JP2020524359A - A conformable alkali metal battery with a conductive deformable quasi-solid polymer electrode - Google Patents

Abstract

In the method of preparing an alkali metal cell, a step of forming a deformable conductive electrode material by combining a certain amount of an active material, a certain amount of an electrolyte, and a conductive additive, wherein a conductive filament is formed. The conductive additive contained forms a 3D network of electron conduction paths, and the electrolyte contains an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent; and (b) the electrode material Forming the electrode as a solid electrode, and transforming the electrode material into an electrode shape without interrupting the 3D network of the electron conduction path so that the electrode maintains a conductivity of 10 −6 S/cm or more. A method comprising: (c) forming a second electrode; and (d) forming an alkali metal cell by combining the quasi-solid electrode with the second electrode. R. The second electrode may also be a quasi-solid polymer electrode. [Selection diagram] Figure 1(C)

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application assigns priority to US Patent Application No. 15/608,597 filed May 30, 2017 and US Patent Application No. 15/610,136 filed May 31, 2017. Claimed and the above patent application is incorporated herein by reference.

The present invention relates generally to the field of rechargeable lithium metal batteries, sodium metal batteries, lithium ion batteries, sodium ion batteries, lithium ion capacitors, and alkali metal batteries including sodium ion capacitors.

Historically, the most favored rechargeable energy storage device today, the lithium-ion battery, actually uses lithium (Li) metal or Li alloy as the anode and Li intercalation compound as the cathode. It evolved from the rechargeable "lithium metal battery" used. Li metal is an ideal anode material due to its light weight (lightest metal), high electronegativity (-3.04V vs. standard hydrogen electrode), and high theoretical capacity (3,860mAh/g). .. Based on these outstanding properties, lithium metal batteries were proposed 40 years ago as an ideal system for high energy density applications. In the mid-1980s, several prototypes of rechargeable Li metal batteries were developed. One notable example is MOLI Energy, Inc. (Canada) developed a Li metal anode and a molybdenum sulfide cathode. This cell, and some others from various manufacturers, have a series of very non-uniform Li growth (formation of Li dendrites) as the metal is re-plated during each subsequent recharge cycle. Limited due to safety issues. As the number of cycles increases, the dendrite or dendritic Li structure can eventually cross the separator and reach the cathode, causing an internal short circuit.

To overcome these safety issues, several alternative approaches with either electrolyte or anode improvements have been proposed. One approach involves replacing the Li metal with graphite (another Li insertion material) as the anode. The operation of such a battery involves reciprocating Li-ions between two Li-insertion compounds, hence the name "Li-ion battery". Perhaps Li-ion batteries are inherently safer than Li-metal batteries because Li is present in the ionic state rather than the metallic state.

Lithium-ion batteries are a prime candidate energy storage device for electric vehicles (EV), renewable energy storage, and smart grid applications. Over the last two decades, lithium-ion batteries have seen continuous improvement in energy density, rate characteristics, and safety, but for some reason, Li-metal batteries with fairly high energy densities have been mostly noticeable. It wasn't aimed. However, the use of graphite-based anodes in Li-ion batteries has some major drawbacks: Low specific capacity (theoretical capacity of 372 mAh/g as opposed to 3,860 mAh/g for Li metal); long Li intercurry requiring long recharge time (eg 7 hours for electric vehicle batteries) Ionization time (eg, low solid diffusion efficiency of Li in and out of graphite and inorganic oxide particles); inability to deliver high pulse power (power density <<1 kW/kg); and prelithiation Cathodes (eg, lithium cobalt oxide) should be used, which limits the choice of available cathode materials. Moreover, these commonly used cathodes have a relatively low specific capacity (typically <200 mAh/g). These factors account for two major drawbacks of today's Li-ion batteries: low weight and volumetric energy density (typically 150-220 Wh/kg and 450-600 Wh/L), and low power density (typically). <0.5 kW/kg and <1.0 kW/L) (all of the above values are based on total battery cell weight or volume).

In the emerging EV and renewable energy industries, much higher gravimetric energy densities (eg, >>250 Wh/kg, and preferably >>300 Wh/kg are required) than can be provided by current Li-ion battery technology, and The availability of rechargeable batteries with high power density (shorter recharge time) is required. Moreover, in the microelectronics industry, consumers are demanding smaller volume and more compact portable devices (eg, smartphones and tablets) to store more energy, so a much larger volumetric energy density (>650 Wh/L, Batteries with preferably >750 Wh/L) are needed. Due to these requirements, a great deal of research effort has been directed towards the development of electrode materials for lithium-ion batteries with higher specific capacities, excellent rate characteristics, and good cycle stability.

Some elements from Groups III, IV, and V of the periodic table can form alloys with Li at certain desired voltages. Therefore, various anode materials and some metal oxides based on such elements have been proposed for lithium-ion batteries. Among them, silicon is recognized as one of the next generation anode materials for high energy lithium ion batteries. This is because silicon has a theoretical weight capacity of about 10 times that of graphite (372 mAh/g for LiC ₆ vs. 3,590 mAh/g based on Li _3.75 Si) and a volume capacity of about 10. Because it is three times. However, the rapid volume change of Si (up to 380%) during lithium ion alloying and dealloying (cell charging and discharging) often led to severe and rapid battery performance degradation. The decrease in performance is mainly due to the fact that Si is powdered due to the volume change and that the binder/conductive additive cannot maintain the electrical contact between the powdered Si particles and the current collector. .. Moreover, the inherently low conductivity of silicon is another challenge that needs to be addressed.

Although some high capacity anode active materials (eg Si) have been found, there is no corresponding high capacity cathode material available. Current cathode active materials commonly used in Li-ion batteries have the following serious drawbacks:
(1) Practical capacities achievable with current cathode materials (eg, lithium iron phosphate and lithium transition metal oxides) are limited to the range 150-250 mAh/g, often less than 200 mAh/g. Has been done.
(2) The insertion and removal of lithium into these commonly used cathodes is a solid with a very low diffusion coefficient (typically 10 ⁻⁸ to 10 ⁻¹⁴ cm ² /s). Relying on the very slow solid state diffusion of Li in the particles, this results in a very low power density, another longstanding problem of today's lithium-ion batteries.
(3) Current cathode materials are electrically insulating and thermally insulating, and are unable to transport electrons and heat effectively and efficiently. Low conductivity means high internal resistance and the need to add large amounts of conductive additives, which substantially reduces the proportion of electrochemically active material in the already low capacity cathode. Also, low thermal conductivity means that they are more prone to thermal runaway, which is a major safety issue in the lithium battery industry.

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

As an entirely different class of energy storage devices, sodium batteries are considered an attractive alternative to lithium batteries. This is because sodium is abundant and the production of sodium is much more environmentally friendly than the production of lithium. Moreover, the high cost of lithium is a major problem.

Sodium ion batteries using a hard carbon based anode (Na-carbon intercalation compound) and sodium transition metal phosphate as cathode have been described by several research groups. However, these sodium-based devices exhibit even lower specific energy and rate capabilities than Li-ion batteries. These conventional sodium ion batteries require diffusion of sodium ions in and out of the sodium intercalation compound at both the anode and cathode. The solid diffusion process required for sodium ions in sodium ion batteries is even slower than the Li diffusion process in Li ion batteries, resulting in much lower power density.

Instead of hard carbon or other carbonaceous intercalation compounds, sodium metal may be used as the anode active material for sodium metal cells. However, the use of metallic sodium as the anode active material is generally considered to be undesirable and dangerous due to problems of dendrite formation, interfacial aging, and electrolyte incompatibility. Most importantly, the same flammable solvents previously used in lithium secondary batteries are also used in most sodium metal or sodium ion batteries.

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

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

High energy density batteries that are conformable so that they can fit into any irregular shape or confined space within the device or vehicle as electronic devices become more compact and electric vehicles (EVs) become lighter The need for is imminent. Allows devices to be made more compact by mounting batteries in spaces that would otherwise be empty (unused or “wasted”) spaces (eg, car doors or parts of rooftops) Or more power can be stored in the EV. In order to make the cell conformable, the electrodes must be deformable, flexible and conformable.

Therefore, the need for lithium and sodium batteries with high active material mass loading (high areal density), high electrode thickness or volume without compromising conductivity, high capacity, high power density, and high energy density is clear. , Urgent. These batteries must be manufactured environmentally friendly. In addition, the cell must be conformable and be able to form any regular shape (eg, rectangular or cylindrical) or amorphous. The present invention provides an alkali metal battery that meets all these criteria.

The present invention is flexible with high active material mass loading, extremely low overhead weight and volume (relative to active material mass and volume), high capacity, and unprecedentedly high energy and power densities. A method of making a conformable lithium or sodium battery is provided. The lithium or sodium battery may be a primary battery (non-rechargeable) or a secondary battery (rechargeable), a rechargeable lithium or sodium metal battery (having a lithium or sodium metal anode), and a lithium ion or sodium ion battery ( For example, having a first lithium intercalation compound as the anode active material and a second lithium intercalation or absorption compound having a much higher electrochemical potential than the first as the cathode active material. )including. The alkaline battery also includes a lithium ion capacitor and a sodium ion capacitor, where the anode is a lithium ion or sodium ion cell type anode and the cathode is a supercapacitor cathode (eg, an electric double layer capacitor or redox capacitor). It is an activated carbon or graphene sheet) as an active material for use in a pseudo capacitor.

In a particular embodiment, the invention provides (a) about 5% to about 40% by volume of a first active material containing about 30% to about 95% by volume of a cathode active material and an alkali salt dissolved in a solvent. A solid-state cathode comprising an electrolyte of claim 1, an ion-conducting polymer dissolved, dispersed, or impregnated in the solvent, and about 0.01% to about 30% by volume of a conductive additive. A quasi-solid cathode, the conductive additive containing: forming a 3D network of electronic conduction paths such that the quasi-solid electrode has a conductivity of about 10 ⁻⁶ S/cm to about 300 S/cm; An alkali metal cell comprising: an anode; and (c) an ion conductive membrane or a porous separator disposed between the anode and the quasi-solid cathode, wherein the quasi-solid cathode has a thickness of 200 μm or more. Preferably, the quasi-solid cathode is 10 mg/cm ² or more, preferably 15 mg/cm ² or more, more preferably 25 mg/cm ² or more, more preferably 35 mg/cm ² or more, even more preferably 45 mg/cm ² or more, Most preferably it contains a mass loading of cathode active material of 65 mg/cm ² or more.

In this cell, the anode comprises about 30% to about 95% by volume of the anode active material, about 5% to about 40% by volume of a second electrolyte containing an alkali salt dissolved in the solvent, and the solvent. May include a quasi-solid anode containing an ion-conducting polymer dissolved, dispersed, or impregnated with a conductive additive and from about 0.01% to about 30% by volume of a conductive additive. The conductive additive forms a 3D network of electronic conduction paths such that the quasi-solid electrode has a conductivity of about 10 ⁻⁶ S/cm to about 300 S/cm, and the quasi-solid anode has a thickness of 200 μm or more. And can be up to 100 cm or more. The quasi-solid anode is preferably 10 mg/cm ² or more, preferably 15 mg/cm ² or more, more preferably 25 mg/cm ² or more, more preferably 35 mg/cm ² or more, even more preferably 45 mg/cm ² or more, most preferably It preferably contains a mass loading of anode active material of 65 mg/cm ² or more. The first electrolyte may be the same or different in composition and structure as the second electrolyte.

In certain embodiments, the invention provides (A) about 30% to about 95% by volume of an anode active material and about 5% to about 40% by volume of an electrolyte containing an alkali salt dissolved in a solvent. A quasi-solid anode containing an ion-conducting polymer dissolved, dispersed or impregnated in the solvent, and about 0.01% to about 30% by volume of a conductive additive, the conductive filament containing a conductive filament. A conductive additive forming a 3D network of electronic conduction paths such that the quasi-solid electrode has a conductivity of from about 10 ⁻⁶ S/cm to about 300 S/cm; a quasi-solid anode; (B) a cathode; (C) An alkali metal cell having an ion conductive membrane or a porous separator disposed between an anode and a quasi-solid cathode, wherein the quasi-solid cathode has a thickness of 200 μm or more.

The quasi-solid polymer electrodes according to the invention allow the formation of deformable, flexible, conformable, conformable batteries.

The present invention also provides a method for preparing an alkali metal cell having a quasi-solid electrode, which comprises (a) a certain amount of an active material (anode active material or cathode active material) and an alkali salt dissolved in a solvent. A step of combining a certain amount of electrolyte, an ion-conducting polymer dissolved, dispersed, or impregnated in this solvent, and a conductive additive to form a deformable and conductive electrode material, A conductive additive containing a conductive filament forms a 3D network of electron conduction paths; and (b) a step of forming the electrode material as a quasi-solid electrode, wherein the electrode is 10 ⁻⁶ S/cm or more ( Preferably, 10 ⁻⁵ S/cm or more, more preferably 10 ⁻³ S/cm or more, further preferably 10 ⁻² S/cm or more, further preferably and typically 10 ⁻¹ S/cm or more, further More typically and preferably 1 S/cm or more, even more typically and preferably 10 S/cm or more, up to 300 S/cm) to maintain a conductivity of 3D network of electron conduction paths. Including transforming the electrode material into an electrode shape without interruption; (c) forming a second electrode (the second electrode may also be a quasi-solid electrode); (d) a quasi-solid electrode And a second electrode having an ion-conducting separator disposed between the two electrodes to form an alkali metal cell.

In some embodiments, the electrolyte (including the first or second electrolyte) is poly(ethylene oxide) (PEO, having a molecular weight of less than 1×10 ⁶ g/mol), polypropylene oxide (PPO), Poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polybis-methoxyethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride) Contains a lithium ion conducting or sodium ion conducting polymer selected from hexafluoropropylene (PVDF-HFP), their sulfonated derivatives, sulfonated polymers, or combinations thereof. It has been found herein that sulfonation provides an improvement in the lithium ion conductivity of the polymer. Molecular weights of PEO higher than 1×10 ⁶ g/mol typically render the PEO insoluble or non-dispersible in the solvent.

Typically and preferably, the ion conducting polymer does not form a matrix (continuous phase) in the electrode.

The ion-conducting polymer is poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivative of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly(ether ether). Ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonated polychloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymer (FEP), sulfonated ethylene-chloro. Trifluoroethylene copolymer (ECTFE), sulfonated polyvinylidene fluoride (PVDF), polyvinylidene fluoride and hexafluoropropene and sulfonated copolymers of tetrafluoroethylene, sulfonated copolymer of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives thereof, copolymers, blends and combinations thereof. Surprisingly, we have observed that these sulfonated polymers have both lithium and sodium ion conductivity.

A "filament" is a solid material body having a largest dimension (eg length) and a smallest dimension (eg diameter or thickness), the ratio of the largest dimension to the smallest dimension being greater than 3, preferably greater than 10. More preferably, it is larger than 100. Typically, this is a wire-like, fiber-like, needle-like, rod-like, platelet-like, sheet-like, ribbon-like or disc-like object, just to name a few. In certain embodiments, the conductive filaments are carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle cokes, carbon whiskers, conductive polymer fibers, conductive material coated fibers, metal nanowires, metal fibers. , Metal wires, graphene sheets, expanded graphite platelets, combinations thereof, or combinations thereof with non-filamentary conductive particles.

In certain embodiments, the electrodes maintain a conductivity of 10 ⁻⁵ S/cm to about 100 S/cm.

In certain embodiments, the deformable electrode material has an apparent viscosity of greater than or equal to about 10,000 Pa·s measured at an apparent shear rate of 1000 s ⁻¹ . In certain embodiments, the deformable electrode material has an apparent viscosity of about 100,000 Pa·s or greater at an apparent shear rate of 1000 s ⁻¹ . The quasi-solid electrode can be conformal to virtually any desired shape, whether regular or amorphous.

In this method, the amount of active material is typically about 20% to about 95% by volume of the electrode material, more typically about 35% to about 85% by volume of the electrode material, most typically. Is about 50% to about 75% by volume of the electrode material.

Preferably, the step of combining the active material, the conductive additive, and the electrolyte (including dissolving the lithium or sodium salt in the liquid solvent) follows a particular sequence. This step involves first dispersing the conductive filaments in a liquid solvent to produce a homogeneous suspension, then adding the active material to the suspension and dissolving the lithium or sodium salt in the liquid solvent, Dissolving or dispersing the ion conductive polymer in a solvent. In other words, the conductive filaments must be uniformly dispersed in the liquid solvent before adding the active material and other components such as the ion-conducting polymer and before dissolving the lithium or sodium salt in the liquid solvent. This order is essential to achieve percolation of the conducting filaments to form a 3D network of electronic conduction paths with a lower conducting filament volume fraction (lower threshold volume fraction). If such a sequence is not followed, percolation of the conducting filaments will not occur, or only if a very large proportion of conducting filaments (eg greater than 10% by volume) is added. Such extremely large proportions of conductive filaments reduce the fraction of active material and thus the energy density of the cell.

