CN110679009B

CN110679009B - Shape conforming alkali metal battery with conductive and deformable quasi-solid polymer electrodes

Info

Publication number: CN110679009B
Application number: CN201880035241.6A
Authority: CN
Inventors: 阿茹娜·扎姆; 张博增
Original assignee: Nanotek Instruments Inc
Current assignee: Nanotek Instruments Inc
Priority date: 2017-05-30
Filing date: 2018-05-08
Publication date: 2022-10-21
Anticipated expiration: 2038-05-08
Also published as: CN110679009A; JP7353983B2; JP2020524359A; KR20200014335A; WO2018222348A1

Abstract

A method of making an alkali metal cell is provided, the method comprising: (a) Combining an amount of active material, an amount of electrolyte, and a conductive additive to form a deformable and conductive electrode material, wherein the conductive additive containing conductive filaments forms a 3D network of electron conducting pathways, and the electrolyte contains an alkali metal salt and an ionically conductive polymer dissolved or dispersed in a solvent; (b) Forming the electrode material into a quasi-solid polymer electrode, wherein the forming comprises deforming the electrode material into an electrode shape without interrupting the 3D network of electron conduction pathways, thereby causing the electrode to remain no less than 10 ^‑6 Conductivity of S/cm; (c) forming a second electrode; and (d) by combining the quasi-solid electrode with a metal electrodeAnd the second electrodes are combined to form an alkali metal battery cell. The second electrode may also be a quasi-solid polymer electrode.

Description

Shape conforming alkali metal battery with conductive and deformable quasi-solid polymer electrodes

Cross Reference to Related Applications

This application claims priority from U.S. patent application No. 15/608,597, filed on 30/5/2017, and U.S. patent application No. 15/610,136, filed on 31/5/2017, which are 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.

Background

Historically, the most popular rechargeable energy storage devices today-lithium ion batteries-were actually developed from rechargeable "lithium metal batteries" that use lithium (Li) metal or Li alloys as the anode and Li intercalation compounds as the cathode. Li metal is an ideal anode material due to its light weight (the lightest metal), high electronegativity (-3.04V relative to the standard hydrogen electrode), and high theoretical capacity (3,860 mah/g). Based on these outstanding characteristics, lithium metal batteries were proposed 40 years ago as an ideal system for high energy density applications. In the mid 1980 s, several prototypes of rechargeable Li metal batteries were developed. A notable example is a cell constructed of a Li metal anode and a molybdenum sulfide cathode developed by MOLI Energy, inc. This and several other batteries from different manufacturers were abandoned due to a series of safety problems caused by the drastic non-uniformity of Li growth (formation of Li dendrites) when the metal was re-plated during each subsequent recharge cycle. As the number of cycles increases, these dendritic or dendritic Li structures may eventually pass through the separator to the cathode, causing an internal short circuit.

To overcome these safety problems, several alternative methods have been proposed in which the electrolyte or anode is modified. One approach involves replacing the Li metal with graphite (another Li insertion material) as the anode. The operation of such batteries involves shuttling Li ions between two Li insertion compounds and are therefore referred to as "Li-ion batteries". It is speculated that Li-ion batteries are inherently safer than Li-metal batteries because Li exists in its ionic rather than metallic state.

Lithium ion batteries are the primary candidate energy storage devices for Electric Vehicles (EV), renewable energy storage, and smart grid applications. The last two decades have witnessed a constant improvement in energy density, rate capability and safety of Li-ion batteries, but for some reason Li metal batteries of significantly higher energy density have been largely ignored. However, the use of graphite-based anodes in Li-ion batteries has several distinct disadvantages: low specific capacity (372 mAh/g theoretical capacity versus 3,860mah/g for Li metal), long Li intercalation times (e.g., low solid state diffusion coefficients of Li into and out of graphite and inorganic oxide particles) require long recharge times (e.g., 7 hours for electric vehicle batteries), inability to deliver high pulse power (power density < <1 kW/kg), and the need to use pre-lithiated cathodes (e.g., lithium cobalt oxide), thereby limiting the choice of available cathode materials. Moreover, these commonly used cathodes have relatively low specific capacities (typically <200 mAh/g). These factors have contributed to two major drawbacks of today's Li-ion batteries-low gravimetric and volumetric energy densities (typically 150-220Wh/kg and 450-600 Wh/L) and low power densities (typically <0.5kW/kg and <1.0 kW/L), all based on total battery cell weight or volume.

The emerging EV and renewable energy industries require the availability of rechargeable batteries with significantly higher gravimetric energy densities (e.g. requirements > >250Wh/kg and preferably > >300 Wh/kg) and higher power densities (shorter recharge times) than current Li-ion battery technologies can provide. Furthermore, the microelectronics industry requires batteries with significantly greater volumetric energy densities (> 650Wh/L, preferably >750 Wh/L) because consumers need to have smaller volume and more compact portable devices (e.g., smartphones and tablets) that store more energy. These requirements have led to considerable research efforts to develop electrode materials for lithium ion batteries with higher specific capacity, excellent rate capability and good cycling stability.

Several elements from groups III, IV and V of the periodic table can alloy with Li at certain desired voltages. Therefore, various anode materials based on such elements and some metal oxides have been proposed for use in lithium ion batteries. Among these, silicon has been considered as one of the next-generation anode materials for high-energy lithium ion batteries because it has nearly 10 times higher theoretical weight capacity (based on Li) than graphite _3.75 Comparative LiC of 3,590mAh/g of Si ₆ 372 mAh/g) and about 3 times greater volumetric capacity. However, during lithium ion alloying and dealloying (cell charging and discharging), significant volume changes of Si (up to 380%) often result in severe and rapid battery performance degradation. The performance decay is mainly due to the pulverization caused by the volume change of Si and the inability of the binder/conductive additive to maintain electrical contact between the pulverized Si particles and the current collector. In addition, the inherently low conductivity of silicon is another challenge to be addressed.

Although several high capacity anode active materials (e.g., si) have been discovered, there are no corresponding high capacity cathode materials available. The cathode active materials commonly used in current Li-ion batteries have the following serious drawbacks:

(1) The practical capacities that can be achieved with current cathode materials (e.g., lithium iron phosphate and lithium transition metal oxides) have been limited to the range of 150-250mAh/g, and in most cases, less than 200mAh/g.

(2) The insertion and extraction of lithium into and out of these conventional cathodes is dependent upon Li having a very low diffusion coefficient (typically 10) ^-8 To 10 ^-14 cm ² S) in the solid particles (leading to very low power density (another long standing problem with present day lithium ion batteries)).

(3) Current cathode materials are electrically and thermally insulating and do not efficiently and effectively transport electrons and heat. Low conductivity means high internal resistance and the need to add large amounts of conductive additives, effectively reducing the proportion of electrochemically active material in the cathode which already has low capacity. Low thermal conductivity also means a higher tendency to suffer thermal runaway, which is a major safety issue in the lithium battery industry.

Low capacity anode or cathode active materials are not the only problems facing the lithium ion battery industry. There are serious design and manufacturing problems that the lithium ion battery industry does not seem to recognize or to largely ignore. For example, despite the high gravimetric capacity at the electrode level (based on the weight of the anode or cathode active material alone) as often required in publications and patent documents, these electrodes unfortunately fail to provide batteries with high capacity at the battery cell or battery pack level (based on the total battery cell weight or battery pack weight). This is due to the following viewpoints: in these reports, the actual active material mass loading of the electrode was too low. In most cases, the active material mass loading (areal density) of the anode is significantly below 15mg/cm ² And most are<8mg/cm ² (areal density = amount of active material per electrode cross-sectional area in 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 proportion of anode active material (e.g., graphite or carbon) in a lithium ion battery is typically from 12% to 17%, and cathode active material (e.g., liMn) ₂ O ₄ ) In a weight proportion of from 17 to 35% (mostly<30%). The weight fraction of the combined cathode active material and anode active material is typically from 30% to 45% of the cell weight.

As a completely different class of energy storage devices, sodium batteries have been considered as an attractive alternative to lithium batteries because of the abundant sodium content and the significantly more environmentally friendly production of sodium compared to the production of lithium. In addition, the high cost of lithium is a major problem.

Several research groups have described sodium-ion batteries using hard carbon-based anodes (Na-carbon intercalation compounds) and sodium transition metal phosphates as cathodes. However, these sodium-based devices exhibit even lower specific energy and rate performance than Li-ion batteries. These conventional sodium ion batteries require the diffusion of sodium ions into and out of the sodium intercalation compound at both the anode and cathode. The required solid state diffusion process of sodium ions in sodium ion batteries is even slower than the Li diffusion process in Li ion batteries, resulting in an excessively low power density.

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

The low active material mass loading is mainly due to the inability to obtain thicker electrodes (thicker than 100-200 μm) using conventional slurry coating procedures. This is not a trivial task as one might think, and for the purpose of optimizing cell performance, electrode thickness is not a design parameter that can be varied arbitrarily and freely. Conversely, thicker samples tend to become extremely brittle or have poor structural integrity, and will also require the use of large amounts of binder resin. The low areal and volumetric densities (associated with thin electrodes and poor packing densities) result in relatively low volumetric capacity and low volumetric energy density of the battery cells.

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

As electronic devices become more compact and Electric Vehicles (EVs) become lighter in weight, there is a pressing need for high energy density batteries that are shape conformable so that they can fit into some odd shapes or confined spaces in the device or vehicle. By implementing the battery in a space (e.g., a portion of a vehicle door or roof) that would otherwise be empty (unused or "wasted") space, the device may be made more compact or the EV may be enabled to store more power. In order for the battery to be shape conformable, the electrodes must be deformable, flexible, and shape conformable.

Therefore, there is a clear and urgent need for lithium and sodium batteries with high active material mass loading (high areal density), high electrode thickness or volume without compromising conductivity, high rate performance, high power density, and high energy density. These batteries must be produced in an environmentally friendly manner. In addition, the battery must be shape conformable so as to be able to form any regular (e.g., rectangular or cylindrical) or irregular shape. The present invention provides an alkali metal battery that meets all of these criteria.

Disclosure of Invention

The present invention provides a method of producing a flexible and shape-conforming lithium or sodium battery having high active material mass loading, exceptionally low overhead weight and volume (relative to active material mass and volume), high capacity, and unprecedentedly high energy and power densities. The lithium or sodium battery may be a primary (non-rechargeable) or secondary (rechargeable) battery, including rechargeable lithium or sodium metal batteries (having a lithium or sodium metal anode) and lithium ion or sodium ion batteries (e.g., having a first lithium intercalation compound as the anode active material and a second lithium intercalation or absorbing compound having a much higher electrochemical potential than the first lithium intercalation compound as the cathode active material). The alkali metal battery also includes a lithium ion capacitor and a sodium ion capacitor, wherein the anode is a lithium ion or sodium ion cell type anode and the cathode is a supercapacitor cathode (e.g., activated carbon or graphene sheets as an active material used in an electric double layer capacitor or a redox quasi-capacitor).

In certain embodiments, the present disclosure provides an alkali metal cell comprising: (a) A quasi-solid cathode comprising from about 30% to about 95% by volume of a cathode active material, from about 5% to about 40% by volume of a first electrolyte comprising an alkali metal salt dissolved in a solvent and an ionically conductive polymer dissolved, dispersed, or impregnated with the solvent, and from about 0.01% to about 30% by volume of a conductive additive, wherein the conductive additive comprising conductive filaments forms a 3D network of electron-conducting pathways, such that the quasi-solid electrode has from about 10 ^-6 A conductivity of S/cm to about 300S/cm; (b) an anode; and (c) an ion-conducting membrane or porous separator disposed between the anode and the quasi-solid cathode; wherein the quasi-solid cathode has a thickness of not less than 200 μm. The quasi-solid cathode preferably contains not less than 10mg/cm ² Preferably not less than 15mg/cm ² And further preferably not less than 25mg/cm ² More preferably not less than 35mg/cm ² Still more preferably not less than 45mg/cm ² And most preferably greater than 65mg/cm ² Mass loading of cathode active material.

In the cell, the anode can comprise a quasi-solid anode comprising from about 30% to about 95% by volume of an anode active material, from about 5% to about 40% by volume of a second electrolyte comprising an alkali metal salt dissolved in a solvent and an ionically conductive polymer dissolved, dispersed, or impregnated by the solvent, and from about 0.01% to about 30% by volume of a conductive additive, wherein the conductive additive comprising conductive filaments forms a 3D network of electronically conductive pathways, such that the quasi-solid electrode has from about 10 ^-6 A conductivity of S/cm to about 300S/cm; wherein the quasi-solid anode has a thickness of not less than 200 μm and may be up to 100cm or more. The quasi-solid anode preferably contains not less than 10mg/cm ² Preferably not less than 15mg/cm ² Further preferably not less than 25mg/cm ² More preferably not less than 35mg/cm ² Still more preferably not less than 45mg/cm ² And most preferably greater than 65mg/cm ² Of yang (Yang)The mass loading of the polar active material. The composition and structure of the first electrolyte may be the same as or different from the second electrolyte.

In certain embodiments, the present disclosure provides an alkali metal cell comprising: (A) A quasi-solid anode comprising from about 30% to about 95% by volume of an anode active material, from about 5% to about 40% by volume of an electrolyte comprising an alkali metal salt dissolved in a solvent and an ionically conductive polymer dissolved, dispersed, or impregnated by the solvent, and from about 0.01% to about 30% by volume of a conductive additive, wherein the conductive additive comprising electrically conductive filaments forms a 3D network of electron conducting pathways, whereby the quasi-solid anode has from about 10 ^-6 A conductivity of S/cm to about 300S/cm; (B) a cathode; and (C) an ion conducting membrane or porous separator disposed between the anode and the quasi-solid cathode; wherein the quasi-solid cathode has a thickness of not less than 200 μm.

The quasi-solid polymer electrodes of the present invention are deformable, flexible, and shape-conformable, thereby enabling the formation of shape-conformable batteries.

The invention also provides a method of making an alkali metal cell with a quasi-solid electrode, the method comprising: (a) Combining a quantity of active material (anode active material or cathode active material), a quantity of electrolyte comprising an alkali metal salt dissolved in a solvent and an ionically conductive polymer dissolved in, dispersed in, or impregnated by the solvent, and a conductive additive to form a deformable and electrically conductive electrode material, wherein the conductive additive comprising conductive filaments forms a 3D network of electron conducting pathways; (b) Forming the electrode material as a quasi-solid electrode, wherein the forming step comprises deforming the electrode material into an electrode shape without interrupting the 3D network of electron conduction pathways, thereby causing the electrode to remain no less than 10 ^-6 S/cm (preferably not less than 10) ^-5 S/cm, more preferably not less than 10 ^-3 S/cm, further preferably not less than 10 ^-2 S/cm, still more preferably and typically not less than 10 ^-1 S/cm, even more typically and preferably notLess than 1S/cm, and further more typically and preferably not less than 10S/cm and up to 300S/cm); (c) Forming a second electrode (the second electrode may also be a quasi-solid electrode); and (d) forming an alkali metal cell by combining the quasi-solid electrode and the second electrode, the alkali metal cell having an ion-conducting membrane disposed between the two electrodes.

In some embodiments, the electrolyte (including the first electrolyte or the second electrolyte) contains a lithium ion conducting polymer or a sodium ion conducting polymer selected from the group consisting of: poly (ethylene oxide) (PEO, with less than 1x10 ⁶ Molecular weight in g/mol), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (methyl methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis (methoxyethoxyethanol-phosphazene), polyvinyl chloride, polydimethylsiloxane, poly (vinylidene fluoride) -hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. It is found herein that sulfonation imparts improved lithium ion conductivity to the polymer. Higher than 1x10 ⁶ The g/mol PEO molecular weight typically renders the PEO insoluble and non-dispersible in the solvent.

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

The ion conducting polymer may be selected from the group consisting of: poly (perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly (ether ketone), sulfonated poly (ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated Polychlorotrifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymers (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymers (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymers of polyvinylidene fluoride with hexafluoropropylene and tetrafluoroethylene, sulfonated copolymers of Ethylene and Tetrafluoroethylene (ETFE), sulfonated Polybenzimidazole (PBI), chemical derivatives, copolymers, blends, and combinations thereof. We have surprisingly found that these sulfonated polymers are lithium ion conductive and sodium ion conductive.

A "filament" is an object of solid material having a largest dimension (e.g. length) and a smallest dimension (e.g. diameter or thickness) and a ratio of largest dimension to smallest dimension of greater than 3, preferably greater than 10, and further preferably greater than 100. Typically, the filament is a thread, fiber, needle, rod, platelet, sheet, ribbon, or disk-like object, by way of example only. In certain embodiments, the conductive filament is selected from a carbon fiber, a graphite fiber, a carbon nanofiber, a graphite nanofiber, a carbon nanotube, an acicular coke, a carbon whisker, a conductive polymer fiber, a conductive material coated fiber, a metal nanowire, a metal fiber, a metal wire, a graphene sheet, an expanded graphite platelet, combinations thereof, or combinations thereof with non-filament conductive particles.

In certain embodiments, the electrode is maintained from 10 ^-5 A conductivity of S/cm to about 100S/cm.

In certain embodiments, the deformable electrode material has a thickness in the range of 1,000s ^-1 An apparent viscosity of not less than about 10,000pa-s measured at an apparent shear rate. In certain embodiments, the deformable electrode material has a thickness in the range of 1,000s ^-1 Is not less than about 100,000pa-s at an apparent shear rate. Quasi-solid electrodes can conform to almost any desired shape (regular or irregular).

In the method, the amount of active material typically comprises 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, and most typically from about 50% to about 75% by volume of the electrode material.

Preferably, the step of combining the active material, the conductive additive, and the electrolyte (including dissolving the lithium or sodium salt in the liquid solvent) follows a specific sequence. This step includes first dispersing the conductive filaments in a liquid solvent to form a homogeneous suspension, then adding the active material in the suspension and then dissolving a lithium or sodium salt in the liquid solvent and then dissolving or dispersing the ionically conductive polymer in the solvent. In other words, the conductive filaments must first be uniformly dispersed in the liquid solvent before adding other ingredients, such as active materials and ion-conducting polymers, and before dissolving lithium or sodium salts in the solvent. This order is crucial for achieving percolation (percolation) of the conductive filaments in order to form a 3D network of electron conducting pathways with a lower volume fraction of conductive filaments (lower threshold volume fraction). Without following this sequence, percolation of the conductive filaments may not occur or only occur when an excessively large proportion of conductive filaments (e.g., >10% by volume) is added, which would reduce the fraction of active material and thus the energy density of the cell.

In certain embodiments, the step of combining and forming the electrode material into a quasi-solid electrode comprises dissolving a lithium salt (or sodium salt) and an ion conducting polymer in a liquid solvent to form a polymer electrolyte having a first salt concentration and a first polymer concentration and then removing a portion of the liquid solvent to increase the salt concentration to obtain a quasi-solid polymer electrolyte having a second salt concentration and a second polymer concentration, the second concentration being higher than the first concentration and preferably higher than 2.5M (and more preferably from 3.0M to 14M) of a salt and polymer combination.

The step of removing a portion of the solvent may be performed in a manner that does not cause precipitation or crystallization of the salt and the polymer and the electrolyte is in a supersaturated state. In certain preferred embodiments, the liquid solvent comprises a mixture of at least a first liquid solvent and a second liquid solvent and the first liquid solvent is more volatile than the second liquid solvent, wherein the step of removing a portion of the liquid solvent comprises partially or completely removing the first liquid solvent.

