM particle sample was placed in a muffle furnace and calcined at 400° C. to 600° C. for 2 hours under air purging to remove the carbon content from the nanocomposite, thereby preparing graphene-free yellow silicon nanopowder. Both Si nanopowder and graphene-encased Si nanoparticles were used as high-capacity anode active materials.

Example 19 Cobalt Oxide (Co ₃ O ₄ ) Fine Particles as Anode Active Material

Since the electrochemical potential of LiCoO ₂ is about +4.0 volts versus Li/Li ⁺ and that of Co ₃ O ₄ is about +0.8 volts versus Li/Li ⁺ , LiCoO ₂ is a cathode active material, but Co ₃ O ₄ is an anode active material of a lithium-ion battery.

An appropriate amount of the inorganic salt Co(NO ₃ ) ₂ 6H ₂ O and then an ammonia solution (NH ₃ .H ₂ O, 25 wt%) were slowly added to the GO suspension. The resulting precursor suspension was stirred under a flow of argon for several hours to ensure complete reaction. The obtained Co(OH) ₂ /graphene precursor suspension was divided into two parts. One portion was filtered and dried under vacuum at 70° C. to obtain a Co(OH) ₂ /graphene composite precursor. This precursor was calcined at 450° C. in air for 2 hours to form a layered Co ₃ O ₄ /graphene composite characterized by having Co ₃ O ₄ -coated graphene sheets overlapping each other. These Co ₃ O ₄ -coated graphene sheets are another high capacity anode active material.

Example 20 : Graphene-reinforced tin oxide fine particles as anode active material

Tin oxide (SnO ₂ ) nanoparticles as the anode active material were obtained by controlled hydrolysis of SnCl ₄ 5H ₂ O with NaOH using the following procedure: SnCl ₄ 5H ₂ O (0.95 g, 2.7 m-mol) and NaOH (0.212 g, 5.3 m-mol) was each dissolved in 50 mL of distilled water. The NaOH solution was added dropwise to the tin chloride solution at a rate of 1 mL/min under vigorous stirring. The solution was homogenized by sonicating for 5 minutes. Then, the resulting hydrosol was reacted with the GO dispersion for 3 hours. A few drops of 0.1 MH ₂ SO ₄ were added to the mixed solution to agglomerate the product. The precipitated solid was collected by centrifugation, washed with water and ethanol, and dried in vacuo. The dried product was heat treated at 400° C. for 2 hours under an Ar atmosphere.

Example 21 : Preparation of graphene-supported MnO ₂ and NaMnO ₂ cathode active materials

MnO ₂ powder was 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 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 a 0.1 mol/L KMnO ₄ solution and a selected amount of GO solution were added to this solution and sonicated for 30 minutes to produce 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 pores of a foam current collector.

In addition, NaMnO ₂ and NaMnO 2 /graphene composites were synthesized by ball milling a mixture of Na ₂ CO ₃ and MnO ₂ (molar ratio of 1:2) with or without graphene sheets _for 12 hours, and then at 870 It was heated at °C for 10 hours.

Example 22: Preparation of Electrode for Potassium Metal Cell

A layer of PVDF-bonded reduced graphene oxide (RGO) sheet supplied by Angstron Materials, Inc. (Dayton, Ohio) was used as the cathode active material, while a sheet of potassium-coated graphene film was used as the anode 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 obtained at different current densities (50 mA/g to 50 A/g) corresponding to different discharge 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, alkali metal-ion cells or alkali metal cells were fabricated using both the present and conventional methods.

In a conventional method, a typical anode composition contains 85 wt % active material (eg, Si- or Co ₃ O ₄ -coated graphene sheet) dissolved in N-methyl-2-pyrrolidinone (NMP), 7 wt% acetylene black (Super-P), and 8 wt% polyvinylidene fluoride binder (PVDF, 5 wt% solids content). After coating the slurry on the Cu foil, the electrode was dried at 120° C. for 2 hours under vacuum to remove the solvent. In the present invention, generally no binder resin is required or used, saving 8% by weight (reduced amount of inactive material). A cathode layer was prepared in a similar manner (using an Al foil as a cathode current collector) using a conventional slurry coating and drying method. The anode layer, separator layer (eg Celgard 2400 membrane), and cathode layer are then laminated together and housed within a plastic-Al enclosure. Then, a 1M LiPF ₆ electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1:1 v/v) is injected into the cell. In some cells, ionic liquids have been used as liquid electrolytes. Cell assemblies were prepared in an argon-filled glove box.

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

In the lithium-ion battery industry, it is common to define the cycle life of a battery as the number of charge/discharge cycles that result in a 20% reduction in capacity in the battery from its initial capacity when measured after the required electrochemical formation.

Example 24 : Representative test results for lithium cells

For each sample, by applying different current densities (representing the charge/discharge rate) and measuring the electrochemical response, it was possible to calculate the energy density and power density values required to construct a Ragon diagram (power density versus energy density). 5 shows a Ragone plot (weight and volumetric power density versus energy density) of a lithium-ion battery cell containing graphite particles as anode active material and carbon-coated LFP particles as cathode active material. Two of the four data curves are for cable-shaped cells made according to embodiments of the present invention and the other two are for conventional cells made by conventional electrode slurry coating (roll-coating). Several important observations can be made from these data:

Both the gravimetric and volumetric energy densities and power densities (indicated by "invention" in the figure legends) of the lithium-ion battery cells produced by the method of the present invention are comparable to those of their counterparts produced through the conventional roll-coating method. Much higher than gravimetric and volumetric energy densities and power densities (labeled "conventional"). An anode thickness of 160 μm (coated on a flat solid Cu foil) turns into a foam rod with a diameter of 160 μm (all accommodated in the pores of Ni foam with 85% porosity), at the cathode to maintain an equilibrium capacity ratio. Due to the corresponding change, the gravimetric energy density increases from 165 Wh/kg to 282 Wh/kg. Even more surprisingly, the volumetric energy density increases from 412.5 Wh/L to 733 Wh/L. This latter value of 733 Wh/L has never been previously achieved with a Li-ion cell using a graphite anode and a lithium iron phosphate cathode.

