WO2019241065A1 - Batterie au lithium à charge rapide - Google Patents

Batterie au lithium à charge rapide Download PDF

Info

Publication number
WO2019241065A1
WO2019241065A1 PCT/US2019/036051 US2019036051W WO2019241065A1 WO 2019241065 A1 WO2019241065 A1 WO 2019241065A1 US 2019036051 W US2019036051 W US 2019036051W WO 2019241065 A1 WO2019241065 A1 WO 2019241065A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
sulfonated
poly
group
anode
Prior art date
Application number
PCT/US2019/036051
Other languages
English (en)
Inventor
Hui He
Chueh LIU
Aruna Zhamu
Bor Z. Jang
Original Assignee
Nanotek Instruments, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/006,131 external-priority patent/US11024849B2/en
Priority claimed from US16/006,138 external-priority patent/US11171388B2/en
Application filed by Nanotek Instruments, Inc. filed Critical Nanotek Instruments, Inc.
Publication of WO2019241065A1 publication Critical patent/WO2019241065A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure provides a fast-chargeable lithium-ion battery and a lithium metal battery (having lithium metal or metal alloy as the main anode active material).
  • Li-ion Rechargeable lithium-ion
  • rechargeable lithium metal batteries e.g. lithium- sulfur, lithium- selenium, 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 or lithium intercalation compound as an anode active material (except Li 4.4 Si, which has a specific capacity of 4,200 mAh/g).
  • Li metal batteries having a lithium metal anode
  • have a significantly higher energy density than lithium-ion batteries e.g. having a graphite anode).
  • rechargeable lithium metal batteries were produced using non-lithiated compounds having relatively high specific capacities, 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 having relatively high specific capacities such as TiS 2 , MoS 2 , Mn0 2 , Co0 2 , and V 2 0 5
  • the cathode active materials When the battery was discharged, 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 caused internal shorting, thermal runaway, and explosion.
  • the production of these types of secondary batteries was stopped in the early l990'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 repeated charge-discharge cycles 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 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.
  • Li-ion batteries are promising energy storage devices for electric drive vehicles
  • state-of-the-art Li-ion batteries have yet to meet the cost, safety, and performance targets.
  • Li-ion cells typically use a lithium transition-metal oxide or phosphate as a positive electrode (cathode) that de/re-intercalates Li + at a high potential with respect to the carbon negative electrode (anode).
  • the specific capacity of lithium transition-metal oxide or phosphate based cathode active material is typically in the range from 140-170 mAh/g.
  • the specific energy of commercially available Li-ion cells is typically in the range from 120-220 Wh/kg, most typically 150-180 Wh/kg. These specific energy values are two to three times lower than what would be required for battery-powered electric vehicles to be widely accepted.
  • the same flammable solvents previously used for lithium metal secondary batteries are also used in most of the lithium-ion batteries.
  • the lithium-ion cell has its own intrinsic safety issue.
  • the transition metal elements in the lithium metal oxide cathode are highly active catalysts that can promote and accelerate the decomposition of organic solvents, causing thermal runaway or explosion initiation to occur at a relatively low electrolyte temperature (e.g. ⁇ 200°C, as opposed to normally > 400°C without the catalytic effect).
  • Ionic liquids are a new class of purely ionic, salt-like materials that are liquid at unusually low temperatures.
  • the official definition of ILs uses the boiling point of water as a point of reference:“Ionic liquids are ionic compounds which are liquid below l00°C”.
  • a particularly useful and scientifically interesting class of ILs is the room temperature ionic liquid (RTIL), which refers to the ionic salts that are liquid at room temperature or below.
  • RTILs are also referred to as organic liquid salts or organic molten salts.
  • An accepted definition of an RTIL is any salt that has a melting temperature lower than ambient temperature.
  • ILs have relatively high viscosity at room or lower temperatures; thus being considered as not amenable to lithium ion transport;
  • ILs are capable of dissolving lithium polysulfides at the cathode and allowing the dissolved species to migrate to the anode (i.e., the shuttle effect remains severe);
  • ILs For lithium metal secondary cells, most of the ILs strongly react with lithium metal at the anode, continuing to consume Li and deplete the electrolyte itself as charges and discharges are repeated. These factors lead to relatively poor specific capacity (particularly under high current or high charge/discharge rate conditions, hence lower power density), low specific energy density, rapid capacity decay and poor cycle life.
  • ILs remain extremely expensive. Consequently, as of today, no commercially available lithium battery makes use of an ionic liquid as the primary electrolyte component.