There is no limitation on the type of anode active material or cathode active material that can be used to practice the present invention. Preferably, however, the anode active material exceeds Li/Li when the battery is charged ⁺ (i.e., with respect to Li → Li as a standard potential) ⁺ +e ^- ) Lithium ions are absorbed at an electrochemical potential of less than 1.0 volt, preferably less than 0.7 volt.

In certain preferred embodiments, the alkali metal cell is a lithium metal battery, a lithium ion battery, or a lithium ion capacitor, wherein the anode active material is selected from the group consisting of: (a) particles of lithium metal or lithium metal alloy; (b) Natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), carbon particles (including soft 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) Alloys or intermetallic compounds of Si, ge, sn, pb, sb, bi, zn, al or Cd with other elements, wherein the alloys or compounds are stoichiometric or non-stoichiometric; (e) Oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, ge, sn, pb, sb, bi, zn, al, fe, ni, co, ti, mn, or Cd, and mixtures or composites thereof; (f) a prelithiated version thereof; (g) pre-lithiated graphene sheets; and combinations thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is an anode active material comprising a sodium intercalation compound selected from: petroleum coke, amorphous carbon, activated carbon, hard carbon (hard-to-graphitize carbon), soft carbon (easily-graphitize carbon), template carbon, hollow carbon nanowire, hollow carbon sphere, titanate, naTi ₂ (PO ₄ ) ₃ 、Na ₂ Ti ₃ O ₇ 、Na ₂ C ₈ H ₄ O ₄ 、Na ₂ TP、Na _x TiO ₂ (x =0.2 to 1.0), na ₂ C ₈ H ₄ O ₄ Materials based on carboxylic acid salts, C ₈ H ₄ Na ₂ O ₄ 、C ₈ H ₆ O ₄ 、C ₈ H ₅ NaO ₄ 、C ₈ Na ₂ F ₄ O ₄ 、C ₁₀ H ₂ Na ₄ O ₈ 、C ₁₄ H ₄ O ₆ 、C ₁₄ H ₄ Na ₄ O ₈ Or a combination thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is an anode active material selected from the group consisting of: (ii) (a) particles of sodium metal or sodium metal alloy; (b) Natural graphite particles, artificial graphite particles, mesophase Carbon Microspheres (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, selenides, tellurides, or antimonides of Si, ge, sn, pb, sb, bi, zn, al, fe, ti, co, ni, mn, cd, and mixtures or composites thereof; (f) a sodium salt; and (g) graphene sheets pre-loaded with sodium ions; and combinations thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is a cathode active material comprising a sodium intercalation compound or a sodium-absorbing compound selected from: inorganic materials, organic or polymeric materials, metal oxide/phosphate/sulfide, or combinations thereof. The metal oxide/phosphate/sulfide may be selected from 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 sulfide, 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 a sodium ion cell and the active material is a cathode active material comprising a sodium intercalation compound selected from: naFePO ₄ 、Na _(1-x) K _x PO ₄ 、Na _0.7 FePO ₄ 、Na _1.5 VOPO ₄ F _0.5 、Na ₃ V ₂ (PO ₄ ) ₃ 、Na ₃ V ₂ (PO ₄ ) ₂ F ₃ 、Na ₂ FePO ₄ F、NaFeF ₃ 、NaVPO ₄ F、Na ₃ V ₂ (PO ₄ ) ₂ F ₃ 、Na _1.5 VOPO ₄ F _0.5 、Na ₃ V ₂ (PO ₄ ) ₃ 、NaV ₆ O ₁₅ 、Na _x VO ₂ 、Na _0.33 V ₂ O ₅ 、Na _x CoO ₂ 、Na _2/3 [Ni _1/3 Mn _2/3 ]O ₂ 、Na _x (Fe _1/ ₂ Mn _1/2 )O ₂ 、Na _x MnO ₂ 、λ-MnO ₂ 、Na _x K _(1-x) MnO ₂ 、Na _0.44 MnO ₂ 、Na _0.44 MnO ₂ /C、Na ₄ Mn ₉ O ₁₈ 、NaFe ₂ Mn(PO ₄ ) ₃ 、Na ₂ Ti ₃ O ₇ 、Ni _1/3 Mn _1/3 Co _1/3 O ₂ 、Cu _0.56 Ni _0.44 HCF、NiHCF、Na _x MnO ₂ 、NaCrO ₂ 、Na ₃ Ti ₂ (PO ₄ ) ₃ 、NiCo ₂ O ₄ 、Ni ₃ S ₂ /FeS ₂ 、Sb ₂ O ₄ 、Na ₄ Fe(CN) ₆ /C、NaV _1-x Cr _x PO ₄ F、Se _z S _y (y/z =0.01 to 100), se, phospho-magadites (Alluaudites), or a combination thereof, wherein x is from 0.1 to 1.0.

In some preferred embodiments, the cathode active material contains a lithium intercalation compound selected from the group consisting of: 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 mixed metal oxide, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, lithium mixed metal phosphate, metal sulfides, and combinations thereof.

The electrolyte may contain water, an organic liquid, an ionic liquid (an ionic salt having a melting temperature below 100 ℃, preferably below 25 ℃ at room temperature), or a mixture of an ionic liquid and an organic liquid in a ratio of from 1/100 to 100/1. Organic liquids are desirable, but ionic liquids are preferred. The electrolyte typically and preferably contains a high solute concentration (combined concentration of lithium/sodium salt and polymer) that places the solute in a saturated or supersaturated state in the resulting electrode (anode or cathode). Such electrolytes are essentially polymer electrolytes that behave like deformable or conformable solids. This is fundamentally different from a liquid electrolyte or a polymer gel electrolyte.

In a preferred embodiment, the quasi-solid electrode has a thickness of from 200 μm to 1cm, preferably from 300 μm to 0.5cm (5 mm), further preferably from 400 μm to 3mm, and most preferably from 500 μm to 2.5mm (2,500 μm). If the active material is an anode active material, the anode active material has not less than 25mg/cm ² (preferably not less than 30 mg/cm) ² And more preferably not less than 35mg/cm ² ) And/or at least 25% (preferably at least 30% and more preferably at least 35%) by weight or by volume of the entire battery cell. If the active material is a cathode active material, the cathode active material preferably has not less than 20mg/cm for organic or polymeric materials in the cathode ² (preferably not less than 25 mg/cm) ² And more preferably not less than 30mg/cm ² ) Or not less than 45mg/cm for inorganic and non-polymeric materials ² (preferably not less than 50 mg/cm) ² And more preferably not less than 55mg/cm ² ) And/or at least 45% (preferably at least 50% and more preferably at least 55%) by weight or by volume of the entire battery cell.

The above requirements for electrode thickness, anode active material areal mass loading or mass fraction relative to the entire battery cell, or cathode active material areal mass loading or mass fraction relative to the entire battery cell are not possible in the case of conventional lithium or sodium batteries using conventional slurry coating and drying processes.

In some embodiments, the anode active material is a pre-lithiated version of a graphene sheet selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof. Surprisingly, the resulting lithium battery cells do not exhibit satisfactory cycle life (i.e., rapid capacity fade) without prelithiation.

In some embodiments of the inventive process, the cells are lithium metal cells or lithium ion cells containing a cathode active material selected from a lithium intercalation compound or lithium absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof. For example, the metal oxide/phosphate/sulfide may be selected from 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 sulfide, or combinations thereof. The inorganic material is 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. These will be discussed further later.

In the lithium metal battery, the cathode active material contains a lithium intercalation compound selected from a metal carbide, a metal nitride, a metal boride, a metal dichalcogenide, or a combination thereof. In some embodiments, the cathode active material contains a lithium intercalation compound selected from: an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in nanowire, nanodisk, nanoribbon, or nanoplatelet form. Preferably, the cathode active material contains a lithium intercalation compound selected from nanodiscs, nanoplatelets, nanocoatings or nanoplatelets of an inorganic material selected from: (ii) (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) a combination thereof; wherein the disc, platelet or sheet has a thickness of less than 100 nm.

In some embodiments, the cathode active material in the lithium metal battery is an organic material or a polymeric material selected from the group consisting of: poly (anthraquinone sulfides) (PAQS), lithium oxycarbide, 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA), poly (anthraquinone sulfides), pyrene-4, 5,9, 10-tetraketone (PYT), polymer-bonded PYT, quinones (triazenes), redox active organic materials, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10, 11-Hexamethoxytriphenylene (HMTP), poly (5-amino-1, 4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymers ([ (NPS) ₂ ) ₃ ]n), lithiated 1,4,5, 8-naphthalenetetraol formaldehyde polymers, hexaazatrinaphthalene (HATN), hexaazatrinexanenitrile (HAT (CN) ₆ ) 5-benzylidenehydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi) ₄ ) N, N ' -diphenyl-2, 3,5, 6-tetraone piperazine (PHP), N ' -diallyl-2, 3,5, 6-tetraone piperazine (AP), N ' -dipropyl-2, 3,5, 6-tetraone piperazine (PRP), thioether polymers, quinone compounds, 1, 4-benzoquinone, 5,7,12, 14-Pentacenetetraone (PT), 5-amino-2, 3-dihydro-1, 4-dihydroxyanthraquinone (ADDAQ), 5-amino-1, 4-dihydroxyanthraquinone (ADAQ), calixarenes of the quinone type (calixquinone), li ₄ C ₆ O ₆ 、Li ₂ C ₆ O ₆ 、Li ₆ C ₆ O ₆ Or a combination thereof.

The thioether polymer is selected from poly (methanetrinitrobenzylnitroamine-tetra (thiomethylene)) (PMTTM), poly (2, 4-dithiopentene) (PDTP), a polymer containing poly (ethylene-1, 2-tetrathiol) (PETT) as a main chain thioether polymer, a side chain thioether polymer having a main chain composed of conjugated aromatic moieties and having thioether side chains as side chains, poly (2-phenyl-1, 3-dithiolane) (PPDT), poly (1, 4-bis (1, 3-dithiolane-2-yl) benzene) (PDDTB), poly (tetrahydrobenzodithiophene) (PTHBDT), poly [1,2,4, 5-tetra (propylthio) benzene ] (PTKPTB), or poly [3,4 (ethylenedithio) thiophene ] (PEDTT).

In a preferred embodiment, the cathode active material is an organic material containing a phthalocyanine compound selected from the group consisting of: copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochrome phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanines, chemical derivatives thereof, or combinations thereof.

In the lithium metal battery, the cathode active material constitutes more than 30mg/cm ² (preferably greater than 40 mg/cm) ² More preferably more than 45mg/cm ² And most preferably greater than 50mg/cm ² ) And/or wherein the electrode has a thickness of not less than 300 μm (preferably not less than 400 μm, more preferably not less than 500 μm, and may be up to or greater than 100 cm). There is no theoretical limit to the thickness of the electrode of the alkali metal battery of the present invention.

Drawings

Fig. 1 (a) a schematic of a prior art lithium ion battery cell comprised of an anode current collector, one or two anode active material layers (e.g., thin Si coatings) coated on both major surfaces of the anode current collector, a porous separator and electrolyte, one or two cathode electrode layers (e.g., sulfur layers), and a cathode current collector;

FIG. 1 (B) schematic of a prior art lithium-ion battery in which the electrode layer is made of active material (e.g., graphite or tin oxide particles in the anode layer or LiCoO in the cathode layer) ₂ ) Of a conductive additive (not shown), and a resin binder (not shown)Shown) is formed.

Fig. 1 (C) is a schematic of a lithium ion battery cell of the present invention comprising a quasi-solid anode (consisting of anode active material particles and conductive filaments mixed or dispersed directly in an electrolyte), a porous separator, and a quasi-solid cathode (consisting of cathode active material particles and conductive filaments mixed or dispersed directly in an electrolyte). In this embodiment, no resin binder is required.

Fig. 1 (D) a schematic of a lithium metal battery cell of the invention comprising an anode (comprising a lithium metal layer deposited on the surface of a Cu foil), a porous separator, and a quasi-solid cathode (consisting of cathode active material particles and conductive filaments mixed or dispersed directly in an electrolyte). In this embodiment, no resin binder is required.

FIG. 2 (A) a schematic of a close-packed highly ordered structure of a solid electrolyte;

FIG. 2 (B) has a cation (e.g., na) ⁺ ) A schematic representation of a fully amorphous liquid electrolyte with a large free volume portion that can easily migrate through;

fig. 2 (C) has a random or amorphous structure of a quasi-solid electrolyte with solvent molecules separating salt species to create amorphous regions that facilitate migration of free (unclustered) cations. The ion-conducting polymer is also in a supersaturated state which is still substantially amorphous.

FIG. 3 (A) Na of electrolyte (e.g. (PEO + NaTFSI salt) in (DOL + DME) solvent) related to sodium salt molecular ratio x ⁺ Number of ion transfer.

FIG. 3 (B) Na of electrolyte (e.g. (PPO + NaTFSI salt) in (EMImTFSI + DOL) solvent) related to sodium salt molecular ratio x ⁺ Number of ion transfer.

Fig. 4 is a schematic diagram of a common process for producing expanded graphite, expanded graphite flakes (thickness >100 nm) and graphene sheets (thickness <100nm, more typically <10nm, and can be as thin as 0.34 nm).

Fig. 5 (a) conductivity (percolation behavior) of conductive filaments in a quasi-solid polymer electrode plotted as a function of volume fraction of conductive filaments (carbon nanofibers).

Fig. 5 (B) conductivity (percolation behavior) of conductive filaments in a quasi-solid polymer electrode plotted as a function of volume fraction of conductive filaments (reduced graphene oxide sheets).

Fig. 6 a la-go plot (gravimetric power density versus energy density) for a lithium ion battery cell containing graphite particles as the anode active material and carbon-coated LFP particles as the cathode active material. Three of the 4 data curves are for cells prepared according to embodiments of the invention, while the remaining one is a cell prepared by conventional electrode paste coating (roll coating).

FIG. 7 Ragong plots (gravimetric power density vs. gravimetric energy density) for three cells, each containing graphene-surrounded Si nanoparticles as anode active material and LiCoO ₂ The nanoparticles serve as a cathode active material. Experimental data were obtained from Li-ion battery cells prepared by the method of the invention (following the sequence S1 and S3) and Li-ion battery cells prepared by conventional electrode slurry coating.

FIG. 8 contains lithium foil as the anode active material, dilithium rhodizonate (Li) ₂ C ₆ O ₆ ) As cathode active material and lithium salt (LiPF) ₆ ) Raegon plot of lithium metal batteries with/PPO-PC/DEC as organic electrolyte. The data are lithium metal cells prepared by the method of the invention (sequences S2 and S3 with 2 different salt concentrations) and lithium metal cells prepared by conventional electrode slurry coating.

FIG. 9 Ragong plots for two sodium ion capacitors, each containing pre-sodiated hard carbon particles as an anode active material and graphene sheets as a cathode active material; one cell has an anode prepared by a conventional slurry coating process and the other cell has a quasi-solid anode prepared according to the method of the invention.

Detailed Description

The present invention is directed to a lithium or sodium battery that exhibits an exceptionally high volumetric energy density that has never been previously achieved. The battery may be a primary battery, but is preferably a secondary battery selected from a lithium ion battery, a lithium metal secondary battery (for example, using lithium metal as an anode active material), a sodium ion battery, a sodium metal battery, a lithium ion capacitor, or a sodium ion capacitor. The cell is based on a quasi-solid polymer electrolyte containing a polymer and 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 is a "quasi-solid polymer electrolyte" containing high concentrations of solutes (lithium or sodium salts and polymers) in a solvent to the extent: it behaves like a solid but is deformable even when the desired amount of conductive filaments and active material are added to the electrolyte (hence the term "deformable quasi-solid polymer electrode"). The electrolyte is not a liquid electrolyte nor a solid electrolyte. The shape of the lithium battery may be cylindrical, square, button-like, etc. The present invention is not limited to any battery shape or configuration.

For convenience, selected materials will be used, such as lithium iron phosphate (LFP), vanadium oxide (V) _x O _y ) Dilithium rhodizonate (Li) ₂ C ₆ O ₆ ) And copper phthalocyanine (CuPc) as an illustrative example of the cathode active material, and graphite, hard carbon, snO, co ₃ O ₄ And Si particles as examples of the anode active material. These should not be construed as limiting the scope of the invention.

As shown in fig. 1 (a), prior art lithium or sodium battery cells typically consist of an anode current collector (e.g., a Cu foil), an anode electrode or anode active material layer (e.g., a Li metal foil, a sodium foil, or a pre-lithiated Si coating deposited on one or both sides of a Cu foil), a porous separator membrane and/or electrolyte components, a cathode electrode or cathode active material layer (or two cathode active material layers coated on both sides of an Al foil), and a cathode current collector (e.g., an Al foil).

In a more common prior art cell construction (fig. 1 (B)), the anode layer is composed of particles of anode active material (e.g., graphite, hard carbon, or Si), conductive additives (e.g., carbon black particles), and a resin binder (e.g., SBR or PVDF). The cathode layer is composed of cathode active material particles (e.g., LFP particles), a conductive additive (e.g., carbon black particles), and a resin binder (e.g., PVDF). Both the anode and cathode layers are typically up to 100-200 μm thick to produce approximately sufficient current flow per unit electrode area. This thickness range is considered an industry-accepted constraint in which battery designers typically work. This thickness constraint is due to several reasons: (a) Existing battery electrode coating machines are not equipped to coat either too thin or too thick electrode layers; (b) Thinner layers are preferred based on considerations of reduced lithium ion diffusion path length; but a layer that is too thin (e.g., <100 μm) does not contain a sufficient amount of active lithium storage material (and therefore, insufficient current output); (c) Thicker electrodes tend to delaminate or crack when dried or handled after roll coating; and (d) all inactive material layers (e.g., current collectors and separators) in the battery cell must be kept to a minimum in order to achieve a minimum overhead weight and maximum lithium storage capacity, and thus maximum energy density (Wk/kg or Wh/L of the cell).

In a less common cell configuration, as shown in fig. 1 (a), the anode active material (e.g., si coating) or cathode active material (e.g., lithium transition metal oxide) is deposited in thin film form directly onto a current collector such as a copper or Al foil. However, such thin film structures with extremely small thickness dimension (typically much less than 500nm, often necessarily thinner than 100 nm) mean that only a small amount of active material can be incorporated into the electrode (given the same electrode or current collector surface area), providing low total lithium storage capacity and low lithium storage capacity per unit electrode surface area. Such films must have a thickness of less than 100nm to be more resistant to cycle-induced cracking (for anodes) or to facilitate the full utilization of the cathode active material. This constraint further reduces the total lithium storage capacity and lithium storage capacity per unit electrode surface area. Such thin film batteries have a very limited range of applications.

On the anode side, si layers thicker than 100nm have been found to exhibit poor resistance to cracking during the cell charge/discharge cycles. The fragmentation of the Si layer requires only a few cycles. On the cathode side, a sputtered layer of lithium metal oxide thicker than 100nm does not allow lithium ions to sufficiently penetrate and reach the entire cathode layer, resulting in poor utilization of the cathode active material. A desirable electrode thickness is at least 100 μm, with individual active material coatings or particles having a size desirably less than 100 nm. Therefore, these thin film electrodes deposited directly on the current collector, where the thickness is <100nm, are three (3) orders of magnitude lower than the desired thickness. As a further problem, all cathode active materials are not capable of conducting both electrons and lithium ions. A large layer thickness means an excessively high internal resistance and poor active material utilization. Sodium batteries have similar problems.