This significant difference cannot be attributed simply to an increase in electrode thickness and mass supply. This difference is due to the much higher active material mass feed (not just the mass feed) associated with the cable cell of the present invention, the reduced overhead (inactive) component ratio to active material weight/volume, the lack of binder resin, and the surprising properties of the electrode active material. better utilization rate (most if not all of the graphite particles and LFP particles contribute to the lithium ion storage capacity; no dry pockets or inefficiencies in the electrode, especially at high charge/discharge rate conditions); and porous conductive layers (foam current collectors). ) appear to be due to the surprising ability of the inventive method to more effectively pack the active material particles into the pores of the . These are not taught, suggested, or even implied in the slightest in the field of lithium-ion batteries. Also, the maximum power density increases from 621 W/kg to 1356 W/kg. This may be due to the significantly reduced internal resistance to electron transport and lithium ion transport.

6 shows the Ragone plots (both gravimetric and volumetric power densities versus gravimetric and volumetric energy densities) of two cells containing graphene-containing Si nanoparticles as anode active material and LiCoO ₂ nanoparticles as cathode active material. Experimental data were obtained from Li-ion battery cells (cable shape) prepared by the method of the present invention and Li-ion battery cells prepared by conventional electrode slurry coating.

These data indicate that both the gravimetric and volumetric energy densities and power densities of battery cells produced by the methods of the present invention are significantly higher than those of their counterparts manufactured via conventional methods. Also, the difference is very large. Conventionally prepared cells exhibit gravimetric energy densities of 265 Wh/kg and volumetric energy densities of 689 Wh/L, whereas the cells of the present invention deliver 423 Wh/kg and 1,227 Wh/L, respectively. A cell-level energy density of 1,227 Wh/L has never before been achieved with any rechargeable lithium battery. Power densities as high as 2213 W/kg and 6,417 W/L are also unprecedented for Li-ion batteries. The power density of a cell made through the process of the present invention is always much higher than that of a corresponding cell made by a conventional process.

These energy density and power density differences are primarily due to the high active material mass feed (>25 mg/cm ² at the anode and >45 mg/cm ² at the cathode) associated with the cell of the present invention, and the reduced overhead relative to active material weight/volume. (inactive) component proportions, not having a binder resin, the ability of the present invention to better utilize active material particles (all particles are accessible to liquid electrolytes and have fast ionic and electron movements), and a foam current collector This is due to the ability to pack the active material particles more effectively within the pores of the

7 is a Ragon diagram of a lithium metal battery containing lithium foil as an anode active material, dilithium rhodizonate (Li ₂ C ₆ O ₆ ) as a cathode active material, and lithium salt (LiPF ₆ )-PC/DEC as an organic liquid electrolyte. indicate Data are for both lithium metal cells prepared by the inventive method and conventional electrode slurry coating. These data indicate that both the gravimetric and volumetric energy densities and power densities of the lithium metal cells produced by the methods of the present invention are significantly higher than those of their counterparts manufactured via conventional methods. Also, this difference is very large, and the need to have a much higher active material mass feed (not just mass feed), reduced overhead (inactive) component ratio relative to active material weight/volume, and binder resins associated with the cell of the present invention. surprisingly better utilization of the electrode active material (most, if not all, of the active material contributes to the lithium ion storage capacity; there are no dry pockets or inefficiencies in the electrode, especially under high charge/discharge rate conditions); This appears to be due to the surprising ability of the present method to more effectively pack the active material particles within the pores.

The observation that the gravimetric energy density of the lithium metal-organic cathode cell of the present invention is as high as 503 Wh/kg, which is higher than that of all rechargeable lithium-metal or lithium-ion cells reported to date, is quite remarkable and unexpected (currently of Li-ion cells store 150-220 Wh/kg based on total cell weight). Furthermore, it is quite surprising to observe that the volumetric energy density of this organic cathode-based cell is as high as 1006 Wh/L, which is the highest value among all lithium-ion and lithium metal cells reported so far. In addition, in the case of a lithium battery based on an organic cathode active material, a gravimetric power density of 1,753 W/kg and a maximum volumetric power density of 5,080 W/L would have been unthinkable.

It is important to point out that reporting energy and power densities per weight of active material alone in a Lagon diagram, as reported by many researchers, may not provide a realistic picture of the performance of an assembled supercapacitor cell. The weight of other device components must also be considered. These overhead components, including current collectors, electrolytes, separators, binders, connectors and packaging are inert materials and do not contribute to charge storage. They only add weight and volume to the device. Therefore, it is desirable to reduce the relative proportion of overhead component weight and increase the active material proportion. However, it has been impossible to achieve this goal using conventional cell manufacturing processes. The present invention overcomes this long-standing and most serious problem in the field of lithium batteries.

In a commercial lithium-ion battery with an electrode thickness of 100-200 μm, the weight proportion of the anode active material (eg graphite or carbon) in the lithium-ion battery is typically 12% to 17%, and the weight proportion of the cathode active material Silver is 22% to 41% (for inorganic materials such as LiMn ₂ O ₄ ) or 10% to 15% for organic or polymeric materials. Thus, a factor of 3 to 4 is often used to extrapolate the energy or power density of a device (cell) from characteristics based on active material weight alone. In most scientific papers, reported properties are usually based on active material weight only and electrodes are typically very thin (<< 100 μm, most << 50 μm). The active material weight is typically 5% to 10% of the total device weight, which can be obtained by dividing the actual cell (device) energy or power density by a factor of 10 to 20 based on the corresponding active material weight. means Considering these coefficients, the properties reported in these papers do not actually look any better than those of commercial cells. Therefore, extreme caution should be exercised when reading and interpreting cell performance data reported in scientific papers and patent applications.

