WO2017048341A1 - Alkali metal or alkali-ion batteries having high volumetric and gravimetric energy densities - Google Patents

Alkali metal or alkali-ion batteries having high volumetric and gravimetric energy densities Download PDF

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Publication number
WO2017048341A1
WO2017048341A1 PCT/US2016/038528 US2016038528W WO2017048341A1 WO 2017048341 A1 WO2017048341 A1 WO 2017048341A1 US 2016038528 W US2016038528 W US 2016038528W WO 2017048341 A1 WO2017048341 A1 WO 2017048341A1
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Prior art keywords
sodium
alkali metal
active material
cathode
potassium
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PCT/US2016/038528
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English (en)
French (fr)
Inventor
Aruna Zhamu
Bor Z. Jang
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Nanotek Instruments, Inc.
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Priority claimed from US14/756,509 external-priority patent/US9564656B1/en
Priority claimed from US14/756,510 external-priority patent/US9735445B2/en
Application filed by Nanotek Instruments, Inc. filed Critical Nanotek Instruments, Inc.
Priority to JP2018513330A priority Critical patent/JP7075338B2/ja
Priority to CN201680053196.8A priority patent/CN108292759B/zh
Priority to KR1020187010603A priority patent/KR102644157B1/ko
Publication of WO2017048341A1 publication Critical patent/WO2017048341A1/en

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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention is directed at a primary (non-rechargeable) or secondary (rechargeable) non-lithium alkali battery (including alkali metal and alkali metal-ion cell) having a high volumetric energy density and a high gravimetric energy density.
  • the alkali metal is selected from sodium, potassium, or a mixture of sodium and/or potassium with lithium (but not lithium alone).
  • Li-ion Rechargeable lithium-ion
  • Li metal Li-sulfur, and Li metal-air batteries
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • portable electronic devices such as lap-top computers and mobile phones.
  • Lithium as a metal element has the highest lithium storage capacity (3,861 mAh/g) compared to any other metal.
  • Li metal batteries having a lithium metal anode
  • Li-ion batteries having a graphite anode with a theoretical specific capacity of 372 mAh/g).
  • rechargeable lithium metal batteries were produced using non-lithiated compounds, such as TiS 2 , MoS 2 , Mn0 2 , Co0 2 , and V 2 0 5 , as the cathode active materials, which were coupled with a lithium metal anode.
  • non-lithiated compounds such as TiS 2 , MoS 2 , Mn0 2 , Co0 2 , and V 2 0 5
  • lithium ions were transferred from the lithium metal anode to the cathode through the electrolyte, and the cathode became lithiated.
  • the lithium metal resulted in the formation of dendrites at the anode that ultimately penetrated through the separator to reach the cathode, causing internal shorting, thermal runaway, and explosion.
  • the production of these types of secondary batteries was stopped in the early 1990's giving ways to lithium -ion batteries.
  • cycling stability and safety concerns remain the primary factors preventing the further commercialization of Li metal batteries (e.g. Lithium-sulfur and Lithium-transition metal oxide cells) for EV, HEV, and microelectronic device applications.
  • Li metal batteries e.g. Lithium-sulfur and Lithium-transition metal oxide cells
  • cycling stability and safety issues of lithium metal rechargeable batteries are primarily related to the high tendency for Li metal to form dendrite structures during cycling or overcharges, leading to internal electrical shorting and thermal runaway. This thermal runaway or even explosion is caused by the organic liquid solvents used in the electrolyte (e.g. carbonate and ether families of solvents), which are unfortunately highly volatile and flammable.
  • lithium-ion secondary batteries in which pure lithium metal sheet or film was replaced by carbonaceous materials (e.g. natural graphite particles) as the anode active material.
  • the carbonaceous material absorbs lithium (through intercalation of lithium ions or atoms between graphene planes, for instance) and desorbs lithium ions during the re-charge and discharge phases, respectively, of the lithium- ion battery operation.
  • the carbonaceous material may comprise primarily graphite that can be intercalated with lithium and the resulting graphite intercalation compound may be expressed as Li x C 6 , where x is typically less than 1, implying a relatively low anode specific capacity
  • sodium batteries have been considered an attractive alternative to lithium batteries since sodium is abundant and the production of sodium is significantly more environmentally benign compared to the production of lithium.
  • the high cost of lithium is a major issue and Na batteries potentially can be of significantly lower cost.
  • the anode active materials for Na intercalation and the cathode active materials for Na intercalation have lower Na storage capacities as compared with their Li storage capacities.
  • hard carbon particles are capable of storing Li ions up to 300- 360 mAh/g, but the same materials can store Na ions up to 150-250 mAh/g and less than 100 mAh/g for K ion storage.
  • sodium metal may be used as the anode active material in a sodium metal cell.
  • metallic sodium as the anode active material is normally considered undesirable and dangerous due to the dendrite formation, interface aging, and electrolyte incompatibility problems.
  • the cathode active material amount is typically 1.5-2.5 times higher than the anode active material amount in a cell.
  • the weight proportion of the anode active material (e.g. carbon) in a Na-ion battery cell is typically from 12% to 17%, and that of the cathode active material (e.g. Na x Mn0 2 ) from 17%) to 35%) (mostly ⁇ 30%>).
  • the weight fraction of the cathode and anode active materials combined is typically from 30%> to 45% of the cell weight.
  • the low active material mass loading is primarily due to the inability to obtain thicker electrodes (thicker than 100-200 ⁇ ) using the conventional slurry coating procedure. This is not a trivial task as one might think, and in reality the electrode thickness is not a design parameter that can be arbitrarily and freely varied for the purpose of optimizing the cell performance.
  • a general object of the present invention is to provide a rechargeable Na metal cell, K metal cell, hybrid Na/K metal cell, Na-ion cell, K-ion cell, or hybrid Na/K-ion cell that exhibits a high gravimetric energy density, high volumetric energy, high power density, long cycle life, and no danger of explosion due to Na/K metal dendrites.
  • This cell includes the Na or K metal secondary cell, Na-ion cell, K-ion cell, or a non-lithium alkali metal hybrid cell, wherein at least one electrode (the cathode alone or both the anode and cathode) operates on Na or K insertion or intercalation.
  • One specific technical goal of the present invention is to provide a safe Na- or K-metal based battery having a long cycle life and a gravimetric energy density greater than 150 Wh/Kg and volumetric energy greater than 450 Wh/L, preferably greater than 250 Wh/Kg and 600 Wh/L, and more preferably greater than 300 Wh/Kg and 750 Wh/L (all based on the total cell weight or cell volume).
  • a specific object of the present invention is to provide a rechargeable non-lithium alkali metal cell based on rational materials and battery designs that overcome or significantly reduce the following issues commonly associated with conventional alkali metal cells: (a) dendrite formation (internal shorting due to sharp dendrite penetrating the separator to reach the cathode); (b) extremely low electric and ionic conductivities of Na intercalation compound in the cathode, requiring large proportion (typically 10-30%) of non-active conductive fillers and having significant proportion of non-accessible or non-reachable cathode active material); and (c) short cycle life.
  • Another object of the present invention is to provide a simple, cost-effective, and easy- to-implement approach to preventing potential Na metal dendrite-induced internal short circuit and thermal runaway problems in various Na metal and Na-ion batteries.
  • the present invention provides an alkali metal battery having a high active material mass loading, exceptionally low overhead weight and volume (relative to the active material mass and volume), high volumetric capacity, and unprecedentedly high volumetric energy density and power density given the same type of battery.
  • This alkali metal (Na, K, Na/K, Na/Li, K/Li, or Na/K/Li, but not Li alone) battery can be a primary battery (non-rechargeable) or a secondary battery (rechargeable), including a rechargeable alkali metal battery (having an alkali metal anode) and an alkali metal-ion battery (e.g. having a first Na or K intercalation compound as an anode active material and a second Na or K intercalation or absorbing compound, having a much higher electrochemical potential than the first one, as a cathode active material).
  • electrochemical potential of the cathode active material is higher than that of the anode active material by at least 1.0 volt, preferably at least 1.5 volts, further preferably at least 2.0 volts, more preferably at least 3.0 volts, even more preferably at least 3.5 volts, and most preferably at least 4.0 volts.
  • the present invention provides an alkali metal-ion battery or alkali metal battery, wherein the alkali metal is selected from sodium (Na), potassium (K), a combination of Na and K, a combination of Na and/or K with lithium (Li) and the alkali metal does not include lithium alone.
  • the battery comprises:
  • the anode active material or the cathode active material constitutes an electrode active material loading greater than 10 mg/cm 2 , the anode active material and the cathode active material combined exceeds 40% by weight of the battery cell weight, and/or the 3D porous anode current collector or cathode current collector has a thickness no less than 200 ⁇ , and wherein the cathode active material releases alkali metal ions and the anode active material absorbs alkali metal ions when the battery is charged, and the anode active material releases alkali metal ions and the cathode active material absorbs alkali metal ions when the battery is discharged
  • This alkali metal-ion secondary battery may be produced by a process comprising:
  • first and/or second conductive foam structure has a thickness no less than 100 ⁇ (preferably greater than 200 ⁇ , more preferably greater than 300 ⁇ , further preferably greater than 400 ⁇ , and most preferably greater than 500 ⁇ ) and at least 80% by volume of pores (preferably at least 85% porosity, more preferably at least 90%, and most preferably at least 95%; these pore volumes referring to amounts of pores prior to being impregnated with a suspension); (b) Preparing a first suspension of an anode active material and an optional conductive additive dispersed in a first liquid electrolyte and a second suspension of a cathode active material and an optional conductive additive dispersed in a second liquid electrolyte; and
  • Impregnating the pores of the first foam structure with the first suspension e.g. injecting the first suspension into pores of the first conductive foam structure
  • impregnating the pores of the second foam structure with the second suspension e.g. injecting the second suspension into pores of the second conductive foam structure
  • the anode active material has a material mass loading no less than 20 mg/cm 2 in the anode or the cathode active material has a material mass loading no less than 15 mg/cm 2 for an organic or polymer material or no less than 30 mg/cm 2 (preferably no less than 40%) for an inorganic and non-polymer material in the cathode
  • the anode current collector, the separator, and the cathode current collector are assembled in a protective housing before, during or after the injecting (or impregnation) of the first suspension and/or the injecting (or impregnation) of the second suspension.