In certain embodiments, combining the electrode materials to form a quasi-solid electrode comprises dissolving a lithium salt (or sodium salt) and an ion-conducting polymer in a liquid solvent to produce a first salt concentration and a first polymer concentration. Forming a polymer electrolyte and then removing a portion of the liquid solvent to increase the salt concentration to obtain a quasi-solid polymer electrolyte having a second salt concentration and a second polymer concentration. The second salt concentration and the second polymer concentration are higher than the first concentration, preferably higher than 2.5M (more preferably 3.0M to 14M) complex salt and polymer.

The step of removing a portion of the solvent may be performed so as not to cause salt or polymer precipitation or crystallization, and to cause the electrolyte to become supersaturated. In certain preferred embodiments, the liquid solvent contains at least a mixture of a first liquid solvent and a second liquid solvent, the first liquid solvent being more volatile than the second liquid solvent, and The step of removing a portion of the solvent includes partially or completely removing the first liquid solvent.

There is no limitation on the type of anode active material or cathode active material that can be used to practice the present invention. However, preferably, the anode active material is less than 1.0 volt (preferably 0 to Li→Li ⁺ +e ⁻ as a standard potential) than Li/Li ⁺ when the battery is charged. Absorbs lithium ions with an electrochemical potential above (less than 0.7 volts).

In certain preferred embodiments, the alkali metal cell is a lithium metal battery, a lithium ion battery, or a lithium ion capacitor, and the anode active material is (a) particles of lithium metal or a lithium metal alloy; and (b) natural graphite. Particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles (including soft carbon and hard carbon), needle coke, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; and (c) 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); and (d) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or an alloy or intermetallic between Cd and another element. Compounds, alloys or intermetallics that are stoichiometric or non-stoichiometric; and (e) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti. , Mn, or Cd oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides, and mixtures or composites thereof; (f) pre-lithiated versions thereof; g) selected from the group consisting of pre-lithiated graphene sheets; and combinations thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is petroleum coke, amorphous carbon, activated carbon, hard carbon (carbon that is difficult to graphitize), soft carbon (easy to use). Graphitizable 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 = 0.2~1.0} ), Na 2 C 8 H 4 O 4, the carboxylic acid-based _{material, C 8 H 4 Na 2 O} 4, C 8 H 6 O 4, C 8 H Sodium intercalation selected from 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 combinations thereof. An anode active material containing a compound.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is (a) particles of sodium metal or sodium metal alloy; and (b) natural graphite particles, artificial graphite particles, meso. Carbon microbeads (MCMB), carbon particles, needle cokes, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; (c) sodium-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 a mixture thereof; (d) a sodium-containing alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and a mixture thereof; (E) Sodium-containing oxides, carbides, nitrides, and sulfides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof. An anode activity selected from the group consisting of: a compound, a phosphide, a selenide, a telluride, or an antimonide; (f) a sodium salt; (g) a graphene sheet preloaded with sodium ions; a combination thereof. It is a substance.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides, or combinations thereof. Is a cathode active material containing a sodium intercalation compound or a sodium absorbing compound. Metal oxides/phosphates/sulfides include sodium cobaltate, sodium nickelate, sodium manganate, sodium vanadate, sodium mixed metal oxides, sodium/potassium transition metal oxides, sodium iron phosphate, iron phosphate It may be selected from sodium/potassium, sodium manganese phosphate, sodium/potassium manganese phosphate, sodium vanadium phosphate, sodium/potassium vanadium phosphate, sodium mixed metal phosphoric acid, 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. In certain embodiments, 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.

In some embodiments, the alkali metal cell is sodium metal cell or sodium ion cells, the active _{material, NaFePO 4, Na (1-} x) K x PO 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, 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 , 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 = 0.01~100), Se, Aruodo stone, or a combination thereof It is a cathode active material containing a sodium intercalation compound selected from, and x is 0.1 to 1.0.

In some preferred embodiments, the cathode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganate, doped lithium manganate, lithium vanadate, Lithium selected from the group consisting of doped lithium vanadate, lithium mixed metal oxides, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, mixed lithium phosphate metal, metal sulfides, and combinations thereof. Includes intercalation compounds.

The electrolyte is water, an organic liquid, an ionic liquid (an ionic salt having a melting point below 100° C., preferably below room temperature of 25° C.), or a mixture of an ionic liquid and an organic liquid at a ratio of 1/100 to 100/1. It can be contained in a ratio. Organic liquids are preferred, but ionic liquids are preferred. The electrolyte typically and preferably contains a high solute concentration (complex concentration of lithium/sodium salt and polymer) that saturates or supersaturates the solute at the resulting electrode (anode or cathode). Such electrolytes are essentially polymer electrolytes that are deformable or adaptable and behave like solids. This is fundamentally different than liquid or polymer gel electrolytes.

In a preferred embodiment, the quasi-solid electrode has a thickness of 200 μm to 1 cm, preferably 300 μm to 0.5 cm (5 mm), more preferably 400 μm to 3 mm, most preferably 500 μm to 2.5 mm (2500 μm). When the active material is an anode active material, the anode active material has a mass loading of 25 mg/cm ² or more (preferably 30 mg/cm ² or more, more preferably 35 mg/cm ² or more) and/or the battery. It makes up at least 25% by weight or volume% (preferably at least 30%, more preferably at least 35%) of the total cell. When the active material is a cathode active material, the cathode active material is preferably 20 mg/cm ² or more (preferably 25 mg/cm ² or more, more preferably 30 mg/cm ² or more in the cathode) with respect to the organic or polymer material. ) Or 45%/cm ² or more (preferably 50 mg/cm ² or more, more preferably 55 mg/cm ² or more) for inorganic and non-polymeric materials, and/or Alternatively, it occupies at least 45% by weight or volume% (preferably at least 50%, more preferably at least 55%) of the entire battery cells.

The aforementioned requirements regarding the thickness of the electrode, the area mass load of the anode active material or the mass fraction of the whole battery cell, or the area mass load of the cathode active material or the mass fraction of the whole battery cell are related to conventional slurry coating and drying methods Was not possible with conventional lithium or sodium batteries using

In some embodiments, the anode active material is pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, boron-doped A pre-lithiated version of graphene sheet selected from graphene, nitrogen-doped graphene, chemically functionalized graphene, physically or chemically activated or etched versions thereof, or combinations thereof. Surprisingly, without prelithiation, the resulting lithium battery cells do not exhibit sufficient cycle life (ie, capacity decays rapidly).

In some embodiments of the method of the present invention, the cell comprises a lithium intercalation compound or lithium absorption compound selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides, or combinations thereof. A lithium metal cell or a lithium ion cell containing a cathode active material selected from compounds. For example, the metal oxide/phosphate/sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate. , Lithium phosphate mixed metal, transition metal sulfide, and combinations thereof. The inorganic material is selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. In particular, the inorganic _{material, TiS 2, TaS 2, MoS} 2, NbSe 3, MnO 2, CoO 2, iron oxide is selected from vanadium oxide, or combinations thereof. These will be discussed further below.

In this lithium metal battery, the cathode active material comprises a lithium intercalation compound selected from metal carbides, metal nitrides, metal borides, metal dichalcogenides, or combinations thereof. In some embodiments, the cathode active material is niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, in the form of nanowires, nanodisks, nanoribbons, or nanoplatelets. It includes a lithium intercalation compound selected from iron or nickel oxides, dichalcogenides, trichalcogenides, sulfides, selenides, or tellurides. Preferably, 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, cobalt, manganese. Nanodiscs, nanoplatelets, nanocoatings of inorganic materials selected from sulfides, selenides, or tellurides of iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof. Or a lithium intercalation compound selected from nanosheets, wherein the disk, platelet, or sheet has a thickness of less than 100 nm.

In some embodiments, in this lithium metal battery, the cathode active material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). ), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino (triazene), redox active organic material, tetracyanoquinodimethane (TCNQ), tetra Cyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5-benzylidene Hydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi ₄ ), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N '-Diallyl-2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone compound, 1,4 -Benzoquinone, 5,7,12,14-pentacentetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDAQ), 5-amino-1,4-dihydroxyanthraquinone (ADAQ) An organic material or a polymer material selected from: caric skinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , or a combination thereof.

The thioether polymer includes poly(methantetryl-tetra(thiomethylene)) (PMTTM), poly(2,4-dithiopentanylene) (PDTP), and poly(ethene-1,1,2,2-tetrathiol) as a main chain thioether polymer. ) (PET)-containing polymer, a side chain thioether polymer having a main chain composed of a conjugated aromatic component, 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(ethylenedithio)thiophene] (PEDTT).

In a preferred embodiment, the cathode active material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, phthalocyanine chloroaluminum, cadmium. An organic material containing a phthalocyanine compound selected from phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or a combination thereof.

In a lithium metal battery, a cathode active material, 30 mg / cm ² greater (preferably 40 mg / cm ^2, more preferably above 45 mg / cm ² greater, and most preferably 50 mg / cm ² than) the electrode active material loading of adult And/or the electrodes have a thickness of 300 μm or more (preferably 400 μm or more, more preferably 500 μm or more, even up to 100 cm or even more than 100 cm). There is no theoretical limit to the electrode thickness of the alkali metal battery according to the present invention.

FIG. 1A shows an anode current collector, one or two anode active material layers (for example, a thin Si coating layer) coated on two main surfaces of the anode current collector, a porous separator and an electrolyte. FIG. 1 is a schematic diagram of a prior art lithium-ion battery cell composed of, one or two cathode electrode layers (eg, a sulfur layer), and a cathode current collector. In FIG. 1B, the electrode layer includes discrete particles of active material (eg, graphite or tin oxide particles in the anode layer or LiCoO ₂ in the cathode layer), a conductive additive (not shown), and a resin. 1 is a schematic diagram of a prior art lithium-ion battery composed of a binder (not shown). FIG. 1(C) shows a quasi-solid anode (comprising anode active material particles and conductive filaments directly mixed or dispersed in an electrolyte), a porous separator, and a quasi-solid cathode (directly mixed or dispersed in an electrolyte). Is a cathode active material particles and conductive filaments) according to the present invention. In this embodiment, no resin binder is needed. FIG. 1(D) shows an anode (containing a lithium metal layer deposited on a Cu foil surface), a porous separator, a quasi-solid cathode (cathode active material particles mixed or dispersed directly in an electrolyte and conductivity). And (comprising a filament). In this embodiment, no resin binder is needed. FIG. 2A is a schematic view of a dense and highly ordered structure of a solid electrolyte. FIG. 2(B) is a schematic diagram of a completely amorphous liquid electrolyte with a large percentage of free volume to which cations (eg, Na ⁺ ) can easily migrate. FIG. 2(C) is a disordered or amorphous quasi-solid electrolyte containing solvent molecules that separate salt species to create an amorphous zone where free (non-clustered) cations can easily migrate. It is a schematic diagram of a structure. Also, the ion-conducting polymer is in a supersaturated state that remains substantially amorphous. FIG. 3A is a diagram showing Na ⁺ ion transport number in the electrolyte (eg, (PEO+NaTFSI salt) in the (DOL+DME) solvent) related to the sodium salt molecule ratio x. FIG. 3(B) is a diagram showing the Na ⁺ ion transport number in the electrolyte (eg, (PPO+NaTFSI salt) in the (EMImTFSI+DOL) solvent) related to the sodium salt molecule ratio x. FIG. 4 is for producing exfoliated graphite, expanded graphite flakes (thickness>100 nm), and graphene sheets (thickness <100 nm, more typically <10 nm, and may be as thin as 0.34 nm). 1 is a schematic diagram of a commonly used method. FIG. 5A is a diagram showing the conductivity (percolation behavior) of the conductive filament in the quasi-solid polymer electrode plotted as a function of the volume fraction of the conductive filament (carbon nanofiber). FIG. 5(B) shows the conductivity (percolation behavior) of the conductive filament in the quasi-solid polymer electrode plotted as a function of the volume fraction of the conductive filament (reduced graphene oxide sheet). FIG. 6 is a diagram showing a Ragone plot (weight power density vs. energy density) of a lithium-ion battery cell containing graphite particles as an anode active material and carbon-coated LFP particles as a cathode active material. Three of the four data curves are for cells prepared according to embodiments of the present invention, the other one is from conventional slurry coating (roll coating) of the electrodes. FIG. 7 is a diagram showing a Ragone plot (weight output density vs. weight energy density) of three cells. Each cell contains graphene-encapsulated Si nanoparticles as an anode active material and LiCoO ₂ nanoparticles as a cathode active material. Experimental data were obtained from the Li-ion battery cells prepared by the method according to the invention (according to the sequence S1 and S3) and the conventional slurry coating of the electrodes. FIG. 8 shows a lithium foil as an anode active material, dilithium rhodizonate (Li ₂ C ₆ O ₆ ) as a cathode active material, and a lithium salt (LiPF ₆ )/PPO-PC/DEC as an organic electrolyte. It is a Ragone plot of the lithium metal battery containing. The data are lithium metal cells prepared by the method according to the invention (sequence S2 and S3 with two different salt concentrations) and conventional slurry coating of the electrodes. FIG. 9 shows a Ragone plot of two sodium ion capacitors, each containing pre-sodiumized hard carbon particles as anode active material and graphene sheet as cathode active material. One cell has an anode prepared by a conventional slurry coating process and the other cell has a quasi-solid anode prepared according to the method according to the invention.

The present invention is directed to lithium or sodium batteries that have shown very high volumetric energy densities not previously realized. This battery may be a primary battery, but is selected from a lithium ion battery, a lithium metal secondary battery (for example, using lithium metal as an anode active material), a sodium ion battery, a sodium metal battery, a lithium ion capacitor, or a sodium ion capacitor. It is preferable that the secondary battery is Batteries are based on a quasi-solid polymer electrolyte containing a polymer and a lithium or sodium salt dissolved in water, an organic solvent, an ionic liquid, or a mixture of organic and ionic liquids. Preferably, the electrolyte is a "quasi-solid polymer electrolyte" containing a high concentration of solutes (lithium or sodium salts and polymer) in the solvent, behaving like a solid, but with the desired amount of conductive filaments and It remains deformable when the active material is added to the electrolyte (hence the term "deformable quasi-solid polymer electrode"). The electrolyte is neither a liquid electrolyte nor a solid electrolyte. The shape of the lithium battery may be cylindrical, square, button-shaped or the like. The present invention is not limited to any battery shape or configuration.

For convenience, illustrative examples of cathode active materials include lithium iron phosphate (LFP), vanadium oxide (V _x O _y ), dilithium rhodizonate (Li ₂ C ₆ O ₆ ), and copper phthalocyanine (CuPc). examples of the anode active material, graphite, hard carbon, SnO, _Co 3 _{O 4,} and the like Si particles, using the selected material. These should not be construed as limiting the scope of the invention.

As shown in FIG. 1A, prior art lithium or sodium battery cells typically include an anode current collector (eg, Cu foil) and an anode electrode or anode active material layer (eg, Cu foil). Metal foil, sodium foil, or pre-lithiated Si coating) deposited on one or two sides of the above, a porous separator and/or an electrolyte component, and a cathode electrode or cathode active material layer (or two sides of Al foil) Two cathode active material layers) and a cathode current collector (for example, Al foil).

In the more commonly used prior art cell configurations (FIG. 1(B)), the anode layer is an anode active material (eg, graphite, hard carbon or Si), a conductive additive (eg, carbon black particles). , And resin binder (eg, SBR or PVDF) particles. The cathode layer is composed of particles of cathode active material (eg, LFP particles), conductive additives (eg, carbon black particles), and resin binder (eg, PVDF). Both the anode and cathode layers are typically up to 100-200 [mu]m thick and will probably produce a sufficient amount of current per unit electrode area. This thickness range is considered to be an industry accepted constraint that battery designers typically work with. This thickness constraint is due to several reasons: (a) existing battery electrode coating machines are not equipped to coat very thin or very thick electrode layers. (B) a thinner layer is preferred in view of shortening the lithium ion diffusion path length; however, if the layer is too thin (eg <100 μm) it does not contain a sufficient amount of active lithium storage material (and therefore (C) thicker electrodes are susceptible to delamination or cracking during drying or handling after roll coating; and (d) minimum overhead weight and maximum lithium storage capacity, and thus maximum energy density ( In order to obtain Wk/kg or Wh/L of the cell, all non-active material layers (eg current collector and separator) in the battery cell must be kept to a minimum.

In less commonly used cell configurations, as shown in FIG. 1(A), an anode active material (eg, Si coating) or a cathode active material (eg, lithium transition metal oxide) may be copper foil or It is deposited in the form of a thin film directly on a current collector such as an Al foil. However, such thin film structures with very small thickness dimension (typically much less than 500 nm and often less than 100 nm if needed) (same surface area of electrode or current collector). Suggesting that only a small amount of active material can be incorporated into the electrode, reducing the total lithium storage capacity and reducing the lithium storage capacity per unit electrode surface area. Such thin films should have a thickness of less than 100 nm in order to be more resistant to cycling-induced cracking (for the anode) or to facilitate full utilization of the cathode active material. Such constraints further reduce the total lithium storage capacity and the lithium storage capacity per unit electrode surface area. Such thin film batteries have a very limited range of applications.