  • Li-S lithium-sulfur
  • a Li-S cell consists of elemental sulfur as the positive electrode and lithium as the negative electrode.
  • the lithium-sulfur cell operates with a redox couple, described by the reaction S 8 + l6Li 8Li 2 S that lies near 2.2 V with respect to Li + /Li°.
  • This electrochemical potential is approximately 2/3 of that exhibited by conventional positive electrodes.
  • Li-S cells have the opportunity to provide a significantly higher energy density (a product of capacity and voltage). Values can approach 2,500 Wh/kg or 2,800 Wh // based on the combined Li and S weight or volume (not based on the total cell weight or volume), respectively, assuming complete reaction to Li 2 S.
  • Li-S cells e.g., rechargeable Li metal cells, Li-S cells, and Li- Air cells
  • conventional Li-ion cells still make use of significant amounts of flammable liquids (e.g. propylene carbonate, ethylene carbonate, l,3-dioxolane, etc.) as the primary electrolyte solvent, risking danger of explosion;
  • flammable liquids e.g. propylene carbonate, ethylene carbonate, l,3-dioxolane, etc.
  • a significant drawback with cells containing cathodes comprising elemental sulfur, organosulfur and carbon-sulfur materials relates to the dissolution and excessive out-diffusion of soluble sulfides, polysulfides, organo-sulfides, carbon- sulfides and/or carbon-polysulfides (hereinafter referred to as anionic reduction products) from the cathode into the rest of the cell.
  • anionic reduction products This phenomenon is commonly referred to as the Shuttle Effect.
  • solid electrolytes are effective in addressing the lithium metal dendrite and flammability issues
  • conventional solid-state electrolytes have the following major deficiencies: low lithium ion conductivities (typically « 10 4 S/cm, more typically « 10 5 S/cm, and further more typically « 10 6 S/cm), difficulty in making solid-state electrolyte (high temperature sintering typically required) and implementing it in a battery cell, extreme brittleness, no flexibility (hence, not being compliant and being in poor ionic contact with the anode and/or cathode and, hence, poor active material utilization efficiency), and high costs.
  • the low lithium ion conductivity typically « 10 4 S/cm, more typically « 10 5 S/cm, and further more typically « 10 6 S/cm
  • difficulty in making solid-state electrolyte high temperature sintering typically required
  • a specific object of the present disclosure is to provide a lithium-ion battery or rechargeable lithium metal battery (e.g. Li-S battery) that can be rapidly recharged and exhibits a high specific energy, a long cycle-life, and a high level of safety.
  • a lithium-ion battery or rechargeable lithium metal battery e.g. Li-S battery
  • a very important object of the present disclosure is to provide a simple, cost-effective, and easy-to-implement approach to preventing potential Li metal dendrite-induced internal short circuit and thermal runaway problems in various fast-charging Li metal and Li-ion batteries.
  • the present disclosure provides a lithium secondary battery, as schematically illustrated in FIG. 1, comprising an anode, a cathode, a porous separator disposed between the anode and the cathode, an electrolyte, and a lithium ion reservoir disposed between the anode and the porous separator and configured to receive lithium ions from the cathode through the porous separator when the battery is charged and enable the lithium ions to enter the anode in a time- delayed manner
  • the lithium ion reservoir comprises an electron-conducting and/or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 pm, and lithium-capturing groups residing in the pores, wherein the lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when said battery is charged; (b) electron-donating groups interspaced between non- electron-donating groups; (c) anions and cations wherein
  • the lithium secondary battery can be a lithium-ion battery wherein the anode contains particles of graphite, Si, SiO x , Sn, Sn0 2 , Ge, etc. as the main anode active material.
  • the battery may be a rechargeable lithium metal battery, such as a lithium-sulfur battery, a lithium- selenium battery, or a lithium-air battery, wherein the anode contains lithium metal (e.g. Li foil) or lithium metal ahoy (containing at least 60% by weight of Li element).
  • the present disclosure also provides a method of improving fast-chargeability of a lithium secondary battery containing an anode, a cathode, a porous separator disposed between the anode and the cathode, and an electrolyte, wherein the method comprises disposing a lithium ion reservoir between the anode and the porous separator and configured to receive lithium ions from the cathode through the porous separator when the battery is charged and to enable the lithium ions to enter the anode in a time-delayed manner.
  • the lithium ion reservoir may comprise an electron-conducting or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 pm, and lithium-capturing groups residing in the pores, wherein the lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when the battery is charged; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li +1 to Li +6 , wherein 0 ⁇ d ⁇ 1.
  • the lithium ion reservoir comprises an ionic liquid hosted by a porous structure.