In other words, when dealing with the design and selection of cathode or anode active materials in terms of material type, size, electrode layer thickness, and active material mass loading, there are several conflicting factors that must be considered simultaneously. To date, any of the teachings of the prior art have not provided an effective solution to these often conflicting problems. We have solved these challenging problems that have plagued cell designers and electrochemical houses for more than 30 years by developing new methods of producing lithium or sodium cells as disclosed herein.

Prior art lithium battery cells are typically made by a process comprising the steps of: (a) The first step is to mix particles of the anode active material (e.g., si nanoparticles or mesocarbon microbeads, MCMB), conductive fillers (e.g., graphite flakes), a resin binder (e.g., PVDF) in a solvent (e.g., NMP) to form an anode slurry. On a separate basis, cathode active material particles (e.g., LFP particles), a conductive filler (e.g., acetylene black), a resin binder (e.g., PVDF), and a solvent (e.g., NMP) are mixed and dispersed to form a cathode slurry. (b) The second step includes coating the anode slurry onto one or both major surfaces of an anode current collector (e.g., cu foil), and drying the coated layer by evaporating a solvent (e.g., NMP) to form a dried anode electrode coated on the Cu foil. Similarly, the cathode slurry was coated and dried to form a dried cathode electrode coated on Al foil. Slurry coating is usually carried out in a roll-to-roll manner in the actual manufacturing situation; (c) The third step involves laminating the anode/Cu foil, porous separator layer and cathode/Al foil together to form a 3-or 5-layer assembly, which is cut and slit to the desired size and stacked to form a rectangular structure (as an example of a shape) or wound into a cylindrical cell structure. (d) The rectangular or cylindrical laminate structure is then enclosed in an aluminum plastic laminate envelope or steel housing. (e) A liquid electrolyte is then injected into the laminate structure to produce a lithium battery cell.

There are several serious problems associated with this method and the resulting lithium battery cell:

1) It is very difficult to produce electrode layers (anode or cathode layers) thicker than 200 μm. There are several reasons for this to occur. Electrodes of 100-200 μm thickness typically require heating zones 30-50 meters long in a slurry coating facility, which is too time consuming, too energy consuming, and not cost effective. For some electrode active materials, such as metal oxide particles, it is not possible to produce electrodes of good structural integrity thicker than 100 μm on a continuous basis in a practical manufacturing environment. The resulting electrode is very fragile and brittle. Thicker electrodes have a high tendency to delaminate and crack.

2) Using conventional methods, as depicted in FIG. 1 (A), the actual mass loading of the electrode and the apparent density of the active material are too low to be achieved>A gravimetric energy density of 200 Wh/kg. In most cases, the mass loading (areal density) of the anode active material of the electrode is significantly less than 25mg/cm ² And even for relatively large graphite particles, the apparent bulk or tap density of the active material is typically less than 1.2g/cm ³ . The cathode active material mass loading (areal density) of the electrode is significantly less than 45mg/cm for lithium metal oxide type inorganic materials ² And less than 15mg/cm for organic or polymeric materials ² . In addition, there are so many other inactive materials (e.g., conductive additives and resin binders) that the additional weight and volume of the electrode is increased without contributing to the cell capacity. These low areal and bulk densities result in relatively low gravimetric and bulk energy densities.

3) The conventional method requires that electrode active materials (an anode active material and a cathode active material) be dispersed in a liquid solvent (e.g., NMP) to manufacture a slurry, and when applied onto a current collector surface, the liquid solvent must be removed to dry the electrode layer. Once the anode and cathode layers are laminated together with the separator layer and encapsulated in a housing to produce a battery cell, a liquid electrolyte is then injected into the cell. In practice, the two electrodes are wetted, then the electrodes are dried and finally they are wetted again. This dry-wet-dry-wet method is not a good method at all.

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

In the literature, energy density data reported based on active material weight or electrode weight alone cannot be directly translated into the energy density of an actual battery cell or device. The "non-contributing weight" or weight of other device components (adhesives, conductive additives, current collectors, separators, electrolytes, and encapsulants) must also be taken into account. Conventional production methods result in a weight proportion of anode active material (e.g. graphite or carbon) in the lithium ion battery typically from 12 to 17% and a weight proportion of cathode active material from 20 to 35% (for inorganic substances such as LiMn) ₂ O ₄ ) Or from 7% to 15% (for organic or polymeric cathode materials).

The present invention provides a lithium or sodium battery cell having high electrode thickness, high active material mass loading, low non-contributing weight and volume, high capacity, and high energy density. In certain embodiments, the present disclosure provides an alkali metal cell comprising: (a) A quasi-solid polymer cathode comprising from about 30% to about 95% by volume of a cathode active material, from about 5% to about 40% by volume of a first electrolyte comprising an alkali metal salt dissolved in a solvent and an ionically conductive polymer dissolved, dispersed, or impregnated with the solvent, and from about 0.01% to about 30% by volume of a conductive additive, wherein the conductive additive comprising conductive filaments forms a 3D network of electron-conducting pathways, thereby rendering the quasi-solid polymer cathodeThe bulk electrode has a thickness of from about 10 ^-6 (iv) a conductivity of from S/cm to about 300S/cm (and possibly higher); (b) An anode (which may be a conventional anode or a quasi-solid polymer electrode); and (c) an ion conducting membrane or porous separator disposed between the anode and the quasi-solid cathode; wherein the quasi-solid cathode has a thickness of not less than 200 μm. The quasi-solid polymer cathode preferably contains not less than 10mg/cm ² Preferably not less than 15mg/cm ² Further preferably not less than 25mg/cm ² More preferably not less than 35mg/cm ² Still more preferably not less than 45mg/cm ² And most preferably greater than 65mg/cm ² Mass loading of cathode active material.

In the cell, the anode can also include a quasi-solid polymer anode comprising from about 30% to about 95% by volume of an anode active material, from about 5% to about 40% by volume of a second electrolyte comprising an alkali metal salt dissolved in a solvent and an ionically conductive polymer dissolved, dispersed, or impregnated by the solvent, and from about 0.01% to about 30% by volume of a conductive additive, wherein the conductive additive comprising electrically conductive filaments forms a 3D network of electron conducting pathways, thereby providing the quasi-solid electrode with from about 10 ^-6 A conductivity of S/cm to about 300S/cm; wherein the quasi-solid anode has a thickness of not less than 200 μm. The quasi-solid anode preferably contains not less than 10mg/cm ² Preferably not less than 15mg/cm ² Further preferably not less than 25mg/cm ² More preferably not less than 35mg/cm ² Still more preferably not less than 45mg/cm ² And most preferably greater than 65mg/cm ² Mass loading of anode active material. The composition and structure of the first electrolyte may be the same as or different from the second electrolyte.

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

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

(a) Combining an amount of active material (anode active material or cathode active material), an amount of quasi-solid polymer electrolyte (containing a polymer and an alkali metal salt dissolved in a solvent), and a conductive additive to form a deformable and conductive electrode material, wherein the conductive additive containing conductive filaments forms a 3D network of electron conducting pathways; ( These conductive filaments, such as carbon nanotubes and graphene sheets, are a large number of randomly aggregated filaments before being mixed with the particles of active material and electrolyte. The mixing procedure involves dispersing these conductive filaments in a highly viscous electrolyte containing particles of active material. This will be discussed further in the following section. )

(b) Forming the electrode material as a quasi-solid electrode, wherein the forming step comprises deforming the electrode material into an electrode shape without interrupting the 3D network of electron conduction pathways, thereby causing the electrode to remain no less than 10 ^- ⁶ S/cm (preferably not less than 10) ^-5 S/cm, more preferably not less than 10 ^-4 S/cm, further preferably not less than 10 ^-3 S/cm, still more preferably and typically not less than 10 ^-2 S/cm, even more typically and preferably not less than 10 ^-1 An electrical conductivity of S/cm, and further more typically and preferably not less than 1S/cm; up to 300S/cm is observed);

(c) Forming a second electrode (which may be a quasi-solid polymer electrode or a conventional electrode); and is provided with

(d) Forming an alkali metal cell by combining the quasi-solid electrode and the second electrode, the alkali metal cell having an ion-conducting separator disposed between the two electrodes.

Either or both of the anode and cathode may be a quasi-solid electrode. In certain embodiments, the step of forming the second electrode comprises (a) combining an amount of a second active material (e.g., an anode active material if the first electrode is a cathode), an amount of an electrolyte, and a conductive additive to form a second deformable and conductive electrode material, wherein the conductive additive comprising conductive filaments forms a 3D network of electron conducting pathways and the electrolyte comprises an alkali metal salt and an ionically conductive polymer dissolved or dispersed in a solvent;and (B) forming the second deformable and conductive electrode material into a second quasi-solid electrode, wherein the forming operation includes deforming the second deformable and conductive electrode material into an electrode shape without interrupting the 3D network of electron conduction pathways, thereby causing the second electrode to remain no less than 10 ^-6 Conductivity of S/cm (typically up to 300S/cm).

As shown in fig. 1 (C), one preferred embodiment of the present invention is an alkali metal ion cell having a conductive quasi-solid polymer anode 236, a conductive quasi-solid polymer cathode 238, and a porous separator 240 (or ion permeable membrane) that electronically separates the anode and cathode. These three components are typically enclosed in a protective housing (not shown) that typically has an anode tab (terminal) connected to the anode and a cathode tab (terminal) connected to the cathode. These tabs are used to connect to an external load (e.g., an electronic device powered by a battery). In this particular embodiment, the quasi-solid polymer anode 236 contains an anode active material (e.g., particles of Si or hard carbon, not shown in fig. 1 (C)), an electrolyte phase (typically containing a lithium or sodium salt dissolved in a solvent and an ion conducting polymer dissolved in, dispersed in, or impregnated by the solvent); also not shown in fig. 1 (C), and a conductive additive (containing conductive filaments) that forms the 3D network 244 of electron conducting pathways. Similarly, a quasi-solid polymer cathode contains a cathode active material, an electrolyte, and a conductive additive (containing conductive filaments) that forms a 3D network 242 of electron conducting pathways.

Another preferred embodiment of the invention, as shown in fig. 1 (D), is an alkali metal cell with an anode comprised of a lithium or sodium metal coating/foil 282 deposited/attached to a current collector 280 (e.g., a Cu foil), a quasi-solid cathode 284, and a separator or ion conducting membrane 282. The quasi-solid polymer cathode 284 contains a cathode active material 272 (e.g., liCoO) ₂ Particles of (b), an electrolyte phase 274 (typically containing a lithium or sodium salt dissolved in a solvent and an ionically conductive polymer dissolved, dispersed, or impregnated with the solvent), and a conductive additive phase (containing conductive filaments) forming a 3D network 270 of electronically conductive pathways. The invention also comprisesLithium ion capacitors and sodium ion capacitors.

The electrolyte is preferably a quasi-solid polymer electrolyte containing a lithium salt or sodium salt and a polymer dissolved in a solvent, the salt/polymer combination concentration being not less than 1.5M, preferably greater than 2.5M, more preferably greater than 3.5M, further preferably greater than 5M, still more preferably greater than 7M, and even more preferably greater than 10M. In certain embodiments, the electrolyte is a quasi-solid polymer electrolyte containing a polymer and a lithium or sodium salt dissolved in a liquid solvent, with a combined salt/polymer concentration of from 3.0M to 14M. The selection of the lithium or sodium salt and the solvent is discussed further in the following section.

In some embodiments, the electrolyte contains a lithium ion conducting polymer or a sodium ion conducting polymer selected from the group consisting of: poly (ethylene oxide) (PEO, with less than 1x10 ⁶ Molecular weight in g/mol), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (methyl methacrylate) (PMMA), poly (vinylidene fluoride) (PVDF), poly bis (methoxyethoxyethanol-phosphazene), polyvinyl chloride, polydimethylsiloxane, poly (vinylidene fluoride) -hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof. It is found herein that sulfonation imparts improved lithium ion conductivity to the polymer. Higher than 1x10 ⁶ The molecular weight of PEO in g/mol typically makes PEO difficult to dissolve or disperse in a solvent.

Typically, the ion-conducting polymer does not form a matrix (continuous phase) in the electrode. Rather, the polymer is dissolved in the solvent as a solution phase or dispersed in the solvent matrix as a discrete phase. The resulting electrolyte is a quasi-solid polymer electrolyte; it is not a liquid electrolyte and not a solid electrolyte.

Both the quasi-solid anode and the quasi-solid cathode preferably have a thickness greater than 200 μm (preferably greater than 300 μm, more preferably greater than 400 μm, further preferably greater than 500 μm, still more preferably greater than 800 μm, further preferably greater than 1mm, and may be greater than 5mm, 1cm, or thicker ² (more typically and preferably not less than 25 mg/cm) ² And more preferably not less than 30mg/cm ² ) The electrode active material loading of (a). For inorganic materials as the cathode active material, the cathode active material composition is not less than 45mg/cm ² (typically and preferably greater than 50 mg/cm) ² And more preferably greater than 60mg/cm ² ) Electrode active material mass loading (not less than 25mg/cm for organic or polymeric cathode active materials) ² )。

In such configurations (fig. 1 (C) -1 (D)), the electrons need only travel a short distance (e.g., a few microns or less) before they are collected by the conductive filaments that make up the 3D network of electron-conducting pathways and are present everywhere throughout the quasi-solid polymer electrode (anode or cathode). In addition, all electrode active material particles are pre-dispersed in electrolyte solvent (no wetting problem), eliminating the presence of dry pockets typically found in electrodes prepared by conventional methods of wet coating, drying, packaging and electrolyte injection. Thus, the process of the present invention has a completely unexpected advantage over conventional battery cell production processes.

These conductive filaments (e.g., carbon nanotubes and graphene sheets) as supplied are initially a large number of randomly aggregated filaments before being mixed with the particles of active material and electrolyte. The mixing procedure involves dispersing these conductive filaments in a highly viscous solid-like electrolyte containing particles of the active material. This is not a trivial task as one might think. It has been known that the dispersion of nanomaterials (particularly nanofilament materials such as carbon nanotubes, carbon nanofibers, and graphene sheets) in highly flowable (non-viscous) liquids is difficult, not to mention in highly viscous quasi-solids such as electrolytes containing high loadings of active materials (e.g., solid particles such as Si nanoparticles for anodes and lithium cobalt oxide for cathodes). In some preferred embodiments, this problem is further exacerbated by the following viewpoints: the electrolyte itself is a quasi-solid polymer electrolyte containing a high concentration of lithium or sodium salt and a polymer in a solvent.

In some preferred embodiments, the electrolyte contains a polymer and an alkali metal salt (lithium salt and/or sodium salt) dissolved in an organic or ionic liquid solvent, where the alkali metal salt/polymer combination concentration is sufficiently high such that the electrolyte exhibits a vapor pressure (when measured at 20 ℃) that is less than 0.01kPa or less than 0.6 (60%) of the vapor pressure of the solvent alone, a flash point that is at least 20 degrees celsius higher than the flash point of the first organic liquid solvent alone (when no lithium salt is present), a flash point that is higher than 150 ℃, or no detectable flash point at all.

Of most surprising and great scientific and technical importance is our finding that: the flammability of any volatile organic solvent can be effectively suppressed provided that a sufficiently high amount of alkali metal salt and polymer is added to and dissolved in the organic solvent to form a solid-like or quasi-solid polymer electrolyte. Generally, such quasi-solid polymer electrolytes exhibit a vapor pressure of less than 0.01kPa and often less than 0.001kPa (when measured at 20 ℃) and less than 0.1kPa and often less than 0.01kPa (when measured at 100 ℃). (the vapor pressure of the corresponding pure solvent in which none of the alkali metal salt and/or polymer is dissolved is typically significantly higher.) in many cases characterized by quasi-solid polymer electrolytes, the vapor molecules are actually too few to be detected.

Very important observations are: the high solubility (macromolecular ratio or mole fraction of alkali metal salt/polymer segment, typically >0.2, more typically >0.3, and often >0.4 or even > 0.5) of the combined alkali metal salt and polymer in an otherwise highly volatile solvent can significantly reduce the amount of volatile solvent molecules that can escape into the vapor phase under thermodynamic equilibrium conditions. In many cases, this effectively prevents flammable solvent gas molecules from initiating the flame, even at extremely high temperatures (e.g., using a torch). The flash point of quasi-solid polymer electrolytes is typically at least 20 degrees (often >50 or >100 degrees) higher than that of pure organic solvent alone. In most cases, the flash point is above 150 ℃ or no flash point can be detected. The electrolyte will not ignite. Furthermore, any accidental fire does not last longer than a few seconds. This is a very important finding in view of the fire and explosion concerns that have been a major obstacle to the widespread acceptance of battery powered electric vehicles. This new technology can significantly help accelerate the rise of the live EV industry.

For safety reasons, no studies have been previously reported on the vapor pressure of ultra-high concentration battery electrolytes (alkali metal salt/polymer segments or combined concentrations of approximately >2.5M or 3.5M with high molecular fractions, e.g., >0.2 or > 0.3). This is indeed unexpected and of great technical and scientific significance.

We have further unexpectedly found that: the presence of a 3D network of electron conducting pathways composed of conductive filaments serves to further reduce the threshold concentration of alkali metal salt required to achieve critical vapor pressure suppression.

Another surprising element of the present invention is the following: we are able to dissolve high concentrations of alkali metal salts and selected ion conducting polymers in almost every type of commonly used battery grade organic solvent to form quasi-solid polymer electrolytes suitable for rechargeable alkali metal batteries. Expressed in more readily recognized terms, the concentration is typically greater than 2.5M (moles/liter), more typically and preferably greater than 3.5M, still more typically and preferably greater than 5M, still more preferably greater than 7M, and most preferably greater than 10M. In the case where the salt/polymer concentration is not less than 2.5M, the electrolyte is no longer a liquid electrolyte; rather, it is a quasi-solid electrolyte. Such high concentrations of alkali metal salts in solvents are generally considered impossible, nor desirable, in the field of lithium or sodium batteries. However, we have found that these quasi-solid polymer electrolytes are surprisingly good electrolytes for both lithium and sodium batteries in terms of significantly improved safety (non-flammability), improved energy density and improved power density.

In addition to the non-flammability and high alkali metal ion transfer number as discussed above, there are several other benefits to using the quasi-solid polymer electrolytes of the present invention. For example, quasi-solid polymer electrolytes, when implemented at least in the anode, can significantly enhance the cycling and safety performance of rechargeable alkali metal batteries by effectively inhibiting dendrite growth. It is generally believed that dendrites begin to grow in the non-aqueous liquid electrolyte when the anions are depleted near the electrode where plating occurs. In ultra-high concentration electrolytes, a large number of anions are present to maintain cations (Li) near the metallic lithium or sodium anode ⁺ Or Na ⁺ ) And anions. In addition, the space charge generated by anion depletion is extremely small, which is detrimental to dendrite growth. In addition, due to the ultra-high Li or Na salt concentration and the high Li ion or Na ion transfer number, the quasi-solid polymer electrolyte provides a large amount of available lithium ion or sodium ion flux and increases the lithium or sodium ion mass transfer rate between the electrolyte and the lithium or sodium electrode, thereby enhancing the deposition uniformity and dissolution of lithium or sodium during charge/discharge. In addition, the locally high viscosity caused by the high concentration will increase the pressure from the electrolyte to inhibit dendrite growth, potentially resulting in a more uniform deposition on the anode surface. The high viscosity may also limit anion convection near the deposition area, thereby promoting more uniform deposition of sodium ions. The same reasoning applies to lithium metal batteries. These reasons are believed to be (individually or in combination) the reasons for the following: to date, no dendrite-like features have been observed for any of the large number of rechargeable alkali metal cells we have studied.