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

That is, in terms of material type, size, electrode layer thickness, and active material mass loading, there are several conflicting factors that must be considered simultaneously when designing and selecting a cathode or anode active material. So far, no effective solution has been provided by any prior art teaching to these often conflicting problems. As disclosed herein, the present inventors have plagued battery designers and also electrochemists for over thirty years by developing new methods of making lithium or sodium batteries. Solved the problem.

Prior art lithium battery cells are typically manufactured by a method that includes the following steps: (a) The first step is the anode active material (eg, Si nanoparticles or mesocarbon microbeads, MCMB). , Conductive fillers (eg, graphite flakes), and particles of a resin binder (eg, PVDF) in a solvent (eg, NMP) to form an anode slurry. Separately, cathode active material (eg, LFP particles), conductive filler (eg, acetylene black), and resin binder (eg, PVDF) particles are mixed and dispersed in a solvent (eg, NMP). Form a cathode slurry. (B) The second step is to coat the anode slurry on one or both major surfaces of the anode current collector (eg Cu foil) and dry the coated layer by evaporating the solvent (eg NMP). To form a dry anode electrode coated on a Cu foil. Similarly, the cathode slurry is coated and dried to form a dried cathode electrode coated on Al foil. In an actual manufacturing situation, slurry coating is usually performed in a roll-to-roll manner; (c) the third step is to laminate the anode/Cu foil sheet, porous separator layer, and cathode/Al foil sheet together. Forming a three-layer or five-layer assembly, which is cut or slit into desired sizes and laminated to form a rectangular structure (as an example of a shape) or rolled into a cylindrical cell structure. Including doing. (D) The rectangular or cylindrical laminated structure is then housed in an aluminum plastic laminated envelope or steel casing. (E) Next, a liquid electrolyte is injected into the laminated structure to manufacture a lithium battery cell.

There are some significant problems associated with this method and the resulting lithium battery cells.
1) It is very difficult to manufacture an electrode layer (anode layer or cathode layer) thicker than 200 μm. There are several reasons. Electrodes 100-200 μm thick typically require a heating zone of 30-50 meters in length in a slurry coating facility, which is too time consuming, energy consuming and cost effective. Absent. For some electrode active materials such as metal oxide particles, electrodes with good structural integrity thicker than 100 μm have not been able to be continuously manufactured in a practical manufacturing environment. The resulting electrode is very fragile and brittle. Thicker electrodes are more prone to delamination and cracking.
2) In the conventional method as shown in FIG. 1(A), the actual mass loading of the electrodes and the apparent density of the active material are too low to achieve a weight energy density of over 200 Wh/kg. Often, even for relatively large graphite particles, the anode active material mass loading (area density) of the electrode is much lower than 25 mg/cm ² , and the apparent bulk or tap density of the active material is typically 1.2 g. /Cm ^{3 or} less. The cathode active material mass loading (area density) of the electrodes is substantially lower than 45 mg/cm ^{2 for} lithium metal oxide based inorganic materials and substantially lower than 15 mg/cm ^{2 for} organic or polymeric materials. .. In addition, there are numerous other non-active materials (eg, conductive additives and resin binders) that add additional weight and volume to the electrode without contributing to battery capacity. These low areal and low volume densities result in relatively low gravimetric energy densities and low volumetric energy densities.
3) In the conventional method, it is necessary to disperse the electrode active material (anode active material and cathode active material) in a liquid solvent (for example, NMP) to form a slurry, and after coating the current collector surface with the liquid solvent, The electrode layer must be removed and dried. After stacking the anode and cathode layers together with the separator layer and packaging in a housing to form a battery cell, a liquid electrolyte is injected into the cell. In practice, the two electrodes are wetted, then the electrodes are dried and finally wetted again. Such a dry-wet-dry-wet process is not a good process.
4) Current lithium ion batteries still have the drawbacks of relatively low weight energy density and low volume energy density. Commercially available lithium ion batteries exhibit a gravimetric energy density of about 150-220 Wh/kg and a volume energy density of 450-600 Wh/L.

The energy density data reported in the literature based on active material weight alone or electrode weight cannot directly derive the energy density of a practical battery cell or device. "Overhead weight", ie the weight of other device components (binders, conductive additives, current collectors, separators, electrolytes, and packaging) must also be taken into account. In the conventional manufacturing method, the weight ratio of the anode active material (for example, graphite or carbon) in the lithium ion battery is typically 12% to 17%, and the weight ratio of the cathode active material is 20% to 35%. % (For inorganics such as LiMn ₂ O ₄ ) or 7-15% (for organic or polymeric cathode materials).

The present invention provides lithium or sodium battery cells with high electrode thickness, high active material mass loading, low overhead weight and volume, high capacity, and high energy density. In a particular embodiment, the invention provides (a) about 5% to about 40% by volume of a first active material containing about 30% to about 95% by volume of a cathode active material and an alkali salt dissolved in a solvent. A semi-solid polymer cathode comprising: an electrolyte of claim 1, an ion-conducting polymer dissolved, dispersed or impregnated in the solvent, and about 0.01% to about 30% by volume of a conductive additive. A conductive additive containing a filament forms a 3D network of electronic conduction paths such that the quasi-solid electrode has a conductivity of from about 10 ⁻⁶ S/cm to about 300 S/cm (which may be higher). A quasi-solid polymer cathode; (b) an anode (which may be a conventional anode or a quasi-solid polymer electrode); and (c) an ion conducting membrane or porous separator disposed between the anode and the quasi-solid cathode. And an alkali metal cell in which the quasi-solid cathode has a thickness of 200 μm or more. Preferably, the quasi-solid polymer cathode is 10 mg/cm ² or more, preferably 15 mg/cm ² or more, more preferably 25 mg/cm ² or more, more preferably 35 mg/cm ² or more, even more preferably 45 mg/cm ² or more. Most preferably containing a cathode active material mass loading of 65 mg/cm ² or greater.

In this cell, the anode comprises about 30% to about 95% by volume of the anode active material, about 5% to about 40% by volume of a second electrolyte containing an alkali salt dissolved in the solvent, and the solvent. May include a quasi-solid polymer anode containing an ion-conducting polymer dissolved, dispersed, or impregnated in the, and a conductive additive of about 0.01% to about 30% by volume, containing a conductive filament. The conductive additive forms a 3D network of electron conduction paths so that the quasi-solid electrode has a conductivity of about 10 ⁻⁶ S/cm to about 300 S/cm, and the quasi-solid anode has a thickness of 200 μm or more. Have. The quasi-solid anode is preferably 10 mg/cm ² or more, preferably 15 mg/cm ² or more, more preferably 25 mg/cm ² or more, more preferably 35 mg/cm ² or more, even more preferably 45 mg/cm ² or more, most preferably It preferably contains a mass loading of anode active material of 65 mg/cm ² or more. The first electrolyte may be the same or different in composition and structure as the second electrolyte.

In some embodiments, the alkali metal battery contains a quasi-solid polymer anode, but contains a conventional cathode.

The present invention also provides a method of manufacturing an alkali metal battery. In a particular embodiment, the method comprises the following steps.
(A) combining an amount of active material (anode active material or cathode active material), an amount of polymer electrolyte (containing polymer and alkali metal salt dissolved in a solvent) and a conductive additive, Forming a deformable conductive electrode material. Here, the conductive additive containing the conductive filaments forms a 3D network of electron conduction paths (before these conductive filaments such as carbon nanotubes and graphene sheets are mixed with the particles of the active material and the electrolyte). The mixing procedure involves dispersing these conductive filaments in a high viscosity electrolyte containing particles of the active material, as described in the section below. For further discussion).
(B) Forming the electrode material as a quasi-solid electrode. Here, in this forming step, the electrode is 10 ⁻⁶ S/cm or more (preferably 10 ⁻⁵ S/cm or more, more preferably 10 ⁻⁴ S/cm or more, further preferably 10 ⁻³ S/cm or more, Even more preferably and typically 10 ⁻² S/cm, even more typically and preferably 10 ⁻¹ S/cm, even more typically and preferably 1 S/cm or more; up to 300 S/cm. Of the electrode material is transformed into an electrode shape without disturbing the 3D network of electron conduction paths, so as to maintain the electrical conductivity of
(C) forming a second electrode (the second electrode may be a quasi-solid polymer electrode or a conventional electrode); and (d) placing the quasi-solid electrode and the second electrode between the two electrodes. Forming an alkali metal cell by having and combining an ion conducting separator disposed in.

Either or both of the anode and cathode may be quasi-solid electrodes. In certain embodiments, the step of forming the second electrode comprises (A) an amount of a second active material (eg, an anode active material if the first electrode is a cathode) and an amount of. A step of combining an electrolyte and a conductive additive to form a second deformable conductive electrode material, wherein the conductive additive containing a conductive filament forms a 3D network of electronic conduction paths. And the electrolyte contains an alkali salt and an ion-conducting polymer dissolved or dispersed in a solvent; and (B) forming a second deformable conductive electrode material as a second quasi-solid electrode. Then, the forming operation does not interrupt the 3D network of the electron conduction path so that the second electrode maintains the conductivity of 10 ⁻⁶ S/cm or more (typically up to 300 S/cm). The method includes transforming a second deformable conductive electrode material into an electrode shape.

As shown in FIG. 1C, one preferred embodiment of the present invention is a conductive quasi-solid polymer anode 236, a conductive quasi-solid polymer cathode 238, and a porous separator that electronically separates the anode and the cathode. It is an alkali metal ion cell having 240 (or an ion permeable membrane). These three components were typically housed in a protective housing (not shown), which was typically connected to the anode tab (terminal) connected to the anode and to the cathode. And a cathode tab (terminal). These tabs are for connecting an external load (eg, an electronic device to be powered by its battery). In this particular embodiment, the quasi-solid polymer anode 236 includes an anode active material (eg, Si or hard carbon particles, not shown in FIG. 1C) and an electrolyte phase (typically a solvent). It contains a dissolved lithium salt or sodium salt and an ion-conducting polymer dissolved, dispersed or impregnated in this solvent; also not shown in FIG. 1C), and a 3D network of electron conduction paths. And a conductive additive that forms 244 (containing a conductive filament). Similarly, the quasi-solid polymer cathode contains a cathode active material, an electrolyte, and conductive additives (containing conductive filaments) that form the 3D network of electron conducting pathways 242.

Another preferred embodiment of the invention shown in FIG. 1(D) is an anode composed of a lithium or sodium metal coating/foil 282 deposited/attached to a current collector 280 (eg Cu foil), and It is an alkali metal cell having a solid cathode 284 and a separator or an ion conductive membrane 282. The semi-solid polymer cathode 284 includes a cathode active material 272 (eg, LiCoO ₂ particles), an electrolyte phase 274 (typically a lithium salt or sodium salt dissolved in a solvent, and a solvent dissolved, diffused, or impregnated in the solvent. An ion-conducting polymer), and a conductive additive phase (containing a conductive filament) that forms the 3D network 270 of the electron-conducting path. The present invention also includes lithium ion capacitors and sodium ion capacitors.

The electrolyte is preferably a quasi-solid polymer electrolyte containing a lithium salt or sodium salt dissolved in a solvent and a polymer, the complex salt/polymer concentration of which is 1.5M or more, preferably 2.5M or more, It is preferably more than 3.5M, more preferably more than 5M, even more preferably more than 7M, even more preferably more than 10M. In certain embodiments, the electrolyte is a quasi-solid polymer electrolyte containing a polymer and a lithium or sodium salt dissolved in a liquid solvent with a complex salt/polymer concentration of 3.0M to 14M. The choice of lithium or sodium salt and liquid solvent is discussed further in a later section.

In some embodiments, the electrolyte is poly(ethylene oxide) (PEO, having a molecular weight of less than 1×10 ⁶ g/mol), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate). (PMMA), poly(vinylidene fluoride) (PVDF), polybis-methoxyethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), sulfones thereof. Containing a lithium ion conducting or sodium ion conducting polymer selected from sulfonated derivatives, sulfonated polymers, or combinations thereof. Here, sulfonation has been found to improve the lithium ion conductivity of the polymer. Molecular weights of PEO higher than 1×10 ⁶ g/mol typically make PEO difficult to dissolve or disperse in the solvent.

Typically, the ion conducting polymer does not form a matrix (continuous phase) in the electrode. Instead, the polymer is either dissolved in the solvent as a solution phase or dispersed as a discrete phase in the solvent matrix. The resulting electrolyte is a quasi-solid polymer electrolyte, which is neither a liquid electrolyte nor a solid electrolyte.

The ion-conducting polymer is poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivative of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly(ether ether). Ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonated polychloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymer (FEP), sulfonated ethylene-chloro. Trifluoroethylene copolymer (ECTFE), sulfonated polyvinylidene fluoride (PVDF), polyvinylidene fluoride and hexafluoropropene and sulfonated copolymers of tetrafluoroethylene, sulfonated copolymer of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives thereof, copolymers, blends and combinations thereof. Surprisingly, we have observed that these sulfonated polymers have both lithium and sodium ion conductivity.

Both the quasi-solid anode and the quasi-solid cathode preferably have a thickness of more than 200 μm (preferably more than 300 μm, more preferably more than 400 μm, even more preferably more than 500 μm, even more preferably more than 800 μm, even more preferably more than 1 mm). And may be greater than 5 mm, greater than 1 cm, or even thicker). There is no theoretical limit to the thickness of the electrodes according to the invention. In the cells of the present invention, the anode active material is typically 20 mg/cm ² or more (more typically and preferably 25 mg/cm ² or more, more preferably 30 mg/cm ² or more) electrode in the anode. Make active material loading. When an inorganic material is used as the cathode active material, the cathode active material has an electrode active material mass of 45 mg/cm ² or more (typically and preferably more than 50 mg/cm ² and more preferably more than 60 mg/cm ² ). Make up the loading (25 mg/cm ² or more for organic or polymeric cathode active materials).

In such a configuration (FIGS. 1C-1D), the electrons are only collected over a short distance (eg, a few micrometers or less) and are collected by the conductive filament. The conductive filaments make up the 3D network of electronic conduction pathways and are ubiquitous throughout the quasi-solid polymer electrode (anode or cathode). In addition, all electrode active material particles are pre-dispersed in the electrolyte solvent (no wettability issues) and are commonly found in electrodes prepared by conventional processes of wet coating, drying, packing, and electrolyte injection. Eliminate existing dry pockets. Therefore, the process or method according to the present invention has quite unexpected advantages over conventional battery cell manufacturing processes.

These conductive filaments (such as carbon nanotubes and graphene sheets) are a large number of filaments that are originally randomly aggregated before being mixed with the particles of the active material and the electrolyte when supplied. The mixing procedure involves dispersing these conductive filaments in an electrolyte such as a high viscosity solid containing particles of active material. This is not as easy as it sounds. Dispersion of nanomaterials (particularly nanofilament materials such as carbon nanotubes, carbon nanofibers, and graphene sheets) in highly fluid (non-viscous) liquids is known to be very difficult, let alone high loading. Needless to say, in a high-viscosity quasi-solid, such as an electrolyte containing the active material (for example, Si nanoparticles for the anode and solid particles such as lithium cobalt oxide for the cathode). In some preferred embodiments, this problem is further exacerbated by the electrolyte itself being a quasi-solid polymer electrolyte, containing high concentrations of lithium or sodium salts in the solvent.

In some preferred embodiments, the electrolyte comprises a polymer and an alkali metal (lithium salt and/or sodium salt) dissolved in an organic or ionic liquid solvent at a sufficiently high combined alkali metal salt/polymer concentration, As a result, the electrolyte has a vapor pressure of less than 0.01 kPa or less than 0.6 (60%) of the vapor pressure of the solvent alone (measured at 20° C.), at least 20 above the flash point of the first organic liquid solvent alone. It shows a flash point above 0° C. (if no lithium salt is present), or above 150° C., or no detectable flash point.

Most surprising, and of great scientific and technical importance, is the addition of sufficiently large amounts of alkali metal salts and polymers into this organic solvent to dissolve and produce a solid-like or quasi-solid electrolyte. For example, it is a discovery by the present inventors that the flammability of any volatile organic solvent can be effectively suppressed. Generally, such quasi-solid polymer electrolytes are less than 0.01 kPa and often less than 0.001 kPa (measured at 20° C.) and less than 0.1 kPa and often less than 0.01 kPa (100). (Measured in °C.) (in the absence of any alkali metal salt and/or polymer dissolved in the solvent, the vapor pressure of the corresponding neat solvent is typically much higher). In many cases featuring quasi-solid polymer electrolytes, vapor molecules are too few to be detected in practice.

A very important observation is that the solubility of the complex of alkali metal salt and polymer in a solvent that is normally highly volatile (typically above 0.2, more typically above 0.3). And, in many cases greater than 0.4, or even greater than 0.5, a large molecular ratio or mole fraction of alkali metal salt/polymer chain segment) to escape into the vapor phase at thermodynamic equilibrium. This means that the amount of volatile solvent molecules that can be produced can be dramatically reduced. In many cases, this effectively prevents flammable solvent gas molecules from producing a flame, even at very high temperatures (eg using a torch). The flash point of quasi-solid polymer electrolytes is typically at least 20 degrees (often above 50 degrees, or above 100 degrees) above the flash point of neat organic solvent alone. In most cases, the flash point is higher than 150°C or the flash point cannot be detected. The electrolyte does not ignite. Moreover, accidental flames do not last longer than a few seconds. Given the view that ignition and explosion concerns are the main obstacles to the widespread acceptance of battery-powered electric vehicles, this is a very significant finding. This new technology can greatly help accelerate the emergence of a vibrant EV industry.