Example 25 : Achievable Electrode Diameter or Thickness and Effect of Electrode Diameter or Thickness on Electrochemical Performance of Lithium Battery Cells

It is easy to think of the electrode thickness of a lithium battery as a design parameter that can be freely adjusted to optimize device performance. Contrary to this perception, in practice, the thickness of lithium battery electrodes is limited in terms of manufacturing, and it is not possible to manufacture electrodes with excellent structural integrity beyond a certain thickness level in an actual industrial manufacturing environment (eg, roll-to-roll slurry coating facility). There is no Conventional cell electrode designs are based on coating electrode layers on flat metal current collectors, which have several major problems: (a) thick coatings on solid Cu foils or Al foils require long drying times; (requires a heated zone 30 to 100 meters long). (b) Thick electrodes tend to delaminate or crack upon drying and subsequent handling, and even with resin binder percentages as high as 15-20% to improve electrode integrity, this remains a major limiting factor. Therefore, these industrial sites of roll-coating slurries onto flat solid current collectors do not allow for high active material mass feeds. (c) Thick electrodes produced by coating, drying and pressing make it difficult for electrolyte (which is injected into the cell after cell fabrication) to penetrate through the electrode; therefore, thick electrodes form dry pockets or dry pockets that are not wetted by the electrolyte. This means that there are many branches. This means that the utilization rate of the active material is poor. The present invention solves this long-standing and very important problem associated with lithium batteries.

Figure 8 shows the cell-level gravimetric energy density (Wh/kg) and volumetric energy density (Wh/L) of a lithium metal cell manufactured by a conventional method and a lithium metal cell manufactured by the method of the present invention without peeling and cracking. Plotted over a range of achievable cathode thicknesses for MnO ₂ /RGO cathodes.

Electrodes can be fabricated up to a thickness of 100-200 μm using a conventional slurry coating process. In contrast, however, there is no theoretical limit to the electrode thickness or diameter that can be achieved with the method of the present invention. Typically, the actual electrode thickness is between 1 μm and 1000 μm, more typically between 10 μm and 800 μm, and most typically between 100 μm and 600 μm.

These data further confirm the surprising efficiency of the present method in making previously unattainable very thick lithium battery electrodes. In lithium metal cells these very thick electrodes are typically much greater than 25 mg/cm ² (more typically greater than 30 mg/cm 2 , more typically greater than 40 mg/cm ² , often greater than 40 mg/cm ² for inorganic cathode active materials). This leads to very high cathode active material mass feeds (>50 mg/cm ² , even >60 mg/cm ² ). Such a high active material mass feed rate could not be obtained with conventional lithium batteries manufactured by a slurry coating process. This high active material mass feed provides very high gravimetric and volumetric energy densities (e.g., 503 Wh/kg and 956 Wh/L for the lithium metal cell of the present invention) that have not been otherwise achieved before when considering the same battery system. brought

Example 26 : Weight percentage of active material achievable in a cell and effect of weight percentage of active material on the electrochemical performance of a lithium battery cell

Since the combined weight of the anode active material and the cathode active material accounts for up to about 30% to 50% of the total mass of a commercially packaged lithium battery, in order to extrapolate the energy density or power density of the device from the performance data of the active material alone, A factor of 50% should be used. Thus, an energy density of 500 Wh/kg for the combined weight of graphite and NMC (lithium nickel manganese cobalt oxide) would translate to about 150-250 Wh/kg for a packaged cell. However, this extrapolation is only valid for electrodes with similar thickness and density as commercial electrodes (150 μm or about 15 mg/cm ² for graphite anode and 30 mg/cm ² for NMC cathode). A thinner or lighter electrode of the same active material would mean a much lower energy density or power density by weight of the cell. Therefore, it is desirable to manufacture a lithium-ion battery cell with a high active material ratio. Unfortunately, it has not been possible to achieve a total active material ratio greater than 45% by weight in most commercial lithium-ion batteries.

The method of the present invention allows lithium cells to far exceed these limits for all active materials investigated. In fact, the present invention can raise the active material ratio above 85% if desired, but typically from 45% to 80%, more typically from 40% to 70%, and most typically from 40% to 65%.

9 shows the cell-level weight and volumetric energy densities of a graphite/NMC cell prepared by the method of the present invention and a graphite/NMC cell prepared by a conventional roll-coating method. These data also support the achievement of unexpectedly high gravimetric and volumetric energy densities (e.g., from 189 Wh/kg to 305 Wh/kg, from 510 Wh/L to 793 Wh/kg), previously not possible when considering the same lithium battery system. Rise to L) shows the result of the ability of the present invention to have a total active material mass greater than 50%.

Example 26 : Representative test results of sodium metal and potassium metal cells

10 is a Ragone plot (weight and volumetric power density versus energy 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. indicate Two of the four data curves are for cells made according to an embodiment of the present invention and the other two are for cells made by conventional electrode slurry coating (roll-coating). Several important observations can be made from these data:

Both the gravimetric and volumetric energy densities and power densities (indicated by "invention" in the figure legends) of the sodium-ion battery cells produced by the method of the present invention are comparable to those of their counterparts produced through the conventional roll-coating method. Much higher than gravimetric and volumetric energy densities and power densities (labeled "conventional"). An anode thickness of 150 μm (coated on a flat solid Cu foil) changes to a diameter of 200 μm (all accommodated in the pores of a carbon foam with 85% porosity), and a corresponding change in the cathode to maintain the equilibrium capacity ratio As a result, the gravimetric energy density increases from 115 Wh/kg to 157 Wh/kg. Even more surprisingly, the volumetric energy density increases from 241 Wh/L to 502 Wh/L. For a sodium-ion battery using a hard carbon anode and a sodium transition metal phosphate-based cathode, this latter value of 502 Wh/L is unusual.

These significant differences include the much higher active material mass feed (relative to other materials) associated with the cell of the present invention, the reduced overhead (inactive) component ratio compared to active material weight/volume, the need not to have a binder resin, the electrode Surprisingly better utilization of active materials (most if not all of the hard carbon particles and Na ₃ V ₂ (PO ₄ ) ₂ F ₃ particles contribute to the sodium ion storage capacity; dry pockets or inefficiencies in the electrodes, especially at high charge/discharge rate conditions) no phosphorus point), and the surprising ability of the present method to more effectively pack the active material particles into the pores of the conductive porous layer (foam current collector).

The sodium-ion cell of the present invention also delivers a much higher energy density than that of conventional cells. This is also unexpected.