  • alkali metal battery (primary or secondary), wherein the alkali metal is selected from sodium (Na), potassium (K), a combination of Na and K, a combination of Na and/or K with lithium (Li) and the alkali metal does not include lithium alone.
  • This alkali metal battery comprises:
  • the cathode active material constitutes an electrode active material loading greater than 20 mg/cm 2 , the anode active material and the cathode active material combined exceeds 30%) by weight of the battery, and/or the 3D porous cathode current collector has a thickness no less than 200 ⁇ , and wherein the cathode active material releases alkali metal ions and the anode active material absorbs alkali metal ions when the battery is charged, and the anode active material releases alkali metal ions and the cathode active material absorbs alkali metal ions when the battery is discharged.
  • This alkali metal battery may be produced by a process comprising:
  • A Assembling a porous cell framework composed of a first conductive foam structure as a cathode current collector, an anode current collector, and a porous separator disposed between said anode and cathode current collectors; wherein said first conductive foam structure has a thickness no less than 100 ⁇ and at least 80% by volume of pores and said anode current collector (e.g. a Cu foil) has two opposed primary surfaces and at least one of the two primary surfaces contains a layer of sodium or potassium metal or alloy having at least 50% by weight of sodium or potassium element in said alloy;
  • the cathode active material contains multiple particles of an alkali metal intercalation compound or a alkali metal-absorbing compound that absorbs alkali metal ions when said alkali metal battery is discharged and said compound has a lithium intercalation or absorption voltage at least 1.0 volt above Na/Na + or K/K + ;
  • anode active material absorbs Na ions or K ions at an electrochemical potential of less than 1.0 volt
  • the anode contains an alkali ion source (as an anode active material) selected from foil, particles, or chips of an alkali metal, an alkali metal alloy, a mixture of alkali metal or alkali metal alloy with an alkali intercalation compound, an alkali element- containing compound, or a combination thereof.
  • an alkali ion source as an anode active material selected from foil, particles, or chips of an alkali metal, an alkali metal alloy, a mixture of alkali metal or alkali metal alloy with an alkali intercalation compound, an alkali element- containing compound, or a combination thereof.
  • the alkali intercalation compound or alkali-containing compound as an anode active material may be selected from the following groups of materials:
  • the cathode active material is a sodium or potassium intercalation compound or sodium- or potassium-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
  • the metal oxide/phosphate/sulfide is selected from a sodium cobalt oxide, sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium-mixed metal oxide,
  • the inorganic material-based cathode active material may be selected from sulfur, sulfur compound, lithium polysulfide, transition metal dichalcogenide, a transition metal
  • the inorganic material is selected from TiS 2 , TaS 2 , MoS 2 , NbSe 3 , Mn0 2 , Co0 2 , an iron oxide, a vanadium oxide, or a combination thereof.
  • the cathode active material contains a sodium intercalation compound or a potassium intercalation compound selected from NaFeP0 4 , KFeP0 4 , Na(i -X )K x P0 4 , Nao 7 FeP0 4 , Nai 5VOPO 4 F05, Na 3 V 2 (P0 4 ) 3 , Na 3 V 2 (P0 4 ) 2 F 3 , Na 2 FeP0 4 F , NaFeF 3 , NaVP0 4 F, KVP0 4 F, Na 3 V 2 (P0 4 ) 2 F 3 , Nai 5 VOPO 4 F 0 5, Na 3 V 2 (P0 4 ) 3 , NaV 6 0i 5 , Na x V0 2 , Na 0 33 V 2 0 5 , Na x Co0 2 , Na 2/3 [Nii /3 Mn 2/3 ]0 2 , Na x (Fei /2 Mni /2 )0 2 , Na x Mn0
  • the cathode active material may be selected from a functional material or nano- structured material having an alkali metal ion-capturing functional group or alkali metal ion-storing surface in direct contact with said electrolyte.
  • the functional group reversibly reacts 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 material or nano- structured material is selected from the group consisting of:
  • a nano-structured or porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, carbon black, activated carbon, nano-cellular carbon foam or partially graphitized carbon;
  • a carbon nanotube selected from a single-walled carbon nanotube or multi-walled carbon nanotube;
  • the functional material or nano-structured material has a specific surface area of at least 500 m 2 /g and, further preferably at least 1,000 m 2 /g.
  • R is a hydrocarbon radical.
  • a foam structure herein refers to an interconnected 2D or 3D network of electron-conducting paths. This can be, for instance, end-connected 2D mats, webs, chicken wire-like metal screens, etc., as illustrated in Fig. 3.
  • the foamed anode current collector extends all the way to an edge of the porous separator and in physical contact therewith.
  • the foamed cathode current collector may also extend all the way to the opposite edge of the porous separator and in physical contact therewith.
  • the pore walls of the anode current collector cover the entire anode layer, and/or the pore walls of the cathode current collector cover the entire cathode layer.
  • the ratio of current collector thickness/active material layer thickness is approximately 1/1 and the electrode thickness is essentially identical to the current collector thickness (the cathode thickness-to- cathode current collector thickness ratio is approximately 1 and the anode thickness-to-anode current collector thickness ratio is approximately 1).
  • conductive pore walls are in the immediate vicinity of every anode active material particle or every cathode active material particle.
  • the ratio of current collector thickness/active material layer thickness can be from approximately 0.8/1.0 to 1.0/0.8.
  • the cathode thickness-to-cathode current collector thickness ratio is from 0.8/1 to 1/0.8 or the anode thickness-to-anode current collector thickness ratio is from 0.8/1 to 1/0.8.
  • the anode (or cathode) current collector is typically a Cu foil (or Al foil) that is 8-12 ⁇ thick.
  • the anode active material layer coated on the Cu foil surface is typically 80-100 ⁇ .
  • the ratio of anode current collector thickness/anode active material layer thickness is typically 8/100 - 12/80.
  • the ratio of current collector thickness/active material layer thickness at the cathode side of a conventional Li-ion or Na-ion cell is also approximately 1/12.5 - 1/6.7.
  • the ratio is from 0.8/1 to 1/0.8, more desirably 0.9/1 to 1/0.9, further more desirably 0.95/1 to 1/0.95, and most desirably and typically 1/1.
  • the pore volume (e.g. > 80%) of a foamed current collector is a critically important requirement to ensure a large proportion of active materials accommodated in the current collector.
  • the pore sizes in the first and/or second conductive foam structure are preferably in the range from 10 nm to 100 ⁇ , more preferably from 100 nm to 50 ⁇ , further preferably from 500 nm to 20 ⁇ , and even more preferably from 1 ⁇ to 10 ⁇ , and most preferably from 1 ⁇ to 5 ⁇ .
  • pore size ranges are designed to accommodate anode active materials (such as carbon particles) and cathode active materials (such as ⁇ - ⁇ 0 2 or sodium iron phosphate), having a primary or secondary particle size typically from 10 nm to 20 ⁇ in diameter, and most typically from 50 nm to 10 ⁇ , further typically from 100 nm to 5 ⁇ , and most typically from 200 nm to 3 ⁇ .
  • anode active materials such as carbon particles
  • cathode active materials such as ⁇ - ⁇ 0 2 or sodium iron phosphate
  • the first liquid electrolyte and the second liquid electrolyte are identical in a battery, but they can be different in composition.
  • the liquid electrolytes can be an aqueous liquid, organic liquid, ionic liquid (ionic salt having a melting temperature lower than 100°C, preferably lower than room temperature, 25°C), or a mixture of an ionic liquid and an organic liquid at a ratio from 1/100 to 100/1.
  • the organic liquid is desirable, but the ionic liquid is preferred.
  • a gel electrolyte can also be used provided the electrolyte has some flowability to enable injection. Some small amount 0.1% to 10% can be incorporated into the liquid electrolyte.
  • the first and/or second conductive foam structure has a thickness no less than 200 ⁇ , and/or has at least 85% by volume of pores
  • said anode active material has a mass loading no less than 25 mg/cm 2 and/or occupies at least 25% by weight or by volume of the entire battery cell
  • the cathode active material has a mass loading no less than 20 mg/cm 2 for an organic or polymer material or no less than 45 mg/cm 2 for an inorganic and non-polymer material in the cathode and/or occupies at least 45 % by weight or by volume of the entire battery cell.
  • the first and/or second conductive foam structure has a thickness no less than 300 ⁇ , has at least 90% by volume of pores, and/or the anode active material has a mass loading no less than 30 mg/cm 2 and/or occupies at least 30% by weight or by volume of the entire battery cell, and/or the cathode active material has a mass loading no less than 25 mg/cm 2 for an organic or polymer material or no less than 50 mg/cm 2 for an inorganic and non-polymer material in said cathode and/or occupies at least 50 % by weight or by volume of the entire battery cell.
  • the first and/or second conductive foam structure has a thickness no less than 400 ⁇ , has at least 95% by volume of pores, and/or said anode active material has a mass loading no less than 35 mg/cm 2 and/or occupies at least 35% by weight or by volume of the entire battery cell, and/or the cathode active material has a mass loading no less than 30 mg/cm 2 for an organic or polymer material or no less than 55 mg/cm 2 for an inorganic and non-polymer material in the cathode and/or occupies at least 55 % by weight or by volume of the entire battery cell.
  • the first and/or second conductive foam structure is selected from metal foam, metal web or screen, perforated metal sheet-based 3-D structure, metal fiber mat, metal nanowire mat, conductive polymer nano-fiber mat, conductive polymer foam, conductive polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, carbon xerox gel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or a combination thereof.
  • the anode active material is a pre-sodiated or pre-potassiated 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, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof.
  • the resulting Na or K battery cell does not exhibit a satisfactory cycle life (i.e. capacity decays rapidly).
  • the volume ratio of the anode active material-to-liquid electrolyte in the first dispersion is from 1/5 to 20/1 (preferably from 1/3 to 5/1) and/or the volume ratio of cathode active material -to-the liquid electrolyte in the second dispersion is from 1/5 to 20/1 (preferably from 1/3 to 5/1).
  • the first and/or second conductive foam structure is selected from metal foam, metal web or screen, perforated metal sheet-based 3-D structure, metal fiber mat, metal nanowire mat, conductive polymer nano-fiber mat, conductive polymer foam, conductive polymer-coated fiber foam, carbon foam, graphite foam, carbon aerogel, carbon xerox gel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or a combination thereof.