For safety considerations, ultra-high concentrations of battery electrolytes (including high molecular weight, eg, greater than 0.2, or greater than 0.3 alkali metal salt/polymer chain segments, or complex concentrations of about 2.5 M No studies have previously been reported for vapor pressures (or above 3.5 M). This is quite unexpected and of highest technical and scientific importance.

Furthermore, we have found that the presence of a 3D network of electronic conduction pathways constituted by conductive nanofilaments further reduces the threshold concentration of alkali metal salt needed to achieve the suppression of critical vapor pressure. Unexpectedly discovered to work.

Another surprising element of the invention is almost all types of battery grade organic solvents that are commonly used to produce quasi-solid polymer electrolytes suitable for use in rechargeable alkali metal batteries, It is the view that high concentrations of alkali metal salts and selected ion-conducting polymers can be dissolved. In simpler terms, this concentration is typically above 2.5M (mol/liter), more typically and more preferably above 3.5M, and even more typically and It is more preferably more than 5M, even more preferably more than 7M, and most preferably more than 10M. Above 2.5 M salt/polymer concentration, the electrolyte is no longer a liquid electrolyte, but a quasi-solid electrolyte. In the field of lithium or sodium batteries, it is generally believed that such high concentrations of alkali metal salts in solvents are not possible or even desirable. However, the present inventors have found that these quasi-solid polymer electrolytes are surprisingly good for both lithium batteries and sodium batteries from the viewpoint of greatly improving safety (incombustibility), energy density, and power density. It has been found to be a good electrolyte.

In addition to the non-flammability and high alkali metal ion transport numbers discussed above, there are some additional benefits associated with the use of the quasi-solid polymer electrolyte according to the present invention. As an example, the quasi-solid polymer electrolyte can significantly improve the cycle performance and safety performance of a rechargeable alkaline metal battery by effectively suppressing the growth of dendrites. The idea that dendrites begin to grow in non-aqueous liquid electrolytes when anions are depleted near the electrodes where plating occurs is generally accepted. In ultra-high-concentration electrolytes, there are large amounts of anions to balance the cations (Li ⁺ or Na ⁺ ) and anions near the metallic lithium or sodium anode. In addition, the space charge generated by anion depletion is minimal, which does not contribute to dendrite growth. In addition, due to both the ultra-high Li or Na salt concentration and high Li-ion or Na-ion transport numbers, the quasi-solid polymer electrolyte provides a large amount of available lithium-ion or sodium-ion flux, and the electrolyte and lithium- or sodium electrode. Increase the lithium or sodium ion mass transfer rate between and, thereby improving the uniformity and dissolution of lithium or sodium deposition during the charge/discharge process. In addition, high local viscosities induced by high concentrations can increase the pressure from the electrolyte and inhibit dendrite growth, resulting in more uniform deposition on the surface of the anode. Also, the high viscosity can limit anion convection near the deposition region and promote more uniform deposition of sodium ions. The same reasoning applies to lithium metal batteries. These reasons, either individually or in combination, are believed to support the view that dendrite-like features are not observed in any of the large number of rechargeable alkali metal cells investigated by the inventors.

Further, those skilled in the chemical or materials science arts should behave due to such high salt/polymer concentration such that the electrolyte behaves like a solid with a very high viscosity, so that the electrolyte is It was expected that it would be difficult to undergo the rapid diffusion of ions. As a result, alkali metal batteries containing polymer electrolytes such as solids do not and do not show high capacity at high charge/discharge rates or under conditions of high current density (i.e. It should have low rate capability). Contrary to those usual and even to these expectations of the skilled artisan, all alkali metal cells containing such quasi-solid polymer electrolytes provide high energy density and high power density over long cycle life. The quasi-solid polymer electrolytes devised and disclosed herein appear to contribute to easy alkali metal ion transport. This surprising observation result is considered to be due to the following two main factors. That is, one factor is associated with the internal structure of the electrolyte and the other is associated with high Na ⁺ or Li ⁺ ion transport numbers (TN).

Without wishing to be bound by any theory, it is possible to visualize the internal structure of three fundamentally different types of electrolytes, as in FIGS. 2(A)-2(C). FIG. 2A schematically illustrates a dense, highly ordered structure of a typical solid electrolyte, which has little free volume for diffusion of alkali metal ions. The migration of ions in such a crystal structure is very difficult, with a very low diffusion coefficient (10 ⁻¹⁶ to 10 ⁻¹² cm ² /sec) and a very low ionic conductivity (typically 10 −7 S). /Cm to 10 ⁻⁴ S/cm). In contrast, as shown schematically in FIG. 2B, the internal structure of the liquid electrolyte is completely amorphous and has a large percentage of free volume through which cations ( For example, Li ^<+> or Na ^<+> can move easily, a high diffusion coefficient (10 ^{< -8 >} -10 ^{< -6} >cm ^{< 2} >/sec) and high ionic conductivity (typically 10 ^<-3 >S/cm). 10 ⁻² S/cm). However, liquid electrolytes containing low concentrations of alkali metal salts are flammable and tend to form dendrites, creating the risk of fire and explosion. Shown schematically in FIG. 2(C) is a solvent molecule that separates salts and polymer chain segments to create an amorphous zone in which free (non-clustered) cations can readily migrate. Is a disordered or amorphous structure of a quasi-solid polymer electrolyte containing. Such a structure is likely to achieve high ionic conductivity values (typically 10 ⁻⁴ S/cm to 8×10 ⁻³ S/cm) and still maintain noncombustibility. Solvent molecules are relatively few and these molecules are conserved (preventing evaporation) by an overwhelming majority of salts, polymer chain segments, and a network of conducting filaments.

In a preferred embodiment, the anode active material is pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride, graphene nitride, chemically functionalized graphene, or A pre-lithiated or pre-sodiumized version of a graphene sheet selected from combinations thereof. The starting graphene material for producing any one of the above 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 a combination thereof. Graphene materials are also good conductivity additives for both anode and cathode active materials in lithium batteries.

Assuming that the interplane van der Waals forces can be overcome, the constituent graphene faces of graphite crystals in natural or artificial graphite particles are exfoliated and extracted or isolated to form individual graphenes of hexagonal carbon atoms. Sheets can be obtained, which are monatomic thick. A typical process is shown in FIG. The isolated individual graphene planes of carbon atoms are commonly referred to as monolayer graphene. A stack of graphene planes joined by van der Waals forces at a graphene plane spacing of about 0.3354 nm in the thickness direction is commonly referred to as multilayer graphene. Multilayer graphene platelets have up to 300 graphene faces (thickness less than 100 nm), but more typically up to 30 graphene faces (thickness less than 10 nm), and even more typically up to 20 layers. It has a graphene surface (thickness less than 7 nm), and most typically up to 10 layers of graphene surface (commonly referred to as few-layer graphene in the scientific community). Single-layer graphene and multilayer graphene sheets are collectively referred to as "nano-graphene platelets" (NGP). Graphene sheets/platelets (collectively NGP) are a new class of carbon nanomaterials (2D nanocarbons) different from 0D fullerenes, 1D CNTs or CNFs, and 3D graphite. For purposes of defining the claims and as is generally understood in the art, graphene materials (isolated graphene sheets) are not carbon nanotubes (CNTs) or carbon nanofibers (CNFs) (they are Not included).

In one method, as shown in FIGS. 5(A) and 5(B), the graphene material is a graphite intercalation compound (GIC) obtained by intercalating natural graphite particles with a strong acid and/or an oxidizing agent. Alternatively, it is obtained by obtaining graphite oxide (GO). The presence of chemical species or functional groups in the interstitial space between the graphene planes in the GIC or GO serves to increase the graphene spacing (d ₀₀₂ ; determined by X-ray diffraction), and thus usually For example, the van der Waals force that holds the graphene surfaces together along the c-axis direction is greatly reduced. GIC or GO is most often produced by immersing natural graphite powder in a mixture of sulfuric acid, nitric acid (oxidizing agent), and another oxidizing agent (eg potassium permanganate or sodium perchlorate). .. When an oxidizing agent is present during the intercalation procedure, the resulting GIC is actually some graphite oxide (GO) particles. The GIC or GO was then repeatedly washed and rinsed in water to remove excess acid, resulting in a graphite oxide suspension or dispersion, which was dispersed in water and was discrete and visually distinct Including graphite oxide particles. One of two process routes can be followed after this rinsing step to produce the graphene material, which is briefly described below.

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

In Route 1A, these graphite worms (exfoliated graphite or “network of interconnected/non-isolated graphite flakes”) are recompressed, typically 0.1 mm (100 μm) to 0.5 mm. Flexible graphite sheets or foils having a thickness in the range of (500 μm) can be obtained. Alternatively, a graphite worm may simply be used using a low-strength air mill or a shearing machine for the purpose of producing so-called "expanded graphite flakes" which mainly contain graphite flakes or platelets thicker than 100 nm (thus not a nanomaterial by definition). It is also possible to choose to crush.

In Route 1B, exfoliated graphite can be used to generate exfoliated graphite (e.g., ultrasonic devices, high-frequency devices, as disclosed in commonly assigned U.S. patent application Ser. No. 10/858,814 (March 6, 2004)). Subjected to high-strength mechanical shear (using a shear mixer, high-strength air jet mill, or high-energy ball mill) to form separated monolayer and multilayer graphene sheets (collectively referred to as NGP). Single-layer graphene can be as thin as 0.34 nm, while multilayer graphene can have a thickness of up to 100 nm, but more typically less than 10 nm (commonly referred to as multi-layer graphene). Multiple graphene sheets or platelets may be formed as a piece of NGP paper using a papermaking process. This NGP paper is an example of a porous graphene structure layer utilized in the method according to the present invention.

Route 2 involves sonicating a graphite oxide suspension (eg, graphite oxide particles dispersed in water) for the purpose of separating/isolating individual graphene oxide sheets from the graphite oxide particles. This is because the graphene surface separation distance is increased from 0.3354 nm in natural graphite to 0.6 to 1.1 nm in highly oxidized graphite, and van der Waals that holds adjacent surfaces together. It is based on the view that it will weaken significantly. 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 can then be chemically or thermally reduced to give "reduced graphene oxide" (RGO), which typically ranges from 0.001 wt% to 10 wt%, More typically it has an oxygen content of 0.01% to 5% by weight and most typically and preferably comprises less than 2% by weight oxygen.

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

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

Graphene oxide (GO) is used in a reaction vessel at a desired temperature over a period of time (typically 0.5-96 hours depending on the nature of the starting material and the type of oxidant used) to produce the starting graphite material. Powder or filament (eg, natural graphite powder) of the above can be obtained by immersing it in an oxidizing liquid medium (eg, a mixture of sulfuric acid, nitric acid, and potassium permanganate). The resulting graphite oxide particles can then be subjected to thermal or ultrasonic induced exfoliation to produce an isolated GO sheet, as described above. These GO sheets can then be converted into various graphene materials by substituting OH groups with other chemical groups such as Br or NH ₂ .

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

Graphite intercalation compound (GIC) C _x F (2≦x≦24) is produced at low temperature, while the interaction between F ₂ and graphite at high temperature is due to covalent fluorinated graphite (CF). _n or (C ₂ F) _n . In (CF) _n , the carbon atoms are sp3 hybridized, so the fluorocarbon layer is corrugated and consists of the translinked cyclohexane chair conformation. In (C 2 _{F) n,} only one half of the C atoms are fluorinated, none pair of carbon sheets adjacent are coupled by covalent C-C bonds. From the systematic study on the fluorination reaction, the obtained F/C ratio is obtained by determining the fluorination temperature, the partial pressure of fluorine in the fluorinated gas, and the physical properties of the graphite precursor such as the degree of graphitization, the particle size, and the ratio. It was shown to be highly dependent on surface area. In addition to fluorine (F ₂ ), other fluorinating agents can be used, but most of the available literature involves fluorination with F ₂ gas, sometimes in the presence of fluoride.

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

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

There is no limitation 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 lithium cell of the present invention, the anode active material is 1.0 volt over Li/Li ⁺ (ie, relative to Li→Li ⁺ +e ⁻ as a standard potential) when the battery is charged. Less than (preferably less than 0.7 Volts) absorbs lithium ions with high electrochemical potential. In one preferred embodiment, the anode active material of the lithium battery is (a) particles of lithium metal or lithium metal alloy; (b) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles ( (Including soft carbon and hard carbon), needle coke, carbon nanotube, carbon nanofiber, carbon fiber, and graphite fiber; and (c) 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). And (d) an alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with another element, which is stoichiometric or non-stoichiometric Alloy or intermetallic compound; (e) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd oxide, carbide, nitride, sulfide, Phosphides, selenides and tellurides, and mixtures or composites thereof; (f) pre-lithiated versions thereof; (g) pre-lithiated graphene sheets; combinations thereof. Selected from the group.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon (carbon that is difficult to graphitize), soft carbon. Carbon (carbon which can be easily graphitized), template carbon, hollow carbon nanowire, 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 = 0.2~1.0), Na 2 C 8 H 4 O 4, the carboxylic acid-based _{material, C 8 H 4 Na 2 O} 4, C 8 H 6 O 4, sodium selected from _{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 combinations thereof, An anode active material containing an intercalation compound.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is (a) particles of sodium metal or sodium metal alloy; and (b) natural graphite particles, artificial graphite particles, meso. Carbon microbeads (MCMB), carbon particles, needle cokes, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers; (c) sodium-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 a mixture thereof; (d) a sodium-containing alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and a mixture thereof; (E) Sodium-containing oxides, carbides, nitrides, and sulfides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof. An anode activity selected from the group consisting of: a compound, a phosphide, a selenide, a telluride, or an antimonide; (f) a sodium salt; (g) a graphene sheet preloaded with sodium ions; a combination thereof. It is a substance.

A variety of cathode active materials can be used to implement the lithium battery according to the present invention. The cathode active material is typically a lithium intercalation compound or lithium absorbing compound capable of storing lithium ions when the lithium battery is discharged and releasing the lithium ions into the electrolyte when recharged. .. The cathode active material can be selected from inorganic materials, organic or polymeric materials, metal oxides/phosphates/sulfides (the most desirable type of inorganic cathode material), or combinations thereof such as:

Lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium vanadate, lithium transition metal oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, A group of metal oxides, metal phosphates, and metal sulfides consisting of transition metal sulfides and combinations thereof. In particular, lithium vanadate _{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 , their doped versions, their derivatives, and combinations thereof (where 0 .1<x<5). The lithium transition metal oxide includes 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 a combination thereof. (Where M is a transition metal or a mixture of transition metals).

Other inorganic materials for use as the cathode active material may be selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. In particular, the inorganic _{material, TiS 2, TaS 2, MoS} 2, NbSe 3, MnO 2, CoO 2, iron oxide is selected from vanadium oxide, or combinations thereof. These will be discussed further below.

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 transition metal sulfides, selenides, or tellurides, (d) boron nitride, or (e) combinations thereof.

Organic materials or polymer materials include poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), and pyrene. -4,5,9,10-Tetraone (PYT), polymer-bonded PYT, quino (triazene), redox active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6 , 7,10,11-Hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ]n), lithiated 1 ,4,5,8-Naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5-benzylidenehydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy -p- benzoquinone derivative (THQLi _4), N, N'- diphenyl-2,3,5,6-diketopiperazine (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- Pentacentetron (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDAQ), 5-amino-1,4-dihydroxyanthraquinone (ADAQ), caric skinone, Li ₄ C ₆ O ₆ , _{Li 2 C 6 O 6, Li} 6 C 6 O 6, or may be combinations thereof.

Thioether polymers include poly[methantetriyl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), and poly(ethene-1,1,2,2-tetrathiol) as the main chain thioether polymer. ) (PET)-containing polymer, a side chain thioether polymer having a main chain composed of a conjugated aromatic component, 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(ethylenedithio)thiophene] (PEDTT).

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

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

The inventors have discovered that various two-dimensional (2D) inorganic materials can be used as the cathode active material in the lithium battery according to the present invention prepared by the direct active material-electrolyte injection method according to the present invention. Layered materials provide various sources of 2D systems that can exhibit unexpected electronic properties and good affinity for lithium ions. Graphite is the most well-known layered material, but transition metal dichalcogenides (TMD), transition metal oxides (TMO), and a wide range of other compounds such as BN, Bi ₂ Te ₃ , and Bi ₂ Se ₃ . Can also be a source of 2D material.