11 shows the Ragone plots (both gravimetric and volumetric power densities versus gravimetric and volumetric energy densities) of two cells containing graphene-containing Sn nanoparticles as anode active material and NaFePO ₄ nanoparticles as cathode active material. Experimental data were obtained from Na-ion battery cells prepared by the method of the present invention and Na-ion battery cells prepared by slurry coating of conventional electrodes.

These data indicate that both the gravimetric and volumetric energy densities and power densities of the sodium battery cells produced by the methods of the present invention are significantly higher than those of their counterparts manufactured via conventional methods. Also, the difference is very large. Conventionally manufactured cells exhibit gravimetric energy densities of 185 Wh/kg and volumetric energy densities of 388 Wh/L, whereas the inventive cable shaped cells deliver 311 Wh/kg and 777 Wh/L, respectively. A cell-level volumetric energy density of 777 Wh/L has never before been achieved with any rechargeable sodium battery. In fact, even recent lithium-ion batteries rarely exhibit volumetric energy densities higher than 750 Wh/L. Power densities as high as 1236 W/kg and 3,585 W/L are also unprecedented for sodium-ion cells as well as typically higher energy lithium-ion cells.

These energy density and power density differences are primarily due to the high active material mass feed rate, reduced overhead (inactive) component ratio relative to active material weight/volume, lack of binder resins, and the present invention's ability to better utilize active material particles (all particles are accessible to liquid electrolytes and have fast ionic and electron motion), and the ability to more effectively pack the active material particles within the pores of the foam current collector.

12 is a Ragone diagram of a sodium metal cell containing sodium foil as an anode active material, disodium rhodizoate (Na ₂ C ₆ O ₆ ) as a cathode active material, and lithium salt (NaPF ₆ )-PC/DEC as an organic liquid electrolyte. indicate Data are for both sodium metal cells prepared by the method of the present invention and conventional electrode slurry coating. These data indicate that both the gravimetric and volumetric energy densities and power densities of the sodium metal cells produced by the method of the present invention are significantly higher than those of their counterparts manufactured via conventional methods. In addition, this difference is very large, and the much higher active material mass feed associated with the cell of the present invention, the reduced overhead (inactive) component ratio relative to the active material weight/volume, the need not to have a binder resin, the surprise of the electrode active material better utilization rate (most, if not all, of the active material contributes to the sodium ion storage capacity; there are no dry pockets or inefficiencies in the electrode, especially under high charge/discharge rate conditions), This appears to be due to the surprising ability of the inventive method to pack.

The observation that the gravimetric energy density of the sodium metal-organic cathode cell of 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 to date, is quite remarkable and unexpected (current Na-ion cells typically store 100 to 150 Wh/kg based on total cell weight). Also, for a sodium battery based on an organic cathode active material (even for a corresponding lithium battery), a gravimetric power density of 1,289 W/kg and a volumetric power density of 3,738 W/L would have been unthinkable.

It is important to point out that reporting energy and power densities per weight of active material alone in the Lagon diagram, as reported by many researchers, may not provide a realistic picture of the performance of the assembled battery cell. The weight of other device components must also be considered. These overhead components, including current collectors, electrolytes, separators, binders, connectors and packaging are inert materials and do not contribute to charge storage. They only add weight and volume to the device. Therefore, it is desirable to reduce the relative proportion of overhead component weight and increase the active material proportion. However, it has not been possible to achieve this goal using conventional cell manufacturing processes. The present invention overcomes this long-standing and most serious problem in the field of lithium batteries.

In a commercial lithium-ion battery with an electrode thickness of 150 μm, the weight percentage of the anode active material (eg graphite or carbon) in the lithium-ion battery is typically 12% to 17%, and the weight percentage of the cathode active material is ( 22% to 41% for inorganic materials such as LiMn ₂ O ₄ , or 10% to 15% for organic or polymeric materials. Since both anode and cathode active materials have similar physical densities between the two types of cells and the ratio of specific cathode to anode capacities is also similar, the corresponding weight fractions in Na-ion cells are expected to be very similar. Thus, a factor of 3 to 4 can be used to extrapolate the energy or power density of a sodium cell from characteristics based on active material weight alone. In most scientific papers, reported properties are usually based on active material weight only and electrodes are typically very thin (<< 100 μm, most << 50 μm). The active material weight is typically 5% to 10% of the total device weight, which can be obtained by dividing the actual cell (device) energy or power density by a factor of 10 to 20 based on the corresponding active material weight. means Considering these coefficients, the properties reported in these papers do not actually look any better than those of commercial cells. Therefore, extreme caution should be exercised when reading and interpreting cell performance data reported in scientific papers and patent applications.

The Ragone plots of a series of K-ion cells made by a conventional slurry coating process and the corresponding cable-shaped K-ion cells made by the process of the present invention are summarized and contrasted in FIG. 13 . These data again confirm that the process of the present invention works well for fabricating both Na metal cells and K metal cells with very high energy and power densities.

Claims (83)