In addition, those skilled in the art of chemistry or material science will envision, e.g.This high salt/polymer concentration should cause the electrolyte to behave like a solid with a very high viscosity, and therefore, the electrolyte should not be suitable for rapid diffusion of alkali metal ions therein. Thus, one skilled in the art would expect that an alkali metal battery containing such a solid-like polymer electrolyte would not and cannot exhibit high capacity (i.e., the battery should have poor rate performance) at high charge-discharge rates or under high current density conditions. Contrary to these expectations of the skilled person or even of a superior skilled person, all alkali metal cells containing such quasi-solid polymer electrolytes impart a high energy density and a high power density, thereby achieving a long cycle life. It appears that quasi-solid polymer electrolytes as invented and disclosed herein facilitate easy alkali metal ion transport. This unexpected finding may be due to two main factors: one associated with the internal structure of the electrolyte and the other with high Na ⁺ Or Li ⁺ Ion Transfer Number (TN) is relevant.

Without wishing to be bound by theory, the internal structure of three fundamentally different types of electrolytes can be visualized by reference to fig. 2 (a) to 2 (C). Fig. 2 (a) schematically shows a close-packed highly ordered structure of a typical solid electrolyte, in which there is little free volume for diffusion of alkali metal ions. Any migration of ions in such a crystal structure is very difficult, resulting in a very low diffusion coefficient (10) ^-16 To 10 ^-12 cm ² S) and extremely low ionic conductivity (typically from 10) ^-7 S/cm to 10 ^-4 S/cm). In contrast, as schematically shown in fig. 2 (B), the internal structure of the liquid electrolyte is completely amorphous, having cations (e.g., or Li) ⁺ Or Na ⁺ ) Large free volume fraction that can easily migrate through, resulting in a high diffusion coefficient (10) ^-8 To 10 ^-6 cm ² S) and high ionic conductivity (typically from 10) ^-3 S/cm to 10 ^-2 S/cm). However, liquid electrolytes containing low concentrations of alkali metal salts are flammable and prone to dendrite formation, creating the risk of fire and explosion. Schematically illustrated in FIG. 2 (C) is a polymer having separate salt species and polymer segmentsTo produce a random or amorphous structure of the quasi-solid polymer electrolyte of solvent molecules in the amorphous region that facilitates the migration of free (unclustered) cations. Such a structure is suitable for achieving high ionic conductivity values (typically 10) ^-4 S/cm to 8x 10 ^-3 S/cm) but remain nonflammable. Relatively few solvent molecules are present and these molecules are retained (against evaporation) by overwhelmingly large numbers of salt species, polymer segments and conductive filament networks.

In a preferred embodiment, the anode active material is a pre-lithiated or pre-sodiated version of graphene sheets selected from pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or combinations thereof. The starting graphite material used to produce any of the above graphene materials may be selected from natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesophase carbon microbeads, soft carbon, hard carbon, coke, carbon fibers, carbon nanofibers, carbon nanotubes, or combinations thereof. Graphene materials are also good conductive additives for anode and cathode active materials for lithium batteries.

The constituent graphene planes of graphite crystallites in natural or artificial graphite particles can be expanded and extracted or isolated to obtain single graphene sheets of hexagonal carbon atoms that are monoatomic in thickness, provided that the interplanar van der waals forces can be overcome. A typical process is shown in fig. 4. An isolated single graphene plane of carbon atoms is commonly referred to as single layer graphene. A stack of a plurality of graphene planes bonded by van der waals forces in the thickness direction with an interval between the graphene planes of about 0.3354nm is generally called multilayer graphene. The multi-layered graphene platelets have up to 300 graphene planes (< 100nm in thickness), but more typically up to 30 graphene planes (< 10nm in thickness), even more typically up to 20 graphene planes (< 7nm in thickness), and most typically up to 10 graphene planes (commonly referred to as few-layer graphene in the scientific community). Single-layer graphene sheets and multi-layer graphene sheets are collectively referred to as "nano-graphene platelets" (NGPs). Graphene sheets/platelets (collectively referred to as NGP) are a new class of carbon nanomaterials (2-D nanocarbons) that differ from 0-D fullerenes, 1-D CNTs, or CNFs and 3-D graphites. For the purposes of defining the claims and as generally understood in the art, graphene materials (isolated graphene sheets) are not (and do not include) Carbon Nanotubes (CNTs) or Carbon Nanofibers (CNFs).

In one approach, graphene materials are obtained by intercalating natural graphite particles with strong acids and/or oxidizing agents to obtain Graphite Intercalation Compounds (GICs) or Graphite Oxides (GO), as shown in fig. 5 (a) and 5 (B). The presence of chemical species or functional groups in the interstitial spaces between graphene planes in a GIC or GO serves to increase the inter-graphene spacing (d) ₀₀₂ As determined by X-ray diffraction) to thereby significantly reduce van der waals forces that would otherwise hold graphene planes together along the c-axis direction. GIC or GO is most often produced by immersing natural graphite powder in a mixture of sulfuric acid, nitric acid (the oxidant) and another oxidant (e.g. potassium permanganate or sodium perchlorate). If an oxidant is present during the intercalation procedure, the resulting GIC is actually some type of Graphite Oxide (GO) particles. The GIC or GO is then repeatedly washed and rinsed in water to remove excess acid, producing a graphite oxide suspension or dispersion containing discrete and visually identifiable graphite oxide particles dispersed in water. To produce graphene materials, one of two processing routes can be followed after this washing step, briefly described as follows:

route 1 involves the removal of water from the suspension to obtain "expandable graphite", which is essentially a mass of dry GIC or dry graphite oxide particles. Upon exposure of the expandable graphite to temperatures in the range of typically 800 c to 1,050 c for about 30 seconds to 2 minutes, the GIC undergoes 30-300 times rapid volume expansion to form "graphite worms," each of which is an assemblage of expanded, yet interconnected, largely unseparated graphite flakes.

In route 1A, these graphite worms (expanded graphite or "network of interconnected/unseparated graphite flakes") can be recompressed to obtain flexible graphite sheets or foils, typically having a thickness in the range of 0.1mm (100 μm) to 0.5mm (500 μm). Alternatively, the use of low intensity air mills or shears may be selected to simply decompose the graphite worms for the purpose of producing so-called "expanded graphite flakes," which contain predominantly graphite flakes or platelets thicker than 100nm (and thus by definition not nanomaterials).

In route 1B, expanded graphite is subjected to high intensity mechanical shearing (e.g., using an ultrasonic generator, a high shear mixer, a high intensity air jet mill, or a high energy ball mill) to form separate single and multi-layered graphene sheets (collectively referred to as NGPs), as disclosed in our U.S. application No. 10/858,814 (06/03/2004). Single-layer graphene can be as thin as 0.34nm, while multi-layer graphene can have a thickness of up to 100nm, but more typically less than 10nm (commonly referred to as few-layer graphene). A plurality of graphene sheets or platelets can be made into sheets of NGP paper using a papermaking process. The sheets of NGP paper are an example of a porous graphene structural layer used in the method of the invention.

Route 2 entails subjecting a graphite oxide suspension (e.g., graphite oxide particles dispersed in water) to ultrasonic treatment for the purpose of separating/isolating individual graphene oxide sheets from the graphite oxide particles. This is based on the following point: the spacing between graphene planes has increased from 0.3354nm in natural graphite to 0.6-1.1nm in highly oxidized graphite oxide, significantly reducing van der waals forces holding adjacent planes together. The ultrasonic power may be sufficient to further separate the graphene planar sheets to form fully separated, isolated or discrete Graphene Oxide (GO) sheets. These graphene oxide sheets may then be chemically or thermally reduced to obtain "reduced graphene oxide" (RGO), typically having an oxygen content of 0.001-10% by weight, more typically 0.01-5% by weight, most typically and preferably less than 2% by weight oxygen.

For the purposes of defining the claims of the present application, NGP or graphene materials include single and multiple layers (typically less than 10 layers) of discrete sheets/platelets of pristine graphene, graphene oxide, reduced Graphene Oxide (RGO), graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, doped graphene (e.g. doped with B or N). Pristine graphene has substantially 0% oxygen. RGO typically has an oxygen content of 0.001% -5% by weight. Graphene oxide (including RGO) may have 0.001% -50% oxygen by weight. All graphene materials, except pristine graphene, have 0.001% -50% by weight of non-carbon elements (e.g., O, H, N, B, F, cl, br, I, etc.). These materials are referred to herein as non-native graphene materials.

Pristine graphene, in the form of smaller discrete graphene sheets (typically 0.3 to 10 μm), can be produced by direct sonication (also known as liquid phase expansion or production) or supercritical fluid expansion of graphite particles. These methods are well known in the art.

Graphene Oxide (GO) may be obtained by immersing powders or filaments of a starting graphite material (e.g. natural graphite powder) in an oxidizing liquid medium (e.g. a mixture of sulfuric acid, nitric acid and potassium permanganate) at a desired temperature in a reaction vessel 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 previously described above, the resulting graphite oxide particles may then be subjected to thermal or ultrasound induced expansion to produce isolated GO sheets. And then by using other chemical groups (e.g. -Br, NH) ₂ Etc.) substitution of-OH groups converts these GO sheets into various graphene materials.

Fluorinated graphene or graphene fluoride are used herein as examples of halogenated graphene material groups. There are two different approaches that have been followed to produce fluorinated graphene: (1) fluorination of pre-synthesized graphene: the process requires the use of a fluorinating agent such as XeF ₂ Or F-based plasma treating graphene prepared by mechanical puffing or by CVD growth; (2) puffing of the multilayer graphite fluoride: both mechanical and liquid phase expansion of graphite fluoride can be readily achieved.

F ₂ Interaction with graphite at high temperatureCovalent graphite fluoride (CF) _n Or (C) ₂ F) _n While forming Graphite Intercalation Compound (GIC) C at low temperature _x F (x is more than or equal to 2 and less than or equal to 24). In (CF) _n The carbon atoms are sp3 hybridized and thus the fluorocarbon layer is corrugated, consisting of trans-linked cyclohexane chairs. In (C) ₂ F) _n Only half of the C atoms are fluorinated and each pair of adjacent carbon sheets are linked together by a covalent C — C bond. Systematic studies of the fluorination reaction show that the resulting F/C ratio depends to a large extent on the fluorination temperature, the partial pressure of fluorine in the fluorination gas, and the physical properties of the graphite precursor, including graphitization degree, particle size, and specific surface area. In addition to fluorine (F) ₂ ) In addition, other fluorinating agents may be used, although most of the prior literature is directed to the use of F ₂ The gas is fluorinated (sometimes in the presence of fluoride).

In order to expand the layered precursor material into the state of a single layer or several layers, the attractive forces between adjacent layers must be overcome and the layers further stabilized. This can be achieved by covalent modification of the graphene surface with functional groups or by non-covalent modification using specific solvents, surfactants, polymers, or donor-acceptor aromatic molecules. The liquid phase expansion process involves ultrasonication of graphite fluoride in a liquid medium.

Nitridation of graphene can be performed by exposing a graphene material (e.g., graphene oxide) to ammonia at high temperatures (200-400 ℃). The graphene nitride can be formed at a lower temperature by a hydrothermal method; for example by sealing GO and ammonia in an autoclave and then warming to 150-250 ℃. Other methods of synthesizing nitrogen-doped graphene include nitrogen plasma treatment on graphene, arc discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and hydrothermal treatment of graphene oxide and urea at different temperatures.

There is no limitation on the type of anode active material or cathode active material that can be used to practice the present invention. Preferably, in the lithium battery cell of the present invention, the anode active material exceeds Li/Li when the battery is charged ⁺ (i.e. with respect to Li as standard potential)→Li ⁺ +e ^- ) Lithium ions are absorbed at an electrochemical potential of less than 1.0 volt, preferably less than 0.7 volt. In a preferred embodiment, the anode active material of the lithium battery is selected from the group consisting of: (ii) (a) particles of lithium metal or lithium metal alloy; (b) Natural graphite particles, artificial graphite particles, mesophase Carbon Microspheres (MCMB), carbon particles (including soft 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) Alloys or intermetallic compounds of Si, ge, sn, pb, sb, bi, zn, al, or Cd with other elements, wherein the alloys or compounds are stoichiometric or non-stoichiometric; (e) Oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, ge, sn, pb, sb, bi, zn, al, fe, ni, co, ti, mn, or Cd, and mixtures or composites thereof; (f) a prelithiated version thereof; (g) pre-lithiated graphene sheets; and combinations thereof.

In certain embodiments, the alkali metal cell is a sodium metal cell or a sodium ion cell and the active material is an anode active material comprising a sodium intercalation compound selected from: petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon (hard graphitizable carbon), soft carbon (graphitizable carbon), template carbon, hollow carbon nanowire, hollow carbon sphere, titanate, naTi ₂ (PO ₄ ) ₃ 、Na ₂ Ti ₃ O ₇ 、Na ₂ C ₈ H ₄ O ₄ 、Na ₂ TP、Na _x TiO ₂ (x =0.2 to 1.0), na ₂ C ₈ H ₄ O ₄ Materials based on carboxylic acid salts, C ₈ H ₄ Na ₂ O ₄ 、C ₈ H ₆ O ₄ 、C ₈ H ₅ NaO ₄ 、C ₈ Na ₂ F ₄ O ₄ 、C ₁₀ H ₂ Na ₄ O ₈ 、C ₁₄ H ₄ O ₆ 、C ₁₄ H ₄ Na ₄ O ₈ Or a combination thereof.

A wide variety of cathode active materials can be used to practice the lithium cell of the present invention. The cathode active material is typically a lithium intercalation 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 oxide/phosphate/sulfide (the most desirable type of inorganic cathode material), or combinations thereof:

the group of metal oxides, metal phosphates, and metal sulfides consists of lithium cobalt oxides, lithium nickel oxides, lithium manganese oxides, lithium vanadium oxides, lithium transition metal oxides, lithium mixed metal oxides, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof. Specifically, the lithium vanadium oxide may be selected from the group consisting of: VO (vacuum vapor volume) 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, wherein 0.1<x<5. The lithium transition metal oxide may be selected from the layered compound LiMO ₂ Spinel type compound LiM ₂ O ₄ An olivine-type compound LiMPO ₄ Silicate compound Li ₂ MSiO ₄ Lithium iron phosphate iron petrochemical compound LiMPO ₄ F. Borate compound LiMBO ₃ Or combinations thereof, wherein M is a transition metal or a mixture of transition metals.

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

In particular, the inorganic material may be selected from: (ii) (a) bismuth selenide or telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metal sulfide, selenide, or telluride; (d) boron nitride, or (e) a combination thereof.

The organic or polymeric material may be selected from poly (anthraquinone sulfides) (PAQS), lithium oxycarbide, 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA), poly (anthraquinone sulfides), pyrene-4, 5,9, 10-tetraone (PYT), polymer-bonded PYT, quinones (triazenes), redox-active organic materials, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10, 11-Hexamethoxytriphenylene (HMTP), poly (5-amino-1, 4-dihydroxyanthraquinone) (PADAQ), phosphazene disulfide polymers ([ (NPS) ₂ ) ₃ ]n), lithiated 1,4,5, 8-naphthalenetetraol formaldehyde polymers, hexaazatrinaphthalene (HATN), hexaazatrinexanenitrile (HAT (CN) ₆ ) 5-benzylidenehydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzeneQuinone derivative (THQLi) ₄ ) N, N ' -diphenyl-2, 3,5, 6-tetraone piperazine (PHP), N ' -diallyl-2, 3,5, 6-tetraone piperazine (AP), N ' -dipropyl-2, 3,5, 6-tetraone piperazine (PRP), thioether polymers, quinone compounds, 1, 4-benzoquinone, 5,7,12, 14-Pentacenetetraone (PT), 5-amino-2, 3-dihydro-1, 4-dihydroxyanthraquinone (ADDAQ), 5-amino-1, 4-dihydroxyanthraquinone (ADAQ), quinoid calixarenes, li ₄ C ₆ O ₆ 、Li ₂ C ₆ O ₆ 、Li ₆ C ₆ O ₆ Or a combination thereof.

The thioether polymer is selected from poly [ methanetrinitrobenzylnitroamine-tetrakis (thiomethylene) ] (PMTTM), poly (2, 4-dithiopentene) (PDTP), a polymer containing poly (ethylene-1, 2-tetrathiol) (PETT) as a main chain thioether polymer, a side chain thioether polymer having a main chain composed of conjugated aromatic moieties and having thioether side chains as side chains, poly (2-phenyl-1, 3-dithiolane) (PPDT), poly (1, 4-bis (1, 3-dithiolane-2-yl) benzene) (PDDTB), poly (tetrahydrobenzodithiophene) (PTHBDT), poly [1,2,4, 5-tetrakis (propylthio) benzene ] (PTKPTB), or poly [3,4 (ethylenedithio) thiophene ] (PEDTT).

The organic material may be selected from phthalocyanine compounds selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, chromium phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanines, chemical derivatives thereof, or combinations thereof.

The lithium intercalation compound or lithium-absorbing compound may be selected from a metal carbide, a metal nitride, a metal boride, a metal dichalcogenide, or a combination thereof. Preferably, the lithium intercalation compound or lithium-absorbing compound is selected from an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in the form of a nanowire, nanodisk, nanoribbon, or nanoplatelet.

We have found that lithium batteries of the invention are prepared by the direct active material-electrolyte injection method of the inventionIn the cell, various two-dimensional (2D) inorganic materials may be used as a cathode active material. Layered materials represent a diverse source of 2D systems that can exhibit unexpected electronic properties and good affinity for lithium ions. 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 And is also a potential source of 2D material.

Preferably, the lithium intercalation compound or lithium-absorbing compound is selected from nanodiscs, nanoplatelets, nanocoatings, or nanoplatelets of an inorganic material selected from: (ii) (a) bismuth selenide or telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or transition metal sulfide, selenide, or telluride; (d) boron nitride, or (e) a combination thereof; wherein the disc, platelet or sheet has a thickness of less than 100 nm. The lithium intercalation compound or lithium-absorbing compound may contain nanodiscs, nanoplatelets, nanocoatings, or nanoplatelets of a compound selected from the group consisting of: (ii) a transition metal dichalcogenide or trisulfide, (iii) a sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (iv) (iv) boron nitride, or (v) a combination thereof, wherein the disk, platelet, coating, or sheet has a thickness of less than 100 nm.

In a rechargeable sodium cell, the cathode active material may contain a sodium intercalation compound selected from: 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 and 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 from 0.01 to 100), se (without S), phosphomanganite, or combinations thereof.

Alternatively, the cathode active material may be selected from a functional material or a nanostructured material having an alkali metal ion capturing functional group or an alkali metal ion storage surface in direct contact with the electrolyte. Preferably, the functional group reacts reversibly with an alkali metal ion, forms a redox pair with an alkali metal ion, or forms a chemical complex with an alkali metal ion. The functional or nanostructured material may be selected from the group consisting of: (a) Nanostructured or porous disordered carbon materials selected from soft carbon, hard carbon, polymeric or carbonized resins, mesophase carbon, coke, carbonized pitch, carbon black, activated carbon, nano-cellular carbon foam, or partially graphitized carbon; (b) A nano-graphene platelet selected from a single layer graphene sheet or a multi-layer graphene platelet; (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 a combination thereof; (e) carbonyl-containing organic or polymeric molecules; (f) functional materials containing carbonyl, carboxyl or amino groups; and combinations thereof.