Preferably, the lithium intercalation 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. A nanodisk, a nanoparticle of an inorganic material selected from sulfides, selenides, or tellurides of titanium, cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof. It is selected from platelets, nanocoatings or nanosheets, where the disks, platelets or sheets have a thickness of less than 100 nm. The lithium intercalation compound or the lithium absorption compound includes (i) bismuth selenide or bismuth telluride, (ii) transition metal dichalcogenide or trichalcogenide, (iii) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, Nanodiscs, nanoplatelets, nanos of compounds selected from sulfides, selenides, or tellurides of cobalt, manganese, iron, nickel, or transition metals, (iv) boron nitride, or (v) combinations thereof It may include a coating, or nanosheet, where the disc, platelet, coating, or sheet has a thickness of less than 100 nm.

In the rechargeable sodium 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 V ₂ (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), 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 (hexacyanoferrate _{nickel), 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, 0.01-100 z/y), Se (no S), arroite, or combinations thereof. It may contain selected sodium intercalation compounds.

Alternatively, the cathode active material may be selected from functional materials or nanostructured materials having alkali metal ion scavenging functional groups or alkali metal ion storage surfaces in direct contact with the electrolyte. Preferably, the functional group reversibly reacts with an alkali metal ion, forms a redox pair with the alkali metal ion, or forms a chemical complex with the alkali metal ion. The functional material or the nanostructured material is (a) soft carbon, hard carbon, polymer carbon or carbonized resin, mesophase carbon, coke, carbonized pitch, carbon black, activated carbon, nanocell carbon foam, or partially graphitized. Carbon;; (b) nanographene platelets selected from single-layer graphene sheets or multilayer graphene platelets; (c) carbon nanotubes selected from single-wall carbon nanotubes or multi-wall carbon nanotubes; (d) carbon nanofibers; Nanowires, metal oxide nanowires or fibers, conductive polymer nanofibers, or combinations thereof; (e) carbonyl-containing organic or polymer molecules; (f) functional materials containing carbonyl, carboxyl, or amine groups; And a combination thereof.

Functional material 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 - muconic acid salt), 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-tetrahydroxyanthraquinone, tetrahydroxy-p-benzoquinone, and combinations thereof. Desirably, the functional material or nanostructured materials, -COOH, = _O, -NH 2, a -OR, or a functional group selected from -COOR, wherein, R represents is a hydrocarbon radical ..

Single-layer or few layers (up to 20 layers) of non-graphene 2D nanomaterials can be produced by several methods such as: Mechanical cutting, laser ablation (eg, ablation of TMD to a single layer using laser pulses), liquid phase exfoliation, and synthesis of thin film techniques, eg, PVD (eg, sputtering), vapor deposition, vapor phase epitaxy, liquid. Phase epitaxy, chemical vapor deposition epitaxy, molecular beam epitaxy (MBE), atomic layer epitaxy (ALE), and their plasma types.

A wide variety of electrolytes can be used in the practice of the present invention. Most preferred are non-aqueous organic and/or ionic liquid electrolytes. The non-aqueous electrolyte employed herein may be produced by dissolving an electrolyte salt in a non-aqueous solvent. Any known non-aqueous solvent used as a solvent for a lithium secondary battery can be used. A non-aqueous solvent mainly composed of a mixed solvent containing ethylene carbonate (EC) and at least one non-aqueous solvent having a melting point lower than that of the above-mentioned ethylene carbonate and having a donor number of 18 or less (hereinafter, referred to as a second solvent). (Referred to as a solvent in step 1) can be preferably employed. This non-aqueous solvent is (a) stable to a negative electrode containing a carbonaceous material well-formed in a graphite structure, (b) effective in suppressing reduction or oxidative decomposition of an electrolyte, and ( c) There is an advantage that the conductivity is high. A non-aqueous electrolyte composed only of ethylene carbonate (EC) has an advantage that it is relatively stable against decomposition due to reduction with a graphitized carbonaceous material. However, the melting point of EC is relatively high at 39 to 40° C., the viscosity of EC is also relatively high, and therefore the conductivity of EC is low. Therefore, EC alone is used as an electrolyte for a secondary battery operated at room temperature or lower. Unsuitable for The second solvent used in the mixture with EC serves to make the viscosity of the solvent mixture lower than that of EC alone, thereby increasing the ionic conductivity of the mixed solvent. Furthermore, when a second solvent having a donor number of 18 or less (the donor number of ethylene carbonate is 16.4) is used, the above ethylene carbonate can be easily and selectively solvated with lithium ions. It is hypothesized that the reduction reaction of the second solvent with the carbonaceous material produced by graphitization of the second solvent is suppressed. Further, when the number of donors of the second solvent is controlled to 18 or less, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, thereby manufacturing a high voltage lithium secondary battery. Will be possible.

Preferred second solvent is dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), γ-butyrolactone (γ-BL), acetonitrile. (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, and methyl acetate (MA). These second solvents may be used alone or in combination of two or more. More desirably, this second solvent should be selected from those having a donor number of 16.5 or less. The viscosity of this second solvent should preferably not exceed 28 cps at 25°C.

The mixing ratio of the above ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of ethylene carbonate is outside this range, the conductivity of the solvent may be lowered, or the solvent tends to be more easily decomposed, which deteriorates the charge/discharge efficiency. A more preferable mixing ratio of ethylene carbonate is 20 to 75% by volume. When the mixing ratio of ethylene carbonate in the non-aqueous solvent is increased to 20% by volume or more, the solvation effect of ethylene carbonate with respect to lithium ions is promoted, and the solvent decomposition suppressing effect can be improved.

Examples of preferred mixed solvents include compositions comprising EC and MEC; compositions comprising EC, PC and MEC; compositions comprising EC, MEC and DEC; compositions comprising EC, MEC and DMC; and EC , MEC, PC, and DEC, and the volume ratio of MEC is controlled within the range of 30 to 80%. By selecting the volume ratio of MEC from the range of 30 to 80%, more preferably 40 to 70%, the conductivity of the solvent can be improved. For the purpose of suppressing the decomposition reaction of the solvent, an electrolyte in which carbon dioxide is dissolved can be adopted, whereby both the capacity and the cycle life of the battery can be effectively improved. The electrolyte salt taken into the non-aqueous electrolyte is lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), trifluoro It may be selected from lithium salts such as lithium metasulphonate (LiCF ₃ SO ₃ ) and bis-trifluoromethylsulfonylimide lithium (LiN(CF ₃ SO ₂ ) ₂ ). Among them, LiPF ₆ , LiBF ₄ , and LiN(CF ₃ SO ₂ ) ₂ are preferable. The content of the electrolyte salt in the non-aqueous solvent is preferably 0.5 to 2.0 mol/l.

For sodium cells, the electrolytes (including non-flammable quasi-solid electrolytes) are sodium perchlorate (NaClO ₄ ), sodium hexafluorophosphate (NaPF ₆ ), sodium borofluoride (NaBF ₄ ), sodium hexafluoroarsenide, trifluoroarsenide, fluoro - sodium methanesulfonic acid _(NaCF 3 _SO 3), bis - trifluoromethyl sulfonyl imide sodium _{(NaN (CF 3 SO 2)} 2), ionic liquid salt, or preferably a combination thereof containing sodium salt selected Sometimes.

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

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

Ionic liquids are basically composed of organic ions that produce an essentially unlimited number of structural changes due to the ease of preparation of the various components. Thus, various types of salts can be used to design ionic liquids with the desired properties for a given application. These include, among others, imidazolium, pyrrolidinium, and quaternary ammonium salts as cations, and bis(trifluoromethanesulfonyl)imides, bis(fluorosulfonyl)imides, and hexafluorophosphates as anions. Based on their composition, ionic liquids basically fall into different classes, including aprotic, protic, and zwitterionic types, each suitable for a particular application.

Common cations of room temperature ionic liquids (RTIL) include, but are not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkylpyrrolidinium, dialkylpiperidinium, tetraalkylammonium. Alkylphosphonium, as well as trialkylsulfonium. General anions of RTIL include, but are not limited to, 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} ^{− and the} like. Relatively speaking, an imidazolium- or sulfonium-based cation and AlCl ₄ ⁻ , BF ₄ ⁻ , CF ₃ CO ₂ ⁻ , CF ₃ SO ₃ ⁻ , NTf ₂ ⁻ , N(SO ₂ F) ₂ ⁻ , or F. _{(HF) 2.3} ^- combination with complex halide anions, such as results in a RTIL having good operation conductivity.

RTILs have a high intrinsic ionic conductivity, high thermal stability, low volatility, low (substantially zero) vapor pressure, non-flammability, and the ability to maintain liquids over a wide temperature range above and below room temperature. , Can have typical properties such as high polarity, high viscosity, and wide electrochemical window. With the exception of high viscosity, these properties are desirable properties when using RTIL as an electrolyte component (salt and/or solvent) in supercapacitors.

In the following, some examples of several different types of anodic active material, cathodic active material, and ion-conducting polymer are provided to show the best mode of carrying out the invention. These exemplary embodiments, as well as elsewhere in the specification and drawings, are individually or in combination sufficient to enable those skilled in the art to practice the invention. However, these examples should not be construed as limiting the scope of the invention.

Example 1: Preparation of graphene oxide (GO) and reduced graphene oxide (RGO) nanosheets from natural graphite powder Huadong Graphite Co. Natural graphite from (Qingdao, China) was used as the starting material. GO was obtained by following the well-known modified Hummers method. This method involved two oxidation steps. In a typical procedure, the first oxidation was achieved under the following conditions. 1100 mg of graphite was placed in a 1000 mL boiling flask. Then K ₂ S ₂ O ₈ , 20 g P ₂ O ₅ , and 400 mL concentrated aqueous H ₂ SO ₄ solution (96%) were added to the flask. The mixture was heated under reflux for 6 hours and then left at room temperature for 20 hours. The graphite oxide was filtered and rinsed with a large amount of distilled water until it had a neutral pH. At the end of this first oxidation, the wet cake was recovered.

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

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

In some lithium batteries according to the present invention, RGO was used as a conductive additive in either or both the anode active material and the cathode active material. Pre-lithiated RGO (eg, RGO+lithium particles or RGO pre-deposited with a lithium coating) was also used as the anode active material in selected lithium-ion cells.

For comparison, a slurry coating and drying procedure was performed to make a conventional electrode. Then, one anode and one cathode, and a separator disposed between the two electrodes are assembled and placed in an Al-plastic laminated packaging envelope, followed by injection of liquid electrolyte to remove lithium from prior art lithium. A battery cell was formed.

Example 2: Preparation of sheets of pure graphene (essentially 0% oxygen) Recognizing the possibility that high defect populations in GO sheets act to reduce the conductivity of individual graphene faces, the present invention. Have high electrical conductivity and thermal conductivity by using sheets of pure graphene (eg, non-oxidized, oxygen-free, non-halogenated, halogen-free) We decided to study whether we could obtain a conductive additive. Pre-lithiated pure graphene was also used as the anode active material. Sheets of pure graphene were prepared by using direct sonication or liquid phase manufacturing methods.

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

The sheet of pure graphene was then used as a conductive additive for anodic activation using both the slurry pouring procedure according to the present invention and the conventional slurry coating, drying, and laminating procedure. It was incorporated into the cell along with the material (or cathode active material for the cathode). Both lithium ion batteries and lithium metal batteries (cathode only injection) were examined.

Example 3: Preparation of Pre-lithiated Graphene Fluoride Sheet as Anode Active Material for Lithium Ion Batteries Several methods were used to make GF, but only one method is described here as an example. In a typical procedure, highly exfoliated graphite (HEG) was prepared from the intercalating compound C ₂ F.xClF ₃ . HEG was further fluorinated with chlorine trifluoride vapor to produce fluorinated highly exfoliated graphite (FHEG). Prechilled teflon (Teflon) reactor was charged with pre-cooled liquid ClF ₃ of 20-30 mL, closing the reactor and cooled to liquid nitrogen temperature. Then, 1 g or less of HEG was placed in a container having a hole that allows ClF ₃ gas to enter the inside of the reactor. In 7-10 days, the product of the gray beige having an approximate expression C _{2 F} are formed.

Then, a small amount of FHEG (about 0.5 mg) is mixed with 20 to 30 mL of organic solvent (separately, methanol and ethanol), and ultrasonication (280 W) is performed for 30 minutes to produce a homogeneous yellowish dispersion. did. After removal of the solvent, the dispersion became a brownish powder. Graphene fluoride powder was mixed with surface-stabilized lithium powder in a liquid electrolyte to cause prelithiation.

Example 4: Some Examples of Preferred Salts, Solvents, and Polymers for Forming Quasi-Solid Polymer Electrolytes Preferred sodium metal salts include: Sodium perchlorate (NaClO ₄ ), sodium hexafluorophosphate (NaPF ₆ ), sodium borofluoride (NaBF ₄ ), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF ₃ SO _{3 ).} ), and bis - trifluoromethyl sulfonyl imide sodium _{(NaN (CF 3 SO 2)} 2). The following are good choices for lithium salts that tend to be well soluble in the organic or ionic liquid solvent of choice. Lithium borofluoride (LiBF ₄ ), lithium trifluoro-metasulfonate (LiCF ₃ SO ₃ ), lithium bis-trifluoromethylsulfonylimide (LiN(CF ₃ SO ₂ ) ₂ or LITFSI), lithium bis(oxalato)borate ( LiBOB), oxalyl difluoro lithium borate _{(LiBF 2 C 2 O 4)} , and bis perfluoro ethyl - imide lithium (LiBETI). A good electrolyte additive that helps stabilize the Li metal is LiNO ₃ . Particularly useful ionic liquid-based lithium salts include lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

The following are mentioned as a preferable organic liquid solvent. Ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), propylene carbonate (PC), acetonitrile (AN), vinylene carbonate (VC), allyl ethyl carbonate (AEC), 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethyl ether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether ( EEE), hydrofluoroethers (eg TPTP), sulfones, and sulfolanes.

Preferred ionic liquid solvents may be selected from room temperature ionic liquids (RTILs) having a cation selected from tetraalkylammonium, di-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, or dialkylpiperidinium. The counter anion is preferably BF ₄ ⁻ , B(CN) ₄ ⁻ , CF ₃ CO ₂ ⁻ , CF ₃ SO ₃ ⁻ , N(SO ₂ CF ₃ ) ₂ ⁻ , N(COCF ₃ ) (SO ₂ CF ₃ ). ) ^-, or _{N (SO 2 F)} 2 ^- it is selected from. Particularly useful ionic liquid-based solvents include: N-n-butyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BEPyTFSI), N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide (PP ₁₃ TFSI), and N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide.

Examples of preferable lithium ion conductive or sodium ion conductive polymers include the following. Poly(ethylene oxide) (PEO, molecular weight less than 1×10 ⁶ g/mol), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), and Sulfonated polymer. The following are mentioned as a preferable sulfonated polymer. Included are poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ether ketone) (S-PEEK), and sulfonated polyvinylidene fluoride (S-PVDF).

Example 5: Several solvents and the corresponding semi-solid vapor pressure borofluoride sodium polymer electrolyte in various sodium salt molar ratio (NaBF _4), sodium perchlorate (NaClO _4), or bis (trifluoromethanesulfonyl) Several solvents (DOL, DME, PC, AN, ionic liquid based co-solvent PP ₁₃ TFSI containing before and after addition of a wide range of sodium salt salts such as sodium imide (NaTFSI) with PEO, or (Not included) was measured. The vapor pressure drops very fast above a complex salt/polymer concentration of 2.3 M and rapidly approaches a minimum or essentially zero above a complex concentration of 3.0 M. If the vapor pressure is too low, the vapor phase of the electrolyte will not be able to generate a flame or sustain it for more than 3 seconds after generation.

Example 6: Complex sodium or lithium salt/flash point and vapor pressure of some solvents and corresponding quasi-solid polymer electrolytes at polymer concentration 3.0M Na or Li salt/some at 3M polymer concentration 3M. The flash points and vapor pressures of the solvents and their electrolytes are shown in Table 1 below. It should be noted that according to the OSHA (US Occupational Safety and Health Administration) classification, liquids with a flash point below 38.7°C are flammable. However, in order to ensure safety, we have a flash point significantly higher than 38.7° C. (for example with a large margin, at least 50° C. higher, preferably higher than 150° C.). A quasi-solid polymer electrolyte was designed as shown. The data in Table 1 indicate that the addition of 3.0M complex alkali metal salt/polymer concentration is usually sufficient to meet these criteria (often 2.3M is sufficient). is there). All of our quasi-solid polymer electrolytes are not flammable.

Example 7: Alkali Metal Ion Transport Numbers in Some Electrolytes The Na ⁺ ion transport numbers of several types of electrolytes (eg (PEO+NaTFSI salt) in (EMImTFSI+DME) solvent) related to the molecular ratio of the lithium salt were studied. did. Representative results are summarized in FIGS. 3(A)-3(B). In general, Na ⁺ ion transport numbers in low salt electrolytes decrease with increasing concentration from x=0 to x=0.2-0.30. However, when the molecular ratio of x=0.20 to 0.30 is exceeded, the transport number increases with an increase in salt concentration, which shows a fundamental change in the Na ⁺ ion transport mechanism. A similar tendency was observed for lithium ions.