An alkali metal battery in the shape of a cable, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, and the shape of the cable has a length and diameter or thickness with an aspect ratio of length to diameter or length to thickness of 10 or more, The battery
(a) a first electrode comprising pores and an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, the first mixture present in the pores of the porous rod;
(b) a porous separator surrounding the first electrode;
(c) an electrically conductive porous layer surrounding or enclosing the porous separator, the conductive porous layer containing pores and a second mixture of a second electrode active material and a second electrolyte, the second mixture of the porous layer a second electrode present in the pores; and
(d) a protective casing or sheath surrounding or surrounding the second electrode;
The inner surface of the porous separator is in contact with the electrically conductive porous rod serving as a current collector, and the outer surface of the porous separator is in contact with the electrically conductive porous layer serving as a current collector.
Alkali metal battery. The alkali metal battery according to claim 1, wherein the first electrode is a cathode or anode and the second electrode is an anode or cathode. The alkali metal battery according to claim 1, wherein the second electrode is a cathode or anode and the first electrode is an anode or cathode. An alkali metal battery in the form of a cable, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, the battery comprising:
(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 a surface of the conductive rod;
(b) a porous separator surrounding the first electrode;
(c) an electrically conductive porous layer surrounding or enclosing the porous separator, the conductive porous layer containing pores and a second mixture of a second electrode active material and a second electrolyte, the second mixture of the porous layer a second electrode present in the pores; and
(d) a protective casing or sheath surrounding or surrounding the second electrode;
The inner surface of the porous separator is in contact with the electrically conductive porous rod serving as a current collector, and the outer surface of the porous separator is in contact with the electrically conductive porous layer serving as a current collector.
Alkali metal battery. An alkali metal battery in the form of a cable, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, the battery comprising:
(a) a first electrode comprising pores and an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, the first mixture present in the pores of the porous rod;
(b) a porous separator surrounding the first electrode;
(c) a second electrode comprising an electrically conductive layer surrounding or enclosing the porous separator, wherein the electrically conductive layer contains a second mixture of a second electrode active material and an optional second electrolyte; and
(d) a protective casing or sheath surrounding or surrounding the second electrode;
The inner surface of the porous separator is in contact with the electrically conductive porous rod serving as a current collector, and the outer surface of the porous separator is in contact with the electrically conductive layer serving as a current collector.
Alkali metal battery. The method of claim 1, wherein the cable-shaped battery has a first end and a second end, and the first electrode is at least one metal wire embedded in, connected to, or integrated with the first electrode, conductive carbon/graphite. An alkali metal battery comprising a first terminal connector comprising a fiber or a conductive polymer fiber. The alkali metal battery of claim 6, wherein the at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber extends from the first end to the second end. The method of claim 1, wherein the cable-shaped battery has a first end and a second end, and the second electrode is at least one metal wire embedded in, connected to, or integrated with the second electrode, conductive carbon/graphite. An alkali metal battery comprising a second terminal connector comprising a fiber or a conductive polymer fiber. The alkali metal battery according to claim 8, wherein the at least one metal wire, conductive carbon/graphite fiber, or conductive polymer fiber extends from the first end to the second end. The method of claim 1, wherein the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode is a metal foam, a metal web, a metal fiber mat, a metal nanowire mat, a conductive polymer fiber mat, a conductive polymer foam, or a conductive material. Polymer-coated fiber foam, carbon foam, graphite foam, carbon airgel, carbon xerogel, graphene airgel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam , or combinations thereof. 11. The alkali metal battery according to claim 10, wherein the porous foam has a circular, elliptical, rectangular, square, hexagonal, hollow, or irregular cross section. The alkali metal battery according to claim 1, wherein the battery has a cable shape with an aspect ratio, which is a ratio of length and diameter or thickness and length/thickness or length/diameter, greater than 10. The alkali metal battery according to claim 1, wherein the first electrode or the second electrode includes particles, foils, or coatings of Li, Na, K, or a combination thereof as an electrode active material. 5. The alkali metal battery according to claim 4, wherein the first electrode or the second electrode includes particles, foils, or coatings of Li, Na, K, or a combination thereof as an electrode active material. The alkali metal battery according to claim 5, wherein the first electrode or the second electrode includes particles, foils, or coatings of Li, Na, K, or a combination thereof as an electrode active material. The method of claim 1, wherein the alkali metal battery is a lithium-ion battery, and the first or second electrode active material is
(a) particles of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), and 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 intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements;
(d) oxides, carbides, nitrides, sulfides, phosphides, selenium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof. cargo, and tellurium cargo;
(e) their pre-lithiated form;
(f) a pre-lithiated graphene sheet;
and an alkali metal battery selected from the group consisting of combinations thereof. 17. The method of claim 16, wherein the pre-lithiated graphene sheet is pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, Pre-lithiation of hydrogenated graphene, nitride graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physically or chemically activated or etched forms thereof, and combinations thereof An alkali metal battery selected from the group consisting of The method 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, template carbon, or 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 to 1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate-based substances, 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 ₄ O ₄ , C ₁₀ H ₂ Na ₄ An alkali metal battery containing an alkali intercalating compound selected from the group consisting of O ₈ , C ₁₄ H ₄ O ₆ , C ₁₄ H ₄ Na ₄ O ₈ , and combinations thereof. The method of claim 1, wherein 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) sodium- or potassium-containing alloys or intermetallics of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
(c) sodium- or potassium-containing oxides, carbides, nitrides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof; sulfide, phosphide, selenide, telluride, or antimonide;
(d) sodium or potassium salts;
(e) a graphene sheet pre-applied with sodium or potassium; and