The functional or nanostructured material may be selected from the group consisting of: poly (2, 5-dihydroxy-1, 4-benzoquinone-3, 6-methylene), na _x C ₆ O ₆ (x＝1-3)、Na ₂ (C ₆ H ₂ O ₄ )、Na ₂ C ₈ H ₄ O ₄ Sodium terephthalate, na ₂ C ₆ H ₄ O ₄ (lithium trans-muconate), 3,4,9, 10-perylenetetracarboxylic-dianhydride (PTCDA) sulfide polymer, PTCDA, 1,4,5, 8-naphthalene-tetracarboxylic-dianhydride (NTCDA), benzene-1, 2,4, 5-tetracarboxylic-dianhydride, 1,4,5, 8-tetrahydroxyanthraquinone, tetrahydroxy-p-benzoquinone, and combinations thereof. Desirably, the functional or nanostructured material has a structure selected from-COOH, = O, -NH ₂ -OR OR-COOR, wherein R is a hydrocarbyl group.

Non-graphene 2D nanomaterials (single or few layers (up to 20 layers)) can be produced by several methods: mechanical cleaving, laser ablation (e.g., ablation of TMD into a single layer using laser pulses), liquid phase expansion, and synthesis by thin film techniques such as PVD (e.g., sputtering), evaporation, vapor phase epitaxy, liquid phase epitaxy, chemical vapor phase epitaxy, molecular Beam Epitaxy (MBE), atomic Layer Epitaxy (ALE), and plasma assisted versions thereof.

A wide range of electrolytes can be used in the practice of the present invention. Most preferred are non-aqueous organic and/or ionic liquid electrolytes. The nonaqueous electrolyte to be used herein may be produced by dissolving an electrolyte salt in a nonaqueous solvent. Any known non-aqueous solvent that has been used as a solvent for a lithium secondary battery may be used. It may be preferable to use a nonaqueous solvent mainly composed of a mixed solvent containing Ethylene Carbonate (EC) and at least one kind of a nonaqueous solvent (hereinafter referred to as a second solvent) having a melting point lower than the above-mentioned ethylene carbonate and having a donor number of 18 or less. This non-aqueous solvent is advantageous because it: (a) Is stable to negative electrodes containing carbonaceous materials that develop well in graphite structures; (b) effective to inhibit reductive or oxidative decomposition of the electrolyte; and (c) high conductivity. A non-aqueous electrolyte consisting of only Ethylene Carbonate (EC) is advantageous because it is relatively stable to decomposition by reduction of the graphitized carbonaceous material. However, the melting point of EC is relatively high, 39 ℃ to 40 ℃, and its viscosity is relatively high, so that its electrical conductivity is low, thus making EC alone unsuitable for use as a secondary battery electrolyte operating at room temperature or lower. The second solvent to be used with the EC in the mixture functions to lower the viscosity of the solvent mixture than the viscosity of the EC alone, thereby promoting the ionic conductivity of the mixed solvent. Further, when the second solvent having the donor number of 18 or less (the donor number of ethylene carbonate is 16.4) is used, the above-described ethylene carbonate can be easily and selectively solvated with lithium ions, so that the reduction reaction of the second solvent with the carbon-containing material which is supposed to well progress in graphitization is suppressed. In addition, when the donor number of the second solvent is controlled to not more than 18, the oxidative decomposition potential of the lithium electrode can be easily increased to 4V or more, so that a high-voltage lithium secondary battery can be manufactured.

Preferred second solvents are dimethyl carbonate (DMC), ethyl methyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene Carbonate (PC), gamma-butyrolactone (gamma-BL), acetonitrile (AN), ethyl Acetate (EA), propyl Formate (PF), methyl Formate (MF), toluene, xylene and Methyl Acetate (MA). These second solvents may be used alone or in a combination of two or more. More desirably, the second solvent should be selected from those having a donor number of 16.5 or less. The viscosity of the second solvent should preferably be 28cps or less at 25 ℃.

The mixing ratio of the above ethylene carbonate in the mixed solvent should preferably be 10% to 80% by volume. If the mixing ratio of ethylene carbonate falls outside this range, the conductivity of the solvent may decrease or the solvent tends to decompose more easily, thereby deteriorating the charge/discharge efficiency. More preferably, the mixing ratio of ethylene carbonate is 20% to 75% by volume. When the mixing ratio of ethylene carbonate in the nonaqueous solvent is increased to 20% by volume or more, the solvating effect of ethylene carbonate on lithium ions is promoted and the solvolysis suppressing effect thereof can be improved.

Examples of preferred mixed solvents are those comprising EC and MEC; comprises EC, PC and MEC; comprises EC, MEC and DEC; comprises EC, MEC and DMC; and compositions comprising EC, MEC, PC and DEC; wherein the volume ratio of the MEC is controlled to be in the range of 30% to 80%. By selecting a volume fraction of MEC in the range of from 30% to 80%, more preferably 40% to 70%, the conductivity of the solvent can be improved. For the purpose of suppressing the decomposition reaction of the solvent, an electrolyte having carbon dioxide dissolved therein may be used, thereby effectively improving both the capacity and the cycle life of the battery. The electrolyte salt to be incorporated into the non-aqueous electrolyte may be selected from lithium salts such as lithium perchlorate (LiClO) ₄ ) Lithium hexafluorophosphate (LiPF) ₆ ) Lithium fluoroborate (LiBF) ₄ ) Lithium hexafluoroarsenate (LiAsF) ₆ ) Lithium trifluoromethanesulfonate (LiCF) ₃ SO ₃ ) And lithium bistrifluoromethylsulfonyl imide (LiN (CF) ₃ SO ₂ ) ₂ ). Wherein, liPF ₆ 、LiBF ₄ And LiN (CF) ₃ SO ₂ ) ₂ Is preferred. The content of the above electrolyte salt in the non-aqueous solvent is preferably 0.5 to 2.0mol/l.

For sodium cells, the electrolyte (including the nonflammable quasi-solid electrolyte) may contain a sodium salt preferably selected from: sodium perchlorate (NaClO) ₄ ) Sodium hexafluorophosphate (NaPF) ₆ ) Sodium fluoroborate (NaBF) ₄ ) Sodium hexafluoroarsenate, sodium trifluoro-methanesulfonate (NaCF) ₃ SO ₃ ) Bis (trifluoromethyl) sulfonimide sodium (NaN (CF) ₃ SO ₂ ) ₂ ) An ionic liquid salt, or a combination thereof.

Ionic liquids are composed of ions only. Ionic liquids are low melting point salts that are molten or liquid when above a desired temperature. For example, a salt is considered an ionic liquid if it has a melting point below 100 ℃. If the melting temperature is equal to or lower than room temperature (25 ℃), the salt is referred to as a Room Temperature Ionic Liquid (RTIL). Due to the combination of large cations and charge delocalized anions, IL salts are characterized by weak interactions. This results in a low tendency to crystallize due to flexibility (anions) and asymmetry (cations).

Typical and well-known ionic liquids are formed by the combination of a 1-ethyl-3-methylimidazolium (EMI) cation and an N, N-bis (trifluoromethane) sulfonamide (TFSI) anion. This combination results in a fluid having an ionic conductivity comparable to many organic electrolyte solutions and a low decomposition tendency and low vapor pressure of up to about 300-400 ℃. This means an electrolyte that is generally low in volatility and non-flammability, and is therefore much safer for batteries.

Ionic liquids are essentially composed of organic ions, and have an essentially infinite number of structural changes due to the ease of preparation of their various components. Thus, various salts can be used to design ionic liquids with desired properties for a given application. These include inter alia imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis (trifluoromethanesulfonyl) imide, bis (fluorosulfonyl) imide and hexafluorophosphate as anions. Based on their composition, ionic liquids come in different classes, which basically include aprotic, protic and zwitterionic types, each suitable for a particular application.

Common cations of Room Temperature Ionic Liquids (RTILs) include, but are not limited to, tetraalkylammonium, di-, tri-and tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium and trialkylsulfonium. Common anions of RTIL include, but are not limited to, BF ₄ ^- 、B(CN) ₄ ^- 、CH ₃ BF ₃ ^- 、CH2CHBF ₃ ^- 、CF ₃ BF ₃ ^- 、C ₂ F ₅ BF ₃ ^- 、n-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 so on. By contrast, imidazolium-or sulfonium-based cations with, for example, alCl ₄ ^- 、BF ₄ ^- 、CF ₃ CO ₂ ^- 、CF ₃ SO ₃ ^- 、NTf ₂ ^- 、N(SO ₂ F) ₂ ^- Or F (HF) _2.3 ^- The combination of isocomplex halide anions results in an RTIL with good working conductivity.

RTILs can have typical characteristics such as high intrinsic ionic conductivity, high thermal stability, low volatility, low (nearly zero) vapor pressure, nonflammability, ability to remain as liquids over a wide range of temperatures above and below room temperature, high polarity, high viscosity, and a wide electrochemical window. These properties are desirable attributes in addition to high viscosity when it comes to using RTILs as electrolyte components (salts and/or solvents) in supercapacitors.

Hereinafter, we provide some examples of several different types of anode active materials, cathode active materials, and ion conducting polymers to illustrate the best mode of practicing the invention. These illustrative examples, as well as other portions of the specification and drawings, individually or in combination, are sufficient to enable one of ordinary skill in the art to practice the invention. However, these examples should not be construed as limiting the scope of the invention.

Example 1: preparation of Graphene Oxide (GO) and Reduced Graphene Oxide (RGO) nanoplates from natural graphite powder

Natural Graphite from Huadong Graphite co. (Huadong Graphite co.) (celadon, china) was used as a starting material. GO is obtained by following the well-known modified hummers method (hummers method), which involves two oxidation stages. In a typical procedure, the first oxidation is effected under the following conditions: 1100mg of graphite was placed in a 1000mL long-necked flask. Then, 20g of K was added to the flask ₂ S ₂ O ₈ 20g of P ₂ O ₅ And 400mL of concentrated H ₂ SO ₄ Aqueous solution (96%). The mixture was heated at reflux for 6 hoursAnd then left undisturbed for 20 hours at room temperature. The graphite oxide was filtered and rinsed with copious amounts of distilled water until neutral pH. The wet cake-like material is recovered at the end of this first oxidation.

For the second oxidation process, the previously collected wet cake was placed in a container containing 69mL of concentrated H ₂ SO ₄ Aqueous solution (96%) in a long-necked flask. The flask was kept in an ice bath while slowly adding 9g KMnO ₄ . Care is taken to avoid overheating. The resulting mixture was stirred at 35 ℃ for 2 hours (the color of the sample turned dark green), then 140mL of water was added. After 15min, the reaction was quenched by the addition of 420mL of water and 15mL of 30wt.% H ₂ O ₂ To stop the reaction. At this stage the color of the sample turned bright yellow. To remove the metal ions, the mixture was filtered and washed with 1. The collected material was gently centrifuged at 2700g and rinsed with deionized water. The final product was a wet cake containing 1.4wt.% GO (as estimated from dry extract). Subsequently, a liquid dispersion of GO platelets was obtained by mild sonication of the wet-cake material diluted in deionized water.

Surfactant stabilized RGO (RGO-BS) is obtained by diluting the wet cake in an aqueous solution of a surfactant, rather than pure water. A mixture of commercially available sodium cholate (50 wt.%) and sodium deoxycholate (50 wt.%) salts supplied by Sigma Aldrich (Sigma Aldrich) was used. Surfactant weight fraction was 0.5wt.%. The fraction remained constant for all samples. Sonication was performed using a Benedict Soifier S-250A equipped with a 13mm step disruptor horn and a 3mm conical microtip operating at a frequency of 20 kHz. For example, 10mL of an aqueous solution containing 0.1wt.% GO was sonicated for 10min and then centrifuged at 2700g for 30min to remove any undissolved large particles, aggregates and impurities. The chemical reduction to obtain as-received GO to produce RGO was performed by following the following procedure, which involved placing 10mL of a 0.1wt.% GO aqueous solution in a 50mL long-necked flask. Then, 10. Mu.L of 35wt.% N ₂ H ₄ (hydrazine) aqueous solution and 70mL of 28wt.% NH ₄ An aqueous OH (ammonia) solution is added to the mixture and stabilized by a surfactant. Heating the solution toAt 90 ℃ and reflux for 1h. The pH value measured after the reaction was about 9. The color of the sample turned dark black during the reduction reaction.

In certain lithium batteries of the invention, RGO is used as a conductive additive in either or both of the anode and cathode active materials. In selected lithium ion cells, pre-lithiated RGO (e.g., RGO + lithium particles or RGO pre-deposited with a lithium coating) is also used as the anode active material.

For comparison purposes, a slurry coating and drying procedure was performed to produce a conventional electrode. An anode and a cathode, and a separator disposed between the two electrodes, were then assembled and encapsulated in an Al plastic laminate encapsulation envelope, and then injected with liquid electrolyte to form a prior art lithium battery cell.

Example 2: preparation of pristine graphene sheets (substantially 0% oxygen)

Recognizing the possibility that the high defect number in GO sheets acts to reduce the electrical conductivity of individual graphene planes, we decided to investigate whether the use of pristine graphene sheets (non-oxidized and oxygen-free, non-halogenated and halogen-free, etc.) could produce an electrically conductive additive with high electrical and thermal conductivity. Prelithiated pristine graphene is also used as the anode active material. Pristine graphene sheets are produced using direct sonication or a liquid phase production process.

In a typical procedure, 5 grams of graphite flakes milled to a size of about 20 μm or less are dispersed in 1,000ml deionized water (containing 0.1% by weight dispersant, from DuPont) containing

FSO) to obtain a suspension. An ultrasonic energy level of 85W (Branson S450 sonicator) was used for the expansion, separation and size reduction of graphene sheets for a period of 15 minutes to 2 hours. The resulting graphene sheets are pristine graphene that has never been oxidized and is oxygen-free and relatively defect-free. The pristine graphene is substantially free of any non-carbon elements.

Pristine graphene sheets are then incorporated into the cell as a conductive additive along with the anode active material (or cathode active material in the cathode) using both the inventive procedure of injecting a slurry into the foam pores and conventional slurry coating, drying, and lamination procedures. Both lithium ion batteries and lithium metal batteries (only implanted into the cathode) were investigated.

Example 3: preparation of prelithiated graphene fluoride sheets as anode active materials for lithium ion batteries

We have used several methods to produce GF, but only one method is described herein as an example. In a typical procedure, highly Expanded Graphite (HEG) is prepared from an intercalation compound ₂ F·xClF ₃ And (4) preparation. HEG was further fluorinated with chlorine trifluoride vapor to produce Fluorinated Highly Expanded Graphite (FHEG). The pre-cooled Teflon (Teflon) reactor is filled with 20-30mL of liquid pre-cooled ClF ₃ The reactor was closed and cooled to liquid nitrogen temperature. Then, no more than 1g of HEG was placed in a container with a container for ClF ₃ The gas enters the reactor and is located in an aperture within the reactor. Form a product with approximate formula C in 7-10 days ₂ F as a grey beige product.

Subsequently, a small amount of FHEG (approximately 0.5 mg) was mixed with 20-30mL of organic solvent (methanol and ethanol respectively) and subjected to sonication (280W) for 30min, resulting in the formation of a homogeneous yellowish dispersion. After removal of the solvent, the dispersion turned into a brown powder. Graphene fluoride powder is mixed with surface-stabilized lithium powder in a liquid electrolyte such that pre-lithiation occurs. Example 4: some examples of preferred salts, solvents, and polymers for forming quasi-solid polymer electrolytes

Preferred sodium metal salts include: sodium perchlorate (NaClO) ₄ ) Sodium hexafluorophosphate (NaPF) ₆ ) Sodium fluoroborate (NaBF) ₄ ) Sodium hexafluoroarsenate, potassium hexafluoroarsenate, sodium trifluoro-methanesulfonate (NaCF) ₃ SO ₃ ) And sodium bis (trifluoromethylsulfonyl) imide (NaN (CF) ₃ SO ₂ ) ₂ ). The following is a good choice of lithium salts that tend to dissolve well in selected organic or ionic liquid solvents: lithium fluoroborate (LiBF) ₄ ) Lithium trifluoromethanesulfonate (LiCF) ₃ SO ₃ ) Bis (trifluoro benzene)Lithium methylsulfonylimide (LiN (CF) ₃ SO ₂ ) ₂ Or LITFSI), lithium bis (oxalato) borate (LiBOB), lithium oxalyldifluoroborate (LiBF) ₂ C ₂ O ₄ ) And lithium bis (per fluoro ethyl sulfonyl) imide (LiBETI). A good electrolyte additive to help stabilize Li metal is LiNO ₃ . Particularly useful ionic liquid-based lithium salts include: lithium bis (trifluoromethanesulfonyl) imide (LiTFSI).

Preferred organic liquid solvents include: ethylene Carbonate (EC), dimethyl carbonate (DMC), ethyl methyl 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), tetraglyme (TEGDME), poly (ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), hydrofluoroethers (e.g., TPTP), sulfones, and sulfolane.

Preferred ionic liquid solvents may be selected from Room Temperature Ionic Liquids (RTILs) having cations selected from the group consisting of: tetraalkylammonium, dialkylimidazolium, alkylpyridinium, dialkylpyrrolidinium, or dialkylpiperidinium. The counter anion is preferably selected from 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 ^- . Particularly useful ionic liquid-based solvents include N-N-butyl-N-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide (BEPyTFSI), N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP) ₁₃ TFSI), and N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide.

Preferred lithium ion conducting polymers or sodium ion conducting polymers include poly (ethylene oxide) (PEO, having a molecular weight of less than 1x10 ⁶ Molecular weight in g/mol), polypropylene oxide (PPO), poly (acrylonitrile) (PAN), poly (vinylidene fluoride) -hexafluoropropylene (PVDF-HFP), and sulfonated polymers. Preferred sulfonated polymer packagesIncluding poly (perfluorosulfonic acid), sulfonated polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly (ether ketone) (S-PEEK), and sulfonated polyvinylidene fluoride (S-PVDF).

Example 5: vapor pressures of some solvents and corresponding quasi-solid polymer electrolytes with various sodium salt molecular ratios.

Several solvents (DOL, DME, PC, AN, with or without co-solvent PP based on ionic liquids) were measured ₁₃ TFSI) in the addition of a wide range of molecular ratios along with sodium salts of PEO (e.g., sodium fluoroborate (NaBF) ₄ ) Sodium perchlorate (NaClO) ₄ ) Or sodium bis (trifluoromethanesulfonyl) imide (NaTFSI)) before and after. The vapor pressure decreases at a very high rate when the salt/polymer combination concentration exceeds 2.3M and rapidly approaches a minimum or essentially zero when the combination concentration exceeds 3.0M. At very low vapor pressures, the vapor phase of the electrolyte cannot ignite or once initiated cannot sustain the flame for longer than 3 seconds.

Example 6: some solvents and corresponding quasi-solid polymer electrolytes with 3.0M sodium or lithium salt/polymer combination concentrations had flash points and vapor pressures.

The flash point and vapor pressure of several solvents and their electrolytes with 3M Na or Li salt/polymer concentrations are presented in table 1 below. It may be noted that any liquid having a flash point below 38.7 ℃ is flammable according to OSHA (occupational safety and health administration) classification. However, to ensure safety, we have designed quasi-solid polymer electrolytes to exhibit a flash point significantly above 38.7 ℃ (by large margin, for example at least 50 ° increase and preferably above 150 ℃). The data in table 1 show that the addition of alkali metal salt/polymer combination concentrations of 3.0M is generally sufficient to meet these criteria (in many cases, 2.3M is sufficient). All of our quasi-solid polymer electrolytes are nonflammable.