  • the lithium-capturing group is selected from a molecule having a core or backbone structure and at least a side group that is ionic or electron rich.
  • the core or backbone structure may contain an aryl, heterocycloalkyl, crown etheryl, cyclamyl, cyclenyl, l,4,7-triazacyclononayl, hexacyclenyl, cryptandyl, naphtalenyl, antracenyl, phenantrenyl, tetracenyl, chrysenyl, tryphenylenyl, pyrenyl, pentacenyl, single-benzene or cyclic structure, double-benzene or bi-cyclic structure, or multiple-cyclic structure having 3-10 benzene rings.
  • the side group may contain C0 2 H, CO 2 M 1 , C0 2 R, SO 3 H, SO 3 M 1 , R(3 ⁇ 4H 2 , PCLM ⁇ , P0 3 M1H, P0 4 H 2 , P0 4 M 1 2 , P0 4 M1H, P0 4 M 2 , C(0)NHOH, NH 2 , NHR, N(R) 2 , N0 2 , COOR, CHO, CH 2 OH, OH, OR, SH, SR, C(0)N(R) 2 , C(0)NHR, C(0)NH 2 , halide, tosylate, mesylate, S0 2 NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano, CF 3 , or Si(OR) 3 ; wherein R is independently selected from methyl, ethyl, isopropyl, n-propyl, alkyl, haloalkyl, cyclo
  • the redox pair with lithium is selected from lithium 4- methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium 2,6-dimethylbenzene- 1, 4-disulfonate, 3,3'-((l,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3'-((4- mercapto-l,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate, poly(lithium-4-styrenesulfonate, lithium sulfate, lithium phosphate, lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium 1,1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8- heptadecafluorooctane-l- sulfonate, lithium 2, 6-di-tert-butylbenzene-l, 4-
  • Electron-donating groups may be selected from those molecules having one to 10 benzene rings or cyclic structure as the core/backbone portion having conjugated double bonds, acidic groups, etc. Examples include sodium 4-methylbenzenesulfonate, sodium 3,5- dicarboxybenzenesulfonate, sodium 2, 6-dimethylbenzene-l, 4-disulfonate, and sodium aniline sulfonate. These molecules in the lithium ion reservoir appear to be capable of partially reducing the incoming lithium ions that pass through the porous separator from the cathode.
  • the lithium ion-capturing group may contain a salt that is dissociated into an anion and a cation in a liquid medium (typically an organic solvent).
  • a salt that is dissociated into an anion and a cation in a liquid medium (typically an organic solvent).
  • the liquid medium to dissolve these salts may contain a solvent selected from l,3-dioxolane (DOL), l,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (g-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (
  • TTSPi tris(trimethylsilyl)phosphite
  • TEP triallyl phosphate
  • DTD ethylene sulfate
  • PS propene sultone
  • DEC diethyl carbonate
  • alkylsiloxane Si-O
  • alkyylsilane Si-C
  • liquid oligomeric silaxane -Si-O-Si-
  • TEGDME tetraethylene glycol dimethylether
  • the lithium ion-capturing groups may contain ionic liquids, which are low melting temperature salts that are in a molten or liquid state when above a desired temperature.
  • a salt is considered as an ionic liquid if its melting point is below l00°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 desired ionic liquids for use in the presently invented lithium ion reservoir preferably have a melting point lower than 60°C, more preferably lower than 0°C, and further more preferably lower than -20°C.
  • the IL 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).
  • the anions of the ionic liquid may be selected to be more mobile than the c
  • a typical and well-known ionic liquid is formed by the combination of a l-ethyl-3- methylimidazolium (EMI) cation and an /V,/V-bis(trifluoromethane)sulfonamide (TFSI) anion.
  • EMI l-ethyl-3- methylimidazolium
  • TFSI /V,/V-bis(trifluoromethane)sulfonamide
  • Ionic liquids are basically composed of organic ions that come in an essentially 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(trifluoromethanesulfonyl) imide, bis(fluorosulfonyl)imide, and hexafluorophosphate as anions. Based on their
  • compositions, ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.
  • RTILs room temperature ionic liquids
  • RTILs include, but not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl- pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium.
  • RTILs include, but not limited to, BF 4 , B(CN) 4 , CH3BF3 , CH2CHBF3 , CF3BF3 , C2F5BFT, ft-C 3 F 7 BF 3 , ft-C 4 F 9 BF 3 , PF 6 , CF 3 C0 2- , CF3SO3-, N(S0 2 CF 3 ) 2- , N(C0CF 3 )(S0 2 CF 3 )-, N(S0 2 F) 2 , N(CN) 2- , C(CN) 3 , SCN-, SeCN , CuCl 2 _ , AlCLf, F(HF) 23 , etc.
