KR20200014335A - Shape compliant alkali metal cell with deformable conductive semisolid polymer electrode - Google Patents

Abstract

A method of making an alkali metal cell, comprising: (a) combining a large amount of active material, a large amount of electrolyte, and a conductive additive to form a deformable conductive electrode material, wherein the electrically conductive additive containing conductive filaments is a 3D network of electronically conductive paths. Forming an electrolyte, the electrolyte containing an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent; (b) forming the electrode material into a semi-solid polymer electrode, the method comprising deforming the electrode material into an electrode shape without blocking the 3D network of the electronically conductive path such that the electrode maintains electrical conductivity of 10 ⁻⁶ S / cm or more; (c) forming a second electrode; And (d) combining the semisolid electrode and the second electrode to form an alkali metal cell. The second electrode may be a semisolid polymer electrode.

Description

Shape compliant alkali metal cell with deformable conductive semisolid polymer electrode

Cross Reference to Related Application

This application claims priority to US Patent Application 15 / 608,597, filed May 30, 2017, and US Patent Application 15 / 610,136, filed May 31, 2017, which is incorporated herein by reference.

Technical Field

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

Historically, today's most preferred rechargeable energy storage devices (lithium ion cells) are actually from rechargeable "lithium metal cells" using lithium (Li) metals or Li alloys as anodes and Li intercalation compounds as cathodes. Developed. Li metal is an ideal anode material because of its light weight (lightest metal), high electronegativity (-3.04 V compared to standard hydrogen electrodes), and high theoretical capacity (3,860 mAh / g). Based on these outstanding properties, lithium metal batteries were proposed 40 years ago as the ideal system for high energy density applications. During the mid-1980s, several prototypes of rechargeable Li metal cells were developed. A notable example was a cell composed of a Li metal anode and molybdenum sulfide cathode developed by MOLI Energy, Inc. (Canada). Several other cells from this and other manufacturers have been abandoned due to a series of safety issues caused by very uneven Li growth (formation of Li dendrites) when the metal is replated during each subsequent recharge cycle. . As the number of cycles increases, these dendritic or tree-like Li structures can eventually reach the cathode across the separator, causing internal short circuits.

To overcome these safety issues, several alternative approaches have been proposed in which the electrolyte or anode is modified. One approach involved replacing Li metal with graphite (another Li insertion material) as an anode. Since the operation of such a cell involves the shuttle of Li ions between two Li intercalating compounds, the name "Li ion cell" is used. Presumably, Li ion cells are inherently safer than Li metal cells because they exist in ionic rather than metallic states.

Lithium ion cells are a major candidate energy storage device for electric vehicle (EV), renewable energy storage, and smart grid applications. Li ion cells have been continuously improved in terms of energy density, rate capability, and safety over the past 20 years, but much higher energy density Li metal cells have been largely overlooked. However, there are several important drawbacks to using graphite-based anodes in Li-ion cells: low specific capacity (theoretical capacity of 372 mAh / g in contrast to 3,860 mAh / g for Li metal). Long Li insertion time (e.g., low solid phase diffusion coefficient of Li into and out of graphite and inorganic oxide particles) requiring long recharge times (e.g., 7 hours in electric vehicle cells), high pulse power Limitation in the selection of available cathode materials due to inability to deliver (power density << 1 kW / kg), and the need to use pre-lithiated cathodes (eg lithium cobalt oxide). In addition, such cathodes which are generally used have a relatively low specific capacity (typically less than 200 mAh / g). These factors are two major drawbacks of current Li-ion cells: low weight and volumetric energy density (typically 150-220 Wh / kg and 450-600 Wh / L) and low power density (typically 0.5 kW / less than kg and less than 1.0 kW / L) (both based on total battery cell weight or volume).

The emerging EV and renewable energy industries require much higher weight energy densities (eg >> 250 Wh / kg, preferably >> 300 Wh / kg) than current Li-ion cell technology can provide. ) And the availability of rechargeable batteries with high power density (shorter recharge time). In addition, because the consumer demands smaller, smaller handheld devices (e.g. smartphones and tablets) to store more energy, the microelectronics industry has a much higher volumetric energy density (above 650 Wh / L, Preferably a battery with greater than 750 Wh / L). From these requirements, considerable research has been attempted on the development of electrode materials with higher specific capacity, excellent discharge capacity ratio, and good cycle stability for lithium ion batteries.

Several elements of Periodic Tables III, IV, and V can form alloys with Li at certain desired voltages. Thus, various anode materials based on these elements and some metal oxides have been proposed for lithium ion batteries. Of these, silicon has a theoretical weight capacity of nearly 10 times higher than graphite (372 mAh / g for LiC ₆ while 3,5950 mAh / g based on Li _3.75 Si) and about 3 times larger volume capacity. It has been recognized as one of the next generation anode materials for high energy lithium ion batteries. However, rapid volume change (up to 380%) of Si during lithium ion alloying and dealloying (cell charging and discharging) often results in severe and rapid deterioration of battery performance. The performance degradation is mainly due to the inability to maintain electrical contact between the powdered Si particles and the current collector, due to the volumetric change of Si and the binder / conductive additive. In addition, the inherently low electrical conductivity of silicon is another challenge to be solved.

Some high capacity anode active materials (eg Si) have been found, but no corresponding high capacity cathode material is available. Current cathode active materials commonly used in Li-ion batteries have the following serious disadvantages.

(1) The actual capacity achievable with current cathode materials (eg lithium iron phosphate and lithium transition metal oxides) is limited to the range of 150-250 mAh / g, in most cases less than 200 mAh / g. .

(2) The insertion and extraction of lithium into and out of these cathodes, which are commonly used, is a very slow solid phase of Li in solid particles having a very low diffusion coefficient (typically 10 ^-8 to 10 ^-14 cm ² / s). Depending on the diffusion, it results in very low power density (another long-standing problem with current lithium ion batteries).

(3) Current cathode materials are electrically thermally insulated and therefore cannot efficiently and efficiently transfer electrons and heat. Low electrical conductivity means that the internal resistance is high and the need to add a large amount of conductive additive substantially reduces the proportion of the electrochemically active material in the already low capacity cathode. Low thermal conductivity also means that the lithium battery industry is more prone to thermal runaway, which is a major safety issue.

Low capacity anode or cathode active materials are not the only problem facing the lithium ion battery industry. There are serious design and manufacturing problems that the lithium ion battery industry may not have recognized or have largely ignored. For example, despite the high weight capacities at the electrode level (based solely on the anode or cathode active material weight), as often claimed in the publications and patent literature, these electrodes unfortunately do not (whole battery cell weight or pack weight). Failing to provide a battery with a high capacity at the battery cell or pack level. This is due to the concept that in this report, the actual mass loading of the active material of the electrode is too low. In most cases, the active material mass feed (area density) of the anode is much lower than 15 mg / cm ² and most is less than 8 mg / cm ² (area density = amount of active material per electrode cross-sectional area along the electrode thickness direction). The amount of cathode active material is typically 1.5-2.5 times higher than the anode active material. As a result, the weight ratio of the anode active material (eg, graphite or carbon) in the lithium ion battery is typically 12% to 17%, and the weight ratio of the cathode active material (eg, LiMn ₂ O ₄ ) is 17% to 35% (mostly less than 30%). The combined weight fraction of the cathode active material and the anode active material is typically 30% to 45% of the cell weight.

Since sodium is rich and the production of sodium is much more environmentally friendly than the production of lithium, as a completely different kind of energy storage device, sodium cells have been considered an attractive alternative to lithium batteries. In addition, the high cost of lithium is a big problem.

Sodium ion batteries using hard carbon-based anodes (Na-carbon intercalating compounds) and sodium transition metal phosphates as cathodes have been described by several research groups. However, such sodium based devices exhibit much lower specific energy and discharge capacity ratios than Li ion cells. Such conventional sodium ion cells require diffusion of sodium ions into and out of the sodium insertion compound at both the anode and the cathode. The solid phase diffusion process required for sodium ions in sodium ion cells is much slower than the Li diffusion process in Li ion cells, resulting in very low power density.

As the anode active material of the sodium metal cell, sodium metal may be used instead of hard carbon or other carbonaceous intercalating compound. However, the use of metal sodium as anode active material is generally considered undesirable and dangerous due to dendrite formation, interfacial aging, and electrolyte incompatibility issues. 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 amount of active material mass supply is mainly because a thicker electrode (thicker than 100 to 200 μm) cannot be obtained using a conventional slurry coating method. This is not as trivial as one might think, and indeed, electrode thickness is not a design parameter that can be arbitrarily changed freely to optimize cell performance. Thicker samples, on the other hand, tend to be extremely brittle or have poor structural integrity, and will also require the use of large amounts of binder resin. Low area density and low volume density (associated with thin electrodes and low packing density) result in a relatively low volume capacity and low volume energy density of the battery cell.

As the demand for smaller, portable energy storage systems increases, there is a growing interest in increasing the volume utilization of batteries. New electrode materials and designs that allow for high volume capacity and high mass feed are essential to achieving improved cell volume capacity and energy density.

As electronic devices become smaller and lighter in electric vehicles (EVs), there is an urgent need for high energy density batteries that are conformable to be mounted in some unusual shape or limited space in a device or vehicle. By implementing the battery in a space that will be empty (unused or "unnecessary"), it can be made smaller or store more power in the EV. In order to make the cell conformable, the electrode must be deformable, flexible, and conformable.

Therefore, the necessity of lithium and sodium batteries having a high active material mass supply (high area density), high electrode thickness or volume, high discharge capacity ratio, high power density, and high energy density without a decrease in conductivity is evident and urgent. Such cells must be manufactured in an environmentally friendly manner. In addition, the cell must have shape compliance that can form any regular (eg, rectangular or cylindrical) or irregular shape. The present invention provides alkali metal cells that meet all these criteria.

The present invention provides a flexible and shape compliant lithium or sodium battery having high active material mass feed, very low overhead weight and volume (relative to active mass and volume), high capacity, and unprecedentedly high energy density and power density. Provide a way to. This lithium or sodium battery is either a primary battery (non-rechargeable) or a rechargeable lithium or sodium metal battery (having a lithium or sodium metal anode) and a first lithium insertion compound (e.g., as an anode active material and the first as a cathode active material). Secondary cells (rechargeable), including lithium ion or sodium ion batteries (with a second lithium insertion or absorption compound) having a much higher electrochemical potential than the compound. This alkaline cell is also an anode in which the anode is a lithium ion or sodium ion cell type and the cathode is a supercapacitor cathode (e.g. activated carbon or graphene sheet as an active material for use in an electric double layer capacitor or a redox like capacitor). Lithium ion capacitors and sodium ion capacitors.

In certain embodiments, the present invention provides a pharmaceutical composition comprising (a) about 30% to about 95% by volume of a cathode active material, an alkali salt dissolved in a solvent, and a first electrolyte agent containing an ion conductive polymer dissolved, dispersed, or impregnated in the solvent. Semi-solid cathodes containing from 5% to about 40% by volume, and from about 0.01% to about 30% by volume of conductive additives (conductive additives containing conductive filaments can be used from about 10 ^-6 S / cm to about 300 To form a 3D network of electronically conductive paths to have an electrical conductivity of S / cm); (b) an anode; And (c) an ion conductive membrane or a porous separator disposed between the anode and the semisolid cathode, wherein the semisolid cathode has a thickness of at least 200 μm. The semisolid cathode is at least 10 mg / cm ² , preferably at least 15 mg / cm ² , more preferably at least 25 mg / cm ² , more preferably at least 35 mg / cm ² , even more preferably 45 mg. / cm ² or more, it is preferable to contain the most preferably at least 65 mg / cm ² cathode active material mass flow.

In this cell, the anode comprises from about 30% to about 95% by volume of the anode active material, from about 5% by volume to about 2% by volume of a second electrolyte containing an alkali salt dissolved in a solvent and an ion conductive polymer dissolved, dispersed, or impregnated in the solvent. And 40% by volume, and a semisolid anode containing from about 0.01% to about 30% by volume of the conductive additive, wherein the conductive additive containing the conductive filament has a semisolid electrode of from about 10 ⁻⁶ S / cm to about A 3D network of electronically conductive paths is formed to have an electrical conductivity of 300 S / cm, and the semisolid anode has a thickness of at least 200 μm and may be at least 100 cm. The semisolid anode is at least 10 mg / cm ² , preferably at least 15 mg / cm ² , more preferably at least 25 mg / cm ² , more preferably at least 35 mg / cm ² , even more preferably 45 mg. / cm ² or more, preferably contains most preferably 65 mg / cm ² or more anode active material mass flow. The first electrolyte may be the same or different in composition and structure from the second electrolyte.

In certain embodiments, the present invention provides a composition comprising (A) about 30% to about 95% by volume of an anode active material, about 5% by volume of an electrolyte containing an alkali salt dissolved in a solvent and an ion conductive polymer dissolved, dispersed, or impregnated in the solvent. Semisolid anodes containing from% to about 40% by volume, and from about 0.01% to about 30% by volume of conductive additives (conductive additives containing conductive filaments have a semisolid electrode having from about 10 ⁻⁶ S / cm to about 300 S / forming a 3D network of electronically conductive paths to have an electrical conductivity of cm); (B) a cathode; And (C) an ion conductive membrane or porous separator disposed between the anode and the semisolid cathode, wherein the semisolid cathode has a thickness of at least 200 μm.

The quasi-solid polymer electrode of the present invention is deformable, flexible, and shape compliant, enabling the formation of a shape compliant battery.

The present invention also provides a method for producing an alkali metal cell having a semi-solid electrode, comprising: (a) a large amount of an active material (anode active material or cathode active material), an alkali salt dissolved in a solvent, and dissolved, dispersed, or impregnated in the solvent. Combining a large amount of electrolyte containing an ion conductive polymer, and a conductive additive to form a deformable electrically conductive electrode material, wherein the electrically conductive additive containing conductive filaments forms a 3D network of electronically conductive pathways; (b) forming the electrode material as a semi-solid electrode, wherein the electrode is at least 10 ⁻⁶ S / cm (preferably at least 10 ⁻⁵ S / cm, more preferably at least 10 ⁻³ S / cm, more preferably At least 10 ⁻² S / cm, even more preferably and usually at least 10 ⁻¹ S / cm, even more usually and preferably at least 1 S / cm, even more usually and preferably at least 10 S / cm The method includes the steps of modifying the electrode material into an electrode shape without blocking the 3D network of the electron conductive path to maintain an electrical conductivity of up to 300 S / cm); (c) forming a second electrode (the second electrode may be a semisolid electrode); And (d) combining the semisolid electrode and the second electrode to form an alkali metal cell having an ion conductive separator disposed between the two electrodes.

In some embodiments, the electrolyte (including the first electrolyte or the second electrolyte) is poly (ethylene oxide) (PEO, less than 1 × 10 ⁶ g / mol), polypropylene oxide (PPO), poly (acrylonitrile) (PAN ), Poly (methyl methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly (vinylidene) Fluoride) -hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof, and lithium ion conductive or sodium ion conductive polymers. Sulfonation is found herein to impart improved lithium ion conductivity to the polymer. PEO molecular weights greater than 1 × 10 ⁶ g / mol typically render PEO insoluble and dispersible in solvent.

Typically and preferably, this ion conductive polymer does not form a matrix (continuous phase) at the electrode.

Ionic conductive polymers include poly (perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives 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), hexafluoropropene and sulfonated copolymers of tetrafluoroethylene and polyvinylidene fluoride, ethylene And sulfonated copolymers of tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives thereof, copolymers, blends, and combinations thereof Luer binary may be selected from the group. The inventors have surprisingly observed that these sulfonated polymers have both lithium ion conductivity and sodium ion conductivity.

A "filament" is an object of solid material having the largest dimension (eg length) and the smallest dimension (eg diameter or thickness), and the ratio of the largest dimension to the smallest dimension is greater than three, preferably Preferably greater than 10, more preferably greater than 100. Typically, these are, for example, wire, fibrous, needle, rod, plate, sheet, ribbon, or disc objects. In certain embodiments, the conductive filaments are carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material-coated fibers, metal nanowires, metal fibers, metal Wire, graphene sheet, expanded graphite plate, combinations thereof, or non-filament conductive particles and combinations thereof.