  • FIG.1(A) Schematic of a prior art sodium-ion battery cell composed of an anode current
  • anode electrode e.g. thin Sn coating layer
  • a porous separator e.g. porous separator
  • a cathode electrode e.g. cathode current collector
  • FIG.1(B) Schematic of a prior art sodium-ion battery, wherein the electrode layer is composed of discrete particles of an active material (e.g. hard carbon particles in the anode layer or Na x Mn0 2 in the cathode layer).
  • an active material e.g. hard carbon particles in the anode layer or Na x Mn0 2 in the cathode layer.
  • FIG.1(C) Schematic of a presently invented sodium -ion or potassium -ion battery cell
  • anode current collector in the form of a highly porous foam, a porous separator, and a cathode current collector in the form of a highly porous foam.
  • Suspensions are being injected or impregnated into pores of the two current collectors. Half of the pores have been filled, for illustration purpose.
  • FIG.1(D) Schematic of a presently invented Na-ion or K-ion battery cell, comprising an anode current collector in the form of a highly porous foam, a porous separator, and a cathode current collector in the form of a highly porous foam.
  • the pores of the two foamed current collectors have been impregnated with their respective suspensions.
  • FIG.1(E) Schematic of a presently invented Na metal or K metal battery cell, comprising an anode current collector containing a layer of Na or K metal or alloy deposited thereon, a porous separator, and a cathode current collector in the form of a highly porous foam.
  • the pores of this foamed current collector have been impregnated with a cathode-electrolyte suspension.
  • FIG.2 An electron microscopic image of graphene sheets that are a good conductive substrate for supporting anode or cathode active materials.
  • FIG.3 Schematic of a foamed or porous current collector, as an example, composed of 5 sheets of highly porous 2D webs (e.g. chicken wire-shaped thin 2D structures) that are end- connected to form a tab.
  • highly porous 2D webs e.g. chicken wire-shaped thin 2D structures
  • FIG.4(A) Schematic of a commonly used process for producing exfoliated graphite, expanded graphite flakes (thickness > 100 nm), and graphene sheets (thickness ⁇ 100 nm, more typically ⁇ 10 nm, and can be as thin as 0.34 nm)
  • FIG.4 (B) Schematic drawing to illustrate the processes for producing exfoliated graphite
  • FIG.5 Ragone plots (gravimetric and volumetric power density vs. energy density) of Na-ion battery cells containing hard carbon particles as the anode active material and carbon- coated Na 3 V 2 (P0 4 )2F 3 particles as the cathode active materials.
  • Two of the 4 data curves are for the cells prepared according to an embodiment of instant invention and the other two by the conventional slurry coating of electrodes (roll -coating).
  • FIG.6 Ragone plots (both gravimetric and volumetric power density vs. gravimetric and
  • volumetric energy density of two cells, both containing graphene-embraced Sn nano particles as the anode active material and NaFeP0 4 nano particles as the cathode active material.
  • the data are for both sodium ionl cells prepared by the presently invented method and those by the conventional slurry coating of electrodes.
  • FIG.7 Ragone plots of sodium metal batteries containing a sodium foil as the anode active
  • FIG.8 Ragone plot of a series of K-ion cells prepared by the conventional slurry coating process and the Ragone plot of corresponding K-ion cells prepared by the presently invented process.
  • FIG.9 Ragone plots of a series of hybrid cells having a hybrid anode active material (a mixture of activated carbon particles and NaTi 2 (P0 4 ) 3 particles) and ⁇ - ⁇ 0 2 particles as a cathode active material prepared by the conventional slurry coating and those by the presently invented process of direct injection into pores of foamed current collectors.
  • FIG.10 The cell-level gravimetric (Wh/kg) and volumetric energy densities (Wh/L) of sodium metal cells plotted over the achievable cathode thickness range of the Mn0 2 /RGO cathode prepared via the conventional method without delamination and cracking and those by the presently invented method. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
  • This invention is directed at a process for producing an alkali metal battery or alkali metal ion battery (e.g. Na-ion or K-ion battery exhibiting) an exceptionally high volumetric energy density that has never been previously achieved for the same type of battery.
  • This alkali metal battery can be a primary battery, but is preferably a secondary battery selected from an alkali metal-ion battery (e.g. using a Na intercalation compound, such as hard carbon particles) or an alkali metal secondary battery (e.g. using Na or K metal as an anode active material).
  • the battery is based on an aqueous electrolyte, an organic electrolyte, a gel electrolyte, an ionic liquid electrolyte, or a mixture of organic and ionic liquid.
  • the shape of an alkali metal battery can be cylindrical, square, button-like, etc.
  • the present invention is not limited to any battery shape or configuration.
  • a conventional sodium-ion battery cell is typically composed of an anode current collector (e.g. Cu foil), an anode electrode (anode active material layer), a porous separator and/or an electrolyte component, a cathode electrode (cathode active material layer), and a cathode current collector (e.g. Al foil).
  • the anode layer is composed of particles of an anode active material (e.g. hard carbon particles), a conductive additive (e.g. expanded graphite flakes), and a resin binder (e.g. SBR or PVDF).
  • the cathode layer is composed of particles of a cathode active material (e.g. NaFeP0 4 particles), a conductive additive (e.g. carbon black particles), and a resin binder (e.g. PVDF). Both the anode and the cathode layers are typically 60-100 ⁇ thick (no more than 200 ⁇ ) to give rise to a presumably sufficient amount of current per unit electrode area.
  • a cathode active material e.g. NaFeP0 4 particles
  • a conductive additive e.g. carbon black particles
  • a resin binder e.g. PVDF
  • This thickness range of 60-100 ⁇ is considered an industry-accepted constraint under which a battery designer normally works under, based on the current slurry coating process (roll coating of active material -binder-additive mixture slurry).
  • This thickness constraint is due to several reasons: (a) the existing battery electrode coating machines are not equipped to coat excessively thin or excessively thick electrode layers; (b) a thinner layer is preferred based on the consideration of reduced lithium ion diffusion path lengths; but, too thin a layer (e.g.
  • ⁇ 60 ⁇ does not contain a sufficient amount of an active alkali metal ion storage material (hence, insufficient current output); and (c) thicker electrodes are prone to delaminate or crack upon drying or handling after roll-coating of slurry.
  • This constraint has made it impossible to freely increase the amount of active materials (those responsible for storing Na or K ions) without increasing the amounts of all non-active materials (e.g. current collectors and separator) in order to obtain a minimum overhead weight and a maximum sodium storage capability and, hence, a maximized energy density (Wk/kg or Wh/L of cell).
  • either the anode active material e.g. NaTi 2 (P0 4 ) 3
  • the cathode active material e.g. sodium transition metal oxide
  • a current collector such as a sheet of copper foil or Al foil using sputtering.
  • a thin film structure with an extremely small thickness-direction dimension typically much smaller than 500 nm, often necessarily thinner than 100 nm implies that only a small amount of active material can be incorporated in an electrode (given the same electrode or current collector surface area), providing a low total Na storage capacity and low lithium storage capacity per unit electrode surface area.
  • Such a thin film must have a thickness less than 100 nm to be more resistant to cycling-induced cracking (for the anode) or to facilitate a full utilization of the cathode active material. Such a constraint further diminishes the total Na storage capacity and the sodium storage capacity per unit electrode surface area.
  • Such a thin-film battery has very limited scope of application.
  • a sputtered NaTi 2 (P0 4 )3 layer thicker than 100 nm has been found to exhibit poor cracking resistance during battery charge/discharge cycles. It takes but a few cycles to get fragmented.
  • a sputtered layer of sodium metal oxide thicker than 100 nm does not allow lithium ions to fully penetrate and reach full body of the cathode layer, resulting in a poor cathode active material utilization rate.
  • a desirable electrode thickness is at least 100 ⁇ , with individual active material particle having a dimension desirably less than 100 nm.
  • these thin-film electrodes (with a thickness ⁇ 100 nm) directly deposited on a current collector fall short of the required thickness by three (3) orders of magnitude.
  • all of the cathode active materials are not very conductive to both electrons and sodium ions.
  • a large layer thickness implies an excessively high internal resistance and a poor active material utilization rate.
  • the prior art sodium or lithium battery cell is typically made by a process that includes the following steps: (a) The first step is mixing particles of the anode active material (e.g. hard carbon particles), a conductive filler (e.g. expanded graphite flakes), a resin binder (e.g. PVDF) in a solvent (e.g. NMP) to form an anode slurry. On a separate basis, particles of the cathode active material (e.g. sodium metal phosphate particles for the Na-ion cell and LFP particles for the Li-ion cell), a conductive filler (e.g. acetylene black), a resin binder (e.g. PVDF) are mixed and dispersed in a solvent (e.g.
  • a solvent e.g.
  • the second step includes coating the anode slurry onto one or both primary surfaces of an anode current collector (e.g. Cu foil), drying the coated layer by vaporizing the solvent (e.g. NMP) to form a dried anode electrode coated on Cu foil.
  • anode current collector e.g. Cu foil
  • the solvent e.g. NMP
  • the cathode slurry is coated and dried to form a dried cathode electrode coated on Al foil.
  • the third step includes laminating an anode/Cu foil sheet, a porous separator layer, and a cathode/ Al foil sheet together to form a 3 -layer or 5-layer assembly, which is cut and slit into desired sizes and stacked to form a rectangular structure (as an example of shape) or rolled into a cylindrical cell structure, (d) The rectangular or cylindrical laminated structure is then encased in an aluminum-plastic laminated envelope or steel casing, (e) A liquid electrolyte is then injected into the laminated structure to make a sodium-ion or lithium battery cell.
  • the actual mass loadings of the electrodes and the apparent densities for the active materials are too low to achieve a gravimetric energy density of > 100 Wh/kg for K-ion cells, > 150 Wh/kg for Na-ion cells or > 200 Wh/kg for Li-ion cells.
  • the anode active material mass loading of the electrodes is significantly lower than 15-25 mg/cm 2 and the apparent volume density or tap density of the active material is typically less than 1.2 g/cm 3 even for relatively large particles of graphite.