(f) An alkali metal battery containing an alkali intercalating compound selected from the group consisting of combinations thereof. The method of claim 1, wherein the second or first electrode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, or doped A lithium intercalating compound selected from the group consisting of lithium vanadium oxide, 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 or an alkali metal cell containing a lithium absorbing compound. The method of claim 1, wherein the second or first electrode active material is NaFePO ₄ , Na _(1-x) K _x PO ₄ , KFePO ₄ , Na _0.7 FePO ₄ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na ₂ FePO ₄ F, NaFeF ₃ , NaVPO ₄ F, KVPO ₄ F, Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , NaV ₆ O ₁₅ , Na _x VO ₂ , Na _0.33 V ₂ O ₅ , 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 . ₄₄ MnO ₂ /C, Na ₄ Mn ₉ O ₁₈ , NaFe ₂ Mn(PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Ni _1/3 Mn _1/3 Co _1/3 O ₂ , Cu _0.56 Ni ₀ . ₄₄ HCF, NiHCF, Na _x MnO ₂ , NaCrO ₂ , KCrO ₂ , Na ₃ Ti ₂ (PO ₄ ) ₃ , NiCo ₂ O ₄ , Ni ₃ S ₂ /FeS ₂ , Sb ₂ O ₄ , Na ₄ Fe(CN) ₆ /C, NaV _1-x Cr _x PO ₄ F, Se _z S _y , (y/z = 0.01 to 100), a sodium intercalating compound or potassium intercalating compound selected from the group consisting of Se, aluoselite, and combinations thereof Alkali metal cell containing compound ( x is 0.1 to 1.0). The method of claim 1, wherein the first electrolyte and/or the second electrolyte contains a lithium salt or a sodium salt dissolved in a liquid solvent, and the liquid solvent is water, an organic solvent, an ionic liquid, an organic solvent and an ionic Alkali metal batteries that are mixtures of liquids, or liquid solvent-polymer gels. The alkali metal battery according to claim 1, wherein the first electrolyte and/or the second electrolyte contains a lithium salt or a sodium salt dissolved in a liquid solvent having a salt concentration greater than 2.5 M. The alkali metal battery according to claim 1, wherein the first electrolyte and/or the second electrolyte contains a lithium salt or a sodium salt dissolved in a liquid solvent having a salt concentration greater than 5.0 M. The alkali metal battery according to claim 1, wherein the first electrolyte and/or the second electrolyte contains a lithium salt or a sodium salt dissolved in a liquid solvent having a salt concentration greater than 7.0 M. The method of claim 1, wherein the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode has pores of at least 85% by volume, and the first or second electrode has a diameter or thickness of 100 μm or more, or An alkali metal battery having an active mass supply that accounts for at least 25% by weight or volume% of the total battery cell, or wherein the sum of the first electrode active material and the second electrode active material accounts for at least 40% by weight or volume% of the total battery cell. The method of claim 1, wherein the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode has pores of at least 90% by volume, and the first or second electrode has a diameter or thickness of 200 μm or more, or An alkali metal battery having an active mass supply that accounts for at least 30% by weight or volume% of the total battery cell, or wherein the sum of the first electrode active material and the second electrode active material accounts for at least 50% by weight or volume% of the total battery cell. The method of claim 1, wherein the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode has pores of at least 95% by volume, and the first or second electrode has a diameter or thickness of 300 μm or more, or An alkali metal battery having an active mass supply that accounts for at least 35% by weight or volume% of the total battery cell, or wherein the sum of the first electrode active material and the second electrode active material accounts for at least 60% by weight or volume% of the total battery cell. The method of claim 1, wherein the first or second electrode active material is an alkali containing an alkali metal intercalating compound or an alkali metal absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof. metal cell. 30. The method of claim 29, wherein the metal oxide/phosphate/sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal An alkali metal battery selected from the group consisting of phosphates, transition metal sulfides, and combinations thereof. 30. The alkali metal battery of claim 29, wherein the inorganic material is selected from transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. 30. The alkali metal battery of claim 29, wherein the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or combinations thereof. 30. The method of claim 29, wherein the metal oxide/phosphate/sulfide is VO ₂ , Li _x VO ₂ , V ₂ O ₅ , Li _x V ₂ O ₅ , V ₃ O ₈ , Li _x V ₃ O ₈ , Li _x V ₃ a vanadium oxide selected from the group consisting of O ₇ , V ₄ O ₉ , Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped forms thereof, derivatives thereof, and combinations thereof; Alkali metal cells containing (0.1 < x < 5). The method of claim 29, wherein the metal oxide/phosphate/sulfide is a layered compound LiMO ₂ , a spinel compound LiM ₂ O ₄ , an olivine compound LiMPO ₄ , a silicate compound Li ₂ MSiO ₄ , a taborite compound LiMPO ₄ F, a borate compound LiMBO ₃ , and combinations thereof, wherein M is a transition metal or a mixture of transition metals. 30. The method of claim 29, wherein the inorganic material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, An alkali metal battery selected from the group consisting of titanium, cobalt, manganese, iron, nickel, or a sulfide, selenide, or telluride of a transition metal, (d) boron nitride, and (e) combinations thereof. 30. The method of claim 29, wherein the organic material or polymeric material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA), poly(anthraqui nonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-linked PYT, quino (triazene), redox active organic substance, tetracyanoquino-dimethane (TCNQ), tetracy Anoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxy anthraquinone) (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 polymer, quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetron (PT), 5-amino-2, 3-dihydro-1,4-dihydroxy anthraquinone (ADDAQ), 5-amino-1,4-dihydroxy anthraquinone (ADAQ), calixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ An alkali metal battery selected from the group consisting of O ₆ , Li ₆ C ₆ O ₆ , and combinations thereof. 37. The method of claim 36, wherein the thioether polymer is poly[methanetetril-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), poly(ethene-1,1, Polymers containing 2,2-tetrathiol) (PETT) as main chain thioether polymers, side chain thioether polymers having a main chain consisting of conjugated aromatic moieties and having thioether side chains as pendants, 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(ethyrendithio)thiophene] (PEDTT), and combinations thereof. 30. The method of claim 29, 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, aluminum phthalocyanine chloride An alkali metal battery containing a phthalocyanine compound selected from the group consisting of cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, and combinations thereof. 3. The alkali metal battery of claim 2, wherein the cathode contains an alkali metal intercalating compound or an alkali metal absorbing compound selected from the group consisting of metal carbides, metal nitrides, metal borides, metal dichalcogenides, and combinations thereof. 4. The method of claim 3, wherein the cathode is made of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, and An alkali metal battery containing an alkali metal intercalating compound or an alkali metal absorbing compound selected from the group consisting of oxides, dichalcogenides, trichalcogenides, sulfides, selenides, and tellurides of nickel. 