In certain embodiments, the electrode maintains an electrical conductivity of 10 ⁻⁵ S / cm to about 100 S / cm.

In certain embodiments, the deformable electrode material has an apparent viscosity of at least about 10,000 Pa-s as measured at an apparent shear rate of 1,000 s ⁻¹ . In certain embodiments, the deformable electrode material has an apparent viscosity of at least about 100,000 Pa-s at an apparent shear rate of 1,000 s ^-1 . The semisolid electrode can conform to any desired shape that is regular or irregular.

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

Preferably, the step of combining the active material, the conductive additive, and the electrolyte (including dissolving lithium salt or sodium salt in the liquid solvent) follows a specific order. This step comprises first dispersing the conductive filaments in a liquid solvent to form a homogeneous suspension, then adding the active material to the suspension, dissolving lithium salt or sodium salt in the liquid solvent and dissolving or dispersing the ion conductive polymer in the solvent. It includes. In other words, the conductive filaments must first be uniformly dispersed in the liquid solvent before the addition of the other components such as the active material and the ion conductive polymer and before the lithium or sodium salts are dissolved in the solvent. This order is essential to achieve percolation of the conductive filaments to form a 3D network of electron conductive paths with lower conductive filament volume fraction (lower critical volume fraction). If this order is not followed, leaching of the conductive filaments does not occur, or can occur only when an excessively large amount of conductive filaments (eg, greater than 10% by volume) is added, which reduces the fraction of the active material to Will reduce energy density.

In certain embodiments, the blending and forming the electrode material into a semisolid electrode comprises dissolving a lithium salt (or sodium salt) and an ion conductive polymer in a liquid solvent to have a polymer electrolyte having a first salt concentration and a first polymer concentration. After forming, a portion of the liquid solvent is removed to increase the salt concentration so that the second is higher than the first concentration and preferably the sum of the salt and the polymer is higher than 2.5 M (more preferably 3.0 M to 14 M). Obtaining a semisolid polymer electrolyte having a salt concentration and a second polymer concentration.

Removing a portion of the solvent may be performed in such a way that the electrolyte is in a supersaturated state without causing precipitation or crystallization of salts and polymers. In certain preferred embodiments, the liquid solvent contains a mixture of at least a first liquid solvent and a second liquid solvent, the first liquid solvent is more volatile than the second liquid solvent, and removing a portion of the liquid solvent comprises: Partially or completely removing the solvent.

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, however, when the cell is charged, the anode active material is at an electrochemical potential of less than 1.0 volts (preferably less than 0.7 volts) higher than Li / Li ⁺ (ie, relative to Li → Li ⁺ + e ⁻ as standard potential). Absorb lithium ions.

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 comprises (a) particles of a 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 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) stoichiometric or nonstoichiometric alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements; (e) oxides, carbides, nitrides, sulfides, phosphides, seleniums of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof Cargoes, and tellurides; (f) their prelithiated forms; (g) prelithiated graphene sheets; And combinations thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or sodium ion cell, and the active material is petroleum coke, amorphous carbon, activated carbon, hard carbon (carbon that is difficult to graphitize), soft carbon (carbon that can be easily graphitized), template Carbon, hollow carbon nanowires, hollow carbon spheres, titanates, NaTi ₂ (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Na ₂ C ₈ H ₄ O ₄ , Na ₂ TP, Na _x TiO ₂ (x = 0.2 To 1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate-based 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 , An anode active material containing a sodium insertion compound selected from 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.

In certain embodiments, the alkali metal cell is a sodium metal cell or sodium ion cell, 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 coke, 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) sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof; (e) sodium-containing oxides, carbides, nitrides, sulfides, phosphides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof Selenides, tellurides, or antimonys; (f) sodium salts; And (g) graphene sheets pre-supplied with sodium ions; And an anode active material selected from the group consisting of a combination thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or sodium ion cell, and the active material comprises a sodium intercalating compound or sodium absorbing compound selected from inorganic materials, organic or polymeric materials, metal oxides / phosphates / sulfides, or combinations thereof. It is a cathode active material to contain. Metal oxides / phosphates / sulfides are sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium mixed metal oxide, sodium / potassium-transition metal oxide, sodium iron phosphate, sodium / potassium iron phosphate, sodium manganese phosphate, Sodium / potassium manganese phosphate, sodium vanadium phosphate, sodium / potassium vanadium phosphate, sodium mixed metal phosphate, transition metal sulfides, or combinations thereof.

The inorganic material may be selected from sulfur, sulfur compounds, lithium polysulfides, 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 a combination thereof.

In some embodiments, the alkali metal cell is a sodium metal cell or sodium ion cell, and the active material is 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 Containing a sodium insertion compound ( x is 0.1 to 1.0) selected from NaV _1-x Cr _x PO ₄ F, Se _z S _y (y / z = 0.01 to 100), Se, aluolite, or a combination thereof Cathode active material.

In some preferred embodiments, the cathode active material is lithium cobalt oxide, doped lithium cobalt oxide, lithium nickel oxide, doped lithium nickel oxide, lithium manganese oxide, doped lithium manganese oxide, lithium vanadium oxide, doped lithium vanadium oxide, lithium A lithium intercalation compound selected from the group consisting of mixed metal oxides, lithium iron phosphates, lithium vanadium phosphates, lithium manganese phosphates, lithium mixed metal phosphates, metal sulfides, and combinations thereof.

The electrolyte may be water, an organic liquid, an ionic liquid (an ionic salt having a melting point of less than 100 ° C., preferably less than 25 ° C. at room temperature), or a mixture of an ionic liquid and an organic liquid in a 1/100 to 100/1 ratio It may contain. Organic liquids are preferred, but ionic liquids are preferred. The electrolyte typically and preferably contains high solute concentrations (lithium / sodium salt and polymer summation concentrations) that make the solute saturated or supersaturated at the resulting electrode (anode or cathode). Such electrolytes are essentially polymeric electrolytes that behave like deformable or shape compliant solids. This is fundamentally different from liquid electrolytes or polymer gel electrolytes.

In a preferred embodiment, the semisolid electrode is between 200 μm and 1 cm, preferably between 300 μm and 0.5 cm (5 mm), more preferably between 400 μm and 3 mm and most preferably between 500 μm and 2.5 mm (2,500 μm). ) Has a thickness. If the active material is an anode active material, the anode active material has a mass feed amount 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 entire battery cell Account for at least 25% (preferably at least 30%, more preferably at least 35%) of the weight or volume. If the active material is a cathode active material, the cathode active material in the cathode is preferably at least 20 mg / cm ² (preferably at least 25 mg / cm ² , more preferably at least 30 mg / cm ² ) for organic or polymeric materials, or For inorganic and non-polymeric materials have a mass feed of at least 45 mg / cm ² (preferably at least 50 mg / cm ² , more preferably at least 55 mg / cm ² ), and / or the weight of the entire battery cell or At least 45% (preferably at least 50%, more preferably at least 55%) of the volume.

The above requirements for electrode thickness, anode active material area mass feed or mass fraction for the entire battery cell, or cathode active material area mass feed or mass fraction for the entire battery cell are known in conventional lithium or sodium using conventional slurry coating and drying processes. It was impossible with a battery.

In some embodiments, the anode active material is pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, graphene nitride , A pre-lithiated form of graphene sheet selected from boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physical or chemically activated or etched forms thereof, or a combination thereof . Surprisingly, without prior lithiation, the resulting lithium battery cells do not exhibit satisfactory cycle life (ie, the capacity is drastically reduced).

In some embodiments of the method of the invention, the cell contains lithium containing a cathode active material selected from lithium intercalation compounds or lithium absorbing compounds selected from inorganic materials, organic or polymeric materials, metal oxides / phosphates / sulfides, or combinations thereof Metal cells or lithium ion cells. For example, metal oxides / phosphates / sulfides may be lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, transition Metal sulfides, or combinations thereof. The inorganic material may be selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. In particular, the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or a combination thereof. This will be further described later.

In this lithium metal battery, the cathode active material contains a lithium insertion compound selected from metal carbides, metal nitrides, metal borides, metal dichalcogenides, or a combination thereof. In some embodiments, the cathode active material is of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in the form of nanowires, nanodisks, nanoribbons, or nanoplates. A lithium intercalation compound selected from 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, Nanodisks, nanoplates, nanocoatings, or nanosheets of inorganic materials selected from sulfides, selenides, or tellurides of manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof And a lithium insertion compound selected from said disks, plates or sheets having a thickness of less than 100 nm.

In some embodiments, the cathode active material of this lithium metal battery is poly (anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly (anthraqui Nonyl sulfide), pyrene-4,5,9,10-tetraon (PYT), polymer-bound PYT, quino (triazene), redox-active organic substance, tetracyanoquinomimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly (5-amino-1,4-dihydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ ] n ), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT (CN) ₆ ), 5-benzylidene hydantoin, isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy- p- benzoquinone derivative (THQLi ₄ ), N, N'-diphenyl-2,3,5 , 6-tetraketopiperazine (PHP), N, N'-diallyl-2,3,5,6-tetraketopiperazine (AP), N, N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether Polymers, quinone compounds, 1,4-benzoquinones, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxy anthraquinones (ADDAQ ), 5-amino-1,4-dihydroxy anthraquinone (ADAQ), calixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , or a combination thereof Are organic or polymeric materials.

Thioether polymers include poly (methanetetryl-tetra (thiomethylene)) (PMTTM), poly (2,4-dithiopentanylene) (PDTP), poly (ethene-1,1,2,2-tetrathiol) A polymer containing (PETT) as a main chain thioether polymer, a side chain thioether polymer having a main chain consisting of a conjugated aromatic moiety and having 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).

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

In lithium metal cells, the cathode active material is an electrode active material of greater than 30 mg / cm ² (preferably greater than 40 mg / cm ² , more preferably greater than 45 mg / cm ² , most preferably greater than 50 mg / cm ² ) Make up the feed amount and / or, the electrode has a thickness of at least 300 μm (preferably at least 400 μm, more preferably at least 500 μm and may be up to 100 cm or more). There is no theoretical limitation on the electrode thickness of the alkali metal battery of the present invention.

FIG. 1A shows an anode current collector, one or two anode active material layers (eg, Si coated thin layers) coated on two primary surfaces of the anode current collector, a porous separator and an electrolyte, and one or two cathode electrode layers ( For example, a schematic view of a prior art lithium ion battery cell consisting of a yellow layer) and a cathode current collector.
1B illustrates a prior art in which an electrode layer is composed of discrete particles of an active material (eg, graphite or tin oxide particles of an anode layer, or LiCoO ₂ of a cathode layer), a conductive additive (not shown), and a resin binder (not shown). It is a schematic diagram of a lithium ion battery.
FIG. 1C includes a semisolid anode (consisting of directly active or dispersed active electrolyte particles and conductive filaments), a porous separator, and a semisolid cathode (consisting directly of active active material particles and conductive filaments). It is a schematic diagram of the lithium ion battery cell of this invention. In this embodiment, no resin binder is needed.
1D illustrates a lithium metal battery cell of the present invention comprising an anode (containing a lithium metal layer deposited on a Cu foil surface), a porous separator, and a semi-solid cathode (consisting of cathode active material particles and conductive filaments directly mixed or dispersed in an electrolyte). Schematic diagram of. In this embodiment, no resin binder is needed.
2A is a schematic diagram of a densely packed highly ordered structure of a solid electrolyte.
2B is a schematic of a completely amorphous liquid electrolyte with a large amount of free volume through which cations (eg, Na ⁺ ) can easily migrate.
2C is a schematic of a random or amorphous structure of a semisolid electrolyte with solvent molecules that separate salt species to create an amorphous region for easy migration of free (non-clustered) cations. The ion conductive polymers also come into a substantially amorphous supersaturated state.
FIG. 3A shows Na ⁺ ion transition water of an electrolyte (eg, (PEO + NaTFSI salt) in (DOL + DME) solvent) for sodium salt molecular ratio x .
3B shows the Na ⁺ ion transition water of the electrolyte (eg, (PPO + NaTFSI salt) in (EMImTFSI + DOL) solvent) for sodium salt molecular ratio x .
4 is a process commonly used to prepare exfoliated graphite, expanded graphite flakes (greater than 100 nm thick), and graphene sheets (less than 100 nm thick, more typically less than 10 nm thick, which may be as thin as 0.34 nm). Schematic diagram of.
5A shows the electrical conductivity (leaching behavior) of the conductive filaments at the semisolid polymer electrode, plotted as a function of the volume fraction of the conductive filaments (carbon nanofibers).
FIG. 5B shows the electrical conductivity (leaching behavior) of the conductive filament at the semisolid polymer electrode, plotted as a function of the volume fraction of the conductive filament (reduced graphene oxide sheet).
FIG. 6 shows a ragon diagram (weight power density versus energy density) of a lithium ion battery cell containing graphite particles as anode active material and carbon-coated LFP particles as cathode active material. Three of the four data curves are for cells made according to an embodiment of the invention and the other is for cells made by conventional electrode slurry coating (roll-coating).
FIG. 7 shows a ragon diagram (weight power density vs. weight energy density) of three cells, each containing graphene-containing Si nanoparticles as anode active material and LiCoO ₂ nanoparticles as cathode active material. Experimental data were obtained from Li-ion battery cells produced by the process of the invention (according to orders S1 and S3) and Li-ion battery cells prepared by conventional electrode slurry coating.
FIG. 8 is a ragon diagram of a lithium metal battery containing lithium foil as an anode active material, lithium lithium disodie (Li ₂ C ₆ O ₆ ) as a cathode active material, and lithium salt (LiPF ₆ ) / PPO-PC / DEC as an organic electrolyte. Indicates. The data are for lithium metal cells produced by the process of the invention (two different salt concentrations, sequences S2 and S3) and conventional electrode slurry coatings.
FIG. 9 shows two sodium ion capacitors (one cell with anode prepared by conventional slurry coating process and present method) each containing pre-sodiumated hard carbon particles as anode active material and graphene sheet as cathode active material. The ragon diagram of another cell with a semisolid anode prepared according to the present invention is shown.

The present invention relates to lithium or sodium cells exhibiting very high volumetric energy densities that have not been achieved previously. This battery may be a primary battery, but is preferably a lithium ion battery, a lithium metal secondary battery (eg, using lithium metal as an anode active material), sodium ion battery, sodium metal battery, lithium ion capacitor, or sodium ion It is a secondary battery selected from a capacitor. The cell is based on a semisolid polymer electrolyte containing a polymer or lithium or sodium salt dissolved in water, an organic solvent, an ionic liquid, or a mixture of an organic liquid and an ionic liquid. Preferably, the electrolyte has a high concentration of solute (lithium) so that the desired amount of conductive filament and active material behaves like a solid even when added to the electrolyte but can still be deformed (thus using the term “deformable semisolid polymer electrode”). Salts or sodium salts and polymers) in a solvent. The electrolyte is not a liquid electrolyte, nor is it 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, in the present invention, illustrative examples of the cathode active material include lithium iron phosphate (LFP), vanadium oxide (V _x O _y ), rhodizone dilithium (Li ₂ C ₆ O ₆ ), and copper phthalocyanine (CuPc), and anode As examples of the active material, selected materials such as graphite, hard carbon, SnO, Co ₃ O ₄ , and Si particles are used. They should not be construed as limiting the scope of the invention.

As shown in FIG. 1A, prior art lithium or sodium battery cells typically comprise an anode current collector (eg, Cu foil), an anode electrode or an anode active material layer (eg, Li metal foil, sodium foil, or Prelithiated Si coating deposited on one or both sides of Cu foil), porous separator and / or electrolyte components, cathode electrode or cathode active material layer (or two cathode active material layers coated on both sides of Al foil), and cathode It consists of an electrical power collector (for example, Al foil).