As Na ⁺ ions migrate through a low salt concentration electrolyte (eg, x<0.2), they can drag with them multiple solvating molecules. If the fluid viscosity is increased by more salt and polymer dissolved in the solvent, the coordinated migration of such clusters of charged species may be further hindered. In contrast, Na ⁺ ions can significantly exceed the number of available solvating molecules in the presence of ultra-high concentrations of sodium salt with x>0.2. Such solvating molecules are normally capable of clustering sodium ions, forming multiionic complex species and slowing the diffusion process of Na ⁺ ions. This high Na ⁺ ion concentration allows having more “free Na ⁺ ions” (not clustered), thereby providing a higher Na ⁺ transport number (and thus easier Na ⁺ transport). To do. The sodium ion transport mechanism is from a multi-ion complex dominating mechanism (having a larger overall hydrodynamic radius) to a single ion dominating mechanism having a large number of available free Na ⁺ ions (having a smaller hydrodynamic radius). Have). This observation further indicates that an appropriate number of Na ⁺ ions can be rapidly moved through or out of the quasi-solid electrolyte, interacting with or reacting with the cathode (during discharge) or the anode (during charge). It claims to be readily available, thereby ensuring a good rate capability of the sodium secondary cell. Most importantly, these concentrated electrolytes are nonflammable and safe. Therefore, it is very difficult to obtain a combination of safety, easy sodium ion transport, and electrochemical performance characteristics for all types of sodium and lithium secondary batteries.

Example 8: Lithium Iron Phosphate (LFP) Cathode for Lithium Metal Batteries Uncoated or carbon coated LFP powders are commercially available from several manufacturers. In this example, an electrode containing LFP particles as a cathode active material and an electrolyte (containing a lithium salt dissolved in an organic solvent), a graphene sheet (RGO) and a carbon nanofiber (CNF) as conductive filaments. Was included separately. The lithium salt used in this example comprises lithium borofluoride (LiBF ₄ ) and the organic solvent is PC, DOL, DEC, and mixtures thereof. This study included a wide range of conductive filament volume fractions from 0.1% to 30%. Formation of the electrode layer was accomplished using the following sequence of steps.

Sequence 1 (S1): First, LiBF ₄ salt and PEO are dissolved in a mixture of PC and DOL to form an electrolyte having complex salt/polymer concentrations of 1.0 M, 2.5 M, and 3.5 M, respectively. (At concentrations above 2.3M, the resulting electrolyte was no longer a liquid electrolyte; in fact, it behaved more like a solid, thus using the term "quasi-solid"). The RGO or CNT filament was then dispersed in the electrolyte to form a filament-electrolyte suspension. Mechanical shear was used to help produce a uniform dispersion (this filament-electrolyte suspension was quite viscous even at low salt concentrations of 1.0M). Then, the LFP particles that are the cathode active material were dispersed in the filament-electrolyte suspension to form a quasi-solid polymer electrode material.

Sequence 2 (S2): First, LiBF ₄ salt and PEO are dissolved in a mixture of PC and DOL to form an electrolyte having complex salt/polymer concentrations of 1.0M, 2.5M, and 3.5M, respectively. did. Next, the LFP particles, which are the cathode active material, were dispersed in the electrolyte to form an active particle-electrolyte suspension. Mechanical shearing was used to help produce a uniform dispersion (this active particle-electrolyte suspension was quite viscous even at low salt concentrations of 1.0M). The RGO or CNT filament was then dispersed in the active particle-electrolyte suspension to form a quasi-solid polymer electrode material.

Sequence 3 (S3): First, the desired amount of RGO or CNT filaments was dispersed in a liquid solvent mixture (PC+DOL) containing no dissolved lithium salt or polymer. Mechanical shear was used to help form a uniform suspension of conductive filaments in the solvent. LiBF ₄ salt, PEO, and LFP particles were then added to the suspension and LiBF ₄ salt and PEO were dissolved in the suspension solvent mixture to give 1.0M, 2.5M, and 3.5M, respectively. An electrolyte was formed having a complex salt/polymer concentration of. Simultaneously or afterwards, the LFP particles were dispersed in the electrolyte to form a deformable quasi-solid electrode material. This quasi-solid electrode material is composed of active material particles and conductive filaments dispersed in a quasi-solid polymer electrolyte (neither a liquid electrolyte nor a solid electrolyte). In this quasi-solid electrode material, the conducting filaments percolate to form a 3D network of electronic conduction paths. This 3D conduction network is maintained when the electrode material is molded into the battery electrodes.

The conductivity of the electrodes was measured using the 4-point probe method. The results are summarized in Figures 5(A) and 5(B). As these data show, typically the percolation of conductive filaments (CNFs or RGOs) to form a 3D network of electronic conduction paths, except for the electrodes formed by Sequence 3 (S3) below. , Does not occur until the volume fraction of the conductive filament exceeds 10 to 12%. In other words, the step of dispersing the conductive filaments in the liquid solvent must be performed before the lithium salt, sodium salt, or ion-conducting polymer is dissolved in the liquid solvent and before the active material particles are dispersed in the solvent. .. Also, such an order allows the threshold of percolation to be lowered to 0.3%-2.0%, with a minimal amount of conductive additive and thus a higher proportion of active material (and higher energy density). Makes it possible to manufacture conductive electrodes. Further, it was found that these observation results are applicable to all types of electrodes containing the active material particles, the conductive filaments, and the electrolyte which have been examined so far. This is a very important and unexpected process requirement for preparing high performance alkali metal batteries with both high energy density and high power density.

The quasi-solid cathode, the porous separator, and the quasi-solid anode (similarly prepared but with artificial graphite particles as the anode active material) are then assembled together to form a unit cell, which is then The battery was formed by enclosing it in a protective housing (laminated aluminum plastic pouch) having two protruding terminals. Batteries containing liquid or polymer gel electrolytes (1M) and quasi-solid polymer electrolytes (2.5M and 3.5M) were prepared and tested.

For comparison, a slurry coating and drying procedure was performed to produce a conventional electrode. Then, one anode and one cathode, and a separator arranged between two electrodes are assembled and housed in an Al plastic laminate packaging container, after which a liquid electrolyte is injected to obtain the solution of the prior art. A lithium battery cell was formed. The battery test results are summarized in Example 19.

Example 9: V ₂ O ₅ as an example of transition metal oxide cathode active material for lithium batteries
V ₂ O ₅ powder is commercially available alone. In a typical experiment, vanadium pentoxide gel was obtained by mixing V ₂ O ₅ with an aqueous LiCl solution for the preparation of graphene supported V ₂ O ₅ powder sample. The Li ⁺ exchange gel obtained by interaction with a LiCl solution (Li:V molar ratio kept at 1:1) was mixed with GO suspension and then placed in a Teflon lined stainless steel 35 ml autoclave. Sealed and heated to 180° C. for 12 hours. After such hydrothermal treatment, the untreated solids were collected, washed thoroughly, sonicated for 2 minutes, dried at 70° C. for 12 hours, then mixed with additional 0.1% GO in water, The nanobelt size was crushed by sonication and then spray dried at 200° C. to obtain graphene-encapsulated composite particles.

The V ₂ O ₅ powder and the graphene-supported V ₂ O ₅ powder were then separately separated using the method according to the present invention and conventional slurry coating, drying, and laminating procedures to provide a conductive additive ( CNT) and liquid electrolyte were incorporated into a battery.

Example 10: LiCoO ₂ as an example of a lithium transition metal oxide cathode active material for lithium ion batteries
Commercially available LiCoO ₂ powder and multi-walled carbon nanotubes (MW-CNT) were dispersed in a quasi-solid polymer electrolyte to form a quasi-solid electrode. Two types of quasi-solid anodes were prepared for bonding to the cathode. One includes graphite particles as an anode active material, and the other includes graphene-encapsulated Si nanoparticles as an anode active material. The electrolyte solvent used was EC-VC (80/20 ratio) and LiBOB+PEO was dissolved in this organic solvent to form a quasi-solid polymer electrolyte. Each cell contains a quasi-solid anode, a separator layer, and a quasi-solid cathode that are assembled together and then hermetically sealed.

LiCoO ₂ powder, MW-CNT, and PVDF resin binder were separately dispersed in NMP solvent to form a slurry, which was applied to both sides of an AL foil current collector and then vacuum dried to form a cathode layer. Formed. The graphite particles and the 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 vacuum dried to form an anode layer. Then, the anode layer, the separator, and the cathode layer were laminated, housed in an Al-plastic housing, and a liquid electrolyte was injected therein to form a conventional lithium ion battery.

カソード活性材料（Ｌｉ_２Ｃ_６Ｏ_６）と導電性添加剤（カーボンブラック、１５％）との混合物を１０分間ボールミル加工し、得られたブレンドを研磨して複合物粒子を製造した。電解質は、ＰＣ−ＥＣ中で２．５Ｍのヘキサフルオロリン酸リチウム（ＬｉＰＦ_６）及びＰＰＯであった Example 11: Organic material as the cathode active material of lithium metal batteries _{(Li 2} C _{6 O 6)}
To synthesize rhodizonate dilithium _{(Li 2 C 6 O 6)} , was used as precursor (seed 1 in the following formula) rhodizonate dihydrate. The basic lithium salt Li ₂ CO ₃ can be used in an aqueous medium to neutralize both enediolic acid functions. Strict stoichiometric amounts of both reactants, rhodizonic acid, and lithium carbonate were reacted for 10 hours to achieve 90% yield. Dilithium rhodizonate (species 2) is readily soluble in even small amounts of water, suggesting that water molecules are present in species 2. Water was removed in vacuo at 180° C. for 3 hours to give the anhydrous form (seed 3).

A mixture of cathode active material (Li ₂ C ₆ O ₆ ) and a conductive additive (carbon black, 15%) was ball milled for 10 minutes and the resulting blend was polished to produce composite particles. Electrolyte, lithium hexafluorophosphate 2.5M in PC-EC (LiPF ₆₎ and was PPO

Note that the two Li atoms in the formula Li ₂ C ₆ O ₆ are part of the fixed structure and are not involved in reversible lithium ion storage and release. This suggests that lithium ions must come from the anode side. Therefore, a lithium source (eg, lithium metal or lithium metal alloy) must be present at the anode. A layer of lithium is deposited on the anode current collector (Cu foil) (eg, by sputtering or electrochemical plating, or by using a lithium foil), as shown in FIG. 1(D). Following this, a lithium coating, a porous separator, and a quasi-solid cathode were assembled into a cell. The cathode active material and the conductive additive (Li ₂ C ₆ O ₆ /C composite particles+CNF) were dispersed in the liquid electrolyte. For comparison, corresponding conventional Li metal cells were also prepared by conventional procedures of slurry coating, drying, laminating, packaging and electrolyte injection.

Example 12: Metal Naphthalocyanine-RGO Hybrid Cathode for Lithium Metal Batteries Copper Naphthalocyanine (CuPc) by vaporizing CuPc in a chamber with graphene film (5 nm) prepared by spin coating of RGO-water suspension. ) A coated graphene sheet was obtained. The obtained coated film was cut and crushed to produce a CuPc-coated graphene sheet, which had a lithium metal foil as an anode active material and had 1.0 M in propylene carbonate (PC) solution as an electrolyte and Used as a cathode active material in a lithium metal battery with 3.0 M LiClO ₄ and PEO.

Example 13: In this example the preparation of MoS 2 / _RGO hybrid material as a cathode active material of a lithium metal batteries, were studied various inorganic materials. For example, at 200° C., a one-step solvothermal reaction of (NH ₄ ) ₂ MoS ₄ and hydrazine in a solution of oxidized graphene oxide (GO) in N,N-dimethylformamide (DMF) is used to produce ultrathin MoS. ₂ /RGO hybrid was synthesized. In a typical procedure, 22 mg (NH ₄ ) ₂ MoS ₄ was added to 10 mg DMF dispersed in 10 ml DMF. The mixture was sonicated at room temperature for about 10 minutes until a clear, homogeneous solution was obtained. After that, 0.1 ml of N ₂ H ₄ .H ₂ O was added. The reaction solution was sonicated for an additional 30 minutes and then transferred to a Teflon-lined 40 mL autoclave. The system was heated at 200° C. for 10 hours in an oven. The product was collected by centrifugation at 8000 rpm for 5 minutes, washed with DI water and recollected by centrifugation. The wash step was repeated at least 5 times to ensure that most DMF was removed. Finally, the dried product was mixed with some carbon fiber and quasi-solid polymer (PAN) electrolyte to produce a deformable quasi-solid cathode.

Example 14: 2-dimensional (2D) Preparation of _Bi 2 Se ₃ chalcogenide nanoribbons layered (2D) Preparation of _Bi 2 Se ₃ chalcogenide nanoribbons layered are well known in the art. For example, the vapor - solid (VLS) method to grow a _Bi 2 Se ₃ nanoribbon with - liquid. The nanoribbons produced herein have an average thickness of 30-55 nm and a width and length in the range of hundreds of nanometers to several micrometers. The relatively large nanoribbons were ball milled to reduce their lateral dimensions (length and width) below 200 nm. Either graphene sheets or exfoliated graphite flakes and nanoribbons prepared by these procedures were combined with quasi-solid polymer electrolytes to produce deformable cathodes for lithium metal batteries.

Example 15: MXene powder + chemically activated RGO
Selected MXenes were produced by partially etching away certain elements from the layered structure of metal carbides such as Ti ₃ AlC ₂ . For example, as an etchant for Ti ₃ AlC ₂ , a 1M NH ₄ HF ₂ aqueous solution was used at room temperature. Typically, MXene surfaces are terminated with O, OH, and/or F groups. This is the reason why they are usually referred to as M _n+1 X _n T _x , where M is an early transition metal, X is C and/or N and T is a terminal group (O, OH, And/or F), n=1, 2, or 3, and x is the number of end groups. The MXene materials investigated include Ti ₂ CT _x , Nb ₂ CT _x , V ₂ CT _x , Ti ₃ CNT _x , and Ta ₄ C ₃ T _x . Typically, 2-35% graphene sheet was mixed with solvent and then added with 35-95% MXene, some Li/Na salt, and polymer to form a quasi-solid electrolyte based cathode. .. The cathode is deformable, adaptable, and conductive.

Example 16: Preparation of graphene-supported MnO ₂ cathode active material MnO ₂ powder was synthesized by two methods (with or without graphene sheet, respectively). In one method, a 0.1 mol/L KMnO ₄ aqueous solution was prepared by dissolving potassium permanganate in deionized water. On the other hand, 13.32 g of a high-purity sodium bis(2-ethylhexyl)sulfosuccinate surfactant was added to 300 mL of isooctane (oil) and well stirred to obtain an optically transparent solution. Then, 32.4 mL of 0.1 mol/L KMnO ₄ solution and a selected amount of GO solution were added to the solution, and it was sonicated for 30 minutes to prepare a dark brown precipitate. .. The product was separated, washed several times with distilled water and ethanol, and dried at 80°C for 12 hours. The sample was powdery graphene-supported MnO ₂ , which was dispersed in a liquid electrolyte to generate a slurry, which was injected into the pores of the foamable current collector. The product was separated, 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 CNT-containing electrolyte with a lithium salt and PEO to form a quasi-solid polymer electrolyte-based cathode electrode.

Example 17: Graphene Reinforced Nano Silicon as Anode Active Material for Lithium Ion Batteries Si particles encapsulated in graphene were loaded onto an Angstron Energy Co. (Dayton, Ohio, USA). Pure graphene sheets (as conductive filaments) are dispersed in a PC-DOL (50/50 ratio) mixture, then graphene-encapsulated Si particles (anode active material) are dispersed in a mixed solvent at 60°C. A quasi-solid anode electrode was prepared by dissolving 3.5 M lithium hexafluorophosphate (LiPF ₆ ) in. Then, the DOL was removed to obtain a quasi-solid electrolyte containing about 5.0 M LiPF ₆ in PC. This causes LiPF ₆ to become supersaturated, as the maximum solubility of LiPF _{6 in} PC is known to be less than 3.0 M at room temperature.

Example 18: Cobalt Oxide (Co ₃ O ₄ ) Fine Particles as Anode Active Material LiCoO ₂ is the cathode active material of a lithium-ion battery, while Co ₃ O ₄ is the anode active material. Because LiCoO ₂ has an electrochemical potential of about +4.0 Volts with respect to Li/Li ⁺ and Co ₃ O ₄ has an electrochemical potential of about +0.8 Volts with respect to Li/Li ⁺ . Is.

Suitable amounts of inorganic salts _{Co (NO 3) 2 · 6H} 2 O, followed by ammonia solution _{(NH 3 · H 2 O,} 25wt%) was added slowly to the GO suspension. The resulting precursor suspension was stirred under a stream of argon for several hours to ensure complete reaction. The resulting Co(OH) ₂ /graphene precursor suspension was filtered and dried under vacuum at 70° C. to obtain a Co(OH) ₂ /graphene composite precursor. The precursor was calcined in air at 450° C. for 2 hours to form a Co ₃ O ₄ /graphene composite, which was mixed into a quasi-solid polymer electrolyte to prepare a quasi-solid electrode.