Table 1: the flash point and vapor pressure of the selected solvent and its electrolyte.

^* Any liquid having a flash point below 38.7 ℃ is flammable, classified according to OSHA (occupational safety and health administration); ^** 1 standard atmospheric pressure =101,325pa =101.325kpa =1,013.25hpa.1 torr =133.3pa =0.1333kpa

Example 7: number of alkali metal ions transferred in several electrolytes

Several types of electrolytes, such as Na in the molecular ratio of (PEO + NaTFSI salt) to lithium salt in (EMImTFSI + DME) solvent, were investigated ⁺ Ion transfer number, and representative results are summarized in fig. 3 (a) to 3 (B). Generally, low salt concentration of Na in the electrolyte ⁺ The ion transfer number decreases with increasing concentration from x =0 to x = 0.2-0.30. However, above the molecular ratio of x =0.2-0.30, the number of transfers increased with increasing salt concentration, indicating Na ⁺ Fundamental changes in ion transport mechanisms. A similar trend was observed for lithium ions.

When Na is present ⁺ Electrolytes with ions at low salt concentrations (e.g. x)<0.2 In traveling in (1), na ⁺ The ions may drag multiple solvated molecules with them. This cooperative migration of clusters of charged species can be further hindered if the fluid viscosity increases as more salt and polymer are dissolved in the solvent. In contrast, when an ultra-high concentration of sodium salt (having x) is present>0.2 In time of (Na) ⁺ The number of ions may greatly exceed available solvated molecules that might otherwise cluster sodium ions, forming polyionic complex species and slowing their diffusion process. The high Na content ⁺ The ion concentration makes it possible to have more "free Na ⁺ Ions "(unclustered), thereby providing higher Na ⁺ Number of transfer (thus providing easy Na) ⁺ Transmission). The sodium ion transport mechanism changes from a polyion complex dominated mechanism (with overall larger hydrodynamic radius) to having a large amount of free Na available ⁺ Mechanism (with single ion dominance) of ionsWith a smaller hydrodynamic radius). The observation is further identified as: a sufficient amount of Na ⁺ Ions can move rapidly through or from the quasi-solid electrolyte to make themselves readily available for interaction or reaction with the cathode (during discharge) or anode (during charge), thereby ensuring good rate performance of the sodium secondary cell. Most importantly, these highly concentrated electrolytes are nonflammable and safe. Up to now, it has been difficult to obtain combined safety, easy sodium ion transport, and electrochemical performance characteristics for all types of sodium and lithium secondary batteries. Example 8: lithium iron phosphate (LFP) cathode for lithium metal batteries

LFP powders (uncoated or carbon coated) are commercially available from several sources. In this example, graphene sheets (RGO) and Carbon Nanofibers (CNF) are separately contained as conductive filaments in an electrode containing LFP particles as a cathode active material and an electrolyte containing a lithium salt and a polymer dissolved in an organic solvent. The lithium salt used in this example includes lithium fluoroborate (LiBF) ₄ ) And the organic solvent is 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 is accomplished by using the following sequence of steps:

sequence 1 (S1): firstly, liBF is put ₄ The salt and PEO were dissolved in a mixture of PC and DOL to form electrolytes with salt/polymer combination concentrations of 1.0M, 2.5M, and 3.5M, respectively. (in the case of concentrations of 2.3M or higher, the resulting electrolyte is no longer a liquid electrolyte. It behaves more like a solid in nature, and is therefore the term "quasi-solid") then, RGO or CNT filaments are dispersed in the electrolyte to form a filament-electrolyte suspension. Mechanical shear is used to help form a uniform dispersion. (the filament-electrolyte suspension is quite viscous even at low salt concentrations of 1.0M). The cathode active material LFP particles are then dispersed in the filament-electrolyte suspension to form a quasi-solid polymer electrode material.

Sequence 2 (S2): firstly, liBF is put ₄ The salt and PEO were dissolved in a mixture of PC and DOL to form a solution with 1, respectively.Electrolytes at salt/polymer combination concentrations of 0M, 2.5M and 3.5M. Then, the cathode active material LFP particles are dispersed in the electrolyte to form an active particle-electrolyte suspension. Mechanical shear is used to help form a uniform dispersion. (the active particle-electrolyte suspension is quite viscous even at low salt concentrations of 1.0M). RGO or CNT filaments are then dispersed in the active particle-electrolyte suspension to form a quasi-solid polymer electrode material.

Sequence 3 (S3): first, a desired amount of RGO or CNT filaments are dispersed in a liquid solvent mixture (PC + DOL) that does not contain a dissolved lithium salt or polymer therein. Mechanical shearing is used to help form a uniform suspension of the conductive filaments in the solvent. Then LiBF is added ₄ Salt, PEO and LFP particles are added to the suspension, allowing for LiBF ₄ The salt and PEO were dissolved in the solvent mixture of the suspension to form electrolytes having salt/polymer combination concentrations of 1.0M, 2.5M, and 3.5M, respectively. Simultaneously or subsequently, LFP particles are dispersed in an electrolyte to form a deformable quasi-solid electrode material consisting of active material particles and conductive filaments dispersed in a quasi-solid polymer electrolyte (not a liquid electrolyte and not a solid electrolyte). In the quasi-solid electrode material, the conductive filaments are percolated to form a 3D network of electron conducting pathways. The 3D conductive network is maintained when the electrode material is formed into an electrode of a battery.

The conductivity of the electrodes was measured using a four-point probe method. The results are summarized in fig. 5 (a) and 5 (B). These data indicate that, except for the electrode made by following sequence 3 (S3), no percolation of the 3D network of conductive filaments (CNF or RGO) used to form the electron conduction path occurs until the volume fraction of conductive filaments exceeds 10% -12%. In other words, the step of dispersing the conductive filaments in the liquid solvent must be performed before dissolving the lithium salt, sodium salt, or ion-conducting polymer in the liquid solvent and before dispersing the active material particles in the solvent. Such a sequence may also bring the percolation threshold as low as 0.3% -2.0%, so that conductive electrodes can be produced by using very small amounts of conductive additives, and thus higher proportions of active material (and higher energy density). To date, these observations have been found to be consistent with all types of electrodes containing active material particles, conductive filaments, and electrolyte. This is a crucial and unexpected process requirement for the preparation of high performance alkali metal batteries with both high energy density and high power density.

The quasi-solid cathode, porous separator and quasi-solid anode (prepared in a similar manner but with artificial graphite particles as the anode active material) were then assembled together to form a unit cell, which was then enclosed in a protective casing (laminated aluminum plastic pouch) with two terminals protruding outward to produce a battery. Cells containing liquid or polymer gel electrolytes (1M) and quasi-solid polymer electrolytes (2.5M and 3.5M) were fabricated and tested.

For comparison purposes, a slurry coating and drying procedure was performed to produce a conventional electrode. An anode and a cathode, and a separator disposed between the two electrodes, were then assembled and encapsulated in an Al plastic laminate encapsulation envelope, and then injected with liquid electrolyte to form a prior art lithium battery cell. The cell test results are summarized in example 19.

Example 9: v as an example of a transition metal oxide cathode active material for a lithium battery ₂ O ₅

V alone ₂ O ₅ Powders are commercially available. To prepare graphene-loaded V ₂ O ₅ Powder samples, in a typical experiment, were prepared by mixing V ₂ O ₅ Mixing in an aqueous solution of LiCl to obtain a vanadium pentoxide gel. Li obtained by interaction with LiCl solution (Li: V molar ratio kept at 1 ⁺ The exchange gel was mixed with the GO suspension and then placed in a teflon lined stainless steel 35ml autoclave, sealed, and heated up to 180 ℃ for 12h. After such hydrothermal treatment, the green solid was collected, thoroughly washed, sonicated for 2 minutes, and dried at 70 ℃ for 12 hours, then mixed with another 0.1% GO in water, sonicated to decompose the nanobelt size, and then spray-dried at 200 ℃ to obtain graphene-surrounded composite microparticles。

V was then treated using both the method of the invention and conventional slurry coating, drying and lamination procedures ₂ O ₅ Powder and graphene loaded V ₂ O ₅ The powders are both separately incorporated into the cell along with a conductive additive (CNT) and a liquid electrolyte.

Example 10: liCoO as an example of a lithium transition metal oxide cathode active material for lithium ion batteries ₂

Commercially available LiCoO ₂ The powder and multi-walled carbon nanotubes (MW-CNTs) are dispersed in a quasi-solid polymer electrolyte to form a quasi-solid electrode. Two types of quasi-solid anodes were prepared to couple with the cathode. One containing graphite particles as an anode active material and the other containing graphene-surrounded Si nanoparticles as an anode active material. The electrolyte solvent used was EC-VC (80/20 ratio) and LiBOB + PEO was dissolved in the organic solvent to form a quasi-solid polymer electrolyte. Each cell contains a quasi-solid anode, a separator layer, and a quasi-solid cathode assembled together and then hermetically sealed.

On a separate basis, liCoO ₂ The powder, MW-CNT and PVDF resin binder were dispersed in NMP solvent to form a slurry, which was coated on both sides of the AL foil current collector and then dried under vacuum to form the cathode layer. Graphite particles and a PVDF resin binder were dispersed in an NMP solvent to form a slurry, which was coated on both sides of a Cu foil current collector and then dried under vacuum to form an anode layer. The anode layer, separator, cathode layer were then laminated and encapsulated in an Al plastic housing, into which a liquid electrolyte was injected to form a conventional lithium ion battery.

Example 11: organic material (Li) as cathode active material of lithium metal battery ₂ C ₆ O ₆ )

To synthesize dilithium rhodizoate (Li) ₂ C ₆ O ₆ ) Rhodobrown acid dihydrate (species 1 in the scheme below) was used as precursor. Basic lithium salt Li ₂ CO ₃ Can be used for neutralizing two ene diol acids (enediolic a) in aqueous mediumcid) functional group. Strictly stoichiometric amounts of the two reactants (rhodizonic acid and lithium carbonate) were allowed to react for 10 hours to achieve a yield of 90%. Dilithium rhodizonate (species 2) is readily soluble even in small amounts of water, which means that there are water molecules in species 2. Water was removed in vacuo at 180 ℃ for 3 hours to give the anhydrous form (species 3).

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

It can be noted that formula Li ₂ C ₆ O ₆ Are part of a fixed structure and they do not participate in reversible lithium ion storage and release. This means that lithium ions must come from the anode side. Thus, a lithium source (e.g., lithium metal or lithium metal alloy) must be present at the anode. As shown in fig. 1 (D), the anode current collector (Cu foil) is deposited with a lithium layer (e.g., by sputtering or electrochemical plating, or by using a lithium foil). This is followed by assembling the lithium coating layer, porous separator, and quasi-solid cathode into a cell. A cathode active material and a conductive additive (Li) ₂ C ₆ O ₆ the/C composite particles + CNF) are dispersed in the liquid electrolyte. For comparison, corresponding conventional Li metal cells were also fabricated by conventional slurry coating, drying, lamination, encapsulation and electrolyte injection procedures.

Example 12: metal naphthalocyanine-RGO hybrid cathode for lithium metal batteries

Copper phthalocyanine (CuPc) coated graphene sheets were obtained by evaporating CuPc in a chamber along with a graphene film (5 nm) prepared from a spin-coated RGO-water suspension. Cutting and grinding the resulting coated film to produce CuPc-coated graphene sheets, which are used as cathode active materials in lithium metal batteries having lithium as an anode active materialMetal foil and 1.0M and 3.0M LiClO in Propylene Carbonate (PC) solution as electrolyte ₄ And PEO. Example 13: moS as cathode active material for lithium metal batteries ₂ Preparation of/RGO hybrid materials

In this example, various inorganic materials were studied. For example, by (NH) ₄ ) ₂ MoS ₄ And hydrazine in N, N-Dimethylformamide (DMF) solution of Graphene Oxide (GO) at 200 ℃ to synthesize ultrathin MoS ₂ the/RGO hybrid. In a typical procedure, 22mg of (NH) ₄ ) ₂ MoS ₄ To 10mg GO dispersed in 10ml DMF. The mixture was sonicated at room temperature for approximately 10min until a clear and homogeneous solution was obtained. Thereafter, 0.1ml of N was added ₂ H ₄ ·H ₂ And O. The reaction solution was further sonicated for 30min before being transferred to a 40mL teflon lined autoclave. The system was heated in an oven at 200 ℃ for 10h. The product was collected by centrifugation at 8000rpm for 5min, washed with DI water and re-collected by centrifugation. The washing step was repeated at least 5 times to ensure removal of most of the DMF. Finally, the dried product is mixed with some carbon fibers and a quasi-solid Polymer (PAN) electrolyte to form a deformable quasi-solid cathode. Example 14: two-dimensional (2D) layered Bi ₂ Se ₃ Preparation of chalcogenide nanoribbons

(2D) Layered Bi ₂ Se ₃ The preparation of chalcogenide nanoribbons is well known in the art. For example, growing Bi using the vapor-liquid-solid (VLS) method ₂ Se ₃ A nanoribbon. On average, the nanoribbons produced herein are 30-55nm thick, with widths and lengths ranging from hundreds of nanometers to several microns. The longer nanobelts were subjected to ball milling to reduce the lateral dimensions (length and width) to below 200nm. The nanoribbons prepared by these procedures and graphene sheets or expanded graphite flakes are combined with a quasi-solid polymer electrolyte to form a deformable cathode for a lithium metal battery.

Example 15: MXene powder + chemically activated RGO

MXene is selected from metal carbides such as Ti ₃ AlC ₂ In the form of a layer knotProduced by partially etching away some elements. For example, 1M NH is used at room temperature ₄ HF ₂ Aqueous solution as Ti ₃ AlC ₂ The etchant of (4). Typically, MXene surfaces are terminated by O, OH and/or F groups, why they are often referred to as M _n+1 X _n T _x Wherein M is the preceding transition metal, X is C and/or N, T represents an end-capping group (O, OH and/or F), N =1, 2 or 3 and X is the number of end-capping groups. MXene materials studied included Ti ₂ CT _x 、Nb ₂ CT _x 、V ₂ CT _x 、Ti ₃ CNT _x And Ta ₄ C ₃ T _x . Typically, 2% -35% graphene sheets are mixed in a solvent, followed by the addition of 35% -95% mxene, some Li/Na salt, and polymer to form a quasi-solid electrolyte based cathode that is deformable, conformable, and electrically conductive.

Example 16: graphene-loaded MnO ₂ Preparation of cathode active Material

MnO ₂ The powder was synthesized by two methods, each with or without graphene sheets present. In one method, 0.1mol/L KMnO is prepared by dissolving potassium permanganate in deionized water ₄ An aqueous solution. While 13.32g of a high purity sodium bis (2-ethylhexyl) sulfosuccinate surfactant was added to 300mL of isooctane (oil) and stirred well to obtain an optically clear solution. Then, 32.4mL of 0.1mol/L KMnO was added ₄ The solution and a selected amount of GO solution were added to the solution, which was sonicated for 30min to prepare a dark brown precipitate. The product was isolated, washed several times with distilled water and ethanol, and dried at 80 ℃ for 12h. The sample is graphene-supported MnO in powder form ₂ Which is dispersed in the CNT-containing electrolyte along with the lithium salt and PEO to form a quasi-solid polymer electrolyte-based cathode electrode.

Example 17: graphene-enhanced nano-silicon as anode active material for lithium ion battery

Graphene-coated Si particles are available from anchorine intense Energy co, dayton, ohio. Quasi-solid anode electrodeThe electrode is prepared by the following method: pristine graphene sheets (as conductive filaments) were dispersed in a PC-DOL (50/50 ratio) mixture, followed by graphene-coated Si particles (anode active material) and 3.5M lithium hexafluorophosphate (LiPF) at 60 ℃ ₆ ) Dissolved in the mixture solvent. Then, DOL was removed to obtain a mixture containing about 5.0M LiPF in PC ₆ The quasi-solid electrolyte of (1). Since LiPF is known at room temperature ₆ The maximum solubility in PC is less than 3.0M, so this renders LiPF ₆ In an oversaturated state.

Example 18: cobalt oxide (Co) as anode active material ₃ O ₄ ) Microparticles

Despite the LiCoO ₂ Is a cathode active material, co ₃ O ₄ Is an anode active material of a lithium ion battery because of LiCoO ₂ In relation to Li/Li ⁺ Electrochemical potential of about +4.0 volts, and Co ₃ O ₄ In relation to Li/Li ⁺ An electrochemical potential of about +0.8 volts.

Adding proper amount of inorganic salt Co (NO) ₃ ) ₂ ·6H ₂ O and subsequent ammonia solution (NH) ₃ ·H ₂ O,25 wt.%) was slowly added to the GO suspension. The resulting precursor suspension was stirred under a stream of argon for several hours to ensure complete reaction. The obtained Co (OH) ₂ Graphene precursor suspension was filtered and dried at 70 ℃ under vacuum to obtain Co (OH) ₂ A graphene composite precursor. The precursor was calcined in air at 450 ℃ for 2h to form Co ₃ O ₄ A graphene composite material, which is mixed into a quasi-solid polymer electrolyte to prepare a quasi-solid electrode.

Example 19: graphene-enhanced tin oxide microparticles as anode active materials

Using the following procedure with SnCl ₄ ·5H ₂ Controlled hydrolysis of O with NaOH to obtain tin oxide (SnO) ₂ ) Nano-particles: snCl ₄ ·5H ₂ O (0.95g, 2.7 m-mol) and NaOH (0.212g, 5.3 m-mol) were each dissolved in 50mL of distilled water. The NaOH solution was added dropwise to the tin chloride solution at a rate of 1mL/min with vigorous stirring. By sonicating 5min homogenizes the solution. Subsequently, the resulting hydrosol was reacted with GO dispersion for 3 hours. To the mixed solution was added a few drops of 0.1M H ₂ SO ₄ To flocculate the product. The precipitated solid was collected by centrifugation, washed with water and ethanol and dried in vacuo. The dried product was heat-treated at 400 ℃ for 2h under an Ar atmosphere and used as an anode active material.

Example 20: preparation and electrochemical testing of various battery cells

For most of the anode and cathode active materials studied, we used both the inventive method and the conventional method to prepare lithium ion or lithium metal cells.

In the case of conventional processes, a typical anode composition comprises 85wt.% active material (e.g., si-or Co) dissolved in N-methyl-2-pyrrolidone (NMP) ₃ O ₄ Coated graphene sheets), 7wt.% acetylene black (Super-P) and 8wt.% polyvinylidene fluoride binder (PVDF, 5wt.% solids content). After coating the slurry on the Cu foil, the electrode was dried in vacuo at 120 ℃ for 2h to remove the solvent. In the case of the process of the present invention, a binder resin is typically not needed or used, thereby saving 8% by weight (reduced amount of inactive material). A cathode layer was prepared in a similar manner (using Al foil as the cathode current collector) using conventional slurry coating and drying procedures. The anode layer, separator layer (e.g., celgard 2400 membrane), and cathode layer are then laminated together and placed in a plastic-Al envelope. For example, the cells were then infused with 1M LiPF dissolved in a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1 ₆ An electrolyte solution. In some cells, an ionic liquid is used as the liquid electrolyte. The cell assembly was made in an argon filled glove box.