In more commonly used prior art cell configurations (FIG. 1B), the anode layer comprises anode active material particles (eg, graphite, hard carbon, or Si), conductive additives (eg, carbon black particles), and resins. Consisting of a binder (eg SBR or PVDF). The cathode layer consists of cathode active material particles (eg, LFP particles), conductive additives (eg, carbon black particles), and resin binder (eg, PVDF). Both the anode layer and the cathode layer typically have a thickness of up to 100-200 μm to generate a sufficient amount of current per unit electrode area. This thickness range is considered an industry acceptable constraint in which battery designers typically work. This thickness constraint is due to several reasons: (a) Conventional cell electrode coaters are not equipped to coat very thin or very thick electrode layers; (b) Thinner layers are preferred given the reduced lithium ion diffusion path length, but too thin layers (e.g., less than 100 μm) do not contain a sufficient amount of active lithium storage material (thus the current output is Insufficient); (c) thicker electrodes are liable to peel or crack upon drying or handling after roll-coating; (d) all inert layers (eg, current collectors and current collectors) of the battery cell to obtain the minimum overhead weight and the maximum lithium storage capacity and thus the maximum energy density (Wk / kg or Wh / L of the cell). Separator) must be kept to a minimum.

In less commonly used cell configurations as shown in FIG. 1A, the anode active material (eg, Si coating) or cathode active material (eg, lithium transition metal oxide) may be a current collector, such as a sheet of copper foil or Al foil. It is deposited directly in the form of a thin film. However, such thin film structures with extremely small thickness direction dimensions (typically smaller than 500 nm and often inevitably thinner than 100 nm) have only a small amount of active material (when the same electrode or current collector surface area) incorporated into the electrode. Which means lower total lithium storage capacity and lower lithium storage capacity per unit electrode surface area. In order to be more resistant to cracking due to cycling or to facilitate the full use of the cathode active material, such thin films should have a thickness of less than 100 nm. This constraint further reduces the total lithium storage capacity and lithium storage capacity per unit electrode surface area. Such thin film cells have a very limited range of applications.

On the anode side, Si layers thicker than 100 nm were found to exhibit low crack resistance during cell charge and discharge cycles. The Si layer fragments in a few cycles. On the cathode side, if the sputtered layer of lithium metal oxide is thicker than 100 nm, the cathode active material utilization becomes poor because lithium ions cannot fully penetrate and reach the entire cathode layer. Preferred electrode thicknesses are at least 100 μm and the individual active material coatings or particles preferably have dimensions of less than 100 nm. Thus, these thin film electrodes (less than 100 nm thick) deposited directly on the current collector are 1000 times thinner than the required thickness. As another problem, not all cathode active materials are conductive to both electrons and lithium ions. Thick layer thicknesses result in excessively high internal resistance and poor utilization of the active material. Sodium cells have a similar problem.

In other words, there are several conflicting factors that must be considered simultaneously with regard to the design and selection of the cathode or anode active material in terms of material type, size, electrode layer thickness, and active material mass feed amount. To date, no effective solution to this often conflicting problem has been provided in any prior art teaching. The inventors have solved this difficult problem that has been a problem for both cell designers and electrochemists for over 30 years by developing new methods of making lithium or sodium cells as disclosed herein.

Prior art lithium battery cells are typically manufactured by a process comprising the following steps: (a) The first step is an anode active material particle (e.g., Si nanoparticles or mesocarbon microbeads, MCMB), conductive filler ( For example, graphite flakes, a resin binder (eg, PVDF) are mixed in a solvent (eg, NMP) to form an anode slurry. As a separate main component, cathode active material particles (e.g., LFP particles), conductive fillers (e.g., acetylene black), resin binders (e.g., PVDF) are mixed and dispersed in a solvent (e.g., NMP) To form a cathode slurry. (b) The second step is to coat the anode slurry on one or both sides of the primary surface of the anode current collector (eg Cu foil), and to dry the coating layer by vaporizing the solvent (eg NMP) to Cu foil. Forming a dry anode electrode coated thereon. Likewise, the cathode slurry is coated and dried to form a dry cathode electrode coated on Al foil. Slurry coating is generally carried out in a roll-to-roll manner in actual manufacturing situations. (c) The third step involves laminating the anode / Cu foil sheet, the porous separator layer, and the cathode / Al foil sheet together to form a three or five layer assembly, which is cut or cut and laminated to the desired size (one of the shape By way of example) forming a rectangular structure or winding it into a cylindrical cell structure. (d) The rectangular or cylindrical laminate structure is then placed in an aluminum-plastic laminate sheath or steel casing. (e) Next, a liquid electrolyte is injected into the laminate structure to prepare a lithium battery cell.

There are several serious problems associated with the process and the lithium battery cells produced.

1) It is very difficult to produce an electrode layer (anode layer or cathode layer) thicker than 200 μm. There are many reasons for this. 100-200 μm thick electrodes typically require a heating zone of 30-50 meters in a slurry coating installation, which is too time consuming, too energy intensive and not cost effective. Some electrode active materials such as metal oxide particles In the case of, it was not possible to continuously manufacture electrodes with structural integrity that is thicker than 100 μm in the actual manufacturing environment. The resulting electrode is very weak and brittle. Thicker electrodes are more prone to peeling and cracking.

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

3) The conventional process requires dispersing the electrode active material (anode active material and cathode active material) in a liquid solvent (for example, NMP) to prepare a slurry, and when coating the current collector surface, the liquid solvent dries the electrode layer. To be removed. When the anode layer and the cathode layer are laminated together with the separator layer and packaged in the housing to prepare a battery cell, a liquid electrolyte is injected into the cell. In practice, both electrodes are wetted, then the electrodes are dried and finally wet again. This dry-wet-dry-wet process is not a good process at all.

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

In the literature, it is not possible to directly convert the reported energy density data based on the active material weight alone or the electrode weight to the energy density of the actual battery cell or device. The weight of the "overhead weight" or other device components (binder, conductive additive, current collector, separator, electrolyte, and packaging) should also be considered. According to the conventional manufacturing process, the weight ratio of the anode active material (eg, graphite or carbon) in the lithium ion battery is typically 12% to 17%, and the weight ratio of the cathode active material is 20% to 35% (LiMn ₂ O). Inorganic materials such as ₄ ) or 7-15% (for organic or polymeric cathode materials).

The present invention provides a lithium battery or sodium battery cell having a thick electrode thickness, high active material mass supply, low overhead weight and volume, high capacity, and high energy density. In certain embodiments, the present invention provides a pharmaceutical composition comprising (a) about 30% to about 95% by volume of a cathode active material, an alkali salt dissolved in a solvent, and a first electrolyte agent containing an ion conductive polymer dissolved, dispersed, or impregnated in the solvent. Semisolid polymer cathodes containing from 5% by volume to about 40% by volume, and from about 0.01% to about 30% by volume of conductive additives (conductive additives containing conductive filaments have a semisolid electrode of from about 10 ⁻⁶ S / cm to about Forming a 3D network of electronically conductive paths to have an electrical conductivity of 300 S / cm (which may be higher); (b) an anode (which may be a conventional anode or semisolid polymer electrode); And (c) an ion conductive membrane or a porous separator disposed between the anode and the semisolid cathode, wherein the semisolid cathode has a thickness of at least 200 μm. The semisolid polymer cathode is at least 10 mg / cm ² , preferably at least 15 mg / cm ² , more preferably at least 25 mg / cm ² , more preferably at least 35 mg / cm ² , even more preferably 45 mg / cm ² or more, it is preferred that most preferably contains at least 65 mg / cm ² cathode active material mass flow.

In this cell, the anode also contains about 30% to about 95% by volume of the anode active material, about 5% by volume of a second electrolyte containing an alkali salt dissolved in a solvent and an ion conductive polymer dissolved, dispersed, or impregnated in the solvent. To about 40% by volume, and about 0.01% to about 30% by volume of the conductive additive, the semisolid polymer anode, wherein the conductive additive containing the conductive filament is about ^10-6 S / A 3D network of electronically conductive paths is formed to have an electrical conductivity of cm to about 300 S / cm, wherein the semisolid anode has a thickness of at least 200 μm. The semisolid anode is at least 10 mg / cm ² , preferably at least 15 mg / cm ² , more preferably at least 25 mg / cm ² , more preferably at least 35 mg / cm ² , even more preferably 45 mg. / cm ² or more, preferably contains most preferably 65 mg / cm ² or more anode active material mass flow. The first electrolyte may be the same or different in composition and structure from the second electrolyte.

In some embodiments, the alkali metal cell comprises a semisolid polymer anode, but includes a conventional cathode.

The present invention also provides a method for producing an alkali metal battery. In certain embodiments, the method

(a) a large amount of active material (anode active material or cathode active material), a large amount of semi-solid polymer electrolyte (containing polymer and alkali metal salt dissolved in solvent), and conductive additives are combined to form a deformable electrically conductive electrode material, the conductive filament The electrically conductive additive containing comprises forming a 3D network of electron conductive paths; (These conductive filaments, such as carbon nanotubes and graphene sheets, are agglomerates of randomly aggregated filaments before mixing with the active material particles and the electrolyte. The mixing process involves dispersing these conductive filaments in a highly viscous electrolyte containing the active material particles. This is further described later.)

(b) forming the electrode material as a semi-solid electrode, wherein the electrode is at least 10 ⁻⁶ S / cm (preferably at least 10 ⁻⁵ S / cm, more preferably at least 10 ⁻⁴ S / cm, more preferably 10 ⁻³ S / cm or more, even more preferably and usually 10 ⁻² S / cm or more, even more usually and preferably 10 ⁻¹ S / cm or more, even more commonly and preferably 1 S deformation of the electrode material into electrode shape without blocking of the 3D network of the electron conductive path to maintain an electrical conductivity of at least 300 cm / cm;

(c) forming a second electrode (the second electrode may be a semisolid polymer electrode or a conventional electrode); And

(d) combining the semisolid electrode and the second electrode to form an alkali metal cell having an ion conductive separator disposed between the two electrodes.

The anode and / or cathode may be a semisolid electrode. In certain embodiments, the step of forming the second electrode comprises (A) combining a large amount of a second active material (eg, an anode active material if the first electrode is a cathode), a large amount of electrolyte, and a conductive additive to deform the electrically deformable Forming a conductive second electrode material, wherein the conductive additive containing the conductive filaments forms a 3D network of electron conductive pathways, and the electrolyte contains an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent; And (B) forming a deformable conductive second electrode material as a second semi-solid electrode, wherein the second electrode maintains electrical conductivity of at least 10 ⁻⁶ S / cm (typically up to 300 S / cm). Deforming the deformable conductive second electrode material into an electrode shape without blocking the 3D network of the path.

As shown in FIG. 1C, one preferred embodiment of the present invention is a conductive semisolid polymer anode 236 , a conductive semisolid polymer cathode 238 , and a porous separator 240 that electronically separates the anode and cathode (or Alkali metal ion cell with ion permeable membrane). These three components are typically encased in a protective housing (not shown), which has an anode tab (terminal) connected to the anode and a cathode tab (terminal) connected to the cathode. These tabs are for connecting to an external load (eg, a battery powered electronic device). In this particular embodiment, the semisolid polymer anode 236 is an anode active material (eg, particles of Si or hard carbon, not shown in FIG. 1C), an electrolyte phase (typically lithium salt or sodium dissolved in a solvent). Containing a salt and an ion conductive polymer dissolved, dispersed or impregnated in this solvent, likewise not shown in FIG. 1C, and a conductive additive (containing conductive filaments) forming a 3D network 244 of the electron conductive pathway. Likewise, the semisolid polymer cathode contains a cathode active material, an electrolyte, and a conductive additive (containing conductive filaments) to form a 3D network 242 of electronically conductive pathways.

Another preferred embodiment of the present invention is an anode, quasi, consisting of lithium or sodium metal coating / foil 282 deposited / attached to current collector 280 (eg, Cu foil), as shown in FIG. 1D. Alkali metal cell with solid cathode 284 and separator or ion conductive membrane 282 . The semisolid polymer cathode 284 is a cathode active material 272 (e.g., LiCoO ₂ particles), an electrolyte phase 274 (typically, a lithium or sodium salt dissolved in a solvent and dissolved, dispersed, or Impregnated ion conductive polymer), and a conductive additive phase (containing conductive filaments) that forms a 3D network 270 of electronically conductive pathways. The invention also includes lithium ion capacitors and sodium ion capacitors.

Preferably the electrolyte is at least 1.5 M, preferably more than 2.5 M, more preferably more than 3.5 M, more preferably more than 5 M, even more preferably more than 7 M, even more preferably more than 10 M salts. It is a semisolid polymer electrolyte containing a lithium salt or a sodium salt and a polymer dissolved in a solvent at a combined polymer concentration. In certain embodiments, the electrolyte is a semisolid polymer electrolyte containing a polymer dissolved in a liquid solvent and a lithium or sodium salt at a salt / polymer combined concentration of 3.0 M to 14 M. The selection of lithium or sodium salts and solvents is further described in the later sections.

In some embodiments, the electrolyte is poly (ethylene oxide) (PEO, having a molecular weight less than 1 × 10 ⁶ g / mol), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (methyl meta Acrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly (vinylidene fluoride) -hexafluoro A lithium ion conductive or sodium ion conductive polymer selected from ropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. Sulfonation is found herein to impart improved lithium ion conductivity to the polymer. PEO molecular weights greater than 1 × 10 ⁶ g / mol typically make it difficult to dissolve or disperse PEO in a solvent.

Typically, this ion conductive polymer does not form a matrix (continuous phase) at the electrode. Rather, the polymer is dispersed in the solvent in solution or discontinuously in the solvent matrix. The resulting electrolyte is a semisolid polymer electrolyte and is not a liquid electrolyte but a solid electrolyte.

Ionic conductive polymers include poly (perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives 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), hexafluoropropene and sulfonated copolymers of tetrafluoroethylene and polyvinylidene fluoride, ethylene And sulfonated copolymers of tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives thereof, copolymers, blends, and combinations thereof Luer binary may be selected from the group. The inventors have surprisingly observed that these sulfonated polymers have both lithium ion conductivity and sodium ion conductivity.

Preferably the semisolid anode and semisolid cathode are both greater than 200 μm (preferably greater than 300 μm, more preferably greater than 400 μm, more preferably greater than 500 μm, even more preferably greater than 800 μm, more preferably Is greater than 1 mm and greater than 5 mm, which may be at least 1 cm. There is no theoretical limit to the electrode thickness of the present invention. In the cells of the present invention, the anode active material typically has an electrode active material supply of at least 20 mg / cm ² (more typically and preferably at least 25 mg / cm ² , more preferably at least 30 mg / cm ² ) at the anode. Configure. The cathode active material constitutes an electrode active material mass supply amount of 45 mg / cm ² or more (typically and preferably more than 50 mg / cm ² , more preferably more than 60 mg / cm ² ) when the cathode active material is an inorganic material ( 25 mg / cm ² or more for organic or polymeric cathode active materials).

In this configuration (FIGS. 1C and 1D), electrons are formed at short distances (eg, before they are collected by conductive filaments that make up a 3D network of electron conductive paths and are present everywhere across the entire semisolid polymer electrode (anode or cathode)). , A few micrometers or less). In addition, all electrode active material particles are predispersed in an electrolyte solvent (no wettability problem), so that dry pockets typically exist in electrodes made by conventional processes of wet coating, drying, packing, and electrolyte injection. Eliminate existence Thus, the process or method of the present invention has absolutely unexpected advantages over conventional battery cell manufacturing processes.

These conductive filaments (eg, carbon nanotubes and graphene sheets) in the fed state are originally agglomerates of randomly aggregated filaments before mixing with the active material particles and the electrolyte. The mixing process involves dispersing these conductive filaments in a highly viscous solid electrolyte containing particles of active material. This is not as trivial as you might think. Nanoporous in solids, such as electrolytes containing high feed amounts of active materials (e.g., solid particles such as Si nanoparticles for anodes and lithium cobalt oxide for cathodes) and nanoparticles in highly fluid (non-viscous) liquids Dispersing materials (particularly nanofilament materials such as carbon nanotubes, carbon nanofibers, and graphene sheets) are known to be very difficult. This problem is further exacerbated by the concept that, in some embodiments, the electrolyte itself is a semisolid polymer electrolyte containing high concentrations of lithium or sodium salts and polymers in the solvent.