Example 19: Using the graphene reinforced tin oxide fine particles follows as an anode active material, tin oxide by hydrolysis of SnCl ₄ · 5H ₂ O and NaOH under the control (SnO ₂₎ to obtain nanoparticles: _{SnCl 4 · 5H 2 O (0.95g} , 2.7m-mol) and NaOH (0.212g, 5.3m-mol) were each dissolved in distilled water 50 mL. The NaOH solution was added dropwise to the tin chloride solution at a rate of 1 mL/min with vigorous stirring. The solution was homogenized for 5 minutes by sonication. Then, the resulting hydrosol was reacted with the GO dispersion for 3 hours. A few drops of 0.1 M H ₂ SO ₄ were added to this mixed solution to aggregate the product. The precipitated solid was collected by centrifugation, washed with water and ethanol and dried under vacuum. The dried product was heat-treated at 400° C. for 2 hours in Ar atmosphere and used as an anode active material.

Example 20: Preparation of Various Battery Cells and Electrochemical Testing For most of the anode and cathode active materials investigated, lithium ion cells or lithium metal cells were prepared using both the method according to the invention and the conventional method. I prepared.

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

In the method according to the invention, preferably the quasi-solid anode, the porous separator and the quasi-solid cathode are assembled in a protective housing. The pouch was then sealed.

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

Example 21: Typical test results For each sample, several current densities (representing charge/discharge rates) were imposed to determine the electrochemical response and a Ragone plot (power density vs. energy density) It enabled calculation of energy density and power density values required for construction. FIG. 6 shows a Ragone plot (weight power density versus energy density) of a lithium-ion battery cell containing graphite particles as the anode active material and carbon-coated LFP particles as the cathode active material. Three of the four data curves relate to cells prepared according to embodiments of the present invention (using sequence S1, S2, and S3, respectively), and the other one is for conventional slurry coating of electrodes. (Roll coating). Some important observations can be made from these data.

The weight energy densities and power densities of lithium ion battery cells prepared by the method according to the invention are significantly higher than those of their counterparts (designated as "conventional") prepared by conventional roll coating methods. From 161 Wh/kg each due to the change from 160 μm anode thickness (coated on flat solid Cu foil) to 420 μm thickness and the corresponding change of cathode to maintain a balanced capacity ratio. An increase in gravimetric energy density to 226 Wh/kg (S1), 227 Wh/kg (S2), and 264 Wh/kg (S3) occurred. Also, surprisingly, a battery comprising a quasi-solid electrode according to the invention with a 3D network of electronic conduction paths (due to the percolation of the conductive filaments) offers considerably higher energy density and higher power density.

These large differences cannot simply be attributed to increased electrode thickness and mass loading. These differences are due to the significantly higher active material mass loading (rather than just mass loading) and higher conductivity associated with cells according to the present invention, the reduction of the ratio of overhead (inactive) component to active material weight/volume, And likely due to the surprisingly good utilization of the electrode active material (higher conductivity and no dry pockets or ineffective spots in the electrode, especially under high charge/discharge rate conditions) Due to this, most if not all graphite particles and LFP particles contribute to the lithium ion storage capacity).

FIG. 7 shows a Ragone plot (weight output density vs. weight energy density) of two cells, both cells having graphene-encapsulated Si nanoparticles as the anode active material and LiCoO ₂ nanoparticles as the cathode active material. Contains. Experimental data were obtained from Li-ion battery cells prepared by the method according to the invention and conventional slurry coating of electrodes.

As these data show, the gravimetric energy and power densities of the battery cells prepared by the method according to the invention are significantly higher than their counterparts prepared by the conventional method. Here too, the difference is significant. Conventionally produced cells exhibit a gravimetric energy density of 265 Wh/kg, whereas cells according to the invention provide energy densities of 382 Wh/kg (S1) and 420 Wh/kg (S3), respectively. High power densities of 1425 W/kg and 1650 W/kg are also unprecedented for lithium-ion batteries.

These energy and power density differences are mainly due to the high active material mass loadings associated with cells according to the invention (greater than 25 mg/cm ^{2 for} anodes, greater than 45 mg/cm ^{2 for} cathodes) and high electrode conductivity, Reduction of the ratio of overhead (inactive) component to active material weight/volume, as well as the ability of the method of the present invention to better utilize active material particles (all particles reachable to liquid electrolyte and fast ions). And electron kinematics).

FIG. 8 shows a lithium foil as an anode active material, dilithium rhodizonate (Li ₂ C ₆ O ₆ ) as a cathode active material, and a lithium salt (LiPF ₆ )-PC/DEC (1. A Ragone plot of a lithium metal battery containing 5M and 5.0M) is shown. A quasi-solid electrode was prepared according to the sequence S2 and S3 as described in Example 8. The data relate to three lithium metal cells prepared by the method according to the invention and a lithium metal cell prepared by conventional slurry coating of the electrodes.

These data show that the lithium metal cells prepared by the method according to the invention have significantly higher gravimetric energy and power densities than their counterparts prepared by conventional methods. Again, the differences are large, probably due to: Significantly higher active material mass loading (rather than just mass loading) and high conductivity associated with electrodes according to the present invention; reduction of the ratio of overhead (inactive) components to active material weight/volume; surprising of electrode active materials Good utilization (mostly if not all active materials contribute to lithium ion storage capacity due to high conductivity and lack of dry pockets or ineffective spots in the electrodes, especially under conditions of high charge/discharge rates) ).

The weight energy density of the lithium metal organic cathode cell according to the present invention is as high as 502 Wh/kg. The observation of higher than 150-220 Wh/kg on a weight basis) is quite remarkable and surprising. Furthermore, for lithium batteries based on organic cathode active materials, a weight power density of 1578 W/kg was not considered. The cell containing the quasi-solid electrode prepared according to Sequence 3 exhibits significantly higher energy and power densities compared to the conventional sequence S2 cell. Also, surprisingly, higher concentrations of electrolyte (quasi-solid electrolyte) contribute to the realization of higher energy and power densities.

The above performance characteristics of lithium batteries are also observed in the corresponding sodium batteries. Due to space limitations, data for sodium batteries are not presented here. However, as an example, FIG. 9 shows a Ragone plot of two sodium ion capacitors, each containing pre-sodiumized hard carbon particles as the anode active material and graphene sheet as the cathode active material. One cell has an anode prepared by a conventional slurry coating process and the other cell has a quasi-solid anode prepared according to the method according to the invention. Again, quasi-solid electrode based cells provide significantly higher energy density and higher power density. It has been found that lithium ion capacitors follow a similar trend.

Reports of energy and power density by weight of active material alone on the Ragone plot, as many researchers have done, may not give a realistic picture of the performance of assembled supercapacitor cells. It is important to point out. The weight of other device components must also be taken into account. These overhead components, including current collectors, electrolytes, separators, binders, connectors, and packaging are non-active materials and do not contribute to charge storage. These components only add weight and volume to the device. Therefore, it is desirable to reduce the relative weight ratio of overhead components and increase the proportion of active material. However, it was not possible to achieve this end using conventional battery manufacturing methods. The present invention overcomes this longstanding and most significant problem in the lithium battery art.

In commercially available lithium-ion batteries with electrode thickness of 100-200 μm, the weight ratio of anode active material (eg, graphite or carbon) in the lithium-ion battery is typically 12-17%, which is greater than that of the cathode active material. The weight ratio (for inorganic materials such as LiMn ₂ O ₄ ) is 22% to 41%, or for organic or polymeric materials 10% to 15%. Therefore, a factor of 3-4 is frequently used to extrapolate the energy or power density of a device (cell) from properties based solely on active material weight. In most scientific papers, the properties reported are typically based solely on active material weight, and electrodes are typically very thin (<<100 μm, and often <<50 μm). The active material weight is typically 5% to 10% of the total device weight, which is the actual cell (device) energy or power density by dividing the corresponding active material weight base value by a factor of 10-20. Suggest that you can get After considering this factor, the properties reported in these papers do not appear to be better than those of commercial batteries. Therefore, one must be very careful in reading and interpreting the battery performance data reported in scientific papers and patent applications.

Claims (91)