  • the cathode active material mass loading of the electrodes is significantly lower than 25-45 mg/cm 2 for lithium metal oxide-type inorganic materials and lower than 8-15 mg/cm 2 for organic or polymer materials.
  • non-active materials e.g. conductive additive and resin binder
  • These low areal densities and low volume densities result in a relatively low gravimetric energy density and low volumetric energy density.
  • the conventional process requires dispersing electrode active materials (anode active material and cathode active material) in a liquid solvent (e.g. MP) to make a slurry and, upon coating on a current collector surface, the liquid solvent has to be removed to dry the electrode layer.
  • a liquid solvent e.g. MP
  • the anode and cathode layers, along with a separator layer, are laminated together and packaged in a housing to make a supercapacitor cell, one then injects a liquid electrolyte (using a salt dissolved in a solvent different than NMP) into the cell.
  • a liquid electrolyte using a salt dissolved in a solvent different than NMP
  • the energy density data reported based on either the active material weight alone or the electrode weight cannot directly translate into the energy densities of a practical battery cell or device.
  • the "overhead weight” or weights of other device components must also be taken into account.
  • the convention production process results in the weight proportion of the anode active material (e.g. carbon particles) in a sodium-ion battery being typically from 12% to 15%, and that of the cathode active material (e.g. sodium transition metal oxide) from 20% to 30%.
  • the present invention provides a process for producing a sodium or potassium battery cell having a high electrode thickness (thickness of the electrode that contains electrode active materials, not including the thickness of any active material-free current collector layer, if existing), high active material mass loading, low overhead weight and volume, high volumetric capacitance, and high volumetric energy density.
  • the invented process comprises:
  • the first and/or second conductive foam structure has a thickness no less than 100 ⁇ (preferably greater than 200 ⁇ , more preferably greater than 300 ⁇ , further preferably greater than 400 ⁇ , and most preferably greater than 500 ⁇ ) and at least 80%) by volume of pores (preferably at least 85%> porosity, more preferably at least 90%), and most preferably at least 95%);
  • foam structures have essentially a porosity level of 80%-99% and remaining l%>-20%> being pore walls (e.g. metal or graphite skeleton). These pores are used to accommodate a mixture of active materials (e.g. carbon particles in the anode + an optional conductive additive) and liquid electrolyte.
  • active materials e.g. carbon particles in the anode + an optional conductive additive
  • (C) Injecting the first suspension into pores of the first conductive foam structure to form an anode and injecting the second suspension into pores of the second conductive foam structure to form a cathode to an extent that the anode active material constitutes an electrode active material loading no less than 20 mg/cm 2 (preferably no less than 25 mg/cm 2 and more preferably no less than 30 mg/cm 2 ) in the anode, or the cathode active material constitutes an electrode active material mass loading no less than 45 mg/cm 2 (preferably greater than 50 mg/cm 2 and more preferably greater than 60 mg/cm 2 ) for an inorganic material in the cathode (no less than 15 mg/cm 2 , preferably no less than 25 mg/cm 2 , for an organic or polymeric cathode active material), wherein the anode, the separator, and the cathode are assembled in a protective housing.
  • the anode active material constitutes an electrode active material loading no less than 20 mg/cm 2
  • substantially all of the pores are filled with the electrode (anode or
  • cathode active material
  • optional conductive additive optional conductive additive
  • liquid electrolyte no binder resin needed
  • FIG. 1(C) Shown in FIG. 1(C) is a situation, wherein the porous foam structure for the anode (anode current collector 236) has been partially filled with the first suspension (anode active material and optional conductive additive dispersed in the liquid electrolyte).
  • the top portion 240 of the anode current collector foam 236 remains empty, but the lower portion 244 has been filled with the anode suspension.
  • the top portion 242 of the cathode current collector foam 238 remains empty and the lower portion 246 has been filled with the cathode suspension (cathode active material dispersed in the liquid electrolyte).
  • the four arrows represent the suspension injection directions.
  • FIG. 1(D) Shown in FIG. 1(D) is a situation, wherein both the anode current collector foam and the cathode current collector foam have been filled with their respective suspensions.
  • a foam pore 250 in an enlarged view, is filled with the anode suspension containing hard carbon particles 252 (an anode active material) and liquid electrolyte 254.
  • a foam pore 260 in an enlarged view, is filled with the cathode suspension containing carbon-coated sodium transition metal oxide particles 262 (a cathode active material) and liquid electrolyte 264.
  • FIG.1(E) An alternative configuration, as schematically illustrated in FIG.1(E), is a presently invented sodium metal or potassium metal battery cell, comprising an anode current collector 280 containing a layer of Na or K metal 282 or Na/K metal alloy deposited thereon, a porous separator, and a cathode current collector in the form of a highly porous foam.
  • the pores 270 of this foamed current collector have been impregnated with a suspension of cathode active material 272 and liquid electrolyte 274.
  • the anode active material is a pre-sodiated or pre-potassiated 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 a combination thereof.
  • the starting graphitic material for producing any one of the above graphene materials may be selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso- carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano- tube, or a combination thereof.
  • Graphene materials are also a good conductive additive for both the anode and cathode active materials of an alkali metal battery.
  • the constituent graphene planes of a graphite crystallite in a natural or artificial graphite particle can be exfoliated and extracted or isolated to obtain individual graphene sheets of hexagonal carbon atoms, which are single-atom thick, provided the inter-planar van der Waals forces can be overcome.
  • An isolated, individual graphene plane of carbon atoms is commonly referred to as single-layer graphene.
  • a stack of multiple graphene planes bonded through van der Waals forces in the thickness direction with an inter-graphene plane spacing of approximately 0.3354 nm is commonly referred to as a multi-layer graphene.
  • a multi-layer graphene platelet has up to 300 layers of graphene planes ( ⁇ 100 nm in thickness), but more typically up to 30 graphene planes ( ⁇ 10 nm in thickness), even more typically up to 20 graphene planes ( ⁇ 7 nm in thickness), and most typically up to 10 graphene planes (commonly referred to as few-layer graphene in scientific community).
  • Single-layer graphene and multi-layer graphene sheets are collectively called “nano graphene platelets" (NGPs).
  • Graphene sheets/platelets are a new class of carbon nano material (a 2-D nano carbon) that is distinct from the 0-D fullerene, the 1-D CNT or CNF, and the 3-D graphite.
  • a graphene material isolated graphene sheets
  • CNF carbon nano-fiber
  • graphene materials are obtained by intercalating natural graphite particles with a strong acid and/or an oxidizing agent to obtain a graphite intercalation compound (GIC) or graphite oxide (GO), as illustrated in FIG. 4(A) and FIG. 4(B) (schematic drawings).
  • GIC graphite intercalation compound
  • GO graphite oxide
  • FIG. 4(A) and FIG. 4(B) schematic drawings.
  • 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 02 , as determined by X- ray diffraction), thereby significantly reducing the van der Waals forces that otherwise hold graphene planes together along the c-axis direction.
  • the GIC or GO is most often produced by immersing natural graphite powder (100 in FIG.
  • Route 1 involves removing water from the suspension to obtain "expandable graphite,” which is essentially a mass of dried GIC or dried graphite oxide particles.
  • expandable graphite essentially a mass of dried GIC or dried graphite oxide particles.
  • the GIC undergoes a rapid volume expansion by a factor of 30-300 to form “graphite worms” (104), which are each a collection of exfoliated, but largely un-separated graphite flakes that remain interconnected.
  • these graphite worms can be re-compressed to obtain flexible graphite sheets or foils (106) that typically have a thickness in the range of 0.1 mm (100 ⁇ ) - 0.5 mm (500 ⁇ ).
  • flexible graphite sheets or foils 106) that typically have a thickness in the range of 0.1 mm (100 ⁇ ) - 0.5 mm (500 ⁇ ).
  • the exfoliated graphite is subjected to high-intensity mechanical shearing
  • NGPs single-layer and multi-layer graphene sheets
  • Single-layer graphene can be as thin as 0.34 nm
  • multi -layer graphene can have a thickness up to 100 nm, but more typically less than 10 nm (commonly referred to as few-layer graphene).
  • Multiple graphene sheets or platelets may be made into a sheet of NGP paper using a paper-making process. This sheet of NGP paper is an example of the porous graphene structure layer utilized in the presently invented process.
  • Route 2 entails ultrasonicating the graphite oxide suspension (e.g. graphite oxide particles dispersed in water) for the purpose of separating/isolating individual graphene oxide sheets from graphite oxide particles.
  • the inter-graphene plane separation bas been increased from 0.3354 nm in natural graphite to 0.6-1.1 nm in highly oxidized graphite oxide, significantly weakening the van der Waals forces that hold neighboring planes together.
  • Ultrasonic power can be sufficient to further separate graphene plane sheets to form fully separated, isolated, or discrete graphene oxide (GO) sheets.
  • RGO reduced graphene oxides
  • NGPs or graphene materials include discrete sheets/platelets of single-layer and multi-layer (typically less than 10 layers) 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 by B or N).
  • Pristine graphene has essentially 0% oxygen.
  • RGO typically has an oxygen content of 0.001%-5% by weight.
  • Graphene oxide (including RGO) can have 0.001%-50% by weight of oxygen.
  • all the graphene materials have 0.001%-50% by weight of non-carbon elements (e.g. O, H, N, B, F, CI, Br, I, etc.). These materials are herein referred to as non-pristine graphene materials.
  • non-carbon elements e.g. O, H, N, B, F, CI, Br, I, etc.
  • Pristine graphene in smaller discrete graphene sheets (typically 0.3 ⁇ to 10 ⁇ ), may be produced by direct ultrasonication (also known as liquid phase exfoliation or production) or supercritical fluid exfoliation of graphite particles. These processes are well-known in the art.
  • the graphene oxide (GO) may be obtained by immersing powders or filaments of a starting graphitic material (e.g. natural graphite powder) in an oxidizing liquid medium (e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel at a desired temperature for a period of time (typically from 0.5 to 96 hours, depending upon the nature of the starting material and the type of oxidizing agent used).
  • an oxidizing liquid medium e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate
  • the resulting graphite oxide particles may then be subjected to thermal exfoliation or ultrasonic wave-induced exfoliation to produce isolated GO sheets.
  • These GO sheets can then be converted into various graphene materials by substituting -OH groups with other chemical groups (e.g. -Br, H 2 , etc.).