In some preferred embodiments, the electrolyte has a vapor pressure of less than 0.01 kPa (measured at 20 ° C.) or less than 0.6 (60%) of the vapor pressure of the solvent alone, when the first organic liquid solvent alone (no lithium salt is present). Polymers and alkali metal salts dissolved in organic or ionic liquid solvents having a flash point at least 20 ° C. higher than 150 ° C., a flash point higher than 150 ° C., or at a sufficiently high alkali metal salt / polymer combined concentration such that no flash point is detected at all. Lithium salt and / or sodium salt).

The inventors find that the flammability of any volatile organic solvent can be effectively suppressed by adding and dissolving a sufficient amount of alkali metal salt and polymer to this organic solvent to form a solid or semisolid polymer electrolyte. It makes sense. In general, such semisolid polymer electrolytes exhibit vapor pressures (measured at 20 ° C.) of less than 0.01 kPa and often less than 0.001 kPa, (measured at 100 ° C.) of less than 0.1 kPa and often less than 0.01 kPa (some alkali metal salts and / or Or the vapor pressure of the pure solvent in which the polymer is also not dissolved is typically much higher). In many cases characterized by semisolid polymer electrolytes, the vapor molecules are actually too small to be detected.

Otherwise the high solubility of alkali metal salts and polymer sums in a highly volatile solvent (large molecular or mole fraction of alkali metal salt / polymer chain segments, typically greater than 0.2, more typically greater than 0.3, often greater than 0.3, or even greater than 0.5) is thermodynamic. It is a significant observation that the amount of volatile solvent molecules that can escape into the vapor phase under equilibrium conditions can be dramatically reduced. In many cases, this effectively prevented flammable solvent gas molecules from initiating flames even at very high temperatures (eg using a torch). The flash point of the semisolid polymer electrolyte is typically 20 degrees (often more than 50 degrees or more than 100 degrees) higher than that of pure organic solvents alone. In most cases, the flash point is higher than 150 ° C., or no flash point is detected. The electrolyte will probably not burn. Also, any flame initiated by accident does not last longer than a few seconds. This is a significant finding given the notion that fire and explosion concerns have been a major barrier to widespread acceptance of battery powered electric vehicles. This new technology can help significantly in accelerating the emergence of a vibrant EV industry.

Previous reports reported on the vapor pressure of ultrahigh concentration cell electrolytes with safety considerations (high molecular weight fractions of alkali metal salt / polymer chain segments, eg greater than 0.2 or greater than 0.3, or combined concentrations greater than about 2.5 M or 3.5 M) There was no study. This is in fact unexpected and of the greatest scientific and technical significance.

The inventors also unexpectedly found that the presence of a 3D network of electronically conductive pathways composed of conductive nanofilaments acts to further reduce the critical concentration of alkali metal salts necessary to achieve critical vapor pressure suppression.

Another surprising element of the present invention is that it is possible to dissolve high concentrations of alkali metal salts and selected ion conductive polymers in almost all battery-grade organic solvents commonly used to form semisolid polymer electrolytes suitable for use in rechargeable alkali metal batteries. Concept. Expressed in more understandable terms, this concentration is typically greater than 2.5 M (mol / liter), more usually and preferably greater than 3.5 M, even more usually and preferably greater than 5 M, even more preferably More than 7 M, most preferably more than 10 M. At salt / polymer concentrations of at least 2.5 M, the electrolyte is no longer a liquid electrolyte, but instead a semisolid electrolyte. In lithium or sodium cell technology, such high concentrations of alkali metal salts in solvents are generally considered neither possible nor desirable. However, the inventors have found that such semisolid polymer electrolytes are surprisingly good electrolytes for both lithium and sodium batteries in view of significantly improved safety (nonflammability), improved energy density, and improved power density.

In addition to the incombustible and high alkali metal ion transition waters discussed above, there are several additional advantages associated with using the semisolid polymer electrolytes of the present invention. In one example, semisolid polymer electrolytes, when implemented at least at the anode, can significantly improve cycle performance and safety performance of rechargeable alkali metal cells through effective suppression of dendrite growth. It is generally accepted that dendrites begin to grow in nonaqueous liquid electrolytes when anions are depleted near the electrodes where plating occurs. In very high concentration electrolytes, many anions are present to balance the anions with cations (Li ⁺ or Na ⁺ ) near the metallic lithium or sodium anode. In addition, the space charge generated by anion depletion is minimal, which is not conducive to dendrites growth. In addition, due to both very high Li or Na salt concentrations and high Li ion or Na ion transition water, the semisolid polymer electrolyte provides a large amount of available lithium ion or sodium ion flux and provides lithium between the electrolyte and the lithium or sodium electrode. Or by increasing the rate of sodium ion transfer to improve lithium or sodium deposition uniformity and dissolution during charge and discharge. In addition, localized high viscosity induced by high concentrations will increase the pressure from the electrolyte to inhibit dendrite growth, potentially creating a more uniform deposition on the surface of the anode. High viscosities can also limit anion convection near the deposition zone, thereby promoting more uniform deposition of sodium ions. The same logic can be applied to lithium metal cells. These reasons are believed to be the cause of the notion that no dendrite-like features were observed in any of the many rechargeable alkali metal cells investigated by the inventors so far, either individually or in combination.

In addition, one of ordinary skill in the chemical or material sciences would have expected that this electrolyte would not be suitable for the rapid diffusion of alkali metal ions therein because such high salt / polymer concentrations make the electrolyte behave like a very high viscosity solid. Thus, those skilled in the art will appreciate that alkali metal batteries containing such solid polymer electrolytes will not exhibit high capacity at high charge and discharge rates or under high current density conditions (ie, they will not have a good discharge capacity ratio). I would have expected. Contrary to these expectations of the skilled person or even the skilled person, all alkali metal cells containing such semisolid polymer electrolytes deliver high energy density and high power density for long cycle life. The semisolid polymer electrolytes disclosed and disclosed herein appear to help promote alkali metal ion transport. This surprising observation seems to be due to two main factors: one related to the internal structure of the electrolyte and the other related to the high Na ⁺ or Li ⁺ ion transition water (TN).

Without wishing to be bound by theory, one can envision the internal structure of three fundamentally different types of electrolytes with reference to FIGS. 2A-2C. Figure 2a schematically illustrates a densely packed highly ordered structure of a conventional solid electrolyte with little free volume for diffusion of alkali metal ions. Ion transport in these crystal structures is very difficult, with very low diffusion coefficients (10 ^-16 to 10 ^-12 cm ² / sec) and very low ionic conductivity (typically 10 ^-7 S / cm to 10 ^-4 S / cm) Leads to. In contrast, as shown schematically in FIG. 2B, the internal structure of the liquid electrolyte is completely amorphous with a large amount of free volume through which cations (eg, Li ⁺ or Na ⁺ ) can easily migrate, resulting in high diffusion. Coefficients (10 ⁻⁸ to 10 ⁻⁶ cm ² / sec) and high ionic conductivity (typically 10 ⁻³ S / cm to 10 ⁻² S / cm). However, liquid electrolytes containing low concentrations of alkali metal salts are flammable and liable to form dendrites, resulting in a fire and explosion hazard. Shown schematically in FIG. 2C is a random or amorphous structure of a semisolid polymer electrolyte with solvent molecules that separate salt species and polymer chain segments to create amorphous regions for easy migration of free (non-clustered) cations. This structure is suitable for achieving high ionic conductivity values (typically 10 ⁻⁴ S / cm to 8 × 10 ⁻³ S / cm) while still maintaining incombustibility. There are relatively few solvent molecules, and these molecules are maintained (prevented from vaporization) by a very large number of salt species, polymer chain segments, and a network of conductive 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, hydrogenated graphene, graphene nitride, chemically It is a pre-lithiated or pre-sodiumated form of graphene sheet selected from functionalized graphene, or a combination thereof. Starting graphite materials for producing any one of the graphene materials are 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 conductive additives for both anode and cathode active materials of lithium batteries.

If the interplanetary van der Waals forces can be overcome, the graphene plane, which is a component of graphite microcrystals in natural or artificial graphite particles, is stripped and extracted or isolated to obtain individual graphene sheets of hexagonal carbon atoms, which are monoatomic thick. Can be. The general process is shown in FIG. Isolated individual graphene faces of carbon atoms are generally referred to as single layer graphene. Stacks of graphene planes bonded together by van der Waals forces in the thickness direction with a graphene plane spacing of about 0.3354 nm are generally referred to as multilayer graphene. Multilayer graphene plates have up to 300 layers of graphene (less than 100 nm thick), but more typically up to 30 graphene faces (less than 10 nm thick), even more typically up to 20 It has graphene planes (less than 7 nm thick), most commonly up to 10 graphene planes (commonly referred to in science as the few-layer graphene). Monolayer graphene and multilayer graphene sheets are collectively referred to as "nanographene plates" (NGP). Graphene sheets / plates (collectively NGP) are a new class of carbon nanomaterials (2-D nanocarbons) that are distinct from 0-D fullerenes, 1-D CNTs or CNFs, and 3-D graphite. To define the claims and as generally understood in the art, graphene materials (isolated graphene sheets) are not carbon nanotubes (CNT) or carbon nanofibers (CNF) (and do not include them). .

In one process, the graphene material is obtained by inserting natural graphite particles with strong acids and / or oxidants to obtain graphite intercalation compounds (GIC) or graphite oxides (GO), as shown in FIGS. 5A and 5B. Lose. The presence of species or functional groups in the interstitial spaces between graphene planes in GIC or GO serves to increase the intergraphene spacing ( d _{002 as} measured by X-ray diffraction), otherwise along the c axis direction Significantly reduces the van der Waals forces that bind the graphene faces together. GIC or GO is in most cases produced by immersing natural graphite powder in a mixture of sulfuric acid, nitric acid (oxidant), and other oxidants (eg, potassium permanganate or sodium perchlorate). If oxidants are present during the insertion process, the resulting GIC is actually some type of graphite oxide (GO) particles. This GIC or GO is then washed repeatedly in water and washed to remove excess acid, resulting in a graphite oxide suspension or dispersion containing visually identifiable discrete graphite oxide particles dispersed in water. To prepare the graphene material, after this cleaning step, one of the two processing paths outlined below can be followed.

Path 1 involves removing water from the suspension to obtain “expandable graphite” which is essentially a large amount of dried GIC or dried graphite oxide particles. When the expandable graphite is exposed to temperatures typically in the range of 800-1,050 ° C. for about 30 seconds to 2 minutes, the GIC undergoes rapid volume expansion of 30-300 times, resulting in a collection of interconnected graphite flakes in the exfoliated but not largely separated state. To form a "graphite worm".

In Path 1A, these graphite worms (a network of exfoliated graphite or “interconnected / unseparated graphite flakes”) are recompressed and are typically flexible with thicknesses ranging from 0.1 mm (100 μm) to 0.5 mm (500 μm). Graphite sheets or foils can be obtained. Alternatively, graphite worms may be prepared using low intensity air mills or shears for the purpose of producing so-called "expanded graphite flakes" (thus by definition not nanomaterials) containing graphite flakes or plates thicker than 100 nm. You can simply choose to destroy it.

In Route 1B, as disclosed in Applicant's U.S. Application No. 10 / 858,814 (June 3, 2004), exfoliated graphite (eg, an ultrasonicator, a high shear mixer, a high intensity air jet mill, or a high energy ball mill) High strength mechanical shearing to form separate monolayer and multilayer graphene sheets (collectively NGP). Single layer graphene may be as thin as 0.34 nm, while multilayer graphene may have a thickness of less than 100 nm, but more typically less than 10 nm (generally referred to as hydrophobic graphene). Several graphene sheets or plates can be made from NGP paper sheets using the papermaking process. This NGP paper sheet is an example of a porous graphene structure layer used in the process of the present invention.

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

In order to define the claims of the present application, NGP or graphene materials may be prepared in mono and multilayer (typically less than 10 layers) pure graphene, graphene oxide, reduced graphene oxide (RGO), graphene fluoride Discrete sheets of graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, graphene nitride, chemically functionalized graphene, doped (e.g., doped with B or N) Includes / edition. Pure graphene has essentially 0% oxygen. RGO typically has an oxygen content of 0.001% to 5% by weight. Graphene oxide (including RGO) may have from 0.001% to 50% by weight of oxygen. In addition to pure graphene, all graphene materials have 0.001% to 50% by weight of non-carbon elements (eg, O, H, N, B, F, Cl, Br, I, etc.). Such materials are referred to herein as non-pure graphene materials.

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

Graphene oxide (GO) is the desired temperature of a starting graphite material powder or filament (eg natural graphite powder) in an oxidizing liquid medium (eg, a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel. Can be obtained by soaking for a period of time (typically from 0.5 to 96 hours depending on the nature of the starting material and the type of oxidant used). As mentioned above, the resulting graphite oxide particles may then be subjected to thermal peeling or ultrasonic-induced peeling to produce an isolated GO sheet. These GO sheets can then be converted to various graphene materials by substituting -OH groups with other chemical groups (eg, -Br, NH _2, etc.).

Graphene fluoride or graphene fluoride is used herein as an example of a group of halogenated graphene materials. There are two different approaches for preparing graphene fluoride. (1) Fluorination of presynthesized graphene: This approach involves treating graphene prepared by mechanical exfoliation or CVD growth with a fluorinating agent, such as XeF ₂ , or an F-based plasma; (2) Peeling of the multilayer graphite fluoride: Both mechanical peeling and liquid phase peeling of the graphite fluoride can be easily achieved.

The interaction of graphite with F ₂ forms covalent graphite fluorides (CF) _n or (C ₂ F) _n at high temperatures, whereas at low temperatures it forms graphite intercalating compounds (GIC) C _x F (2 ≦ x ≦ 24). . Since the carbon atom at (CF) _n is sp3-hybridized, the fluorocarbon layer is a waveform consisting of trans-linked cyclohexane chains. In (C ₂ F) _n only half of the C atoms are fluorinated, and all pairs of adjacent carbon sheets are connected to each other by CC covalent bonds. A systematic study of the fluorination reaction shows that the resulting F / C ratio is highly dependent on the fluorination temperature, the partial pressure of fluorine in the fluorination gas, and the physical properties of the graphite precursor (including the degree of graphitization, particle size and specific surface area). appear. Most available literature includes fluorination with F ₂ gas (sometimes in the presence of fluoride), but other fluorides may be used in addition to fluorine (F ₂ ).

In order to exfoliate the layered precursor material in the state of individual layers or hydrophobic layers, it is necessary to overcome the attraction between adjacent layers and to further stabilize these layers. This can be accomplished by covalent modification of the graphene surface by functional groups or by non-covalent modification with specific solvents, surfactants, polymers, or donor-receptor aromatic molecules. The liquid phase stripping process includes sonication of graphite fluoride in a liquid medium.

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

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, when the battery is charged, the anode active material is less than 1.0 volts (preferably less than 0.7 volts) than Li / Li ⁺ (ie, Li versus Li ⁺ + e ⁻ as standard potential). Absorb lithium ions at high electrochemical potentials. In a preferred embodiment, the anode active material of a lithium battery comprises (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 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) stoichiometric or nonstoichiometric alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements; (e) oxides, carbides, nitrides, sulfides, phosphides, seleniums of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof Cargoes, and tellurides; (f) their prelithiated forms; (g) prelithiated graphene sheets; And combinations thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or 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 that can be easily graphitized). ), Template carbon, hollow carbon nanowires, hollow carbon spheres, titanates, NaTi ₂ (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Na ₂ C ₈ H ₄ O ₄ , Na ₂ TP, Na _x TiO ₂ ( x = 0.2 to 1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate, 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 An anode active material containing a sodium insertion compound selected from 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.

In certain embodiments, the alkali metal cell is a sodium metal cell or sodium ion cell, 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 coke, 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) sodium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof; (e) sodium-containing oxides, carbides, nitrides, sulfides, phosphides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof Selenides, tellurides, or antimonys; (f) sodium salts; And (g) graphene sheets pre-supplied with sodium ions; And an anode active material selected from the group consisting of a combination thereof.