In the method of the present invention, preferably, the quasi-solid anode, the porous separator, and the quasi-solid cathode are assembled in a protective housing. The bag is then sealed.

Cyclic Voltammetry (CV) measurements were performed using an Abin electrochemical workstation at a typical scan rate of 1 mV/s. In addition, the electrochemical performance of each cell was also evaluated by constant current charge/discharge cycling at current densities from 50mA/g to 10A/g. For long-term cycling tests, a multi-channel battery tester manufactured by LAND was used.

Example 21: representative test results

For each sample, several current densities (representing charge/discharge rates) were applied to determine the electrochemical response, allowing the energy density values and power density values required to construct a ravigneaux plot (power density versus energy density) to be calculated. A charpy plot (gravimetric power density versus energy density) of a lithium ion battery cell containing graphite particles as the anode active material and carbon-coated LFP particles as the cathode active material is shown in fig. 6. Three of the 4 data curves are for cells prepared according to embodiments of the present invention (with sequences S1, S2, and S3, respectively), while the remaining one is a cell prepared by conventional electrode paste coating (roll coating). From these data several important observations can be drawn:

the gravimetric energy density and power density of lithium ion battery cells prepared by the method of the present invention are both significantly higher than the gravimetric energy density and power density of their counterparts (denoted "conventional") prepared by conventional roll coating methods. The change from 160 μm anode thickness (coated on a flat solid Cu foil) to 420 μm thickness and the corresponding change of the cathode to maintain the balanced capacity ratio resulted in an increase in gravimetric energy density from 161Wh/kg to 226Wh/kg (S1), 227Wh/kg (S2), and 264Wh/kg (S3), respectively. It is also surprising that batteries containing the quasi-solid electrodes of the invention with a 3D network of electron conducting pathways (due to percolation of the conductive filaments) give significantly higher energy densities and higher power densities.

These large differences cannot be simply attributed to the increase in electrode thickness and mass loading. The differences may be due to the significantly higher active material mass loading (not only mass loading) and higher conductivity associated with the cells of the invention, the reduced proportion of non-contributing (inactive) components relative to the active material weight/volume, and the unexpectedly better utilization of the electrode active material (most if not all of the graphite particles and LFP particles contribute to lithium ion storage capacity due to higher conductivity and the absence of drying pockets or dead spots in the electrode, especially under high charge/discharge rate conditions).

Fig. 7 shows the ralong plots (weight power density versus weight energy density) for two cells, both containing graphene-surrounded Si nanoparticles as anode active material and LiCoO ₂ The nanoparticles serve as a cathode active material. Experimental data were obtained from Li-ion battery cells prepared by the method of the invention and Li-ion battery cells prepared by conventional electrode slurry coating.

These data indicate that the gravimetric energy density and power density of the battery cells prepared by the inventive process are significantly higher than their counterparts prepared by conventional processes. Also, the differences are large. The conventionally prepared cells exhibited a gravimetric energy density of 265Wh/kg, but the cells of the present invention were given energy densities of 382Wh/kg (S1) and 420Wh/kg (S3), respectively. For lithium ion batteries, power densities of up to 1425W/kg and 1,650W/kg are also unprecedented.

These energy density and power density differences are primarily due to the high active material mass loading (in the anode) associated with the cells of the present invention>25mg/cm ² And in the cathode>45mg/cm ² ) And high electrode conductivity, reduced proportion of non-contributing (inactive) components relative to the active material weight/volume, and the ability of the inventive method to better utilize the active material particles (all particles being liquid electrolyte and accessible by fast ionic and electronic kinetics).

FIG. 8 shows dilithium rhodizonate (Li) containing a lithium foil as an anode active material ₂ C ₆ O ₆ ) As cathode active material and lithium salt (LiPF) ₆ ) Latte plot of lithium metal batteries with PC/DEC as organic electrolyte (both 1.5M and 5.0M). According to the sequence S2 and S3 as described in example 8, a quasi-solid electrode was prepared. The data are for three lithium metal cells prepared by the method of the invention and lithium metal cells prepared by conventional electrode slurry coating.

These data indicate that the gravimetric energy density and power density of lithium metal cells prepared by the inventive process are significantly higher than their counterparts prepared by conventional processes. Again, the differences are large and may be due to the significantly higher active material mass loading (not just mass loading) and higher conductivity associated with the electrodes of the invention, the reduced proportion of non-contributing (inactive) components relative to the active material weight/volume, and the unexpectedly better utilization of the electrode active material (most if not all of the active material contributes to lithium ion storage capacity due to higher conductivity and no dry pockets or dead spots in the electrode, especially under high charge/discharge rate conditions).

Quite noteworthy and unexpected are the following observations: the gravimetric energy density of the lithium metal-organic cathode cells of the present invention is as high as 502Wh/kg, higher than that reported for all rechargeable lithium metal or lithium ion batteries (recall that current Li-ion batteries store 150-220Wh/kg based on total cell weight). Furthermore, for lithium batteries based on organic cathode active materials, a gravimetric power density of 1,578W/kg is not imaginable. Cells containing quasi-solid electrodes prepared according to sequence 3 exhibited significantly higher energy and power densities than cells of conventional sequence S2. In addition, higher concentrations of electrolyte (quasi-solid electrolyte) are surprisingly more favorable for achieving higher energy and power densities.

The above performance characteristics of lithium batteries are also observed with respect to the corresponding sodium batteries. Due to the page limitation, data for the sodium cell is no longer presented here. However, for example, fig. 9 indicates the ralong plots for two sodium ion capacitors, each containing pre-sodiated hard carbon particles as the anode active material and graphene sheets as the cathode active material; one cell has an anode prepared by a conventional slurry coating process and the other cell has a quasi-solid anode prepared according to the method of the invention. Also, quasi-solid electrode based cells give significantly higher energy densities and higher power densities. Lithium ion capacitors were found to follow a similar trend.

It is important to note that reporting the energy density and power density per weight of active material alone on a raleigh plot, as done by many researchers, may not give a realistic picture of the performance of an assembled supercapacitor cell. The weight of the other apparatus components must also be taken into account. These non-contributing components, including current collectors, electrolytes, separators, adhesives, connectors, and encapsulants, are inactive materials and do not contribute to charge storage capacity. They merely add weight and bulk to the device. Therefore, it is desirable to reduce the relative proportion of the non-contributing components by weight and to increase the active material proportion. However, this goal has not been possible using conventional battery production methods. The present invention overcomes this long standing most serious problem in the field of lithium batteries.

In commercial lithium ion batteries with electrode thicknesses of 100-200 μm, the weight proportion of anode active material (e.g. graphite or carbon) in the lithium ion battery is typically from 12% to 17%, and the weight proportion of cathode active material (for inorganic materials, such as LiMn ₂ O ₄ ) From 22% to 41%, or from 10% to 15% for organic or polymeric materials. Therefore, a factor of 3 to 4 is often used to extrapolate the energy or power density of the device (cell) from the properties based on the weight of the active material alone. In most scientific papers, the reported properties are typically based on the active material weight alone, and the electrodes are typically very thin (c: (b) (c))<<100 μm, and most<<50 μm). The active material weight is typically from 5% to 10% of the total device weight, which means that the actual cell (device) energy density or power density can be obtained by dividing the corresponding value based on the active material weight by a factor of 10 to 20. Taking this factor into account, the properties reported in these papers do not actually appear to be better than those of commercial batteries. Therefore, great care must be taken in reading and interpreting the performance data of batteries reported in scientific papers and patent applications.

Claims

1. An alkali metal cell, comprising:

(a) A quasi-solid cathode containing 30 to 95% by volume of a cathode active material, 5 to 40% by volume of a first electrolyte containing an alkali metal salt and an ionically conductive polymer dissolved or dispersed in a solvent, wherein the first electrolyte is a quasi-solid polymer electrolyte and the alkali metal salt and the ionically conductive polymer concentration is higher than 2.5M, and 0.01 to 30% by volume of a conductive additive, wherein the conductive additive containing conductive filaments forms a 3D network of electron conducting pathways, whereby the quasi-solid cathode has from 10 to 95% by volume ^-6 Conductivity of S/cm to 300S/cm;

(b) An anode; and

(c) An ion-conducting membrane or porous separator disposed between the anode and the quasi-solid cathode; wherein the quasi-solid cathode has a thickness of not less than 200 μm.

2. The alkali metal cell of claim 1, wherein the anode comprises a quasi-solid anode comprising 30% to 95% by volume of an anode active material, 5% to 40% by volume of a second electrolyte comprising an alkali metal salt dissolved or dispersed in a solvent and an ionically conductive polymer, and 0.01% to 30% by volume of a conductive additive, wherein the conductive additive comprising conductive filaments forms a 3D network of electron conducting pathways, thereby providing the quasi-solid anode with from 10 ^-6 Conductivity of S/cm to 300S/cm; wherein the quasi-solid anode has a thickness of not less than 200 μm.

3. The alkali metal cell of claim 1, wherein the first electrolyte comprises the quasi-solid polymer electrolyte comprising an ion-conducting polymer selected from: having a refractive index of less than 1x10 ⁶ Polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), poly (bis-methoxyethoxyethanol-phosphazene), polyvinyl chloride, polydimethylsiloxane, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, and the likeA sulfonated polymer, or a combination thereof.

4. The alkali metal cell of claim 2, wherein the first electrolyte or the second electrolyte comprises a quasi-solid polymer electrolyte comprising an ionically conductive polymer selected from: having a refractive index of less than 1x10 ⁶ Polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), poly bis (methoxyethoxyethanol) phosphazene, polyvinyl chloride, polydimethylsiloxane, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof in g/mol molecular weight.

5. The alkali metal cell of claim 1, wherein the ionically conductive polymer is selected from the group consisting of: polyperfluorosulfonic acid, sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated polyetherketone, sulfonated polyetheretherketone, sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated Polychlorotrifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymers (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymers (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymers of polyvinylidene fluoride with hexafluoropropylene and tetrafluoroethylene, sulfonated copolymers of Ethylene and Tetrafluoroethylene (ETFE), sulfonated Polybenzimidazole (PBI), chemical derivatives, copolymers, blends, and combinations thereof.

6. The alkali metal cell of claim 2, wherein the ionically conductive polymer is selected from the group consisting of: polyperfluorosulfonic acid, sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated polyetherketone, sulfonated polyetheretherketone, sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated Polychlorotrifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymers (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymers (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymers of polyvinylidene fluoride with hexafluoropropylene and tetrafluoroethylene, sulfonated copolymers of Ethylene and Tetrafluoroethylene (ETFE), sulfonated Polybenzimidazole (PBI), chemical derivatives, copolymers, blends, and combinations thereof.

7. The alkali metal cell of claim 1, wherein the electrically conductive filaments are selected from carbon fibers, carbon nanotubes, needle coke, carbon whiskers, electrically conductive polymer fibers, electrically conductive material coated fibers, metal wires, combinations thereof, or combinations thereof with non-filament electrically conductive particles.

8. The alkali metal cell of claim 1, wherein the ionically conductive polymer does not form a matrix in the quasi-solid cathode.

9. The alkali metal cell of claim 1, wherein the quasi-solid cathode is maintained from 10 ^-3 A conductivity of S/cm to 10S/cm.

10. The alkali metal cell of claim 1, wherein the conductive filaments are bonded together at intersections between the conductive filaments by a resin.

11. The alkali metal cell of claim 1, wherein the quasi-solid cathode comprises 0.1% to 20% by volume of a conductive additive.

12. The alkali metal cell of claim 1, wherein the quasi-solid cathode comprises 1% to 10% by volume of a conductive additive.

13. The alkali metal cell of claim 1, wherein the amount of cathode active material comprises from 40% to 90% by volume of the quasi-solid cathode.

14. The alkali metal cell of claim 1, wherein the amount of cathode active material comprises 50% to 85% by volume of the quasi-solid cathode.

15. The alkali metal cell of claim 1, wherein the first electrolyte is in a supersaturated state.

16. The alkali metal cell of claim 2, wherein the first electrolyte or the second electrolyte is in a supersaturated state.

17. 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.

18. The alkali metal cell of claim 2, wherein the first electrolyte or the second electrolyte comprises a solvent selected from the group consisting of: water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid.

19. The alkali metal cell of claim 2, wherein the alkali metal cell is a lithium metal cell, or a lithium ion cell, and the anode active material is selected from the group consisting of:

(a) Particles of lithium metal or lithium metal alloy;

(b) Natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), needle coke, carbon nanotubes, and carbon 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) Alloys or intermetallic compounds of Si, ge, sn, pb, sb, bi, zn, al, or Cd with other elements, wherein the alloys or compounds are stoichiometric or non-stoichiometric;

(e) Oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, ge, sn, pb, sb, bi, zn, al, fe, ni, co, ti, mn, or Cd, and mixtures or composites thereof;

(f) A prelithiated version thereof;

(g) Pre-lithiated graphene sheets; and

combinations thereof.

20. The alkali metal cell of claim 19, wherein the pre-lithiated graphene sheets are selected from pre-lithiated versions of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, physical or chemical activation or etching versions thereof, or combinations thereof.

21. The alkali metal cell of claim 2, wherein the alkali metal cell is a sodium metal cell, or a sodium ion cell, and the anode active material comprises an alkali intercalation compound selected from: petroleum coke, carbon black, active carbon, template carbon, hollow carbon nano wire, hollow carbon ball, titanate and 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 Materials based on carboxylic acid salts, C ₈ H ₆ O ₄ 、C ₈ H ₅ NaO ₄ 、C ₈ Na ₂ F ₄ O ₄ 、C ₁₀ H ₂ Na ₄ O ₈ 、C ₁₄ H ₄ O ₆ 、C ₁₄ H ₄ Na ₄ O ₈ Or a combination thereof, wherein x =0.2 to 1.0.

22. The alkali metal cell of claim 2, wherein the alkali metal cell is a sodium metal cell, or a sodium ion cell, and the anode active material is selected from the group consisting of:

a) Particles of sodium metal or sodium metal alloy;

b) Natural graphite particles, artificial graphite particles, mesocarbon microbeads (MCMB), needle coke, carbon nanotubes, and carbon 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 intermetallics 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, selenides, tellurides, or antimonides of Si, ge, sn, pb, sb, bi, zn, al, fe, ti, co, ni, mn, cd, and mixtures or composites thereof;

f) A sodium salt;

g) Graphene sheets pre-loaded with sodium ions; and combinations thereof.

23. The alkali metal cell of claim 1, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell and the cathode active material comprises a lithium intercalation compound selected from the group consisting of: 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 iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, metal sulfides, and combinations thereof.

24. The alkali metal cell of claim 1, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell and the cathode active material comprises a lithium intercalation compound or a lithium absorption compound selected from: inorganic materials, organic materials, or combinations thereof.

25. The alkali metal cell of claim 24, wherein the inorganic material comprises a metal oxide, a metal phosphate, a metal sulfide, or a combination thereof.

26. The alkali metal cell of claim 25, wherein the metal oxide, metal phosphate, or metal sulfide is selected from 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 sulfide, or a combination thereof.

27. The alkali metal cell of claim 24, wherein the inorganic material is selected from sulfur, lithium polysulfide, transition metal dichalcogenide, transition metal trichalcogenide, or a combination thereof.

28. The alkali metal cell of claim 24, 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.

29. The alkali metal cell of claim 25, wherein the metal oxide, metal phosphate, or metal sulfide comprises a vanadium oxide selected from the group consisting of: VO (volatile organic compound) 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, wherein 0.1<x<5。

30. The alkali metal cell of claim 25, wherein the metal oxide, metal phosphate, or metal sulfide is selected from the layered compound LiMO ₂ Spinel type compound LiM ₂ O ₄ An olivine-type compound LiMPO ₄ Silicate compound Li ₂ MSiO ₄ Lithium iron phosphate iron petrochemical compound LiMPO ₄ F. Borate compound LiMBO ₃ Or combinations thereof, wherein M is a transition metal or transition metalsA mixture of genera.

31. The alkali metal cell of claim 24, wherein the inorganic material is selected from: (ii) a sulfide, selenide, or telluride of (a) bismuth selenide or telluride, (b) a disulfide or trisulfide of a transition metal, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, or nickel; (d) boron nitride, or (e) a combination thereof.

32. The alkali metal cell of claim 24, wherein the organic material is selected from the group consisting of a polyanthraquinone sulfide (PAQS), 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA), a polyanthraquinone sulfide, pyrene-4, 5,9, 10-tetraone (PYT), a polymer-bonded PYT, a quinotriazene, a Tetracyanoquinodimethane (TCNQ), a Tetracyanoethylene (TCNE), 2,3,6,7,10, 11-Hexamethoxytriphenylene (HMTP), a poly 5-amino-1, 4-dihydroxyanthraquinone (PADAQ), a phosphazene disulfide polymer ([ (NPS), and a polymer of phosphonitrile ₂ ) ₃ ]n), lithiated 1,4,5, 8-naphthalenetetraol formaldehyde polymers, hexaazatrinaphthalene (HATN), hexaazatriphenylene hexacarbonitrile (HAT (CN) ₆ ) 5-benzylidenehydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi) ₄ ) N, N ' -diphenyl-2, 3,5, 6-tetraone piperazine (PHP), N ' -diallyl-2, 3,5, 6-tetraone piperazine (AP), N ' -dipropyl-2, 3,5, 6-tetraone piperazine (PRP), 1, 4-benzoquinone, 5,7,12, 14-Pentacenetetraketone (PT), 5-amino-2, 3-dihydro-1, 4-dihydroxyanthraquinone (ADD), 5-amino-1, 4-dihydroxyanthraquinone (ADAQ), quinoid calixarene, li AQ ₄ C ₆ O ₆ 、Li ₂ C ₆ O ₆ 、Li ₆ C ₆ O ₆ Or a combination thereof.

33. An alkali metal cell according to claim 32, wherein the organic material comprises a thioether polymer selected from poly [ methanetrinitrobenzylnitroaniline-tetrakis (thiomethylene) ] (PMTTM), poly 2, 4-dithiopentene (PDTP), a polymer comprising polyethylene-1, 2-tetrathiol (PETT) as a backbone thioether polymer, a pendant thioether polymer having a backbone consisting of conjugated aromatic moieties and having thioether side chains as side chains, poly 2-phenyl-1, 3-dithiolane (PPDT), poly 1, 4-bis (1, 3-dithiolane-2-yl) benzene (PDDTB), polytetrahydrobenzodithiophene (PTHBDT), poly [1,2,4, 5-tetrakis (propylthio) benzene ] (PTKPTB), or poly [3,4 (ethylenedithio) thiophene (PEDTT).

34. The alkali metal cell of claim 24, wherein the organic material comprises a phthalocyanine compound selected from: copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, chromium phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanines, chemical derivatives thereof, or combinations thereof.

35. The alkali metal cell of claim 24, wherein the lithium intercalation compound or lithium-absorbing compound is selected from a metal carbide, a metal nitride, a metal boride, a metal dichalcogenide, or a combination thereof.

36. The alkali metal cell of claim 24, wherein the lithium intercalation compound or lithium-absorbing compound is selected from an oxide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in nanowire, nanodisk, nanoribbon, or nanoplatelet form.

37. The alkali metal cell of claim 24, wherein the lithium intercalation compound or lithium-absorbing compound is selected from a nanodisk, nanoplatelet, or nanocoating of an inorganic material selected from: (ii) (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenides or trichalcogenides, (c) sulfides, selenides, or tellurides of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, or nickel; (d) boron nitride, or (e) a combination thereof; wherein the disc, platelet or sheet has a thickness of less than 100 nm.