  • Fluorinated graphene or graphene fluoride is herein used as an example of the halogenated graphene material group.
  • fluorination of pre-synthesized graphene This approach entails treating graphene prepared by mechanical exfoliation or by CVD growth with fluorinating agent such as XeF 2 , or F-based plasmas;
  • Exfoliation of multilayered graphite fluorides Both mechanical exfoliation and liquid phase exfoliation of graphite fluoride can be readily accomplished.
  • the process of liquid phase exfoliation includes ultra- sonic treatment of a graphite fluoride in a liquid medium.
  • the nitrogenation of graphene can be conducted by exposing a graphene material, such as graphene oxide, to ammonia at high temperatures (200-400°C). Nitrogenated graphene could also be formed at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to 150-250°C. Other methods to synthesize nitrogen doped graphene include nitrogen plasma treatment on graphene, arc- discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and hydrothermal treatment of graphene oxide and urea at different temperatures.
  • a graphene material such as graphene oxide
  • Nitrogenated graphene could also be formed at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to 150-250°C.
  • Other methods to synthesize nitrogen doped graphene include nitrogen plasma treatment on graphene,
  • a graphite particle (e.g. 100) is typically composed of multiple graphite crystallites or grains.
  • a graphite crystallite is made up of layer planes of hexagonal networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another in a particular crystallite. These layers of hexagonal-structured carbon atoms, commonly referred to as graphene layers or basal planes, are weakly bonded together in their thickness direction
  • the graphite crystallite structure is usually characterized in terms of two axes or directions: the c-axis direction and the a-axis (or b-axis) direction.
  • the c- axis is the direction perpendicular to the basal planes.
  • the a- or ⁇ -axes are the directions parallel to the basal planes (perpendicular to the c-axis direction).
  • natural graphite can be treated so that the spacing between the graphene layers can be appreciably opened up so as to provide a marked expansion in the c-axis direction, and thus form an expanded graphite structure in which the laminar character of the carbon layers is substantially retained.
  • the process for manufacturing flexible graphite is well-known in the art.
  • flakes of natural graphite e.g. 100 in FIG. 4(B)
  • the GICs are washed, dried, and then exfoliated by exposure to a high temperature for a short period of time.
  • the exfoliated graphite flakes are vermiform in appearance and, hence, are commonly referred to as graphite worms 104.
  • These worms of graphite flakes which have been greatly expanded can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, foils, mats or the like (typically referred to as "flexible graphite" 106) having a typical density of about 0.04-2.0 g/cm 3 for most applications.
  • Acids such as sulfuric acid
  • intercalating agent intercalant
  • Many other types of intercalating agents such as alkali metals (Li, K, Na, Cs, and their alloys or eutectics), can be used to intercalate graphite to stage 1, stage 2, stage 3, etc.
  • Stage n implies one intercalant layer for every n graphene planes.
  • a stage-1 potassium-intercalated GIC means there is one layer of K for every graphene plane; or, one can find one layer of K atoms inserted between two adjacent graphene planes in a G/K/G/K/G/KG ....
  • a stage-2 GIC will have a sequence of GG/K/GG/K/GG/K/GG .... and a stage-3 GIC will have a sequence of GGG/K/GGG/K/GGG ...., etc.
  • These GICs can then be brought in contact with water or water-alcohol mixture to produce exfoliated graphite and/or separated/isolated graphene sheets.
  • Exfoliated graphite worms may be subjected to high -intensity mechanical
  • NGPs nano graphene platelets
  • An NGP is composed of a graphene sheet or a plurality of graphene sheets with each sheet being a two-dimensional, hexagonal structure of carbon atoms.
  • a mass of multiple NGPs including discrete sheets/platelets of single-layer and/or few-layer graphene or graphene oxide may be made into a graphene film/paper (114 in FIG.
  • graphite worms tend to be separated into the so-called expanded graphite flakes (108 in FIG. 4(B) having a thickness > 100 nm.
  • expanded graphite flakes can be formed into graphite paper or mat 106 using a paper- or mat-making process, with or without a resin binder.
  • Expanded graphite flakes can be used as a conductive filler in a battery.
  • Separated NGPs (individual single-layer or multilayer graphene sheets) can be used as an anode active material or as a supporting conductive material in the cathode of an alkali metal battery.
  • the anode active material absorbs sodium or potassium ions at an electrochemical potential of less than 1.0 volt (preferably less than 0.7 volts) above the Na/Na + (i.e. relative to Na ⁇ Na + + e " as the standard potential), or above the K/K + (i.e. relative to K ⁇ K + + e " as the standard potential), when the battery is charged.
  • the anode active material is selected from the group consisting of: (a) Sodium- or potassium-doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), and mixtures thereof; (b) Sodium- or potassium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures; (c) Sodium- or potassium-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 composite
  • the anode may contain an alkali ion source selected from an alkali metal, an alkali metal alloy, a mixture of alkali metal or alkali metal alloy with an alkali intercalation compound, an alkali element-containing compound, or a combination thereof.
  • an anode active material that contains an alkali intercalation compound selected from petroleum coke, carbon black, amorphous carbon, hard carbon, templated carbon, hollow carbon nanowires, hollow carbon sphere, titanates, NaTi 2 (P0 4 )3, Na 2 Ti 3 07 (Sodium titanate), Na 2 C 8 H 0 4 (Disodium Terephthalate), Na 2 TP (Sodium
  • the anode may contain a mixture of 2 or 3 types of anode active materials (e.g. mixed particles of activated carbon + NaTi 2 (P0 4 ) 3 ) and the cathode can be a sodium intercalation compound alone (e.g. Na x Mn0 2 ), an electric double layer capacitor-type cathode active material alone (e.g. activated carbon), a redox pair of -Mn0 2 /activated carbon for pseudo-capacitance.
  • anode active materials e.g. mixed particles of activated carbon + NaTi 2 (P0 4 ) 3
  • the cathode can be a sodium intercalation compound alone (e.g. Na x Mn0 2 ), an electric double layer capacitor-type cathode active material alone (e.g. activated carbon), a redox pair of -Mn0 2 /activated carbon for pseudo-capacitance.
  • the first or second liquid electrolyte in the invented process or battery may be selected from an aqueous electrolyte, organic electrolyte, ionic liquid electrolyte, mixture of an organic electrolyte and an ionic electrolyte, or a mixture thereof with a polymer.
  • the aqueous electrolyte contains a sodium salt or a potassium salt dissolved in water or a mixture of water and alcohol.
  • the sodium salt or potassium salt is selected from Na 2 S0 4 , K 2 S0 4 , a mixture thereof, NaOH, KOH, NaCl, KC1, NaF, KF, NaBr, KBr, Nal, KI, or a mixture thereof.
  • the organic solvent may contain a liquid solvent selected from the group consisting of 1,3-dioxolane (DOL), 1,2-dimethoxy ethane (DME), tetraethylene glycol dimethylether
  • TEGDME polyethylene glycol) dimethyl ether
  • DEGDBE diethylene glycol dibutyl ether
  • EEE 2-ethoxyethyl ether
  • sulfone sulfolane
  • ethylene carbonate EC
  • DMC dimethyl carbonate
  • MEC methylethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • PC propylene carbonate
  • y-BL gamma-butyrolactone
  • AN acetonitrile
  • EA propyl formate
  • MF methyl formate
  • MA fluoroethylene carbonate
  • FEC vinylene carbonate
  • VC allyl ethyl carbonate
  • AEC a hydrofloroether
  • the organic electrolyte may contain an alkali metal salt preferably selected from sodium perchlorate (NaC10 4 ), potassium perchlorate (KC10 4 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), sodium borofluoride (NaBF 4 ), potassium borofluoride (KBF 4 ), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro- metasulfonate (NaCF 3 S0 3 ), potassium trifluoro-metasulfonate (KCF 3 S0 3 ), bis-trifluorom ethyl sulfonylimide sodium (NaN(CF 3 S0 2 ) 2 ), bis-trifluorom ethyl sulfonylimide potassium
  • the electrolyte may further contain a lithium salt (as an additive to the sodium or potassium salt) selected from lithium perchlorate (LiC10 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- metasulfonate (LiCF 3 S0 3 ), bis-trifluorom ethyl sulfonylimide lithium (LiN(CF 3 S0 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4 ), lithium oxalyl- difluoroborate (LiBF 2 C 2 0 4 ), lithium nitrate (LiN0 3 ), Li-Fluoroalkyl-Phosphates
  • LiPF 3 (CF 2 CF 3 ) 3
  • LiBETI lithium bisperfluoro-ethysulfonylimide
  • ionic liquid is composed of ions only.
  • Ionic liquids are low melting temperature salts that are in a molten or liquid state when above a desired temperature. For instance, an ionic salt is considered as an ionic liquid if its melting point is below 100°C. If the melting temperature is equal to or lower than room temperature (25°C), the salt is referred to as a room temperature ionic liquid (RTIL).
  • RTIL room temperature ionic liquid
  • the IL-based lithium salts are characterized by weak interactions, due to the combination of a large cation and a charge-delocalized anion. This results in a low tendency to crystallize due to flexibility (anion) and asymmetry (cation).
  • Some ILs may be used as a co-solvent (not as a salt) to work with the first organic solvent of the present invention.
  • a well-known ionic liquid is formed by the combination of a l-ethyl-3- methyl-imidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulphonamide (TFSI) anion.
  • EMI l-ethyl-3- methyl-imidazolium
  • TFSI N,N-bis(trifluoromethane)sulphonamide
  • Ionic liquids are basically composed of organic or inorganic ions that come in an unlimited number of structural variations owing to the preparation ease of a large variety of their components.
  • various kinds of salts can be used to design the ionic liquid that has the desired properties for a given application. These include, among others, imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis(trifluoromethanesulphonyl) imide, bis(fluorosulphonyl)imide and hexafluorophosphate as anions.
  • Useful ionic liquid-based sodium salts may be composed of sodium ions as the cation and
  • sodium trifluoromethanesulfonimide NaTFSI is a particularly useful sodium salt.
  • ionic liquids come in different classes that include three basic types: aprotic, protic and zwitterionic types, each one suitable for a specific application.
  • RTILs room temperature ionic liquids
  • 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.