Various cathode active materials can be used in the practice of the lithium cells of the present invention. The cathode active material is typically a lithium insertion compound or a lithium absorbing compound capable of storing lithium ions when the lithium battery is discharged and releasing lithium ions into the electrolyte when recharged. The cathode active material may be selected from inorganic materials, organic or polymeric materials, metal oxides / phosphates / sulfides (an inorganic cathode material of the most preferred type), or combinations thereof.

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

Other inorganic materials for use as the cathode active material may be selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. In particular, the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or a combination thereof. This will be further described later.

In particular, inorganic materials include (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese , Sulfides, selenides, or tellurides of iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof.

Organic or polymeric materials include poly (anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly (anthraquinonyl sulfide), pyrene-4 , 5,9,10-tetraon (PYT), polymer-bonded PYT, quino (triazene), redox active organic substance, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3 , 6,7,10,11-hexamethoxytriphenylene (HMTP), poly (5-amino-1,4-dihydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS ₂ ) ₃ n ), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT (CN) ₆ ), 5-benzylidene Hydantoin, isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy- p- benzoquinone derivative (THQLi ₄ ), N, N'-diphenyl-2,3,5,6-tetraketopipera Jean, N, N'-diallyl-2,3,5,6-tetrake Piperazine (AP), N, N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone compound, 1,4-benzoquinone, 5,7,12 , 14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxy anthraquinone (ADDAQ), 5-amino-1,4-dihydroxy anthraquinone (ADAQ ), Calixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , or a combination thereof.

Thioether polymers include poly [methanetetryl-tetra (thiomethylene)] (PMTTM), poly (2,4-dithiopentanylene) (PDTP), poly (ethene-1,1,2,2-tetrathiol) A polymer containing (PETT) as a main chain thioether polymer, a side chain thioether polymer having a main chain consisting of a conjugated aromatic moiety and having 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).

Organic materials include copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadil phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chlorotin , Cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or combinations thereof.

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

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

Preferably, the lithium intercalating compound or lithium absorbing compound comprises (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten Nanodisks, nanoplates, nanoparticles of inorganic materials selected from sulfides, selenides, or tellurides of titanium, cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof Selected from the coating, or nanosheet, and the disk, plate, or sheet has a thickness of less than 100 nm. Lithium intercalating compounds or lithium absorbing compounds may include (i) bismuth selenide or bismuth telluride, (ii) transition metal dichalcogenide or trichalcogenide, (iii) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, Nanodisks, nanoplates, nanocoatings, or nanosulfides of compounds selected from cobalt, manganese, iron, nickel, or sulfides, selenides, or tellurides of transition metals, (iv) boron nitride, or (v) combinations thereof The sheet may be contained and the disk, plate, coating, or sheet has a thickness of less than 100 nm.

In rechargeable sodium cells, the cathode active material is NaFePO ₄ (sodium iron phosphate), Na _0.7 FePO ₄ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , Na ₃ V2 (PO ₄ ) ₂ F ₃ , Na ₂ FePO ₄ F, NaFeF ₃ , NaVPO ₄ F, Na ₃ V ₂ (PO ₄ ) ₂ F ₃ , Na _1.5 VOPO ₄ F _0.5 , Na ₃ V ₂ (PO ₄ ) ₃ , NaV ₆ O ₁₅ , Na _x VO ₂ , Na _0.33 V ₂ O ₅ , Na _x CoO ₂ (sodium cobalt oxide), Na _2/3 [Ni _1/3 Mn _2/3 ] O ₂ , Na _x (Fe _1/2 Mn _1/2 ) O ₂ , Na _x MnO ₂ (sodium manganese bronze), Na _0.44 MnO ₂ , Na ₀ . ₄₄ MnO ₂ / C, Na ₄ Mn ₉ O ₁₈ , NaFe ₂ Mn (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Ni _1/3 Mn _1/3 Co _1/3 O ₂ , Cu _0.56 Ni ₀ . ₄₄ HCF (copper and nickel hexacyanoferrate), NiHCF (nickel hexacyanoferrate), Na _x CoO ₂ , NaCrO ₂ , Na ₃ Ti ₂ (PO ₄ ) ₃ , NiCo ₂ O ₄ , Ni ₃ S ₂ / FeS ₂ , Sb ₂ O ₄ , Na ₄ Fe (CN) ₆ / C, NaV _1-x Cr _x PO ₄ F, Se _y S _z (selenium and selenium / sulfur, z / y is 0.01 to 100), Se Sodium containing compound selected from (S-free), aluolite, or a combination thereof.

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

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

Non-graphene 2D nanomaterials, monolayers or hydrophobic layers (up to 20 layers) can be prepared by several methods: mechanical cutting, laser ablation (eg, ablation of TMD into a monolayer using laser pulses), liquid phase Exfoliation, and thin film techniques such as PVD (eg sputtering), evaporation, vapor phase epitaxy, liquid phase epitaxy, chemical vapor phase epitaxy, molecular beam epitaxy (MBE), atomic layer epitaxy (ALE), and their plasmas Synthesis by auxiliary form.

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

Preferred second solvents are dimethyl carbonate (DMC), methylethyl 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 preferably, this second solvent should be selected from solvents having a donation water of 16.5 or less. Preferably, the viscosity of this second solvent should be 28 cps or less at 25 ° C.

The mixing ratio of said ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of ethylene carbonate is out of this range, the conductivity of the solvent may be lowered or the solvent tends to be more easily decomposed, and the charge and discharge efficiency is lowered. More preferred ethylene carbonate mixing ratio is 20 to 75% by volume. If the mixing ratio of ethylene carbonate in the nonaqueous solvent is increased to 20 vol% or more, the solvation effect of ethylene carbonate to lithium ions will be promoted, and the effect of inhibiting solvent decomposition can be improved.

Examples of preferred mixed solvents include compositions comprising EC and MEC, wherein the volume ratio of MEC is controlled in the range of 30 to 80%; Compositions comprising EC, PC and MEC; Compositions comprising EC, MEC and DEC; Compositions comprising EC, MEC and DMC; And EC, MEC, PC and DEC. By selecting the volume ratio of the MEC in the range of 30 to 80%, more preferably 40 to 70%, the conductivity of the solvent can be improved. In order to suppress the decomposition reaction of the solvent, an electrolyte in which carbon dioxide is dissolved can be used, thereby effectively improving both the capacity and the cycle life of the battery. The electrolyte salts incorporated into the non-aqueous electrolyte include lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium hexafluoroarsenide (LiAsF ₆ ), and lithium trifluoro-meta Lithium salts such as sulfonate (LiCF ₃ SO ₃ ) and bis-trifluoromethyl sulfonylimide lithium (LiN (CF ₃ SO ₂ ) ₂ ). Among them, LiPF ₆ , LiBF ₄ and LiN (CF ₃ SO ₂ ) ₂ are preferred. The content of the electrolyte salt in the nonaqueous solvent is preferably 0.5 to 2.0 mol / l.

In the case of sodium cells, the electrolytes (including nonflammable semisolid electrolytes) are preferably sodium perchlorate (NaClO ₄ ), sodium hexafluorophosphate (NaPF ₆ ), sodium borofluoride (NaBF ₄ ), sodium hexafluoroacenide, sodium Sodium salt selected from trifluoro-methsulfonate (NaCF ₃ SO ₃ ), bis-trifluoromethyl sulfonylimide sodium (NaN (CF ₃ SO ₂ ) ₂ ), ionic liquid salts, or a combination thereof It may contain.

Ionic liquids consist only of ions. Ionic liquids are low melting salts that are in the molten or liquid state when they are above the desired temperature. If the melting point is below room temperature (25 ° C.), the salt is referred to as room temperature ionic liquid (RTIL). If the melting point is below room temperature (25 ° C.), the salt is referred to as room temperature ionic liquid (RTIL). IL salts are characterized by weak interactions due to the combination of large cations and charge-unlocalized anions. As a result, the tendency to crystallization is lowered due to flexibility (anion) and asymmetry (cationic).

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

Basically, ionic liquids consist of organic ions which are subjected to an essentially unlimited number of structural modifications due to the ease of preparation of a wide variety of components. Thus, various types of salts can be used to design ionic liquids with desired properties for a given application. These include, inter alia, imidazolium, pyrrolidinium and quaternary ammonium salts as cations, and bis (trifluoromethanesulfonyl) imides as anions, bis (fluorosulfonyl) imides, and hexafluorophosphate do. Ionic liquids are divided into different classes based on their composition, basically including the aprotic, proton, and zwitterionic types, each of which is suitable for a particular application.

Common cations of room temperature ionic liquids (RTIL) include tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkylpyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, And trialkylsulfonium. Typical anions of RTIL is ^{_{BF 4 -, B (CN)}} 4 -, CH 3 BF 3 -, CH2CHBF 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, but is not limited thereto It is not. Relatively speaking, imidazole ryumgye or sulfo nyumgye cations and complex halide anions, such as _{^{AlCl 4 -, BF 4 -,}} CF 3 CO 2 -, CF 3 SO 3 -, NTf 2 -, N (SO 2 F) 2 -, Or a combination of F (HF) _2.3 ⁻ results in RTIL with good functional conductivity.

RTIL has high intrinsic ionic conductivity, high thermal stability, low volatility, low (substantially zero) vapor pressure, nonflammability, ability to hold liquids over a wide temperature range above and below room temperature, high polarity, high viscosity, and extensive electrical It may have typical properties such as chemical windows. Except for high viscosity, these properties are desirable attributes when using RTIL as an electrolyte component (salts and / or solvents) in supercapacitors.

Hereinafter, some examples of various types of anode active materials, cathode active materials, and ion conductive polymers are provided to illustrate the best mode for practicing the present invention. These exemplary embodiments and other parts and figures in this specification are sufficiently suitable to enable those skilled in the art to practice the invention, either individually or in combination. 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 Powders

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

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

The wet cake was diluted in an aqueous solution of surfactant instead of pure water to obtain surfactant-stabilized RGO (RGO-BS). A commercially available mixture 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 in all samples. Sonication was performed using a Branson Sonifier S-250A operating at a 20 kHz frequency equipped with a 13 mm step disruptor horn and a 3 mm tapered microtip. For example, 10 mL of an aqueous solution containing 0.1 wt% GO was sonicated for 10 minutes and then centrifuged at 2700 g for 30 minutes to remove large particles, aggregates, and impurities that did not dissolve. The GO in the obtained state was chemically reduced in accordance with a method comprising adding 10 mL of 0.1 wt% GO aqueous solution to a 50 mL boiling flask to obtain an RGO. Then 10 μL of 35 wt% N ₂ H ₄ (hydrazine) aqueous solution and 70 mL of 28 wt% aqueous NH ₄ OH (ammonia) solution were added to the mixture, which was stabilized with a surfactant. 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.

RGO was used as a conductive additive in the anode active material and / or cathode active material of certain lithium batteries of the present invention. Prelithiated RGO (eg, RGO + lithium particles or RGO predeposited with a lithium coating) was also used as anode active material in selected lithium ion cells.

For comparison, slurry coating and drying procedures were performed to prepare conventional electrodes. Subsequently, one anode, one cathode, and a separator disposed between the two electrodes were assembled, placed in an Al-plastic laminate packaging enclosure, and then injected with a liquid electrolyte to form a lithium battery cell of the prior art.

Example 2 Preparation of Pure Graphene Sheet (essentially 0% Oxygen)

Recognizing the possibility of a large number of defects in the GO sheet, which acts to reduce the conductivity of the individual graphene planes, pure graphene sheets (such as non-oxidized, oxygen free, halogenated and halogen free) It was decided to study whether the use of can induce conductive additives with high electrical and thermal conductivity. Pre-lithiated pure graphene was also used as anode active material. Pure graphene sheets were prepared using direct sonication or liquid phase manufacturing.

In a general procedure, 5 g of graphite flakes ground to a size of about 20 μm or less were dispersed in 1,000 mL of deionized water (containing 0.1% by weight of dispersant (Zonyl® FSO from DuPont)) to obtain a suspension. Graphene sheets were peeled, separated, and sized for 15 minutes to 2 hours using an ultrasonic energy level of 85 W (Branson S450 sonicator). The resulting graphene sheet is pure graphene that has never been oxidized, contains no oxygen and is relatively free of defects. Pure graphene is essentially free of any non-carbon elements.

Then, using both the method of the present invention injecting the slurry into the foam pores and the conventional methods of slurry coating, drying and layer lamination, a pure graphene sheet as a conductive additive is combined with the anode active material (or cathode active material in the case of cathode). Integrated into the cell. Both lithium ion batteries and lithium metal batteries (injected only to the cathode) were investigated.

Example 3 Preparation of Prelithiated Graphene Fluoride Sheets as Anode Active Materials in Lithium Ion Batteries

Although GFs were prepared using several processes, only one process is described herein as an example. In a general procedure, highly peeled graphite (HEG) was prepared from intercalating compound C ₂ F. × ClF ₃ . HEG was further fluorinated with the vapor of chlorine trifluoride to obtain fluorinated highly delaminated graphite (FHEG). The precooled Teflon reactor was charged with 20-30 mL of liquid precooled ClF ₃ , the reactor was closed and cooled to liquid nitrogen temperature. Subsequently, up to 1 g of HEG was placed in a vessel with a hole accessible by ClF ₃ gas and placed inside the reactor. After 7-10 days, a grey-beige product with an approximate formula of C ₂ F was formed.

A small amount of FHEG (about 0.5 mg) was then mixed with 20-30 mL of organic solvents (individually methanol and ethanol) and sonicated (280 W) for 30 minutes to form a homogeneous yellow dispersion. Upon removal of the solvent, the dispersion became a brown powder. Graphene fluoride powder was mixed with the surface stabilized lithium powder to allow prelithiation to occur.

Example 4 Some Examples of Preferred Salts, Solvents, and Polymers for Forming Semisolid Polymer Electrolytes

Preferred sodium metal salts are sodium perchlorate (NaClO ₄ ), sodium hexafluorophosphate (NaPF ₆ ), sodium borofluoride (NaBF ₄ ), sodium hexafluoroacenade, potassium hexafluoroacenade, sodium trifluoro-meta Sulfonate (NaCF ₃ SO ₃ ), and bis-trifluoromethyl sulfonylimide sodium (NaN (CF ₃ SO ₂ ) ₂ ). Good choices for lithium salts that tend to dissolve well in selected organic or ionic liquid solvents are: lithium borofluoride (LiBF ₄ ), lithium trifluoro-methsulfonate (LiCF ₃ SO ₃ ), lithium Bis-trifluoromethyl sulfonylimide (LiN (CF ₃ SO ₂ ) ₂ or LITFSI), lithium bis (oxalato) borate (LiBOB), lithium oxalyldifluoroborate (LiBF ₂ C ₂ O ₄ ), And lithium bisperfluoroethysulfonylimide (LiBETI). A good electrolyte additive to help stabilize the Li metal is LiNO ₃ . Particularly useful ionic liquid based lithium salts include lithium bis (trifluoro methanesulfonyl) imide (LiTFSI).

Preferred organic liquid solvents are ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl 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 dimethylether (TEGDME), poly (ethylene glycol) dimethyl ether (PEGDME), diethylene Glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), hydrofluoroethers (eg TPTP), sulfones, and sulfolane.

Preferred ionic liquid solvents can be selected from room temperature ionic liquids (RTIL) having a cation selected from tetraalkylammonium, di-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, or dialkylpiperidinium. Can be. 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 ^- is selected from. Particularly useful ionic liquid based solvents are N - n -butyl- N -ethylpyrrolidinium bis (trifluoromethane sulfonyl) imide (BEPyTFSI), N -methyl- N -propylpiperidinium bis (trifluoro Methyl sulfonyl) imide (PP ₁₃ TFSI), and N , N -diethyl- N -methyl- N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide.

Preferred lithium ion conductive or sodium ion conductive polymers are poly (ethylene oxide) (PEO, having a molecular weight less than 1 × 10 ⁶ g / mol), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (Vinylidene fluoride) -hexafluoropropylene (PVDF-HFP), and sulfonated polymers. Preferred sulfonated polymers include poly (perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly (ether ether ketone) (S-PEEK), and sulfonated polyvinylidene fluoride ( S-PVDF).