38. The alkali metal cell of claim 1, wherein the alkali metal cell is a sodium metal cell or a sodium ion cell and the cathode active material comprises a sodium intercalation compound or a sodium-absorbing compound selected from: inorganic materials, organic materials, or combinations thereof.

39. The alkali metal cell of claim 38, wherein the inorganic material comprises a metal oxide, a metal phosphate, a metal sulfide, or a combination thereof.

40. The alkali metal cell of claim 39, wherein the metal oxide, metal phosphate, or metal sulfide is selected from sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium 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, transition metal sulfide, or a combination thereof.

41. The alkali metal cell of claim 38, wherein the inorganic material is selected from sulfur, lithium polysulfide, transition metal dichalcogenide, transition metal trichalcogenide, or a combination thereof.

42. The alkali metal cell of claim 38, 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.

43. The alkali metal cell of claim 38, wherein the cathode active material comprises a sodium intercalation compound selected from: naFePO ₄ 、Na _(1-x) K _x PO ₄ 、Na _0.7 FePO ₄ 、Na _1.5 VOPO ₄ F _0.5 、Na ₃ V ₂ (PO ₄ ) ₃ 、Na ₃ V ₂ (PO ₄ ) ₂ F ₃ 、Na ₂ FePO ₄ F、NaFeF ₃ 、NaVPO ₄ F、Na ₃ V ₂ (PO ₄ ) ₂ F ₃ 、Na _1.5 VOPO ₄ F _0.5 、Na ₃ V ₂ (PO ₄ ) ₃ 、NaV ₆ O ₁₅ 、Na _x VO ₂ 、Na _0.33 V ₂ O ₅ 、Na _x CoO ₂ 、Na _2/3 [Ni _1/3 Mn _2/3 ]O ₂ 、Na _x (Fe _1/2 Mn _1/2 )O ₂ 、Na _x MnO ₂ 、λ-MnO ₂ 、Na _x K _(1-x) MnO ₂ 、Na _0.44 MnO ₂ 、Na _0.44 MnO ₂ /C、Na ₄ Mn ₉ O ₁₈ 、NaFe ₂ Mn(PO ₄ ) ₃ 、Na ₂ Ti ₃ O ₇ 、Ni _1/3 Mn _1/3 Co _1/3 O ₂ 、Cu _0.56 Ni _0.44 HCF、NiHCF、Na _x MnO ₂ 、NaCrO ₂ 、Na ₃ Ti ₂ (PO ₄ ) ₃ 、NiCo ₂ O ₄ 、Ni ₃ S ₂ /FeS ₂ 、Sb ₂ O ₄ 、Na ₄ Fe(CN) ₆ /C、NaV _1-x Cr _x PO ₄ F、Se _z S _y Se, phosphomanalite, or a combination thereof, wherein x is from 0.1 to 1.0, y/z =0.01 to 100.

44. The alkali metal cell of claim 1, wherein the cathode active material comprises greater than 15mg/cm ² Electrode active material mass loading.

45. The alkali metal cell of claim 2, wherein the anode active material comprises greater than 20mg/cm ² Electrode active material mass loading.

46. The alkali metal cell of claim 1, wherein the cathode active material comprises greater than 30mg/cm ² Electrode active material mass loading.

47. An alkali metal cell, comprising:

a) A quasi-solid anode comprising 30 to 95% by volume of an anode active material, 5 to 40% by volume of an electrolyte comprising an alkali metal salt and an ionically conductive polymer dissolved or dispersed in a solvent, and 0.01 to 30% by volume of a conductive additive, wherein the electrolyte is a quasi-solid polymer electrolyte and the alkali metal salt and the ionically conductive polymer are in a concentration of greater than 2.5M, wherein the conductive additive comprising conductive filaments forms a 3D network of electron conducting pathways, whereby the quasi-solid anode has from 10 to 95% by volume ^-6 Conductivity of S/cm to 300S/cm;

b) A cathode; and

c) An ion conducting membrane or porous separator disposed between the quasi-solid anode and the cathode; wherein the quasi-solid anode has a thickness of not less than 200 μm.

48. The alkali metal cell of claim 47, wherein the electrolyte is the quasi-solid electrolyte comprising an ionically conductive polymer selected from the group consisting of: having a refractive index of less than 1x10 ⁶ Polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), poly bis (methoxyethoxyethanol) phosphazene, polyvinyl chloride, polydimethylsiloxane, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof in g/mol molecular weight.

49. The alkali metal cell of claim 47, wherein the ionically conductive polymer is selected from the group consisting of: polyperfluorosulfonic acid, sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated polyetherketone, sulfonated polyetheretherketone, sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated Polychlorotrifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymers (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymers (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymers of polyvinylidene fluoride with hexafluoropropylene and tetrafluoroethylene, sulfonated copolymers of Ethylene and Tetrafluoroethylene (ETFE), sulfonated Polybenzimidazole (PBI), chemical derivatives, copolymers, blends, and combinations thereof.

50. The alkali metal cell of claim 47, wherein the ionically conductive polymer does not form a matrix in the quasi-solid anode.

51. A method of making an alkali metal cell having a quasi-solid electrode, the method comprising:

(a) Combining an amount of active material, an amount of electrolyte, and a conductive additive to form a deformable and conductive electrode material, wherein the conductive additive containing conductive filaments forms a 3D network of electron conducting pathways, and the electrolyte contains an alkali metal salt and an ionically conductive polymer dissolved or dispersed in a solvent;

(b) Forming the electrode material as a quasi-solid electrode, wherein the forming comprises deforming the electrode material into an electrode shape without interrupting the 3D network of electron conduction pathways, thereby causing the electrode to remain no less than 10 ^-6 Conductivity of S/cm;

(c) Forming a second electrode; and is provided with

(d) Forming an alkali metal cell by combining the quasi-solid electrode and the second electrode;

wherein the step of combining and forming the electrode material into a quasi-solid electrode comprises dissolving a lithium salt or sodium salt and the polymer in a liquid solvent to form an electrolyte having a first salt/polymer concentration and subsequently removing a portion of the liquid solvent to increase the first salt/polymer concentration to obtain a quasi-solid polymer electrolyte having a second salt/polymer concentration that is higher than the first salt/polymer concentration and higher than 2.5M.

52. The method of claim 51, wherein the quasi-solid 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.

53. The method of claim 51, wherein the electrolyte comprises a quasi-solid polymer electrolyte comprising an ion conducting polymer selected from the group consisting of: having a refractive index of less than 1x10 ⁶ Polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVdF), poly bis methoxyethoxyethanol-phosphazene, polyvinyl chloride, polydimethylsiloxane, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), sulfonated derivatives thereof, sulfonated polymers, or combinations thereof in g/mol molecular weight.

54. A method according to claim 51, wherein the ion-conducting polymer is selected from the group consisting of: polyperfluorosulfonic acid, sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated polyetherketone, sulfonated polyetheretherketone, sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated Polychlorotrifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymers (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymers (ECTFE), sulfonated polyvinylidene fluoride (PVDF), sulfonated copolymers of polyvinylidene fluoride with hexafluoropropylene and tetrafluoroethylene, sulfonated copolymers of Ethylene and Tetrafluoroethylene (ETFE), sulfonated Polybenzimidazole (PBI), chemical derivatives, copolymers, blends, and combinations thereof.

55. The method of claim 51, wherein the conductive filament is selected from carbon fibers, carbon nanotubes, needle coke, carbon whiskers, conductive polymer fibers, conductive material coated fibers, metal wires, graphene sheets, expanded graphite platelets, combinations thereof, or combinations thereof with non-filament conductive particles.

56. The method of claim 51, wherein the ionically conductive polymer does not form a matrix in the quasi-solid electrode.

57. The method of claim 51, wherein the electrode is held from 10 ^-3 A conductivity of S/cm to 10S/cm.

58. The method of claim 51, wherein the quasi-solid electrode contains 0.1% to 20% by volume of a conductive additive.

59. The method of claim 51, wherein the quasi-solid electrode contains 1% to 10% by volume of a conductive additive.

60. The method of claim 51, wherein the amount of active material is 40% to 90% by volume of the electrode material.

61. The method of claim 51, wherein the amount of active material is 50% to 85% by volume of the electrode material.

62. The method of claim 51, wherein the removing does not cause precipitation or crystallization of the salt or the polymer, and the electrolyte is in a supersaturated state.

63. The method of claim 51, wherein the liquid solvent comprises a mixture of at least a first liquid solvent and a second liquid solvent and the first liquid solvent is more volatile than the second liquid solvent, and wherein the removing a portion of the liquid solvent comprises removing the first liquid solvent.

64. The method of claim 51, wherein the step of forming a second electrode comprises (A) combining an amount of a second active material, an amount of an electrolyte, and a conductive additive to form a second deformable and conductive electrode materialA material in which the conductive additive containing conductive filaments forms a 3D network of electron conducting pathways, and the electrolyte contains an alkali metal salt and an ion conducting polymer dissolved or dispersed in a solvent; and (B) forming the second deformable and conductive electrode material into a second quasi-solid electrode, wherein the forming comprises deforming the second deformable and conductive electrode material into an electrode shape without interrupting the 3D network of electron conduction pathways, thereby causing the second electrode to remain no less than 10 ^- ⁶ Conductivity of S/cm.

65. The method of claim 51, wherein the solvent is selected from water, an organic solvent, an ionic liquid, or a mixture of an organic solvent and an ionic liquid.

66. The method of claim 51, wherein the alkali metal cell is a lithium metal cell, or a lithium ion cell, and the active material is an anode active material selected from the group consisting of:

(a) Particles of lithium metal or lithium metal alloy;

(d) Alloys or intermetallic compounds of Si, ge, sn, pb, sb, bi, zn, al or Cd with other elements, wherein the alloys or compounds are stoichiometric or non-stoichiometric;

(f) A prelithiated version thereof;

(g) Pre-lithiated graphene sheets; and

combinations thereof.

67. The method of claim 66, wherein the pre-lithiated graphene sheets are selected from pre-lithiated versions of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, physically or chemically activated or etched versions thereof, or combinations thereof.

68. The method of claim 51, wherein the alkali metal cell is a sodium metal cell, or a sodium ion cell, and the active material is an anode active material comprising an alkali intercalation compound selected from: petroleum coke, carbon black, active carbon, template carbon, hollow carbon nano-wire, hollow carbon ball, titanate, naTi ₂ (PO ₄ ) ₃ 、Na ₂ Ti ₃ O ₇ 、Na ₂ C ₈ H ₄ O ₄ 、Na ₂ TP、Na _x TiO ₂ Materials based on carboxylic acid salts, C ₈ H ₆ O ₄ 、C ₈ H ₅ NaO ₄ 、C ₈ Na ₂ F ₄ O ₄ 、C ₁₀ H ₂ Na ₄ O ₈ 、C ₁₄ H ₄ O ₆ 、C ₁₄ H ₄ Na ₄ O ₈ Or a combination thereof, wherein x =0.2 to 1.0.

69. The method of claim 51, wherein the alkali metal cell is a sodium metal cell, or a sodium ion cell, and the active material is an anode active material selected from the group consisting of:

a) Particles of sodium metal or sodium metal alloy;

f) A sodium salt;

g) Graphene sheets pre-loaded with sodium ions; and combinations thereof.

70. The method of claim 51, wherein the alkali metal cell is a lithium metal cell or a lithium ion cell and the cathode active material contains a lithium intercalation compound selected from the group consisting of: 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 iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, metal sulfides, and combinations thereof.

71. The method of claim 51, wherein the alkali metal cells are lithium metal cells or lithium ion cells and the cathode active material contains a lithium intercalation compound or a lithium absorbing compound selected from: inorganic materials, organic materials, or combinations thereof.

72. The method of claim 71, wherein the inorganic material comprises a metal oxide, a metal phosphate, a metal sulfide, or a combination thereof.

73. The method of claim 72, wherein the metal oxide, metal phosphate, or metal sulfide is selected from 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 sulfide, or a combination thereof.

74. The method of claim 71, wherein the inorganic material is selected from sulfur, lithium polysulfide, transition metal dichalcogenide, transition metal trichalcogenide, or a combination thereof.

75. 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.

76. The method of claim 72, wherein the metal oxide, metal phosphate, or metal sulfide comprises a vanadium oxide selected from the group consisting of: VO (vacuum vapor volume) 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, wherein 0.1<x<5。

77. The method of claim 72, wherein the metal oxide, metal phosphate, or metal sulfide is selected from the layered compound LiMO ₂ Spinel type compound LiM ₂ O ₄ An olivine-type compound LiMPO ₄ Silicate compound Li ₂ MSiO ₄ Lithium iron phosphate Hydroxyphosphorus Compound LiMPO ₄ F. Borate compound LiMBO ₃ Or combinations thereof, wherein M is a transition metal or a mixture of transition metals.

78. The method of claim 71, wherein the inorganic material is selected from the group consisting of: (ii) a sulfide, selenide, or telluride of (a) bismuth selenide or telluride, (b) a disulfide or trisulfide of a transition metal, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, or nickel; (d) boron nitride, or (e) a combination thereof.

79. The method of claim 71, wherein the organic material is selected from the group consisting of a poly (anthraquinone) sulfide (PAQS), 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA), a poly (anthraquinone) sulfide, pyrene-4, 5,9, 10-tetraone (PYT), a polymer-bonded PYT, a quinotriazene, a Tetracyanoquinodimethane (TCNQ), a Tetracyanoethylene (TCNE), 2,3,6,7,10, 11-Hexamethoxytriphenylene (HMTP), a poly (5-amino-1, 4-dihydroxyanthraquinone) (PADAQ), a phosphazene disulfide polymer ([ (NPS) ₂ ) ₃ ]n), lithiated 1,4,5, 8-naphthalenetetraol formaldehyde polymers, hexaazatrinaphthalene (HATN), hexaazatriphenylene hexacarbonitrile (HAT (CN) ₆ ) 5-benzylidenehydantoin, isatin lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivative (THQLi) ₄ ) N, N ' -diphenyl-2, 3,5, 6-tetraone piperazine (PHP), N ' -diallyl-2, 3,5, 6-tetraone piperazine (AP), N ' -dipropyl-2, 3,5, 6-tetraone piperazine (PRP), 1, 4-benzoquinone, 5,7,12, 14-Pentacenetetraketone (PT), 5-amino-2, 3-dihydro-1, 4-dihydroxyanthraquinone (ADD), 5-amino-1, 4-dihydroxyanthraquinone (ADAQ), quinoid calixarene, li ₄ C ₆ O ₆ 、Li ₂ C ₆ O ₆ 、Li ₆ C ₆ O ₆ Or a combination thereof.

80. The method of claim 79, wherein the organic material comprises a thioether polymer selected from poly [ methanetrinitrobenzylnitroaniline-tetrakis (thiomethylene) ] (PMTTM), poly 2, 4-dithiopentene (PDTP), a polymer comprising polyethylene-1, 2-tetrathiol (PETT) as a backbone thioether polymer, a pendant thioether polymer having a backbone composed of conjugated aromatic moieties and having thioether side chains as side chains, poly 2-phenyl-1, 3-dithiolane (PPDT), poly 1, 4-bis (1, 3-dithiolane-2-yl) benzene (PDDTB), polytetrahydrofenzodithiophene (PTHBDT), poly [1,2,4, 5-tetrakis (propylthio) benzene ] (PTKPTB), or poly [3,4 (ethylenedithio) thiophene ] (PEDTT).

81. The method of claim 71, wherein the organic material comprises a phthalocyanine compound selected from the group consisting of: copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, chromium phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, metal-free phthalocyanines, chemical derivatives thereof, or combinations thereof.

82. The method of claim 71, wherein the lithium intercalation compound or lithium-absorbing compound is selected from a metal carbide, a metal nitride, a metal boride, a metal dichalcogenide, or a combination thereof.

83. The method of claim 71, wherein the lithium intercalation compound or lithium-absorbing compound is selected from an oxide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in nanowire, nanodisk, nanoribbon, or nanoplatelet form.

84. The method of claim 71, wherein the lithium intercalation compound or lithium-absorbing compound is selected from a nanodisk, nanoplatelet, or nanocoating of an inorganic material selected from the group consisting of: (ii) a sulfide, selenide, or telluride of (a) bismuth selenide or telluride, (b) a disulfide or trisulfide of a transition metal, (c) niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, or nickel; (d) boron nitride, or (e) a combination thereof; wherein the disc, platelet or sheet has a thickness of less than 100 nm.

85. The method of claim 51, wherein the alkali metal cells are sodium metal cells or sodium ion cells and the cathode active material comprises a sodium intercalation compound or a sodium absorbing compound selected from: inorganic materials, organic materials, or combinations thereof.

86. The method of claim 85, wherein the inorganic material comprises a metal oxide, a metal phosphate, a metal sulfide, or a combination thereof.

87. The method of claim 86, wherein the metal oxide, metal phosphate, or metal sulfide is selected from sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium 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, potassium sodium vanadium phosphate, transition metal sulfide, or a combination thereof.

88. The method of claim 85, wherein the inorganic material is selected from sulfur, lithium polysulfide, transition metal dichalcogenide, transition metal trichalcogenide, or a combination thereof.

89. The method of claim 85, 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.

90. The method of claim 51, wherein the active material comprises a sodium intercalation compound selected from: naFePO ₄ 、Na _(1-x) K _x PO ₄ 、Na _0.7 FePO ₄ 、Na _1.5 VOPO ₄ F _0.5 、Na ₃ V ₂ (PO ₄ ) ₃ 、Na ₃ V ₂ (PO ₄ ) ₂ F ₃ 、Na ₂ FePO ₄ F、NaFeF ₃ 、NaVPO ₄ F、Na ₃ V ₂ (PO ₄ ) ₂ F ₃ 、Na _1.5 VOPO ₄ F _0.5 、Na ₃ V ₂ (PO ₄ ) ₃ 、NaV ₆ O ₁₅ 、Na _x VO ₂ 、Na _0.33 V ₂ O ₅ 、Na _x CoO ₂ 、Na _2/3 [Ni _1/3 Mn _2/3 ]O ₂ 、Na _x (Fe _1/2 Mn _1/2 )O ₂ 、Na _x MnO ₂ 、λ-MnO ₂ 、Na _x K _(1-x) MnO ₂ 、Na _0.44 MnO ₂ 、Na _0.44 MnO ₂ /C、Na ₄ Mn ₉ O ₁₈ 、NaFe ₂ Mn(PO ₄ ) ₃ 、Na ₂ Ti ₃ O ₇ 、Ni _1/3 Mn _1/3 Co _1/3 O ₂ 、Cu _0.56 Ni _0.44 HCF、NiHCF、Na _x MnO ₂ 、NaCrO ₂ 、Na ₃ Ti ₂ (PO ₄ ) ₃ 、NiCo ₂ O ₄ 、Ni ₃ S ₂ /FeS ₂ 、Sb ₂ O ₄ 、Na ₄ Fe(CN) ₆ /C、NaV _1-x Cr _x PO ₄ F、Se _z S _y Se, phosphomanalite, or a combination thereof, wherein x is from 0.1 to 1.0, y/z =0.01 to 100.

91. The method of claim 51, wherein the active material composition is greater than 15mg/cm ² Electrode active material mass loading.

92. The method of claim 51, wherein the active material composition is greater than 25mg/cm ² Electrode active material mass loading.

93. The method of claim 51, wherein the active material composition is greater than 45mg/cm ² Electrode active material mass loading.