  • RTILs include, but are not limited to, BF 4 " , B(CN) 4 “ , CH 3 BF 3 “ , CH 2 CHBF 3 “ , CF 3 BF 3 “ , C 2 F 5 BF 3 " , n- C 3 F 7 BF 3 -, «-C 4 F 9 BF 3 -, PF 6 ⁇ CF 3 C0 2 " , CF 3 S0 3 " , N(S0 2 CF 3 ) 2 " , N(COCF 3 )(S0 2 CF 3 ) “ , N(S0 2 F) 2 “ , N(CN) 2 “ , C(CN) 3 “ , SCN “ , SeCN “ , CuCl 2 " , A1C1 4 “ , F(HF) 2.3 “ , etc.
  • RTILs can possess archetypical properties such as high intrinsic ionic conductivity, high thermal stability, low volatility, low (practically zero) vapor pressure, non-flammability, the ability to remain liquid at a wide range of temperatures above and below room temperature, high polarity, high viscosity, and wide electrochemical windows. These properties, except for the high viscosity, are desirable attributes when it comes to using an RTIL as an electrolyte co-solvent in a rechargeable lithium cell.
  • the cathode active material may contain a sodium intercalation compound (or their potassium counterparts) selected from NaFeP0 4 (Sodium iron phosphate), Na 0 7 FeP0 4 , Nai .5 VOPO 4 F 0 5, Na 3 V 2 (P0 4 ) 3 , Na 3 V2(P0 4 ) 2 F 3 , Na 2 FeP0 4 F, NaFeF 3 , NaVP0 4 F, Na 3 V 2 (P0 4 )2F3, Nai 5VOPO4F0 5, Na 3 V 2 (P0 4 ) 3 , NaV 6 0i 5 , Na x V0 2 , Na 0 33 V 2 0 5 , Na x Co0 2 (Sodium cobalt oxide), Na 2/3 [Nii /3 Mn 2/3 ]0 2 , Na x (Fei /2 Mni /2 )0 2 , Na x Mn0 2 (Sodium manganese bronze), ⁇ - ⁇ 0 2 ,
  • the cathode active material may be selected from a functional material or nano-structured material having an alkali metal ion-capturing functional group or alkali metal ion-storing surface in direct contact with the electrolyte.
  • the functional group reversibly reacts 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 material or nano-structured material may be selected from the group consisting of (a) a nano-structured or porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso- phase 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 multi-layer graphene platelet; (c) a carbon nanotube selected from a single- walled carbon nanotube or multi-walled carbon nanotube; (d) a carbon nano-fiber, nano-wire, metal oxide nano-wire or fiber, conductive polymer nano-fiber, or a combination thereof; (e) a carbonyl-containing organic or polymeric molecule; (f) a functional material containing a carbonyl, carboxylic, or amine group; and combinations thereof.
  • a nano-structured or porous disordered carbon material selected from a soft carbon, hard carbon,
  • the functional material or nano-structured material has a specific surface area of at least 500 m 2 /g, preferably at least 1,000 m 2 /g.
  • the cathode active materials are not electrically conducting.
  • the cathode active material may be mixed with a conductive filler, such as carbon black (CB), acetylene black (AB), graphite particles, expanded graphite particles, activated carbon, meso-porous carbon, meso-carbon micro bead (MCMB), carbon nano-tube (CNT), carbon nano-fiber (CNF), graphene sheet (also referred to as nano graphene platelet, NGP), carbon fiber, or a combination thereof.
  • CB carbon black
  • AB acetylene black
  • graphite particles expanded graphite particles
  • activated carbon meso-porous carbon
  • MCMB meso-carbon micro bead
  • CNT carbon nano-tube
  • CNF carbon nano-fiber
  • NGP nano graphene platelet
  • carbon fiber or a combination thereof.
  • the nano-scaled filaments are formed into a porous nano- structure that contains massive surfaces to support either the anode active material (e.g. Na or K coating) or the cathode active material (e.g. NaFeP0 4 ).
  • the porous nano-structure should have pores having a pore size preferably from 2 nm to 50 nm, preferably 2 nm-10 nm. These pores are properly sized to accommodate the electrolyte at the cathode side and to retain the cathode active material in the pores during repeated
  • nano-structure may be implemented at the anode side to support the anode active material.
  • multiple conductive nano- filaments are processed to form an integrated aggregate structure, preferably in the form of a closely packed web, mat, or paper, characterized in that these filaments are intersected, overlapped, or somehow bonded (e.g., using a binder material) to one another to form a network of electron-conducting paths.
  • the integrated structure has substantially interconnected pores to accommodate electrolyte.
  • the nano-filament may be selected from, as examples, a carbon nano fiber (CNF), graphite nano fiber (GNF), carbon nano-tube (CNT), metal nano wire (MNW), conductive nano-fibers obtained by electro-spinning, conductive electro-spun composite nano- fibers, nano-scaled graphene platelet (NGP), or a combination thereof.
  • the nano-filaments may be bonded by a binder material selected from a polymer, coal tar pitch, petroleum pitch, meso- phase pitch, coke, or a derivative thereof.
  • the nano-structure provides an environment that is conducive to uniform deposition of alkali metal ions during the battery re-charge, to the extent that no geometrically sharp structures or dendrites were found in the anode after a large number of cycles.
  • the 3-D network of highly conductive nano-filaments provide a substantially uniform attraction of alkali metal ions back onto the filament surfaces during re-charging.
  • This ultra-high specific surface area offers the alkali metal ions an opportunity to uniformly deposit a thin coating on filament surfaces.
  • the high surface area readily accepts a large amount of alkali metal ions in the liquid electrolyte, enabling high recharge rates for an alkali metal secondary battery. Examples
  • raw materials such as silicon, germanium, bismuth, antimony, zinc, iron, nickel, titanium, cobalt, and tin were obtained from either Alfa Aesar of Ward Hill, Mass., Aldrich Chemical Company of Milwaukee, Wis. or Alcan Metal Powders of Berkeley, CA.
  • X-ray diffraction patterns were collected using a diffractometer equipped with a copper target x-ray tube and a diffracted beam monochromator. The presence or absence of characteristic patterns of peaks was observed for each of the alloy samples studied. For example, a phase was considered to be amorphous when the X-ray diffraction pattern was absent or lacked sharp, well-defined peaks.
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • anode or cathode foam structure e.g. Ni foam, Cu foam, Al foam, Ti foam, Ni mesh/web, stainless steel fiber mesh, etc.
  • Metal-coated polymer foams and carbon foams are also used as current collectors.
  • EXAMPLE 3 Graphitic foam -based current collectors from pitch-based carbon foams
  • Pitch powder, granules, or pellets are placed in a aluminum mold with the desired final shape of the foam.
  • Mitsubishi ARA-24 meso-phase pitch was utilized.
  • the sample is evacuated to less than 1 torr and then heated to a temperature approximately 300°C. At this point, the vacuum was released to a nitrogen blanket and then a pressure of up to 1,000 psi was applied.
  • the temperature of the system was then raised to 800°C. This was performed at a rate of 2 degree C/min. The temperature was held for at least 15 minutes to achieve a soak and then the furnace power was turned off and cooled to room temperature at a rate of approximately 1.5 degree C/min with release of pressure at a rate of approximately 2 psi/min.
  • Final foam temperatures were 630°C and 800°C.
  • Preferred non-lithium alkali metal salts include: sodium perchlorate (NaC10 4 ), potassium perchlorate (KC10 4 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), sodium borofluoride (NaBF 4 ), potassium borofluoride (KBF 4 ), sodium
  • sodium salt or potassium salt is preferably selected from
  • the salt concentrations used in the present study were from 0.3M to 3.0 M (most often 0.5M to 2.0M).
  • lithium salts can be added as a second salt (a modifier additive) dissolved in an organic liquid solvent (alone or in a mixture with another organic liquid or an ionic liquid), if so desired.
  • organic liquid solvent alone or in a mixture with another organic liquid or an ionic liquid
  • a good electrolyte additive for helping to stabilize Li metal is
  • Preferred organic liquid solvents include: ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), propylene carbonate (PC), acetonitrile (AN), vinylene carbonate (VC), allyl ethyl carbonate (AEC), 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethyl ether (TEGDME), Poly(ethylene glycol) dimethyl ether (PEGDME), di ethylene glycol dibutyl ether (DEGDBE), 2-ethoxy ethyl ether (EEE), hydrofloroether (e.g. TPTP), sulfone, and sulfolane.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • MEC methylethyl carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • AN aceton
  • Preferred ionic liquid solvents may be selected from a room temperature ionic liquid (RTIL) having a cation selected from tetraalkyl ammonium, di-alkylimidazolium,
  • RTIL room temperature ionic liquid
  • alkylpyridinium, dialkyl-pyrrolidinium, or dialkylpiperidinium is preferably selected from BF 4 " , B(CN) 4 " , CF 3 C0 2 " , CF 3 S0 3 " , N(S0 2 CF 3 ) 2 " , N(COCF 3 )(S0 2 CF 3 ) " , or
  • N(S0 2 F) 2 " Particularly useful ionic liquid-based solvents include N-n-buty ⁇ -N- ethylpyrrolidinium bis(trifluoromethane sulfonyl)imide (BEPyTFSI), iV-methyl-N- propylpiperidinium bis(trifluorom ethyl sulfonyl)imide (PP 13 TFSI), and V,N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis(trifluoromethyl sulfonyl)imide.
  • BEPyTFSI N-n-buty ⁇ -N- ethylpyrrolidinium bis(trifluoromethane sulfonyl)imide
  • PP 13 TFSI iV-methyl-N- propylpiperidinium bis(trifluorom ethyl sulfonyl)imide
  • Natural graphite from Huadong Graphite Co. (Qingdao, China) was used as the starting material.
  • GO was obtained by following the well-known modified Hummers method, which involved two oxidation stages.
  • the first oxidation was achieved in the following conditions: 1100 mg of graphite was placed in a 1000 mL boiling flask. Then, 20 g of K 2 S 2 0 8 , 20 g of P 2 0 5 , and 400 mL of a concentrated aqueous solution of H 2 S0 (96%) were added in the flask. The mixture was heated under reflux for 6 hours and then let without disturbing for 20 hours at room temperature.
  • Oxidized graphite was filtered and rinsed with abundant distilled water until neutral pH. A wet cake-like material was recovered at the end of this first oxidation.