Example 5 Vapor Pressure of Corresponding Semisolid Polymer Electrolytes with Some Solvents and Various Sodium Salt Molecular Ratios

Before and after addition of PEO with a wide range of molecular salts, such as sodium borofluoride (NaBF ₄ ), sodium perchlorate (NaClO ₄ ), or sodium bis (trifluoromethanesulfonyl) imide (NaTFSI) Vapor pressure of various solvents (DOL, DME, PC, AN, with or without ionic liquid based cosolvent, PP ₁₃ TFSI) was measured. The vapor pressure decreases very rapidly when the salt / polymer total concentration exceeds 2.3 M and rapidly approaches the minimum or essentially zero when the combined concentration exceeds 3.0 M. If the vapor pressure is very low, the vapor phase of the electrolyte cannot ignite or, once initiated, it cannot sustain the flame for longer than three seconds.

Example 6 Flash Point and Vapor Pressure of Some Solvents and Corresponding Semisolid Polymer Electrolytes with Sodium or Lithium Salt / Polymer Concentration Concentration of 3.0 M

The flash points and vapor pressures of the various solvents and their electrolytes with Na or Li salt / polymer concentrations of 3 M are shown in Table 1 below. According to the OSHA classification, all liquids with flash points below 38.7 ° C are flammable. However, to ensure safety, the semisolid polymer electrolytes of the present invention are designed to exhibit flash points much higher than 38.7 ° C. (eg, increased by at least 50 ° C. and preferably by a large difference greater than 150 ° C.). . The data in Table 1 show that the addition of an alkali metal salt / polymer combined concentration of 3.0 M is generally sufficient to meet this criterion (in many cases, 2.3 M is sufficient). The semisolid polymer electrolytes of the present invention are all flammable.

TABLE 1

Example 7 Alkali Metal Ion Transition Water in Various Electrolytes

Regarding the lithium salt molecular ratio, (PEO + in various types of electrolytes (e.g., (EMImTFSI + DME) solvent) The Na ⁺ ion transition water of NaTFSI salt)) was reviewed and representative results are summarized in FIGS. 3A-3B. In general, the number of Na ⁺ ions of the transition from the low salt concentration of the electrolyte decreases as from x = 0 x = 0.2 ~ 0.30 in concentration. However, beyond the molecular ratio of x = 0.2-0.30, the number of transitions increases with increasing salt concentration, indicating a fundamental change in the Na ⁺ ion transport mechanism. Similar trends were observed for lithium ions.

When Na ⁺ ions migrate in electrolytes with low salt concentrations (eg, x <0.2), the Na ⁺ ions can attract several solvating molecules together. Increased fluid viscosity due to more salts and polymers dissolved in the solvent can further impede co-movement of clusters of these charged species. On the other hand, in the presence of very high concentrations of sodium salts with x > 0.2, there are significantly more Na ⁺ ions than available solvating molecules that can cluster with sodium ions to form multi-ion complex species and slow their diffusion progression. Can be. This high Na ⁺ ion concentration can give more (non-clustered) "free Na ⁺ ions", thereby providing higher Na ⁺ transition water (and thus easy Na ⁺ transfer). The sodium ion transport mechanism turns into a single ion governing mechanism (smaller hydrodynamic radius) with a higher number of free Na ⁺ ions available in the multiple ion complex governing mechanism (the overall hydrodynamic radius is larger). This observation provides an excellent discharge capacity ratio of the sodium secondary cell by allowing an appropriate number of Na ⁺ ions to move quickly through or away from the semi-solid electrolyte to easily interact or react with the cathode (at discharge) or anode (at charge). Further assurance. Most importantly, these high concentrations of electrolytes are nonflammable and safe. The combination of safety, easy sodium ion transfer, and electrochemical performance characteristics in all types of sodium and lithium secondary cells has been difficult until now.

Example 8 Lithium Iron Phosphate (LFP) Cathode of Lithium Metal Battery

Uncoated or carbon coated LFP powders are commercially available from several sources. In this embodiment, graphene sheets (RGO) and carbon nanofibers (CNF) were included as conductive filaments in electrodes containing LFP particles as a cathode active material and an electrolyte (containing lithium salt and polymer dissolved in an organic solvent). The lithium salt used in this example includes lithium borofluoride (LiBF ₄ ) and the organic solvents are PC, DOL, DEC, and mixtures thereof. A wide range of conductive filament volume fractions from 0.1% to 30% were included in this study. The formation of the electrode layer was achieved using the following sequence of steps.

Step 1 (S1) : First, LiBF ₄ salt and PEO were dissolved in a mixture of PC and DOL to form an electrolyte having a salt / polymer summation concentration of 1.0 M, 2.5 M, and 3.5 M, respectively. (At concentrations above 2.3 M, the resulting electrolyte was no longer a liquid electrolyte. In fact, it behaves more like a solid and therefore uses the term "subsolid".) Then, the RGO or CNT filaments are dispersed in the electrolyte to filament-electrolyte A suspension was formed. Mechanical shear was used to help form a uniform dispersion (this filament-electrolyte suspension was also very viscous at low salt concentrations of 1.0 M). Subsequently, LFP particles as cathode active materials were dispersed in a filament-electrolyte suspension to form a semi-solid polymer electrode material.

Step 2 (S2) : First, LiBF ₄ salt and PEO were dissolved in a mixture of PC and DOL to form an electrolyte having a salt / polymer summation concentration of 1.0 M, 2.5 M, and 3.5 M, respectively. The cathode active material, LFP particles, was then dispersed in an electrolyte to form an active particle-electrolyte suspension. Mechanical shear was used to help form a uniform dispersion (this active particle-electrolyte suspension was also very viscous at low salt concentrations of 1.0 M). The RGO or CNT filaments were then dispersed in the active particle-electrolyte suspension to form a semisolid polymer electrode material.

Step 3 (S3) : First, the desired amount of RGO or CNT filaments was dispersed in a liquid solvent mixture (PC + DOL) in which no lithium salt or polymer was dissolved. Mechanical shear was used to help form a uniform suspension of conductive filaments in a solvent. LiBF ₄ salt, PEO, and LFP particles are then added to the suspension to allow the LiBF ₄ salt and PEO to dissolve in the solvent mixture of the suspension, having salt / polymer sum concentrations of 1.0 M, 2.5 M, and 3.5 M, respectively. An electrolyte was formed. At the same time or later, the LFP particles were dispersed in an electrolyte to form a deformable semisolid electrode material consisting of active material particles and conductive filaments dispersed in a semisolid polymer electrolyte (not a liquid electrolyte and not a solid electrolyte). In this semisolid electrode material, the conductive filaments are leached to form a 3D network of electron conductive paths. This 3D conductive network is maintained when the electrode material is processed into the electrode shape of the cell.

The electrical conductivity of the electrodes was measured using a four point probe method. The results are summarized in FIGS. 5A and 5B. These data, except for the electrodes prepared according to step 3 (S3), are generally conductive filaments (CNF) for forming a 3D network of electronically conductive paths until the volume fraction of the conductive filaments exceeds 10-12%. Or RGO) does not occur. In other words, the step of dispersing the conductive filaments in the liquid solvent should be performed before the lithium salt, sodium salt, or ion conductive polymer is dissolved in the liquid solvent and before the active material particles are dispersed in the solvent. This sequence can also lower the leaching threshold from 0.3% to 2.0%, allowing the production of conductive electrodes using a minimum amount of conductive additives and thus higher proportions of active material (and higher energy density). This observation was found to correspond to all types of electrodes containing active material particles, conductive filaments, and electrolytes investigated so far. This is a very important and unexpected process requirement for the production of high performance alkali metal cells with both high energy density and high power density.

Subsequently, the semi-solid cathode, the porous separator, and the semi-solid anode (made in a similar manner but having artificial graphite particles as the anode active material) were assembled together to form a unit cell, which was then exposed to a protective housing (with two terminals exposed) Into a laminated aluminum-plastic pouch) to prepare a cell. Batteries containing liquid or polymer gel electrolytes (1 M) and semisolid polymer electrolytes (2.5 M and 3.5 M) were constructed and tested.

For comparison, slurry coating and drying procedures were performed to prepare conventional electrodes. Subsequently, one anode, one cathode, and a separator disposed between the two electrodes were assembled, placed in an Al-plastic laminate packaging enclosure, and then injected with a liquid electrolyte to form a lithium battery cell of the prior art. Cell test results are summarized in Example 19.

Example 9 V ₂ O ₅ as an Example of a Transition Metal Oxide Cathode Active Material of a Lithium Battery

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

Subsequently, both the V ₂ O ₅ powder and the graphene-supported V ₂ O ₅ powder were individually prepared, both conductive additive (CNT) and liquid, using both the method of the present invention and conventional methods of slurry coating, drying and layer laminating. Integrated into the cell with electrolyte.

Example 10 LiCoO ₂ as an Example of a Lithium Transition Metal Oxide Cathode Active Material for Lithium Ion Batteries

Commercially available LiCoO ₂ powders and multi-walled carbon nanotubes (MW-CNT) were dispersed in a semisolid polymer electrolyte to form a semisolid electrode. Two types of semisolid anodes were prepared to bind the cathode. One contains graphite particles as an anode active material, and the other includes graphene-containing 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 semisolid polymer electrolyte. Each cell includes a semisolid anode, a separator layer, and a semisolid cathode, which are assembled together and hermetically sealed.

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

Example 11 Organic Material as a Cathode Active Material of Lithium Metal Battery (Li ₂ C ₆ O ₆ )

In order to synthesize the didi lithium of the disodie acid (Li ₂ C ₆ O ₆ ), a rodizone acid dihydrate (species 1 in the following scheme) was used as a precursor. A basic lithium salt Li ₂ CO ₃ can be used in the aqueous medium to neutralize both functions of endioic acid. The exact stoichiometric amount of both reactants, lodizone acid and lithium carbonate, was reacted for 10 hours to achieve 90% yield. Dilithium rhodiate (species 2) was readily soluble in small amounts of water, indicating the presence of water molecules in species 2. Water was removed for 3 hours in a vacuum at 180 ° C. to obtain an anhydride form (species 3).

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

It may be noted that two Li atoms in the formula Li ₂ C ₆ O ₆ are part of the fixed structure and do not participate in reversible storage and release of lithium ions. This means that lithium ions must be provided from the anode side. Therefore, the anode must have a lithium source (eg lithium metal or lithium metal alloy). As shown in FIG. 1D, the anode current collector (Cu foil) is deposited into a layer of lithium (eg, via sputtering or electrochemical plating, or using lithium foil). Thereafter, the lithium-coated layer, the porous separator, and the quasi-solid cathode were assembled to form 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 fabricated by conventional methods of slurry coating, drying, laminating, packaging, and electrolyte injection.

Example 12 Metal Naphthalocyanine-RGO Hybrid Cathodes of Lithium Metal Cells

CuPc was vaporized in a chamber with graphene film (5 nm) made from spin coating of RGO-water suspension to obtain a copper phthalocyanine (CuPc) -coated graphene sheet. The resulting coating film was cut and milled to produce a CuPc-coated graphene sheet, which was fabricated in a lithium metal battery with 1.0 M and 3.0 M LiClO ₄ solutions in lithium metal foil as anode active material and propylene carbonate (PC) as electrolyte. It was used as a cathode active material.

Example 13 : Preparation of MoS ₂ / RGO Hybrid Material as Cathode Active Material of Lithium Metal Battery

H₂O를 첨가하였다. 반응 용액을 40 mL의 테프론-라이닝 오토클레이브로 옮기기 전에 30분 동안 추가로 초음파 처리하였다. 이 시스템을 200℃의 오븐에서 10시간 동안 가열하였다. 생성물을 8000 rpm으로 5분 동안 원심분리하여 모으고, 탈이온수로 세척하고 원심분리로 다시 모았다. 세척 단계는 대부분의 DMF가 확실히 제거되도록 적어도 5회 반복하였다. 마지막으로, 건조된 생성물을 약간의 탄소 섬유 및 준고체 고분자(PAN) 전해질과 혼합하여 변형 가능한 준고체 캐소드를 형성하였다.In this example, various inorganic materials were investigated. For example, ultra-thin MoS ₂ by single step solvent thermosynthesis reaction of (NH ₄ ) ₂ MoS ₄ with hydrazine at 200 ° C. in N , N -dimethylformamide (DMF) solution of oxidized graphene oxide (GO) / RGO hybrids were synthesized. In a general procedure, 22 mg (NH ₄ ) ₂ MoS ₄ was added to 10 mg GO dispersed in 10 ml DMF. The mixture was sonicated at room temperature for about 10 minutes until a clear and homogeneous solution was obtained. After that, 0.1 ml of N ₂ H ₄

H ₂ O was added. The reaction solution was further sonicated for 30 minutes before transferring to 40 mL of Teflon-lining autoclave. The system was heated in an oven at 200 ° C. for 10 hours. The product was collected by centrifugation at 8000 rpm for 5 minutes, washed with deionized water and collected again by centrifugation. The washing step was repeated at least five times to ensure that most of the DMF was removed. Finally, the dried product was mixed with some carbon fiber and a semisolid polymer (PAN) electrolyte to form a deformable semisolid cathode.

Example 14 Preparation of Two-Dimensional (2D) Layered Bi ₂ Se ₃ Chalcogenide Nanoribbons

The preparation of (2D) layered Bi ₂ Se ₃ chalcogenide nanoribbons is well known in the art. For example, Bi ₂ Se ₃ nanoribbons were grown using the vapor-liquid-solid (VLS) method. The nanoribbons prepared herein, on average, range from 30 to 55 nm in thickness and range from several hundred nanometers to several micrometers in width and length. Larger nanoribbons were ball milled to reduce the transverse dimension (length and width) to less than 200 nm. The nanoribbons and graphene sheets or exfoliated graphite flakes prepared by this procedure were combined with semisolid polymer electrolytes to form deformable cathodes of lithium metal batteries.

Example 15 MXenes Powder + Chemically Activated RGO

The maxine selected was prepared by partially etching away certain elements from the layered structure of metal carbide such as Ti ₃ AlC ₂ . For example, aqueous 1 M NH ₄ HF ₂ was used as an etchant for Ti ₃ AlC ₂ at room temperature. Typically, maxine surfaces are terminated with O, OH, and / or F groups, for which reason they are generally referred to as M _{n + 1} X _n T _x (where M is the initial transition metal and X is C and / or N, T represents terminators (O, OH, and / or F), n = 1, 2, or 3 and x is the number of terminators). Maxine substances 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 to 35% graphene sheets are mixed in a solvent, followed by addition of 35 to 95% maxine, some Li / Na salts, and polymers to deformable, conformable, conductive semi-conductors. Solid electrolyte based cathodes were formed.

Example 16 Preparation of Graphene-Supported MnO ₂ Cathode Active Materials

MnO ₂ powders were synthesized in two ways (with or without graphene sheets, respectively). In one method, 0.1 mol / L aqueous KMnO ₄ solution was prepared by dissolving potassium permanganate in deionized water. Meanwhile, 13.32 g of high-purity sodium bis (2-ethylhexyl) sulfosuccinate surfactant was added to 300 mL of isooctane (oil) and stirred well to obtain an optically clear solution. To this solution was then added 32.4 mL of 0.1 mol / L KMnO ₄ solution and a selected amount of GO solution and sonicated for 30 minutes to give 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 graphene-supported MnO ₂ in powder form, which was dispersed in a CNT-containing electrolyte with lithium salt and PEO to form a semi-solid polymer electrolyte based cathode electrode.

Example 17 : Graphene-Reinforced Nanosilicon as Anode Active Material in Lithium Ion Battery

Graphene-wrapped Si particles were available from Angstron Energy Co. (Dayton, Ohio). After dispersing the pure graphene sheet (conductive filament) in the PC-DOL (50/50 ratio) mixture, the Si particles (anode active material) wrapped with graphene were dispersed and 3.5 M lithium hexafluoride in a mixed solvent at 60 ° C. A semi-solid anode electrode was prepared by dissolving rophosphate (LiPF ₆ ). Subsequently, the DOL was removed to obtain a semi-solid electrolyte containing about 5.0 M of LiPF ₆ in the PC. This is because the maximum solubility of LiPF ₆ in PC is so known to be less than 3.0 M at room temperature and the LiPF ₆ in a supersaturated state.