3. The method of claim 2, wherein the cathode active material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, Nanodisks, nanoplatelets of an inorganic material selected from the group consisting of titanium, cobalt, manganese, iron, nickel, or sulfides, selenides, or tellurides of transition metals, (d) boron nitride, and (e) combinations thereof An alkali metal cell comprising a superstructure, nanocoating, or nanosheet, wherein the disk, platelet, or sheet has a thickness of less than 100 nm. The alkali metal battery according to claim 1, wherein the length of the battery is greater than 1 m. 2. The alkali metal cell of claim 1, wherein the cell is bendable with a radius of curvature greater than 10 cm. The method of claim 1, wherein the battery is an empty space or internal compartment of the vehicle (the empty space or interior compartment is a trunk, a door, a hatch, a spare tire compartment, an area inside a seat, an area inside a seatback, an area under a seat, or an area under a dashboard) Alkali metal battery that can be bent to substantially conform to the shape of (including). 45. The alkali metal battery of claim 44, wherein the battery is removable from the vehicle and is bendable to conform to the shape of another void or interior compartment. 2. The method of claim 1 wherein one or more units of said cells are used in clothing, belts, support straps, carrying straps, luggage straps, weapon straps, musical instrument straps, helmets, hats, boots, foot covers, gloves, wrist covers, watch bands, jewelry. Alkali metal batteries incorporated into articles, animal collars or animal harnesses. 2. The method of claim 1 wherein one or more units of said cells are used in clothing, belts, support straps, carrying straps, luggage straps, weapon straps, musical instrument straps, helmets, hats, boots, foot covers, gloves, wrist covers, watch bands, jewelry. An alkali metal battery that is removably integrated into an article, animal leash or animal harness. The alkali metal battery of claim 1, wherein the battery fits into an inner cavity of a hollow bicycle frame. A method for producing a cable-shaped alkali metal battery, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, the cable shape has a length-to-thickness or length-to-diameter ratio of 10 or more, the method comprising:
(e) providing a first electrode comprising pores and an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, the first mixture being within the pores of the porous rod;
(f) forming a porous separator-protecting structure by surrounding or wrapping the first electrode with a porous separator;
(g) surrounding or wrapping the porous separator-protecting structure with a second electrode comprising an electrically conductive porous layer, wherein the conductive porous layer contains pores and a second mixture of a second electrode active material and a second electrolyte; the second mixture is present in the pores of the porous layer; and
(h) forming the battery by surrounding or wrapping the second electrode with a protective casing or sheath;
The inner surface of the porous separator is in contact with the electrically conductive porous rod serving as a current collector, and the outer surface of the porous separator is in contact with the electrically conductive porous layer serving as a current collector.
method. A method for producing a cable-shaped alkali metal battery, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, the 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 a surface of the conductive rod;
(b) forming a porous separator-protecting structure by surrounding or wrapping the first electrode with a porous separator;
(c) surrounding or wrapping the porous separator-protecting structure with a second electrode comprising an electrically conductive porous layer, wherein the conductive porous layer contains pores and a second mixture of a second electrode active material and a second electrolyte; the second mixture is present in the pores of the porous layer; and
(d) forming the battery by surrounding or wrapping the second electrode with a protective casing or sheath;
The inner surface of the porous separator is in contact with the electrically conductive porous rod serving as a current collector, and the outer surface of the porous separator is in contact with the electrically conductive porous layer serving as a current collector.
method. A method for producing a cable-shaped alkali metal battery, wherein the alkali metal is selected from Li, Na, K, or a combination thereof, the method comprising:
(a) providing a first electrode comprising pores and an electrically conductive porous rod having pores and a first mixture of a first electrode active material and a first electrolyte, the first mixture being within the pores of the porous rod;
(b) forming a porous separator-protecting structure by surrounding or wrapping the first electrode with a porous separator;
(c) surrounding or surrounding the porous separator-protecting structure with a second electrode comprising an electrically conductive layer, wherein the electrically conductive layer contains a second mixture of a second electrode active material and an optional second electrolyte; and
(d) forming the battery by surrounding or wrapping the second electrode with a protective casing or sheath;
The inner surface of the porous separator is in contact with the electrically conductive porous rod serving as a current collector, and the outer surface of the porous separator is in contact with the electrically conductive layer serving as a current collector.
method. 50. The method of claim 49, wherein step (e) further comprises introducing at least one metal wire, conductive carbon/graphite fiber, or conductive polymeric fiber into the conductive porous rod. 50. The method of claim 49, wherein the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of 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 airgel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam , or combinations thereof. 54. The method of claim 53, wherein the porous foam has a circular, elliptical, rectangular, square, hexagonal, hollow, or irregularly shaped cross-section. 50. The method of claim 49, wherein step (e) or step (g) introduces particles, foils, or coatings of Li, Na, K, or combinations thereof as an active electrode material into the first electrode or the second electrode. How to include courses. 51. The method of claim 50, wherein step (a) or step (c) introduces particles, foils, or coatings of Li, Na, K, or combinations thereof as an active electrode material into the first electrode or the second electrode. How to include courses. 52. The method of claim 51, wherein step (a) or step (c) introduces particles, foils, or coatings of Li, Na, K, or combinations thereof as an active electrode material into the first electrode or the second electrode. How to include courses. 50. The method of claim 49, wherein step (e) comprises: (i) continuously supplying the electrically conductive porous rod comprising interconnected electron conduction pathways and having at least one porous surface to a first electrode active material impregnation zone; and (ii) impregnating the first mixture from the at least one porous surface into the electrically conductive porous rod to form the first electrode. 59. The method of claim 58, wherein step (e) continuously or on demand applies the first mixture to the at least one porous surface via spraying, printing, coating, casting, conveyor film transfer, and/or roller surface transfer. A method comprising intermittently delivering. 50. The method of claim 49, wherein step (g) comprises: (i) continuously supplying the electrically conductive porous layer comprising interconnected electron conduction pathways and having at least one porous surface to the impregnation zone of the second electrode active material; ; and (ii) impregnating the second mixture from the at least one porous surface into the electrically conductive porous layer to form the second electrode. 61. The method of claim 60, wherein step (g) continuously or on demand applies the second mixture to the at least one porous surface via spraying, printing, coating, casting, conveyor film transfer, and/or roller surface transfer. A method comprising intermittently delivering. 50. The method of claim 49, wherein step (f) includes wrapping the first electrode with a porous separator band in a coiled or spiral fashion to form the porous separator-protecting structure. 50. The method according to claim 49, wherein step (f) comprises forming a porous shell structure covering the first electrode by spraying an electrical insulating material to wrap the first electrode to form the porous separator-protecting structure. . 50. The method of claim 49, wherein step (g) includes enclosing or wrapping the porous separator-protecting structure with the second electrode in a linear or spiral fashion. 50. The method of claim 49, wherein the alkali metal battery is a lithium-ion battery, and the first or second electrode active material is