  • the previously collected wet cake was placed in a boiling flask that contains 69 mL of a concentrated aqueous solution of H 2 S0 4 (96%). The flask was kept in an ice bath as 9 g of KMn0 4 was slowly added. Care was taken to avoid overheating. The resulting mixture was stirred at 35°C for 2 hours (the sample color turning dark green), followed by the addition of 140 mL of water.
  • RGO-BS Surfactant-stabilized RGO
  • Sonication was performed using a Branson Sonifier S-250A equipped with a 13 mm step disruptor horn and a 3 mm tapered micro-tip, operating at a 20 kHz frequency. For instance, 10 mL of aqueous solutions containing 0.1 wt.
  • % of GO was sonicated for 10 min and subsequently centrifuged at 2700g for 30 min to remove any non-dissolved large particles, aggregates, and impurities.
  • Chemical reduction of as-obtained GO to yield RGO was conducted by following the method, which involved placing 10 mL of a 0.1 wt. % GO aqueous solution in a boiling flask of 50 mL. Then, 10 ⁇ L of a 35 wt. % aqueous solution of N 2 H 4 (hydrazine) and 70 mL of a 28 wt. % of an aqueous solution of H 4 OH (ammonia) were added to the mixture, which was stabilized by surfactants. The solution was heated to 90°C and refluxed for 1 h. The pH value measured after the reaction was approximately 9. The color of the sample turned dark black during the reduction reaction.
  • RGO was used as a conductive additive in either or both of the anode and cathode in certain alkali metal batteries presently invented.
  • Pre-sodiated RGO e.g. RGO + sodium particles or RGO pre-deposited with sodium coating
  • RGO + sodium particles or RGO pre-deposited with sodium coating was also use as an anode active material in selected sodium -ion cells.
  • slurry coating and drying procedures were conducted to produce conventional electrodes. Electrodes and a separator disposed between two electrodes were then assembled and encased in an Al-plastic laminated packaging envelop, followed by liquid electrolyte injection to form a sodium or potassium battery cell.
  • EXAMPLE 5 Preparation of pristine graphene sheets (0% oxygen)
  • Pristine graphene sheets, as a conductive additive, along with an anode active material (or cathode active material in the cathode) were then incorporated in a battery using both the presently invented procedure of slurry injection into foam pores and conventional procedure of slurry coating, drying and layer laminating. Both alkali metal-ion batteries and alkali metal batteries (injection into cathode only) were investigated. In the latter batteries, primary or secondary, the anode is either Na foil or K chips supported by graphene sheets.
  • EXAMPLE 6 Preparation of pre-sodiated graphene fluoride sheets as an anode active material of a sodium-ion battery
  • HEG highly exfoliated graphite
  • FHEG fluorinated highly exfoliated graphite
  • Pre-cooled Teflon reactor was filled with 20-30 mL of liquid pre-cooled C1F 3 , the reactor was closed and cooled to liquid nitrogen temperature. Then, no more than 1 g of HEG was put in a container with holes for C1F 3 gas to access and situated inside the reactor. In 7-10 days a gray-beige product with approximate formula C 2 F was formed.
  • FHEG FHEG
  • an organic solvent methanol and ethanol, separately
  • an ultrasound treatment 280 W
  • the dispersion became a brownish powder.
  • the graphene fluoride powder was mixed with sodium chips in a liquid electrolyte, allowing for pre-sodiation to occur before or after injection into pores of an anode current collector.
  • EXAMPLE 7 Preparation of disodium terephthalate (Na 2 C 8 H 4 0 4 ) as an anode active material of a sodium-ion battery
  • Disodium terephthalate was obtained by the recrystallization method.
  • An aqueous solution was prepared via the addition of terephthalic acid to an aqueous NaOH solution and then ethanol (EtOH) was added to the mixture to precipitate disodium terephthalate in a water/EtOH mixture.
  • EtOH ethanol
  • terephtalic acid has relatively low pKa values, which allow easy deprotonation by NaOH, affording disodium terephthalate (Na 2 TP) through the acid-base chemistry.
  • terephthalic acid (3.00 g, 18.06 mmol) was treated with sodium hydroxide (1.517 g, 37.93 mmol) in EtOH (60 mL) at room temperature. After 24 h, the suspended reaction mixture was centrifuged and the supernatant solution was decanted. The precipitate was re-dispersed in EtOH and then centrifuged again. This procedure was repeated twice to yield a white solid. The product was dried in vacuum at 150°C for 1 h. Compounds, reagents, and solvents were purchased from standard suppliers and used without further purification. In a separate sample, GO was added to aqueous NaOH solution (5% by wt. of GO sheets) to prepare sheets of graphene-supported disodium terephthalate under comparable reaction conditions.
  • Nio .25 Mno . 75(OH) 2 cathode active material, Na 2 C0 3 , and Li 2 C0 3 were used as starting
  • a sheet of aluminum foil was coated with N-methylpyrrolidinone ( MP) slurry of the cathode mixture.
  • the electrode mixture is composed of 82 wt% active oxide material, 8 wt% conductive carbon black (Timcal Super-P), and 10 wt. % PVDF binder (Kynar).
  • the electrode was initially dried at 70° C for 2 h, followed by dynamic vacuum drying at 80° C for at least 6 h.
  • the sodium metal foil was cut from sodium chunks (Aldrich, 99%) that were cleaned of any oil using hexanes, then rolled and punched out.
  • NMP was replaced by a liquid electrolyte (propylene carbonate with 1 M of NaC10 4 ). Such a slurry was directly injected into the pores of a cathode current collector.
  • the electrolyte was propylene carbonate with 1 M of NaC10 4 electrolyte salt (Aldrich,
  • Pouch cells were galvanostatically cycled to a cutoff of 4.2 V vs. Na/Na + (15 mA/g) and then discharged at various current rates to a cutoff voltage of 2.0 V.
  • the specific discharge capacity herein referred to is the total charge inserted into the cathode during the discharge, per unit mass of the composite cathode (counting the weights of cathode active material, conductive additive or support, binder, and any optional additive combined, but excluding the current collector).
  • the specific charge capacity refers to the amount of charges per unit mass of the composite cathode.
  • the specific energy and specific power values presented in this section are based on the total cell weight for all pouch cells. The morphological or micro-structural changes of selected samples after a desired number of repeated charging and recharging cycles were observed using both transmission electron microscopy (TEM) and scanning electron microscopy (SEM).
  • the Na 3 V 2 (P0 4 ) 3 /C sample was synthesized by a solid state reaction according to the following procedure: a stoichiometric mixture of NaH 2 P0 4 -2H 2 0 (99.9%, Alpha) and V 2 0 3 (99.9%), Alpha) powders was put in an agate j ar as a precursor and then the precursor was ball- milled in a planetary ball mill at 400 rpm in a stainless steel vessel for 8 h. During ball milling, for the carbon coated sample, sugar (99.9%, Alpha) was also added as the carbon precursor and the reductive agent, which prevents the oxidation of V3 + .
  • the mixture was pressed into a pellet and then heated at 900°C for 24 h in Ar atmosphere.
  • the Na 3 V 2 (P0 4 ) 3 /Graphene cathode was prepared in a similar manner, but with sugar replaced by graphene oxide.
  • EXAMPLE 10 Organic material (Na 2 C 6 0 6 ) as a cathode active material of a sodium metal battery
  • disodium rhodizonate Na 2 C 6 0 6
  • the rhodizonic acid dihydrate (species 1 in the following scheme) was used as a precursor.
  • a basic sodium salt, Na 2 C0 3 can be used in aqueous media to neutralize both enediolic acid functions.
  • Disodium rhodizonate (species 2) was readily soluble even in a small amount of water, implying that water molecules are present in species 2. Water was removed in a vacuum at 180°C for 3 hours to obtain the anhydrous version (species 3).
  • the electrolyte was 1M of sodium hexafluorophosphate (NaPF 6 ) in PC-EC.
  • the two Na atoms in the formula Na 2 C 6 0 6 are part of the fixed structure and they do not participate in reversible lithium ion storing and releasing. This implies that sodium ions must come from the anode side. Hence, there must be a sodium source (e.g. sodium metal or sodium metal alloy) at the anode.
  • the anode current collector (Cu foil) is deposited with a layer of sodium (e.g. via sputtering or electrochemical plating). This can be done prior to assembling the sodium-coated layer or simply a sodium foil, a porous separator, and a foamed cathode current collector into a dry cell.
  • the pores of the cathode current collector are them infiltrated with the suspension of cathode active material and conductive additive (Na 2 C 6 06/C composite particles) dispersed in the liquid electrolyte.
  • conductive additive Na 2 C 6 06/C composite particles
  • EXAMPLE 11 Metal naphthalocyanine-RGO hybrid cathode of a sodium metal battery
  • CuPc-coated graphene sheets were obtained by vaporizing CuPc in a chamber along with a graphene film (5 nm) prepared from spin coating of RGO-water suspension. The resulting coated film was cut and milled to produce CuPc-coated graphene sheets, which were used as a cathode active material in a sodium metal battery having a sodium metal foil as the anode active material and 1 M of NaC10 4 in propylene carbonate (PC) solution as the electrolyte.
  • PC propylene carbonate
  • EXAMPLE 12 Preparation of MoS 2 /RGO hybrid material as a cathode active material of a Na metal battery
  • Nanoribbons herein produced are, on average, 30-55 nm thick with widths and lengths ranging from hundreds of nanometers to several micrometers. Larger nanoribbons were subjected to ball- milling for reducing the lateral dimensions (length and width) to below 200 nm. Nanoribbons prepared by these procedures (with or without the presence of graphene sheets or exfoliated graphite flakes) were used as a cathode active material of a Na or K metal battery. Surprisingly, Bi 2 Se 3 chalcogenide nanoribbons are capable of storing both Na and K ions on their surfaces.
  • MXenes were produced by partially etching out certain elements from layered structures of metal carbides such as Ti 3 AlC 2 . For instance, an aqueous 1 M NH 4 FIF 2 was used at room temperature as the etchant for Ti 3 AlC 2 .
  • MXene materials investigated include
  • EXAMPLE 15 Preparation of graphene-supported Mn0 2 and NaMn0 2 cathode active material
  • the Mn0 2 powder was synthesized by two methods (each with or without the presence of graphene sheets).