  • the porous framework structure is configured to receive lithium ions coming from the cathode through the porous separator and tentatively or partially retain the lithium ions (not lithium metal) in the pores of this lithium ion reservoir, typically a thin layer between the anode and the separator.
  • This thin layer of lithium ion reservoir preferably has a thickness from 10 nm to 500 pm, more preferably from 100 nm to 100 pm.
  • This lithium ion reservoir may further contain some electrolyte (e.g. liquid electrolyte).
  • the porous framework structure contains a conducting foam, which can be a closed-cell foam or open-cell foam.
  • the open-cell foam is preferred.
  • the pores preferably contain mesoscaled pores having a pore size from 2 nm to 100 nm, more preferably from 2 nm to 50 nm, which are more effective in holding certain lithium ion-capturing species..
  • the electron-conducting porous structure has pore walls comprising an electron-conducting material selected from carbon nanotubes, carbon nanofibers, graphene sheets, expanded graphite platelets, carbon fibers, graphite fibers, graphite particles, needle coke, mesocarbon microbeads, carbon particles, carbon black, acetylene black, activated carbon particles, or a combination thereof.
  • Multiple fibers or particles of electron-conducting materials optionally may be bonded by a resin binder (0.1% - 10%) to improve the structural integrity of the porous structure.
  • the electron-conducting porous structure contains a graphene foam.
  • the lithium ion-conducting porous structure comprises a polymer foam or polymer fabric having pores and pore walls.
  • the pore walls comprise a lithium ion- conducting polymer having a lithium ion conductivity from 10 -8 to 10 -2 S/cm when measured at 25 °C.
  • the polymer foam may contain some desired amount of an electron-conducting material selected from, for instance, carbon nanotubes, carbon nanofibers, graphene sheets, expanded graphite platelets, carbon fibers, graphite fibers, graphite particles, needle coke, mesocarbon microbeads, carbon particles, carbon black, acetylene black, activated carbon particles, or a combination thereof.
  • the lithium ion-conducting polymer is selected from sulfonated polyaniline, sulfonated polypyrrole, a sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, or a combination thereof.
  • the lithium ion-conducting polymer is selected from sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated styrene- butadiene rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, metallocene-based sulfonated poly(ethylene-co-octene) elastomer, sulfonated poly(ethylene-co-butene) elastomer, sulfonated styrene-ethylene- butadiene- styrene elastomer, sulfonated epichlorohydrin rubber,
  • the lithium ion-conducting polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride,
  • the lithium ion-conducting polymer is selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, and poly(vinylidene fluoride) -hexafluoropropylene (PVDF-HFP) copolymer, modified polyacrylic acid-based copolymer, polyester polyamine amide-based copolymer, polycarboxylic acid-based copolymer, polyalkylol amino amide-based copolymer, polysiloxane polyacryl-based copolymer, polysiloxane polycarboxylic acid-based copolymer, polyalkoxylate-based copolymer, a copolymer
  • the anode typically is composed of an anode active material, a conductive additive (e.g. carbon black, acetylene black, graphite platelets, carbon nanotubes, etc.), and a resin binder (e.g. the well-known SBR rubber, PVDF, CMC, etc.).
  • the anode electrode may comprise an anode active material comprising an element selected from Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn, Al, Co, Ni, Ti, or an alloy thereof.
  • the anode comprises an anode active material selected from the group consisting of:
  • lithiated and un-lithiated oxides carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Mn, V, or Cd, and their mixtures, composites, or lithium-containing composites;
  • lithium titanate lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide;
  • the particles of an anode active material preferably have a diameter from 10 nm to 1 pm, more preferably from 20 to 500 nm, and most preferably from 20 to 100 nm.
  • the electrolyte used in the instant lithium battery may be selected from a non-aqueous liquid electrolyte, polymer gel electrolyte, polymer electrolyte, quasi-solid electrolyte, solid-state inorganic electrolyte, ionic liquid electrolyte, or a combination thereof.
  • the electrolyte comprises a lithium ion-conducting inorganic species or lithium salt selected from lithium perchlorate (LiCl0 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro- methanesulfonate (L1CF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3S0 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4 ), lithium nitrate (L1NO3), Li-fluoroalkyl-phosphate (LiPF3(CF 2 CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluorome
  • the electrolyte may comprise a solvent selected from l,3-dioxolane (DOL), 1,2- dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (g-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylen
  • the electrolyte is preferably a non-flammable electrolyte e.g. an electrolyte having a flash point higher than 150°C, preferably higher than 200°C, and most preferably no detectable flash point (flash point being too high to be detectable or the amount of organic vapor being too little to detect at a temperature as high as 200°C).