(A) about 30% to about 95% by volume of the cathode active material, and about 5% to about 40% by volume of a first electrolyte containing an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent; A quasi-solid cathode containing from about 0.01% to about 30% by volume of a conductive additive, said conductive additive containing a conductive filament forming a 3D network of electronic conduction paths, A quasi-solid cathode, wherein the quasi-solid electrode has a conductivity of about 10 ⁻⁶ S/cm to about 300 S/cm;
(B) an anode,
(C) In an alkali metal cell including an ion conductive membrane or a porous separator disposed between the anode and the quasi-solid cathode, the quasi-solid cathode has a thickness of 200 μm or more. Alkaline metal cell. The alkali metal cell of claim 1, wherein the anode comprises about 30% to about 95% by volume of the anode active material, and about 5% by volume containing an alkali salt dissolved or dispersed in a solvent and an ion conductive polymer. To about 40% by volume of the second electrolyte and about 0.01% to about 30% by volume of the conductive additive, the conductive additive containing conductive filaments. Forming a 3D network of electronic conduction paths, the quasi-solid electrode having a conductivity of about 10 ⁻⁶ S/cm to about 300 S/cm, and the quasi-solid anode having a thickness of 200 μm or more. An alkali metal cell characterized by. A) about 30% to about 95% by volume cathode active material, about 5% to about 40% by volume electrolyte containing an alkali salt and an ion conducting polymer dissolved or dispersed in a solvent, and about 0.01%. A quasi-solid anode containing from about 30% by volume to about 30% by volume of a conductive additive, wherein the conductive additive containing conductive filaments has a quasi-solid electrode from about 10 ⁻⁶ S/cm to about 300 S. A quasi-solid state anode forming a 3D network of electronic conduction paths to have a conductivity of /cm;
B) a cathode,
C) An alkali metal cell comprising an ion conductive membrane or a porous separator arranged between an anode and a quasi-solid cathode, wherein the quasi-solid cathode has a thickness of 200 μm or more. .. The alkali metal cell of claim 1, wherein the first electrolyte is poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN) having a molecular weight of less than 1×10 ⁶ g/mol. ), poly(methylmethacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polybis-methoxyethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF) -HFP), sulfonated derivatives thereof, sulfonated polymers, or quasi-solid polymer electrolytes containing ion-conducting polymers selected from combinations thereof. The alkali metal cell according to claim 2, wherein the first electrolyte or the second electrolyte has a poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly having a molecular weight of less than 1×10 ⁶ g/mol. (Acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polybis-methoxyethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)- An alkali metal cell comprising a quasi-solid polymer electrolyte containing an ion conducting polymer selected from hexafluoropropylene (PVDF-HFP), their sulfonated derivatives, sulfonated polymers, or combinations thereof. The alkali metal cell according to claim 3, wherein the electrolyte has a poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly having a molecular weight of less than 1×10 ⁶ g/mol. (Methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polybis-methoxyethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP) An alkali metal cell comprising a quasi-solid polymer electrolyte containing an ion-conducting polymer selected from sulfonated derivatives thereof, sulfonated polymers, or a combination thereof. The alkali metal cell according to claim 1, wherein the ion conductive polymer is poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivative of polytetrafluoroethylene, sulfonated polysulfone, sulfonated. Poly(ether ketone), sulfonated poly(ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonated polychloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene Copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymer of polyvinylidene fluoride with hexafluoropropene and tetrafluoroethylene, Characterized in that it is selected from the group consisting of sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazoles (PBI), their chemical derivatives, copolymers, blends and combinations thereof. And an alkali metal cell. The alkali metal cell according to claim 2, wherein the ion conductive polymer is poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivative of polytetrafluoroethylene, sulfonated polysulfone, sulfonated. Poly(ether ketone), sulfonated poly(ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonated polychloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene Copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymer of polyvinylidene fluoride with hexafluoropropene and tetrafluoroethylene, Characterized in that it is selected from the group consisting of sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazoles (PBI), their chemical derivatives, copolymers, blends and combinations thereof. And an alkali metal cell. The alkali metal cell according to claim 3, wherein the ion conductive polymer is poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivative of polytetrafluoroethylene, sulfonated polysulfone, sulfonated. Poly(ether ketone), sulfonated poly(ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonated polychloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene Copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymer of polyvinylidene fluoride with hexafluoropropene and tetrafluoroethylene, Characterized in that it is selected from the group consisting of sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazoles (PBI), their chemical derivatives, copolymers, blends and combinations thereof. And an alkali metal cell. The alkali metal cell according to claim 1, wherein the conductive filament is carbon fiber, graphite fiber, carbon nanofiber, graphite nanofiber, carbon nanotube, needle coke, carbon whisker, conductive polymer fiber, conductive material coated fiber. Alkali metal cell selected from metal nanowires, metal fibers, metal wires, graphene sheets, expanded graphite platelets, combinations thereof, or combinations thereof with non-filamentary conductive particles. The alkali metal cell of claim 1, wherein the ion conducting polymer does not form a matrix within the quasi-solid cathode. The alkali metal cell of claim 3, wherein the ion conducting polymer does not form a matrix within the quasi-solid cathode. The alkali metal cell of claim 1, wherein the electrode maintains a conductivity of about 10 ⁻³ S/cm to about 10 S/cm. The alkali metal cell according to claim 1, wherein the conductive filaments are bonded to each other by a resin at intersections between the conductive filaments. The alkali metal cell of claim 1, wherein the quasi-solid cathode contains from about 0.1% to about 20% by volume of a conductive additive. The alkali metal cell of claim 1, wherein the quasi-solid cathode contains from about 1% to about 10% by volume conductive additive. The alkali metal cell according to claim 1, wherein the amount of the active material is about 40% by volume to about 90% by volume of the electrode material. The alkali metal cell according to claim 1, wherein the amount of the active material is about 50% by volume to about 85% by volume of the electrode material. The alkali metal cell according to claim 1, wherein the first electrolyte is in a supersaturated state. The alkali metal cell according to claim 2, wherein the first electrolyte or the second electrolyte is in a supersaturated state. The alkali metal cell according to claim 1, wherein the solvent is selected from water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid. The alkali metal cell according to claim 2, wherein the first electrolyte or the second electrolyte contains a solvent selected from water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid. Characteristic alkali metal cell. The alkali metal cell according to claim 2, wherein the alkali metal cell is a lithium metal cell, a lithium ion cell, or a lithium ion capacitor cell, and the anode active material is
(A) particles of lithium metal or lithium metal alloy,
(B) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle cokes, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers,
(C) 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),
(D) An alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with another element, which is stoichiometric or non-stoichiometric, or An intermetallic compound,
(E) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd oxides, carbides, nitrides, sulfides, phosphides, selenides, and Telluride, and mixtures or composites thereof,
(F) their pre-lithiated versions,
(G) a prelithiated graphene sheet,
An alkali metal cell selected from the group consisting of a combination thereof. The alkali metal cell of claim 23, wherein the pre-lithiated graphene sheet comprises pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogen. Prelithiated graphene, nitrogenated graphene, boron doped graphene, nitrogen doped graphene, chemically functionalized graphene, physically or chemically activated or etched versions thereof, or combinations thereof Alkali metal cell characterized by being selected from versions. The alkali metal cell according to claim 2, wherein the alkali metal cell is a sodium metal cell, a sodium ion cell, or a sodium ion capacitor, and the anode active material is petroleum coke, carbon black, amorphous carbon, or activated carbon. , Hard carbon, soft carbon, template carbon, hollow carbon nanowire, 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 = 0.2~1.0} ), Na 2 C 8 H 4 O 4, 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 an alkali intercalated selected from combinations thereof An alkali metal cell containing a cation compound. The alkali metal cell according to claim 2, wherein the alkali metal cell is a sodium metal cell, a sodium ion cell, or a sodium ion capacitor, and the anode active material is
a) particles of sodium metal or sodium metal alloy,
b) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle cokes, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers,
c) Sodium-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,
d) a sodium-containing alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
e) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd sodium-containing oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurium Compounds, or antimony compounds, and mixtures or composites thereof,
f) a sodium salt,
g) An alkali metal cell, which is selected from the group consisting of graphene sheets preloaded with sodium ions and combinations thereof. The alkali metal cell according to claim 1, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell, and the cathode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, or doped. Lithium nickelate, lithium manganate, doped lithium manganate, lithium vanadate, doped lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed An alkali metal cell comprising a lithium intercalation compound selected from the group consisting of metal phosphates, metal sulfides, and combinations thereof. The alkali metal cell according to claim 1, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell, and the cathode active material is an inorganic material, an organic or polymer material, a metal oxide/phosphate/sulfide. An alkali metal cell comprising a lithium intercalation compound or a lithium absorption compound selected from the group consisting of compounds, or a combination thereof. 29. The alkali metal cell according to claim 28, wherein the metal oxide/phosphate/sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium vanadate, lithium mixed metal oxide, lithium iron phosphate. Alkali metal cell selected from lithium manganese phosphate, lithium vanadium phosphate, lithium phosphate mixed metal, transition metal sulfide, and combinations thereof. 29. The alkali metal cell of claim 28, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. cell. In the alkali metal cell of claim 28, wherein the inorganic _{material, TiS 2, TaS 2, MoS} 2, NbSe 3, MnO 2, CoO 2, iron oxide, vanadium oxide, or be combinations thereof Characteristic alkali metal cell. In the alkali metal cell of claim 28, wherein the metal oxide / phosphate / _{sulphides, 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, their doped versions, their derivatives, and their An alkali metal cell comprising vanadium oxide selected from the group consisting of: The alkali metal cell according to claim 28, 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 , An alkali metal cell selected from the taborite compound LiMPO ₄ F, the borate compound LiMBO ₃ or a combination thereof, wherein M is a transition metal or a mixture of transition metals. The alkali metal cell according to claim 28, wherein the inorganic material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum. Alkali, selected from the group consisting of sulfides, selenides or tellurides of tungsten, titanium, cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof. Metal cell. 29. The alkali metal cell of claim 28, wherein the organic or polymeric material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride ( PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer bonded PYT, quinone (triazene), redox active organic material, tetracyanoquinodimethane (TCNQ), tetra Cyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ] _n ), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatriphenylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5-benzylidenehydantoin, isatin Lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi ₄ ), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N′-diallyl- 2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone compound, 1,4-benzoquinone, 5 , 7,12,14-Pentacentetron (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDAQ), 5-amino-1,4-dihydroxyanthraquinone (ADAQ), caric skinone, _{Li 4 C 6 O 6, Li} 2 C 6 O 6, Li 6 C 6 O 6, or an alkali metal cell wherein the combinations thereof. 36. The alkali metal cell of claim 35, wherein the thioether polymer is poly[methantetryl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), and the main chain thioether polymer is poly(. Polymer containing ethene-1,1,2,2-tetrathiol) (PETT), side chain thioether polymer having main chain composed of conjugated aromatic moiety and thioether side chain as pendant, poly(2-phenyl-1) , 3-dithiolane) (PPDT), poly(1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2, An alkali metal cell selected from 4,5-tetrakis(propylthio)benzene] (PTKPTB) or poly[3,4(ethylenedithio)thiophene] (PEDTT). The alkali metal cell according to claim 28, wherein the organic material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine. An alkali metal cell containing a phthalocyanine compound selected from aluminum chloride phthalocyanine, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or a combination thereof. 29. The alkali metal cell of claim 28, wherein the lithium intercalation compound or lithium absorbing compound is selected from metal carbides, metal nitrides, metal borides, metal dihalides, or combinations thereof. Alkali metal cell to do. 29. The alkali metal cell of claim 28, wherein the lithium intercalation compound or lithium absorbing compound is in the form of nanowires, nanodisks, nanoribbons, or nanoplatelets, niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, An alkali metal cell selected from oxides of titanium, vanadium, chromium, cobalt, manganese, iron or nickel, dichalcogenides, trichalcogenides, sulfides, selenides or tellurides. The alkali metal cell according to claim 28, wherein the lithium intercalation compound or the lithium absorption compound is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, Selected from zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides, (d) boron nitride, or (e) combinations thereof. Alkali metal cell selected from nanodiscs, nanoplatelets, nanocoatings, or nanosheets of inorganic materials according to claim 1, wherein said discs, platelets or sheets have a thickness of less than 100 nm. The alkali metal cell according to claim 1, wherein the alkali metal cell is a sodium metal cell or a sodium ion cell, and the cathode active material is an inorganic material, an organic or polymer material, a metal oxide/phosphate/sulfide. An alkali metal cell containing a sodium intercalation compound or a sodium absorption compound selected from the group consisting of the compounds, or a combination thereof. 42. The alkali metal cell of claim 41, wherein the metal oxide/phosphate/sulfide is sodium cobaltate, sodium nickelate, sodium manganate, sodium vanadate, sodium mixed metal oxide, sodium/potassium transition. Metal oxides, sodium iron phosphate, sodium iron phosphate, potassium manganese phosphate, sodium manganese phosphate, potassium vanadium phosphate, sodium vanadium phosphate phosphate, sodium/potassium phosphate, mixed metal phosphoric acid, transition metal sulfide , Or a combination thereof, an alkali metal cell. 42. The alkali metal cell of claim 41, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. cell. In the alkali metal cell according to claim 41, wherein the inorganic _{material, TiS 2, TaS 2, MoS} 2, NbSe 3, MnO 2, CoO 2, iron oxide, vanadium oxide, or be combinations thereof Characteristic alkali metal cell. In the alkali metal cell according to claim 41, wherein the cathode active _{material, NaFePO 4, Na (1-} x) K x PO 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, 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, 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=0.01-100), Se, arhodolite, or a sodium intercalation compound selected from a combination thereof. Is contained and x is 0.1-1.0, The alkali metal cell characterized by the above-mentioned. The alkali metal cell of claim 1, wherein the cathode active material comprises an electrode active material loading of greater than 15 mg/cm ² . The alkali metal cell according to claim 2, wherein the anode active material has an electrode active material loading of more than 20 mg/cm ² . The alkali metal cell of claim 1, wherein the cathode active material comprises an electrode active material loading of greater than 30 mg/cm ² . In a method of preparing an alkali metal cell having a quasi-solid electrode,
(A) combining an amount of active material, an amount of electrolyte, and a conductive additive to form a deformable conductive electrode material, the conductive additive containing a conductive filament. The agent forms a 3D network of electron conduction pathways, and the electrolyte contains an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent,
(B) forming the electrode material as a quasi-solid electrode, wherein the electrode maintains the conductivity of 10 ⁻⁶ S/cm or more without interrupting the 3D network of the electron conduction path. Transforming the material into an electrode shape,
(C) forming a second electrode,
(D) forming an alkali metal cell by combining the quasi-solid electrode and the second electrode. 50. The method of claim 49, wherein the quasi-solid electrode comprises 30-95% by volume of the active material, 5-40% by volume of the electrolyte, and 0.01-30% by volume of the conductive additive. A method comprising: 50. The method of claim 49, wherein the electrolyte has a molecular weight of less than 1 x 10< ⁶ > g/mol, poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl). Methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polybis-methoxyethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), they A sulfonated derivative, a sulfonated polymer, or a combination thereof, comprising a quasi-solid polymer electrolyte containing an ion-conducting polymer. 50. The method of claim 49, wherein the ion conductive polymer is poly(perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivative of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly( Ether ketone), sulfonated poly(ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymer, sulfonated polychloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymer Polymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymer of polyvinylidene fluoride with hexafluoropropene and tetrafluoroethylene, ethylene and Characterized by being selected from the group consisting of sulfonated copolymers with tetrafluoroethylene (ETFE), sulfonated polybenzimidazoles (PBI), their chemical derivatives, copolymers, blends and combinations thereof. Method. The method according to claim 49, wherein the conductive filament is carbon fiber, graphite fiber, carbon nanofiber, graphite nanofiber, carbon nanotube, needle coke, carbon whisker, conductive polymer fiber, conductive material-coated fiber, or metal. A method characterized by being selected from nanowires, metal fibers, metal wires, graphene sheets, expanded graphite platelets, combinations thereof, or combinations thereof with non-filamentary conductive particles. 50. The method of claim 49, wherein the ion conducting polymer does not form a matrix within the quasi-solid cathode. 50. The method of claim 49, wherein the electrode maintains a conductivity of about ^10-3 S/cm to about 10 S/cm. 50. The method of claim 49, wherein the quasi-solid cathode contains from about 0.1 vol% to about 20 vol% conductive additive. 50. The method of claim 49, wherein the quasi-solid cathode contains from about 1% to about 10% by volume conductive additive. 50. The method of claim 49, wherein the amount of active material is from about 40% to about 90% by volume of the electrode material. 50. The method of claim 49, wherein the amount of active material is from about 50% to about 85% by volume of the electrode material. 50. The method of claim 49, wherein the combining step comprises dispersing the conductive filaments in a liquid solvent to form a homogeneous suspension, after which the active material is added to the suspension and the alkali Dissolving a metal salt and the ion-conducting polymer in the liquid solvent of the suspension. 52. The method of claim 49, wherein the step of combining electrode materials to form a quasi-solid electrode comprises dissolving a lithium salt or sodium salt and the polymer in a liquid solvent to provide an electrolyte having a first salt/polymer concentration. And then removing a portion of the liquid solvent to increase the salt/polymer concentration to have a second salt/polymer concentration higher than the first concentration and higher than 2.5M. A method comprising obtaining a quasi-solid polymer electrolyte. 61. The method of claim 60, wherein the removal does not cause precipitation or crystallization of the salt or the polymer and the electrolyte is supersaturated. 61. The method of claim 60, wherein the liquid solvent comprises at least a mixture of a first liquid solvent and a second liquid solvent, the first liquid solvent being more volatile than the second liquid solvent. Highly reactive, said step of removing a portion of said liquid solvent comprises removing said first liquid solvent. 52. The method of claim 49, wherein the step of forming a second electrode comprises (A) combining a quantity of a second active material, a quantity of an electrolyte, and a conductive additive to form a second Forming a deformable conductive electrode material, wherein the conductive additive containing a conductive filament forms a 3D network of electronic conduction paths, and the electrolyte is dissolved or dispersed in a solvent. A step of containing an alkali salt and an ion-conducting polymer; and (B) forming a second deformable conductive electrode material as a second quasi-solid electrode, wherein the formation of the second electrode is Transforming the second deformable conductive electrode material into an electrode shape without interrupting the 3D network of electron conduction paths so as to maintain a conductivity of 10 ⁻⁶ S/cm or more; A method comprising: 50. The method of claim 49, wherein the solvent is selected from water, organic solvents, ionic liquids, or mixtures of organic solvents and ionic liquids. The method according to claim 49, wherein the alkali metal cell is a lithium metal cell, a lithium ion cell, or a lithium ion capacitor cell, and the anode active material is
(A) particles of lithium metal or lithium metal alloy,
(B) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle cokes, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers,
(C) 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),
(D) An alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with another element, which is stoichiometric or non-stoichiometric, or An intermetallic compound,
(E) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd oxides, carbides, nitrides, sulfides, phosphides, selenides, and Telluride, and mixtures or composites thereof,
(F) their pre-lithiated versions,
(G) a prelithiated graphene sheet,
A method comprising: an anode active material selected from the group consisting of a combination thereof. 67. The method of claim 66, wherein the pre-lithiated graphene sheet is pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, graphene hydride. From nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physically or chemically activated or etched versions thereof, or pre-lithiated versions of combinations thereof A method characterized by being selected. The method according to claim 49, wherein the alkali metal cell is a sodium metal cell, a sodium ion cell, or a sodium ion capacitor, and the active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon. , Soft carbon, template carbon, hollow carbon nanowire, 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. 2 (x = 0.2~1.0), Na} 2 C 8 H 4 O 4, carboxylate-based _{material, C 8 H 4 Na 2 O} 4, C 8 H 6 O 4, C 8 H 5 NaO ₄ , an alkaline intercalation compound selected from 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 a combination thereof. A method of containing an anode active material. The method according to claim 49, wherein the alkali metal cell is a sodium metal cell, a sodium ion cell, or a sodium ion capacitor, and the active material is
a) particles of sodium metal or sodium metal alloy,
b) natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles, needle cokes, carbon nanotubes, carbon nanofibers, carbon fibers, and graphite fibers,
c) Sodium-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,
d) a sodium-containing alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
e) Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and a sodium-containing oxide, carbide, nitride or sulfide of a mixture or composite thereof. , Phosphide, selenide, telluride, or antimonide,
f) a sodium salt,
g) A method comprising an anode active material selected from the group consisting of graphene sheets preloaded with sodium ions, and combinations thereof. 50. The method of claim 49, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell and the cathode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped nickel. Lithium oxide, lithium manganate, doped lithium manganate, lithium vanadate, doped lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphorus A method comprising a lithium intercalation compound selected from the group consisting of acid salts, metal sulfides, and combinations thereof. 50. The method of claim 49, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell and the cathode active material is an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, Or a lithium intercalation compound or a lithium absorption compound selected from the combination thereof. 72. The method of claim 71, wherein the metal oxide/phosphate/sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium vanadate, lithium mixed metal oxide, lithium iron phosphate, phosphorus. Lithium manganese oxide, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof are selected. 72. The method of claim 71, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. The method of claim 71, and wherein said inorganic material _{is, TiS 2, TaS 2, MoS} 2, NbSe 3, MnO 2, CoO 2, iron oxide, is selected from vanadium oxide, or a combination thereof how to. The method of claim 71, wherein the metal oxide / phosphate / _{sulphides, 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, their doped versions, their derivatives, and combinations thereof A method comprising vanadium oxide selected from the group consisting of: wherein 0.1<x<5. The method of claim 71, wherein the metal oxide / phosphate / sulphides, layered compound LiMO _2, spinel compounds _LiM 2 _{O 4,} olivine compound LiMPO _4, silicate compounds _Li 2 MSiO _4, tavorite compound A method selected from LiMPO ₄ F, the borate compound LiMBO ₃ , or combinations thereof, wherein M is a transition metal or a mixture of transition metals. 72. The method of claim 71, wherein the inorganic material is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten. , Titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides, (d) boron nitride, or (e) combinations thereof. 72. The method of claim 71, wherein the organic or polymeric material is poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). , Poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer bonded PYT, quino (triazene), redox active organic material, tetracyanoquinodimethane (TCNQ), tetracyano Ethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN) ₆ ), 5-benzylidene hydantoin , isatin lithium salt, pyromellitic diimide lithium salts, tetra-hydroxy -p- benzoquinone derivative (THQLi _4), N, N'- diphenyl-2,3,5,6-diketopiperazine (PHP), N, N ' -Diallyl-2,3,5,6-tetraketopiperazine (AP), N,N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone compound, 1,4- Benzoquinone, 5,7,12,14-pentacentetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxyanthraquinone (ADDAQ), 5-amino-1,4-dihydroxyanthraquinone (ADAQ), calyx _{quinone, Li 4 C 6 O 6,} Li 2 C 6 O 6, Li 6 C 6 O 6, or wherein the selected from these combinations. 79. The method of claim 78, wherein the thioether polymer is poly[methantetryl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), and poly(ethene-) as the backbone thioether polymer. 1,1,2,2-tetrathiol) (PETT)-containing polymer, a side chain thioether polymer having a main chain composed of a conjugated aromatic moiety and a thioether side chain as a pendant, poly(2-phenyl-1, 3-dithiolane) (PPDT), poly(1,4-di(1,3-dithiolan-2-yl)benzene)(PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4 , 5-Tetrakis(propylthio)benzene] (PTKPTB), or poly[3,4(ethylenedithio)thiophene] (PEDTT). 72. The method of claim 71, wherein the organic material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, phthalocyanine. A method comprising a phthalocyanine compound selected from chloroaluminum, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or a combination thereof. 72. The method of claim 71, wherein the lithium intercalation compound or lithium absorbing compound is selected from metal carbides, metal nitrides, metal borides, metal dihalides, or combinations thereof. .. 72. The method of claim 71, wherein the lithium intercalation compound or lithium absorbing compound is in the form of nanowires, nanodisks, nanoribbons, or nanoplatelets, niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, A method characterized in that it is selected from oxides of vanadium, chromium, cobalt, manganese, iron or nickel, dichalcogenides, trichalcogenides, sulphides, selenides or tellurides. 72. The method of claim 71, wherein the lithium intercalation compound or lithium absorbing compound is (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, Inorganic selected from molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metal sulfides, selenides, or tellurides, (d) boron nitride, or (e) combinations thereof. A method selected from nanodiscs, nanoplatelets, nanocoatings, or nanosheets of material, said discs, platelets or sheets having a thickness of less than 100 nm. 50. The method of claim 49, wherein the alkali metal cell is a sodium metal cell or a sodium ion cell and the cathode active material is an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, Or a sodium intercalation compound or a sodium absorbing compound selected from combinations thereof. 85. The method of claim 84, wherein the metal oxide/phosphate/sulfide is sodium cobaltate, sodium nickelate, sodium manganate, sodium vanadium oxide, sodium mixed metal oxide, sodium/potassium transition metal oxide. , Sodium iron phosphate, sodium iron/potassium phosphate, sodium manganese phosphate, sodium manganese phosphate, potassium vanadium phosphate, sodium vanadium phosphate/potassium, sodium mixed metal phosphoric acid, transition metal sulfide, or A method characterized by being selected from a combination thereof. 85. The method of claim 84, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfide, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. The method of claim 84, and wherein said inorganic material _{is, TiS 2, TaS 2, MoS} 2, NbSe 3, MnO 2, CoO 2, iron oxide, is selected from vanadium oxide, or a combination thereof how to. The method of claim 49, wherein the active _{material, NaFePO 4, Na (1-} x) K x PO 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, 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 , 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=0.01-100), Se, arhodolite, or a sodium intercalation compound selected from a combination thereof. , X is 0.1 to 1.0. The method of claim 49, wherein said active material is characterized by forming an electrode active material weight loading of greater than 15 mg / cm ^2. The method of claim 49, wherein said active material is characterized by forming an electrode active material weight loading of greater than 25 mg / cm ^2. 50. The method of claim 49, wherein the active material comprises an electrode active material loading of greater than 45 mg/cm< ² >.

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