  • a 0.1 mol/L KMn0 4 aqueous solution was prepared by dissolving potassium permanganate in deionized water.
  • 13.32 g surfactant of high purity sodium bis(2-ethylhexyl) sulfosuccinate was added in 300mL iso-octane (oil) and stirred well to get an optically transparent solution.
  • NaMn0 2 and NaMn0 2 /graphene composite were synthesized by ball- milling mixtures ofNa 2 C0 3 and Mn0 2 (at a molar ratio of 1 :2), with or without graphene sheets, for 12 h followed by heating at 870°C for 10 h.
  • a sheet of potassium film was used as the anode active material while a layer of PVDF- bonded reduced graphene oxide (RGO) sheets, supplied from Angstron Materials, Inc. (Dayton, Ohio), was used as the cathode active material.
  • the electrolyte used was 1 M of KC10 4 salt dissolved in a mixture of propylene carbonate and DOL (1/1 ratio). Charge-discharge curves were obtained at several current densities (from 50 mA/g to 50 A/g), corresponding to different C rates, with the resulting energy density and power density data measured and calculated.
  • a typical anode composition includes 85 wt. % active material (e.g., Sn- or Na 2 C 8 H 4 0 4 -coated graphene sheets), 7 wt. % acetylene black (Super-P), and 8 wt. % polyvinylidene fluoride binder (PVDF, 5 wt. % solid content) dissolved in N- methyl-2-pyrrolidinoe ( MP).
  • active material e.g., Sn- or Na 2 C 8 H 4 0 4 -coated graphene sheets
  • Super-P acetylene black
  • PVDF polyvinylidene fluoride binder
  • MP N- methyl-2-pyrrolidinoe
  • Cathode layers are made in a similar manner (using Al foil as the cathode current collector) using the conventional slurry coating and drying procedures.
  • An anode layer, separator layer (e.g. Celgard 2400 membrane), and a cathode layer are then laminated together and housed in a plastic-Al envelop.
  • the cell is then injected with 1 M NaPF 6 electrolyte solution dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC-DEC, 1 : 1 v/v).
  • EC-DEC ethylene carbonate
  • DEC-DEC diethyl carbonate
  • ionic liquids were used as the liquid electrolyte.
  • the cell assemblies were made in an argon-filled glove-box.
  • the anode current collector, the separator, and the cathode current collector are assembled in a protective housing before or after the injecting (or impregnation) of the first suspension and/or the injecting (or impregnation) of the second suspension.
  • a protective housing before or after the injecting (or impregnation) of the first suspension and/or the injecting (or impregnation) of the second suspension.
  • the first suspension was then injected into the anode current collector and the second suspension was injected into the cathode current collector.
  • the pouch was then sealed.
  • the anode layer, a porous separator layer, and the cathode layer were then assembled and housed in a pouch to form a cell.
  • electrochemical workstation at a typical scanning rate of 1 mV/s.
  • electrochemical performances of various cells were also evaluated by galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g.
  • galvanostatic charge/discharge cycling at a current density of from 50 mA/g to 10 A/g.
  • multi-channel battery testers manufactured by LAND were used.
  • cycle life of a battery it is a common practice to define the cycle life of a battery as the number of charge-discharge cycles that the battery suffers 20% decay in capacity based on the initial capacity measured after the required electrochemical formation.
  • cycle life of a Na-ion or K-ion cell is herein followed.
  • volumetric energy density is increased from 241 Wh/L to 493 Wh/L.
  • This latter value of 493 Wh/L is exceptional for a sodium-ion battery using a hard carbon anode and a sodium transition metal phosphate-type cathode.
  • Figure 6 shows the Ragone plots (both gravimetric and volumetric power density vs. gravimetric and volumetric energy density) of two cells, both containing graphene-embraced Sn nano particles as the anode active material and NaFeP0 4 nano particles as the cathode active material.
  • the experimental data were obtained from the Na-ion battery cells that were prepared by the presently invented method and those by the conventional slurry coating of electrodes.
  • FIG.7 Shown in FIG.7 are Ragone plots of sodium metal batteries containing a sodium foil as the anode active material, disodium rhodizonate (Na 2 C 6 0 6 ) as the cathode active material, and lithium salt (NaPF 6 )-PC/DEC as organic liquid electrolyte.
  • the data are for both sodium metal cells prepared by the presently invented method and those by the conventional slurry coating of electrodes. These data indicate that both the gravimetric and volumetric energy densities and power densities of the sodium metal cells prepared by the presently invented method are significantly higher than those of their counterparts prepared via the conventional method.
  • the differences are huge and are likely due to the significantly higher active material mass loading associated with the presently invented cells, reduced proportion of overhead (non-active) components relative to the active material weight/volume, no need to have a binder resin, surprisingly better utilization of the electrode active material (most, if not all, of the active material contributing to the sodium ion storage capacity; no dry pockets or ineffective spots in the electrode, particularly under high charge/discharge rate conditions), and the surprising ability of the inventive method to more effectively pack active material particles in the pores of the foamed current collector.
  • the gravimetric energy density of the presently invented sodium metal-organic cathode cell is as high as 320 Wh/kg, higher than those of all rechargeable sodium metal or sodium-ion batteries ever reported (recall that current Na-ion batteries typically store 100-150 Wh/kg based on the total cell weight).
  • a gravimetric power density of 1,204 W/kg and volumetric power density of 3490 W/L would have been un-thinkable.
  • overhead components including current collectors, electrolyte, separator, binder, connectors, and packaging, are non-active materials and do not contribute to the charge storage amounts. They only add weights and volumes to the device. Hence, it is desirable to reduce the relative proportion of overhead component weights and increase the active material proportion. However, it has not been possible to achieve this objective using conventional battery production processes.
  • the present invention overcomes this long-standing, most serious problem in the art of lithium batteries.
  • the weight proportion of the anode active material (e.g. graphite or carbon) in a lithium-ion battery is typically from 12% to 17%, and that of the cathode active material (for inorganic material, such as LiMn 2 0 4 ) from 22% to 41%, or from 10% to 15% for organic or polymeric.
  • the anode active material e.g. graphite or carbon
  • the cathode active material for inorganic material, such as LiMn 2 0 4
  • the active material weight is typically from 5% to 10% of the total device weight, which implies that the actual cell (device) energy or power densities may be obtained by dividing the corresponding active material weight-based values by a factor of 10 to 20. After this factor is taken into account, the properties reported in these papers do not really look any better than those of commercial batteries. Thus, one must be very careful when it comes to read and interpret the performance data of batteries reported in the scientific papers and patent applications.
  • FIG. 9 Shown in FIG. 9 are the Ragone plots of a series of hybrid cells having a hybrid anode active material (a mixture of activated carbon particles and NaTi 2 (P0 4 ) 3 particles) and ⁇ - ⁇ 0 2 particles as a cathode active material prepared by the conventional slurry coating and those by the presently invented process of direct injection into pores of foamed current collectors.
  • the liquid electrolyte is aqueous solution of 2 M of Na 2 S0 4 in water.
  • the electrode thickness of an alkali metal battery is a design parameter that can be freely adjusted for optimization of device performance. Contrary to this perception, in reality, the alkali metal battery electrode thickness is manufacturing-limited and one cannot produce electrodes of good structural integrity that exceed certain thickness level in a real industrial manufacturing environment (e.g. a roll-to-roll coating facility).
  • the conventional battery electrode design is based on coating an electrode layer on a flat metal current collector, which has several major problems: (a) A thick coating on Cu foil or Al foil requires a long drying time (requiring a heating zone 30-100 meters long), (b) Thick electrodes tend to get delaminated or cracked upon drying and subsequent handling, and even with a resin binder proportion as high as 15-20% to hopefully improve the electrode integrity this problem remains a major limiting factor.
  • FIG.10 Shown in FIG.10 are the cell-level gravimetric (Wh/kg) and volumetric energy densities
  • the Mn0 2 /RGO cathode prepared via the conventional method without delamination and cracking and those by the presently invented method.
  • the data points are labelled as the gravimetric ( ⁇ ) and volumetric (A) energy density of the conventional Na-Mn0 2 /RGO batteries and the gravimetric ( ⁇ ) and volumetric (X) energy density of the presently invented ones.
  • the electrodes can be fabricated up to a thickness of 100-200 ⁇ using the conventional slurry coating process.
  • the electrode thickness there is no theoretical limit on the electrode thickness that can be achieved with the presently invented method.
  • the practical electrode thickness is from 10 ⁇ to 1000 ⁇ , more typically from 100 ⁇ to 800 ⁇ , and most typically from 200 ⁇ to 600 ⁇ .
  • the weight of the anode and cathode active materials combined accounts for up to about 30%-50% of the total mass of the packaged commercial lithium batteries, a factor of 30%-50% must be used to extrapolate the energy or power densities of the device from the performance data of the active materials alone.
  • the energy density of 300 Wh/kg of combined hard carbon and sodium nickel manganese oxide) weights will translate to about 90- 150 Wh/kg of the packaged cell.
  • this extrapolation is only valid for electrodes with thicknesses and densities similar to those of commercial electrodes (150 ⁇ or about 15 mg/cm 2 of the carbon anode and 30 mg/cm 2 of transition metal oxide cathode).
  • An electrode of the same active material that is thinner or lighter will mean an even lower energy or power density based on the cell weight.
  • the presently invented method enables the Na, K, and Na/K batteries to go well beyond these limits for all active materials investigated.
  • the instant invention makes it possible to elevate the active material proportion above 90% if so desired; but typically from 45% to 85%), more typically from 40% to 80%>, even more typically from 40% to 75%, and most typically from 50% to 70%.
  • Dendrite issues commonly associated with Li, Na, and K metal secondary cells are also resolved by using the presently invented foamed current collector strategy. Hundreds of cells have been investigated and those cells having a foamed anode current collector were not found to fail due to dendrite penetration through the separator. SEM examination of samples from presently invented sodium and potassium cells confirms that the re-deposited alkali metal surfaces on pore walls in a porous anode current collector appear to be smooth and uniform, exhibiting no sign of sharp metal deposit or tree-like features as often observed with

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CN114744163A (zh) * 2022-04-21 2022-07-12 电子科技大学 一种有机正极材料、制备方法及在碱金属离子电池中的应用
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