Example 18 Cobalt Oxide (Co ₃ O ₄ ) Fine Particles as Anode Active Materials

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

Appropriate amount of inorganic salt Co (NO ₃ ) ₂ .6H ₂ O and then ammonia solution (NH ₃ · H ₂ O, 25 wt%) was added slowly to the GO suspension. The resulting precursor suspension was stirred for several hours under argon flow to ensure complete reaction. The obtained Co (OH) ₂ / graphene precursor suspension was filtered and dried in vacuo at 70 ° C to obtain a Co (OH) ₂ / graphene composite precursor. The precursor was calcined at 450 ° C. for 2 hours in air to form a Co ₃ O ₄ / graphene composite, which was mixed with a semisolid polymer electrolyte to prepare a semisolid electrode.

Example 19 Graphene-Reinforced Tin Oxide Fine Particles as Anode Active Materials

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

Example 20 Preparation and Electrochemical Testing of Various Battery Cells

For most of the anode active material and cathode active material investigated, a lithium ion cell or a lithium metal cell was produced using both the method of the present invention and the conventional method.

In conventional methods, conventional anode compositions comprise 85 wt% of active material (eg, Si- or Co ₃ O ₄ -coated graphene sheets) dissolved in N-methyl-2-pyrrolidinone (NMP), 7 wt% acetylene black (Super-P), and 8 wt% polyvinylidene fluoride binder (PVDF, 5 wt% solids content). After coating the slurry on Cu foil, the electrode was vacuum dried at 120 ° C. for 2 hours to remove the solvent. In the present invention, binder resins are generally unnecessary or not used, saving 8% by weight (reducing the amount of inert material). The cathode layer is prepared in a similar manner (using Al foil as cathode current collector) using conventional slurry coating and drying methods. The anode layer, separator layer (eg Celgard 2400 membrane), and cathode layer are then laminated together and housed in a plastic-Al enclosure. As an example, 1 M LiPF ₆ electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1: 1 v / v) is injected into the cell. In some cells, ionic liquids were used as the liquid electrolyte. The cell assembly was prepared in an argon filled glove box.

In the process of the invention, the semisolid anode, porous separator, and semisolid 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 scanning rate of 1 mV / sec. In addition, electrochemical performance of various cells was also evaluated by constant current charge / discharge cycling at current densities from 50 mA / g to 10 A / g. For the long term cycling test, a multi-channel cell tester manufactured by LAND was used.

Example 21 Representative Test Results

For each sample, by applying different current densities (indicating charge and discharge rates) to measure the electrochemical response, the energy density and power density values needed to construct the ragon plot (power density versus energy density) could be calculated. FIG. 6 shows a ragon diagram (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 made according to embodiments of the present invention (in order S1, S2, and S3, respectively) and the other is made by conventional electrode slurry coating (roll-coating) It is about. Several important observations can be made from these data.

The weight energy density and power density of the lithium ion battery cells produced by the method of the present invention are both much higher than the weight energy density and power density (expressed as "conventional") of their counterparts produced through conventional roll-coating methods. high. The weight energy density is 226 Wh at 161 Wh / kg as the anode thickness of 160 μm (coated on a flat solid Cu foil) changes to 420 μm and a corresponding change is made in the cathode to maintain the equilibrium capacity ratio. to / kg (S1), to 227 Wh / kg (S2), and to 264 Wh / kg (S3) respectively. Surprisingly, cells containing the semisolid electrodes of the present invention having a 3D network of electronically conductive paths (due to leaching of conductive filaments) deliver even higher energy densities and higher power densities.

This significant difference cannot simply be attributed to the increase in electrode thickness and mass feed. This difference is due to the much higher active material mass feed (not just mass feed) and higher conductivity associated with the cell of the present invention, reduced overhead (inactive) component ratio relative to active material weight / volume, and surprisingly of the electrode active material. It appears to be due to better utilization (particularly not all but most of the graphite particles and LFP particles contribute to lithium ion storage capacity due to higher conductivity and the absence of dry pockets or inefficient points in the electrodes, especially at high charge and discharge conditions). .

FIG. 7 shows a ragon plot (weight power density vs. weight energy density) of two cells containing graphene containing Si nanoparticles as anode active material and LiCoO ₂ nanoparticles as cathode active material. Experimental data were obtained from Li ion battery cells produced by the method of the present invention and Li ion battery cells prepared by conventional electrode slurry coating.

These data indicate that the weight energy density and power density of the battery cells produced by the method of the present invention are much higher than the weight energy density and power density of the counterparts produced via conventional methods. In addition, the difference is very large. Conventionally produced cells exhibit a weight energy density of 265 Wh / kg, but the cells of the present invention deliver energy densities of 382 Wh / kg (S1) and 420 Wh / kg (S3), respectively. Power densities as high as 1425 W / kg and 1650 W / kg are also unprecedented in lithium ion batteries.

These energy density and power density differences are mainly due to the high active material mass feed (greater than 25 mg / cm ² at the anode and greater than 45 mg / cm ² at the cathode) and high electrode conductivity, active material weight / volume associated with the cells of the present invention. It is due to the reduced overhead (inactive) component ratio, and the ability of the present invention to better utilize the active material particles (all particles have access to the liquid electrolyte and have fast ionic and electron motion).

FIG. 8 contains lithium foil as an anode active material, di lithium rhodioneate as a cathode active material (Li ₂ C ₆ O ₆ ), and lithium salt as an organic electrolyte (LiPF ₆ ) -PC / DEC (both 1.5 M and 5.0 M) The ragon diagram of a lithium metal battery is shown. Semi-solid electrodes were prepared according to the procedures S2 and S3 described in Example 8. The data is for three lithium metal cells produced by the method of the present invention and conventional electrode slurry coatings.

These data indicate that the weight energy density and power density of the lithium metal cells produced by the method of the present invention are much higher than the weight energy density and power density of the counterparts produced via conventional methods. Again, the difference is very large, with much higher active material mass feed (not just mass feed) and higher conductivity associated with the electrode of the present invention, higher overhead (inactive) component ratio relative to active material weight / volume, and electrode It appears to be due to the surprisingly better utilization of the active material (particularly at most if not all of the active material contributes to lithium ion storage capacity due to higher conductivity and no dry pockets or inefficient points in the electrode, especially at high charge and discharge conditions). .

The observation that the weight energy density of the lithium metal-organic cathode cell of the present invention is as high as 502 Wh / kg, which is higher than the value of all rechargeable lithium metal or lithium ion batteries reported so far is quite noteworthy and unexpected (current Li Ion cells store 150-220 Wh / kg based on the total cell weight). In addition, for an organic cathode active material based lithium battery, a weight power density of 1,578 W / kg would not have been conceivable. The cell comprising the semisolid electrode prepared according to step 3 exhibits much higher energy density and power density than the cells of the conventional step S2. In addition, higher concentrations of electrolytes (subsolid electrolytes) are surprisingly more helpful in achieving higher energy and power densities.

This performance characteristic of lithium cells is also observed in the corresponding sodium cells. Due to page limitations, data for sodium cells will not be presented herein. However, as an example, FIG. 9 shows two sodium ion capacitors (one cell with anode prepared by conventional slurry coating process) each containing pre-sodiumated hard carbon particles as anode active material and graphene sheet as cathode active material. And another cell with a semisolid anode prepared according to the method). Again, semisolid electrode based cells deliver much higher energy densities and higher power densities. Lithium ion capacitors have been found to follow a similar trend.

As many researchers have reported, it is meaningful to point out that reporting the energy and power density per weight of the active material alone in the Ragon plot may not provide a realistic picture of the performance of the assembled supercapacitor cell. 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 inert materials and do not contribute to charge storage. They add only weight and volume to the device. Thus, it is desirable to reduce the relative proportions of the overhead component weights and increase the proportion of active material. However, it was not possible to achieve this goal using conventional battery manufacturing processes. The present invention overcomes this long lasting most serious problem in the field of lithium batteries.

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

Claims (91)