(g) particles of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), and 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 intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements;
(j) oxides, carbides, nitrides, sulfides, phosphides, selenium of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or composites thereof. cargo, and tellurium cargo;
(k) their pre-lithiated forms;
(l) a pre-lithiated graphene sheet;
and combinations thereof. 50. The method of claim 49, 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, template 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 to 1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate-based substances, 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 ₄ O ₄ , C ₁₀ H ₂ Na ₄ A method containing an alkali intercalating compound selected from the group consisting of O ₈ , C ₁₄ H ₄ O ₆ , C ₁₄ H ₄ Na ₄ O ₈ , and combinations thereof. 50. The method of claim 49, wherein the alkali metal battery is a sodium-ion battery, and the first or second electrode active material is
(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 intermetallics of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
(i) sodium- or potassium-containing oxides, carbides, nitrides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof; sulfide, phosphide, selenide, telluride, or antimonide;
(j) sodium or potassium salts;
(k) a graphene sheet pre-applied with sodium or potassium; and
(1) A method containing an alkali intercalating compound selected from the group consisting of combinations thereof. 50. The method of claim 49, wherein the second or first electrode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, doped a lithium intercalating compound selected from the group consisting of lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, metal sulfide, lithium selenide, and combinations thereof; Methods of containing the compound. The method of claim 49, wherein the second or first electrode active material is NaFePO ₄ , Na _(1-x) K _x PO ₄ , KFePO ₄ , Na _0.7 FePO ₄ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na ₂ FePO ₄ F, NaFeF ₃ , NaVPO ₄ F, KVPO ₄ F, Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , NaV ₆ O ₁₅ , Na _x VO ₂ , Na _0.33 V ₂ O ₅ , 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 . ₄₄ MnO ₂ /C, Na ₄ Mn ₉ O ₁₈ , NaFe ₂ Mn(PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Ni _1/3 Mn _1/3 Co _1/3 O ₂ , Cu _0.56 Ni ₀ . ₄₄ HCF, NiHCF, Na _x MnO ₂ , NaCrO ₂ , KCrO ₂ , Na ₃ Ti ₂ (PO ₄ ) ₃ , NiCo ₂ O ₄ , Ni ₃ S ₂ /FeS ₂ , Sb ₂ O ₄ , Na ₄ Fe(CN) ₆ /C, NaV _1-x Cr _x PO ₄ F, Se _z S _y , (y/z = 0.01 to 100), a sodium intercalating compound or potassium intercalating compound selected from the group consisting of Se, aluoselite, and combinations thereof A method containing a compound ( x is from 0.1 to 1.0). 50. The method of claim 49, wherein the first electrolyte and/or the second electrolyte contains a lithium salt or a sodium salt dissolved in a liquid solvent, wherein the liquid solvent is water, an organic solvent, an ionic liquid, an organic solvent and an ionic liquid A method that is a mixture of liquids, or liquid solvent-polymer gels. 50. The method of claim 49, wherein the first electrolyte and/or the second electrolyte contains a lithium salt or a sodium salt dissolved in a liquid solvent having a salt concentration of 2.5 M to 14 M. 50. The method of claim 49, wherein the electrically conductive porous rod of the first electrode or the electrically conductive porous layer of the second electrode has between 70% and 99% by volume of pores. 50. The method of claim 49, wherein the first or second electrode active material comprises an alkali metal intercalating compound or an alkali metal absorbing compound selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides, or combinations thereof. . 74. The method of claim 73, wherein the metal oxide/phosphate/sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal A method selected from the group consisting of phosphates, transition metal sulfides, and combinations thereof. 74. The method of claim 73, wherein the inorganic material is selected from the group consisting of TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, and combinations thereof. 74. The method of claim 73, wherein the metal oxide/phosphate/sulfide is VO ₂ , Li _x VO ₂ , V ₂ O ₅ , Li _x V ₂ O ₅ , V ₃ O ₈ , Li _x V ₃ O ₈ , Li _x V ₃ a vanadium oxide selected from the group consisting of O ₇ , V ₄ O ₉ , Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped forms thereof, derivatives thereof, and combinations thereof; method containing (0.1 < x < 5). 74. The method of claim 73, wherein the metal oxide/phosphate/sulfide is a layered compound LiMO ₂ , a spinel compound LiM ₂ O ₄ , an olivine compound LiMPO ₄ , a silicate compound Li ₂ MSiO ₄ , a taborite compound LiMPO ₄ F, a borate compound LiMBO ₃ , and combinations thereof, wherein M is a transition metal or a mixture of several transition metals. 74. The method of claim 73, wherein the inorganic material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, A method selected from the group consisting of titanium, cobalt, manganese, iron, nickel, or a sulfide, selenide, or telluride of a transition metal, (d) boron nitride, and (e) combinations thereof. 74. The method of claim 73, wherein the organic or polymeric material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraqui nonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-linked PYT, quino (triazene), redox active organic substance, tetracyanoquino-dimethane (TCNQ), tetracy Anoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxy anthraquinone) (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 polymer, quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetron (PT), 5-amino-2, 3-dihydro-1,4-dihydroxy anthraquinone (ADDAQ), 5-amino-1,4-dihydroxy anthraquinone (ADAQ), calixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ A method selected from the group consisting of O ₆ , Li ₆ C ₆ O ₆ , and combinations thereof. 74. The method of claim 73, 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, aluminum phthalocyanine chloride A method containing a phthalocyanine compound selected from the group consisting of cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, and combinations thereof. 51. The method of claim 50, wherein the cathode contains an alkali metal intercalating compound or an alkali metal absorbing compound selected from the group consisting of metal carbides, metal nitrides, metal borides, metal dichalcogenides, and combinations thereof. 52. The method of claim 51, wherein the cathode is made of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, and A method containing an alkali metal intercalating compound or an alkali metal absorbing compound selected from the group consisting of oxides, dichalcogenides, trichalcogenides, sulfides, selenides, and tellurides of nickel. 51. The method of claim 50, wherein the cathode active material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, Nanodisks, nanoplatelets of an inorganic material selected from the group consisting of titanium, cobalt, manganese, iron, nickel, or sulfides, selenides, or tellurides of transition metals, (d) boron nitride, and (e) combinations thereof A method comprising a superstrate, nanocoating, or nanosheet, wherein the disk, platelet, or sheet has a thickness of less than 100 nm.