From about 30% to about 95% by volume of the cathode active material, from about 5% to about 40% by volume of the first electrolyte containing an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent, and from about 0.01% to about 30% by volume of the conductive additive. Semi-solid cathodes containing% by volume (the conductive additives containing conductive filaments form a 3D network of electronically conductive paths such that the semi-solid electrodes have an electrical conductivity of about 10 ⁻⁶ S / cm to about 300 S / cm) ;
(b) an anode; And
(c) an alkali metal cell comprising an ion conductive membrane or a porous separator disposed between the anode and the semisolid cathode, wherein the semisolid cathode has a thickness of at least 200 μm. The method of claim 1, wherein the anode is 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 and an ion conductive polymer dissolved or dispersed in a solvent, and The conductive additive contains a semisolid anode containing from about 0.01% to about 30% by volume of the conductive additive, wherein the conductive additive containing the conductive filament has an electrical conductivity of about ^10-6 S / cm to about 300 S / cm of the semisolid electrode. And a semi-solid anode having a thickness of at least 200 μm, forming a 3D network of electron conducting paths. From about 30% to about 95% by volume of the anode active material, from about 5% to about 40% by volume of the electrolyte containing alkali salts dissolved in or dispersed in a solvent and the ion conductive polymer, and from about 0.01% to about 30% by volume of the conductive additive. A semisolid anode containing (the conductive additive containing a conductive filament forms a 3D network of electron conductive paths such that the semisolid electrode has an electrical conductivity of about 10 ⁻⁶ S / cm to about 300 S / cm);
B) cathode; And
C) An alkali metal cell comprising an ion conductive membrane or a porous separator disposed between an anode and a semisolid cathode, wherein the semisolid cathode has a thickness of at least 200 μm. The method of claim 1, wherein the first electrolyte is poly (ethylene oxide) (PEO), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly having a molecular weight of less than 1 x 10 ⁶ g / mol (Methyl methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly (vinylidene fluoride) -An alkali metal cell containing a semisolid polymer electrolyte containing an ion conductive polymer selected from hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. The method of claim 2, wherein the first electrolyte or the second electrolyte has a poly (ethylene oxide) (PEO), polypropylene oxide (PPO), poly (acrylonitrile) (with a molecular weight of less than 1 × 10 ⁶ g / mol). PAN), poly (methyl methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly (vinyl An alkali metal cell containing a semi-solid polymer electrolyte containing an ion conducting polymer selected fromidene fluoride) -hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. 4. The electrolyte of claim 3 wherein the electrolyte is poly (ethylene oxide) (PEO), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (methyl) having a molecular weight of less than 1 x 10 ⁶ g / mol. Methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly (vinylidene fluoride) -hexa An alkali metal cell, which is a semisolid electrolyte containing an ion conductive polymer selected from fluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. The method of claim 1, wherein the ion conductive polymer is poly (perfluoro sulfonic 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), hexafluoropropene and tetrafluoroethylene and polyvinylidene fluoride Sulfonated copolymers, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives, copolymers, blends thereof, And a combination thereof. The method of claim 2, wherein the ion conductive polymer is poly (perfluoro sulfonic 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), hexafluoropropene and tetrafluoroethylene and polyvinylidene fluoride Sulfonated copolymers, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives, copolymers, blends thereof, And a combination thereof. The method of claim 3, wherein the ion conductive polymer is poly (perfluoro sulfonic 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), hexafluoropropene and tetrafluoroethylene and polyvinylidene fluoride Sulfonated copolymers, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives, copolymers, blends thereof, And a combination thereof. The method of claim 1, wherein the conductive filaments are carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material-coated fibers, metal nanowires, metal fibers Alkali metal cell, selected from metal wires, graphene sheets, expanded graphite plates, combinations thereof, or combinations thereof with non-filament conductive particles. The alkali metal cell of claim 1, wherein the ion conductive polymer does not form a matrix at the semisolid cathode. The alkali metal cell of claim 3, wherein the ion conductive polymer does not form a matrix at the semisolid anode. The alkali metal cell of claim 1, wherein the electrode maintains an electrical conductivity of about 10 ⁻³ S / cm to about 10 S / cm. The alkali metal cell of claim 1, wherein the conductive filaments are bonded to each other by a resin at the intersection between the conductive filaments. The alkali metal cell of claim 1, wherein the semisolid cathode contains from about 0.1 volume% to about 20 volume% of a conductive additive. The alkali metal cell of claim 1, wherein the semisolid cathode contains from about 1% by volume to about 10% by volume of conductive additive. The alkali metal cell of claim 1, wherein the amount of active material is from about 40% to about 90% by volume of the electrode material. The alkali metal cell of claim 1, wherein the amount of active material is from about 50% to about 85% by volume of the electrode material. The alkali metal cell of claim 1, wherein the first electrolyte is in a supersaturated state. The alkali metal cell of claim 2, wherein the first electrolyte or the second electrolyte is in a supersaturated state. The alkali metal cell of 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 of 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. The method of claim 2, wherein the alkali metal cell is a lithium metal cell, a lithium ion cell, or a lithium ion capacitor cell, 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 coke, 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) stoichiometric or nonstoichiometric alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements;
(e) oxides, carbides, nitrides, sulfides, phosphides, seleniums of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof Cargoes, and tellurides;
(f) their prelithiated forms;
(g) prelithiated graphene sheets; And
An alkali metal cell, selected from the group consisting of combinations thereof. 24. The method of claim 23, wherein the prelithiated graphene sheet comprises pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, Pre-lithiated forms of hydrogenated graphene, graphene nitride, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physical or chemically activated or etched forms thereof, or combinations thereof Alkali metal cells. The method of claim 2, wherein the alkali metal cell is a sodium metal cell or sodium ion cell, or sodium ion capacitor, the anode active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon, template carbon, hollow Carbon nanowires, hollow carbon spheres, titanates, NaTi ₂ (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Na ₂ C ₈ H ₄ O ₄ , Na ₂ TP, Na _x TiO ₂ (x = 0.2 to 1.0) , Na ₂ C ₈ H ₄ O ₄ , carboxylate, 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 An alkali metal cell containing an alkali insertion compound selected from ₂ Na ₄ O ₈ , C ₁₄ H ₄ O ₆ , C ₁₄ H ₄ Na ₄ O ₈ , or a combination thereof. The method of claim 2, wherein the alkali metal cell is a sodium metal cell, sodium ion cell, or sodium ion capacitor, 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 coke, 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) sodium containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
e) sodium-containing oxides, carbides, nitrides, sulfides, phosphides, seleniums of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof Cargo, telluride, or antimony cargo;
f) sodium salts;
g) graphene sheets pre-supplied with sodium ions; And a combination thereof. The method of 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, doped lithium nickel oxide, lithium manganese oxide, doped Lithium selected from the group consisting of lithium manganese oxide, lithium vanadium oxide, doped lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, metal sulfides, and combinations thereof An alkali metal cell containing an intercalation compound. The lithium intercalating compound of claim 1, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell, and the cathode active material is a lithium intercalating compound selected from an inorganic material, an organic or polymeric material, a metal oxide / phosphate / sulfide, or a combination thereof. An alkali metal cell containing a lithium absorption compound. 29. The method of claim 28, wherein the metal oxide / phosphate / sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal An alkali metal cell, selected from phosphates, transition metal sulfides, or a combination thereof. The alkali metal cell of claim 28, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. The alkali metal cell of claim 28, wherein the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or a combination thereof. The method of claim 28, wherein the metal oxide / phosphate / sulfide is VO ₂ , Li _x VO ₂ , V ₂ O ₅ , Li _x V ₂ O ₅ , V ₃ O ₈ , Li _x V ₃ O ₈ , Li _x V ₃ Vanadium oxide selected from the group consisting of O ₇ , V ₄ O ₉ , Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped forms thereof, derivatives thereof, and combinations thereof ( Alkali metal cell containing 0.1 <x <5). The method of claim 28, wherein the metal oxide / phosphate / sulfide is layered compound LiMO ₂ , spinel compound LiM ₂ O ₄ , olivine compound LiMPO ₄ , silicate compound Li ₂ MSiO ₄ , tabolite compound LiMPO ₄ F, borate compound LiMBO ₃ Alkali metal cells, wherein M is a transition metal or a mixture of several transition metals. 29. The method of claim 28, wherein the inorganic material comprises (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, An alkali metal cell selected from sulfides, selenides, or tellurides of titanium, cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof. The method of claim 28 wherein the organic or polymeric material is poly (anthraquinonyl sulfide) (PAQS), lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly (anthraquin) Nonyl sulfide), pyrene-4,5,9,10-tetraon (PYT), polymer-bound PYT, quino (triazene), redox active organic substance, tetracyanoquino-dimethane (TCNQ), tetracy Anoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly (5-amino-1,4-dihydroxy anthraquinone) (PADAQ), phosphazene Disulfide polymer ([(NPS ₂ ) ₃ ] n ), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT ( CN) ₆ ), 5-benzylidene hydantoin, isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy- p- benzoquinone derivative (THQLi ₄ ), N, N'-diphenyl-2,3 , 5,6-tetraketopiperazine (PHP), N, N ' Diallyl-2,3,5,6-tetraketopiperazine (AP), N, N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymers, Quinone compounds, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxy anthraquinone (ADDAQ), Alkali selected from 5-amino-1,4-dihydroxy anthraquinone (ADAQ), carlixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , or a combination thereof Metal cell. 36. The thioether polymer of claim 35 wherein the thioether polymer is poly [methanetetrile-tetra (thiomethylene)] (PMTTM), poly (2,4-dithiopentanylene) (PDTP), poly (ethene-1,1, A polymer containing 2,2-tetrathiol) (PETT) as a main chain thioether polymer, a side chain thioether polymer having a main chain consisting of a conjugated aromatic moiety and having 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). The method of claim 28 wherein the organic material is copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadil phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum An alkali metal cell containing a phthalocyanine compound selected from cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or a combination thereof. The alkali metal cell of claim 28, wherein the lithium insertion compound or lithium absorbing compound is selected from metal carbides, metal nitrides, metal borides, metal dichalcogenides, or combinations thereof. The method of claim 28, wherein the lithium insertion compound or lithium absorbing compound is in the form of nanowires, nanodisks, nanoribbons, or nanoplates, niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, An alkali metal cell, selected from oxides, dichalcogenides, trichalcogenides, sulfides, selenides, or tellurides of manganese, iron, or nickel. 29. The method of claim 28, wherein the lithium intercalation compound or lithium absorbing compound comprises (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium , Nanodisks of inorganic materials selected from sulfides, selenides, or tellurides of tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof, An alkali metal cell selected from nanoplates, nanocoats, or nanosheets, wherein the disc, plate, or sheet has a thickness of less than 100 nm. The sodium intercalating compound of claim 1, wherein the alkali metal cell is a sodium metal cell or a sodium ion cell, and the cathode active material is a sodium intercalating compound selected from an inorganic material, an organic or polymeric material, a metal oxide / phosphate / sulfide, or a combination thereof. An alkali metal cell containing a sodium absorbing compound. The method of claim 41, wherein the metal oxide / phosphate / sulfide is sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium mixed metal oxide, sodium / potassium-transition metal oxide, sodium iron phosphate, sodium / potassium An alkali metal cell selected from iron phosphate, sodium manganese phosphate, sodium / potassium manganese phosphate, sodium vanadium phosphate, sodium / potassium vanadium phosphate, sodium mixed metal phosphate, transition metal sulfides, or a combination thereof. The alkali metal cell of claim 41, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. The alkali metal cell of claim 41, wherein the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or a combination thereof. The method of claim 41, wherein the cathode active material is 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 Containing a sodium insertion compound ( x is 0.1 to 1.0) selected from NaV _1-x Cr _x PO ₄ F, Se _z S _y (y / z = 0.01 to 100), Se, aluolite, or a combination thereof Alkali metal cells. The alkali metal cell of claim 1, wherein the cathode active material constitutes a mass feed amount of an electrode active material of greater than 15 mg / cm ² . The alkali metal cell of claim 2, wherein the anode active material constitutes a mass feed amount of an electrode active material of greater than 20 mg / cm ² . The alkali metal cell of claim 1, wherein the cathode active material constitutes a mass feed amount of an electrode active material of greater than 30 mg / cm ² . As a method of manufacturing an alkali metal cell having a semisolid electrode,
(a) combining a large amount of active material, a large amount of electrolyte, and a conductive additive to form a deformable electrically conductive electrode material, wherein the electrically conductive additive containing conductive filaments forms a 3D network of electron conductive pathways, the electrolyte Containing an alkali salt and an ion conductive polymer dissolved or dispersed in a solvent;
(b) forming the electrode material into a semi-solid electrode, wherein the electrode material is deformed into an electrode shape without blocking the 3D network of the electronically conductive path such that the electrode maintains electrical conductivity of 10 ⁻⁶ S / cm or more;
(c) forming a second electrode; And
(d) combining the semisolid electrode and the second electrode to form an alkali metal cell. The method of claim 49, wherein the semisolid electrode contains 30% to 95% by volume of the active material, 5% to 40% by volume of the electrolyte, and 0.01% to 30% by volume of the conductive additive. . The method of claim 49, wherein the electrolyte is poly (ethylene oxide) (PEO), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (methyl) having a molecular weight of less than 1 × 10 ⁶ g / mol. Methacrylate) (PMMA), poly (vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly (vinylidene fluoride) -hexa A semi-solid polymer electrolyte containing an ion conductive polymer selected from fluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. The method of claim 49, wherein the ion conductive polymer is poly (perfluoro sulfonic 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), hexafluoropropene and tetrafluoroethylene and polyvinylidene fluoride Sulfonated copolymers, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), chemical derivatives, copolymers, blends thereof , And combinations thereof. The method of claim 49, wherein the conductive filaments are carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material-coated fibers, metal nanowires, metal fibers , Metal wire, graphene sheet, expanded graphite plate, combinations thereof, or non-filament conductive particles and combinations thereof. The method of claim 49, wherein the ion conductive polymer does not form a matrix at the semisolid cathode. The method of claim 49, wherein the electrode maintains an electrical conductivity of 10 ⁻³ S / cm to 10 S / cm. The method of claim 49, wherein the semisolid cathode contains 0.1% to 20% by volume conductive additive. The method of claim 49, wherein the semisolid cathode contains 1% by volume to 10% by volume of conductive additive. The method of claim 49, wherein the amount of active material is from 40 volume percent to 90 volume percent of the electrode material. The method of claim 49, wherein the amount of active material is from 50 volume percent to 85 volume percent of the electrode material. 50. The method of claim 49, wherein the blending step comprises dispersing the conductive filaments in a liquid solvent to form a homogeneous suspension, wherein the step is prior to adding the active material to the suspension and in the liquid solvent in the suspension. Before the alkali metal salt and the ion conductive polymer are dissolved. The method of claim 49, wherein the blending step and forming the electrode material into a semisolid electrode comprises dissolving a lithium salt or a sodium salt and the polymer in a liquid solvent to form an electrolyte having a first salt / polymer concentration, Removing a portion of the liquid solvent to increase salt / polymer concentration to obtain a semisolid polymer electrolyte having a second salt / polymer concentration above the first concentration and above 2.5 M. 61. The method of claim 60, wherein said removing step does not cause precipitation or crystallization of said salt or said polymer and said electrolyte is in a supersaturated state. 61. The method of claim 60, wherein the liquid solvent contains a mixture of at least a first liquid solvent and a second liquid solvent, wherein the first liquid solvent is more volatile than the second liquid solvent, and wherein removing the portion of the liquid solvent comprises Removing the first liquid solvent. 50. The method of claim 49, wherein forming the second electrode comprises (A) combining a large amount of second active material, a large amount of electrolyte, and a conductive additive to form a deformable electrically conductive second electrode material, wherein the conductive filament contains conductive filaments. Wherein said conductive additive forms a 3D network of electronically conductive pathways, said electrolyte containing alkali salts and ion conductive polymers dissolved or dispersed in a solvent; And (B) forming a deformable conductive second electrode material into a second semi-solid electrode, wherein the deformable conductive second electrode material is deformable without interruption of the 3D network of the electronic conductive path such that the second electrode maintains electrical conductivity of 10 ⁻⁶ S / cm or more. And deforming the conductive second electrode material into an electrode shape. The method of claim 49, 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 method of claim 49, wherein the alkali metal cell is a lithium metal cell, a lithium ion cell, or a lithium ion capacitor cell, wherein the 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 coke, 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) stoichiometric or nonstoichiometric alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements;
(e) oxides, carbides, nitrides, sulfides, phosphides, seleniums of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and mixtures or complexes thereof Cargoes, and tellurides;
(f) their prelithiated forms;
(g) prelithiated graphene sheets; And
And an anode active material selected from the group consisting of combinations thereof. 67. The method of claim 66, wherein the prelithiated graphene sheet is pure graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene Selected from pre-lithiated forms of graphene nitride, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, physical or chemically activated or etched forms thereof, or combinations thereof , Way. The method of claim 49, wherein the alkali metal cell is a sodium metal cell, sodium ion cell, or sodium ion capacitor, and the active material is petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon, template carbon, hollow carbon Nanowires, hollow carbon spheres, titanates, NaTi ₂ (PO ₄ ) ₃ , Na ₂ Ti ₃ O ₇ , Na ₂ C ₈ H ₄ O ₄ , Na ₂ TP, Na _x TiO ₂ (x = 0.2 to 1.0), Na ₂ C ₈ H ₄ O ₄ , carboxylate, 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 A method comprising: an anode active material containing an alkali insertion compound selected from Na ₄ O ₈ , C ₁₄ H ₄ O ₆ , C ₁₄ H ₄ Na ₄ O ₈ , or a combination thereof. The method of claim 49, wherein the alkali metal cell is a sodium metal cell, sodium ion cell, or 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 coke, 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) sodium containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and mixtures thereof;
e) sodium-containing oxides, carbides, nitrides, sulfides, phosphides, seleniums of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or complexes thereof Cargo, telluride, or antimony cargo;
f) sodium salts;
g) graphene sheets pre-supplied with sodium ions; And an anode active material selected from the group consisting of combinations thereof. 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 lithium nickel oxide, lithium manganese oxide, doped Lithium selected from the group consisting of lithium manganese oxide, lithium vanadium oxide, doped lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, metal sulfides, and combinations thereof Containing an intercalation compound. 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 a lithium insertion compound selected from inorganic materials, organic or polymeric materials, metal oxides / phosphates / sulfides, or combinations thereof. A method containing a lithium absorbing compound. 72. The method of claim 71 wherein the metal oxide / phosphate / sulfide is lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal The phosphate, transition metal sulfide, or a combination thereof. The method of claim 71, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. The method of claim 71, wherein the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or a combination thereof. The method of claim 71, wherein the metal oxide / phosphate / sulfide is VO ₂ , Li _x VO ₂ , V ₂ O ₅ , Li _x V ₂ O ₅ , V ₃ O ₈ , Li _x V ₃ O ₈ , Li _x V ₃ Vanadium oxide selected from the group consisting of O ₇ , V ₄ O ₉ , Li _x V ₄ O ₉ , V ₆ O ₁₃ , Li _x V ₆ O ₁₃ , doped forms thereof, derivatives thereof, and combinations thereof ( 0.1 <x <5). 72. The method according to claim 71, wherein the metal oxide / phosphate / sulfide is selected from the group consisting of layered compound LiMO ₂ , spinel compound LiM ₂ O ₄ , olivine compound LiMPO ₄ , silicate compound Li ₂ MSiO ₄ , tabolite compound LiMPO ₄ F, borate compound LiMBO ₃ Or M is a transition metal or a mixture of several transition metals. 72. The method of claim 71, wherein the inorganic material comprises (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, And sulfides, selenides, or tellurides of titanium, cobalt, manganese, iron, nickel, or transition metals, (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 (anthraquin) Nonyl sulfide), pyrene-4,5,9,10-tetraon (PYT), polymer-bound PYT, quino (triazene), redox active organic substance, tetracyanoquino-dimethane (TCNQ), tetracyano Ethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly (5-amino-1,4-dihydroxy anthraquinone) (PADAQ), phosphazene disulfide Polymer ([(NPS ₂ ) ₃ ] n ), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphthylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT (CN ) ₆ ), 5-benzylidene hydantoin, isatin lithium salt, pyromellitic acid diimide lithium salt, tetrahydroxy- p- benzoquinone derivative (THQLi ₄ ), N, N'-diphenyl-2,3, 5,6-tetraketopiperazine (PHP), N, N'- Diallyl-2,3,5,6-tetraketopiperazine (AP), N, N'-dipropyl-2,3,5,6-tetraketopiperazine (PRP), thioether polymer, quinone Compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dihydroxy anthraquinone (ADDAQ), 5 -Amino-1,4-dihydroxy anthraquinone (ADAQ), kalixquinone, Li ₄ C ₆ O ₆ , Li ₂ C ₆ O ₆ , Li ₆ C ₆ O ₆ , or a combination thereof . 79. The method of claim 78, wherein the thioether polymer is selected from the group consisting of poly [methanetetrile-tetra (thiomethylene)] (PMTTM), poly (2,4-dithiopentanylene) (PDTP), poly (ethene-1,1, A polymer containing 2,2-tetrathiol) (PETT) as a main chain thioether polymer, a side chain thioether polymer having a main chain consisting of a conjugated aromatic moiety and having 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, vanadil phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine aluminum chloride. And a phthalocyanine compound selected from cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanine, chemical derivatives thereof, or combinations thereof. The method of claim 71, wherein the lithium insertion compound or lithium absorbing compound is selected from metal carbides, metal nitrides, metal borides, metal dichalcogenides, or combinations thereof. 72. The method of claim 71, wherein the lithium insertion compound or lithium absorption compound is in the form of nanowires, nanodisks, nanoribbons, or nanoplatelets, niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, And an oxide of manganese, iron, or nickel, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride. 72. The method of claim 71, wherein the lithium intercalating compound or lithium absorbing compound comprises (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium , Nanodisks of inorganic materials selected from sulfides, selenides, or tellurides of tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metals, (d) boron nitride, or (e) combinations thereof, Wherein the disc, plate, or sheet has a thickness of less than 100 nm. 50. The sodium intercalating compound of claim 49, wherein said alkali metal cell is a sodium metal cell or a sodium ion cell, and said cathode active material is a sodium intercalating compound selected from inorganic materials, organic or polymeric materials, metal oxides / phosphates / sulfides, or combinations thereof. Containing a sodium absorbing compound. 85. The method of claim 84, wherein the metal oxide / phosphate / sulfide is sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium mixed metal oxide, sodium / potassium-transition metal oxide, sodium iron phosphate, sodium / potassium Iron phosphate, sodium manganese phosphate, sodium / potassium manganese phosphate, sodium vanadium phosphate, sodium / potassium vanadium phosphate, sodium mixed metal phosphate, transition metal sulfides, or combinations thereof. 85. The method of claim 84, wherein the inorganic material is selected from sulfur, sulfur compounds, lithium polysulfides, transition metal dichalcogenides, transition metal trichalcogenides, or combinations thereof. 85. The method of claim 84, wherein the inorganic material is selected from TiS ₂ , TaS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , CoO ₂ , iron oxide, vanadium oxide, or a combination thereof. The method of claim 49, wherein the active material is 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 Containing a sodium insertion compound ( x is 0.1 to 1.0) selected from NaV _1-x Cr _x PO ₄ F, Se _z S _y (y / z = 0.01 to 100), Se, aluolite, or a combination thereof , Way. The method of claim 49, wherein the active material constitutes a mass feed amount of electrode active material of greater than 15 mg / cm ² . The method of claim 49, wherein the active material constitutes a mass feed amount of electrode active material of greater than 25 mg / cm ² . The method of claim 49, wherein the active material constitutes a mass feed amount of electrode active material of greater than 45 mg / cm ² .

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