  • a non-flammable electrolyte e.g. an electrolyte having a flash point higher than 150°C, preferably higher than 200°C, and most preferably no detectable flash point (flash point being too high to be detectable or the amount of organic vapor being too little to detect at a temperature as high as 200°C).
  • the non-flammable electrolyte can be a room temperature ionic liquid.
  • the non-flammable electrolyte contains a solid polymer electrolyte or an inorganic solid electrolyte.
  • a non-flammable quasi-solid electrolyte contains a lithium salt dissolved in a liquid solvent having a lithium salt concentration from 3.5 M to 14.0 M (more typically from 3.5 M to 10 M and further more typically from 5.0 M to 7.5 M) so that the electrolyte exhibits a vapor pressure less than 0.01 kPa when measured at 20°C, a vapor pressure less than 60% of the vapor pressure of the liquid solvent alone, a flash point at least 20 degrees Celsius higher than a flash point of the liquid solvent alone, a flash point higher than 150°C, or no flash point.
  • a non-flammable quasi-solid electrolyte contains a lithium salt dissolved in a mixture of a liquid solvent and a liquid additive having a lithium salt concentration from 1.5 M to 5.0 M so that the electrolyte exhibits a vapor pressure less than 0.01 kPa when measured at 20°C, a vapor pressure less than 60% of the vapor pressure of the liquid solvent alone, a flash point at least 20 degrees Celsius higher than a flash point of the liquid solvent alone, a flash point higher than 150°C, or no flash point.
  • the liquid additive is selected from hydrofluoro ether (HFE), trifluoro propylene carbonate (FPC), methyl nonafluorobutyl ether (MFE), fluoroethylene carbonate (FEC), tris(trimethylsilyl)phosphite (TTSPi), triallyl phosphate (TAP), ethylene sulfate (DTD), 1,3-propane sultone (PS), propene sultone (PES), diethyl carbonate (DEC), alkylsiloxane (Si-O), alkyylsilane (Si-C), liquid oligomeric silaxane (-Si-O-Si-), tetraethylene glycol dimethylether (TEGDME), canola oil, or a combination thereof.
  • HFE hydrofluoro ether
  • FPC trifluoro propylene carbonate
  • MFE methyl nonafluorobutyl ether
  • FEC fluoroethylene carbonate
  • the liquid additive-to-liquid solvent ratio in the mixture is from 5/95 to 95/5 by weight, preferably from 15/85 to 85/15 by weight, further preferably from 25/75 to 75/25 by weight, and most preferably from 35/65 to 65/35 by weight.
  • cathode active materials there is no limitation on the type of cathode active materials that can be incorporated in the cathode. Any commonly used cathode active material for a lithium-ion battery or lithium metal battery can be used for practicing the present disclosure.
  • the cathode active material may be selected from an inorganic material, an organic or polymeric material, a metal oxide, metal phosphate, metal sulfide, metal halide, metal selenide, or a combination thereof.
  • the metal oxide/phosphate/sulfide/selenide/halide may be selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide (e.g.
  • lithium iron phosphate lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, sodium cobalt oxide sodium nickel oxide, sodium manganese oxide, sodium vanadium oxide, sodium-mixed metal oxide, sodium iron phosphate, sodium manganese phosphate, sodium vanadium phosphate, sodium mixed metal phosphate, transition metal sulfide, lithium polysulfide, sodium polysulfide, lithium selenide, magnesium poly sulfide, or a combination thereof.
  • the cathode active material is selected from sulfur, sulfur compound, sulfur-carbon composite, sulfur-polymer composite, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
  • the inorganic material may be 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 metal oxide/phosphate/sulfide contains a vanadium oxide selected from the group consisting of V0 2 , Li x V0 2 , V 2 Os, Li x V 2 Os, V 3 0 8 , Li x V 3 0 8 , Li x V 3 0 7 , V4O9, Li x V 4 09, V 6 O l3 , Li x V 6 0i 3 , their doped versions, their derivatives, and combinations thereof, wherein 0.1 ⁇ x ⁇ 5.
  • the metal oxide/phosphate/sulfide is selected from a layered compound LiM0 2 , spinel compound LiM 2 0 4 , olivine compound LiMP0 4 , silicate compound Li 2 MSi0 4 , Tavorite compound LiMP0 4 F, borate compound LiMB0 3 , or a
  • M is a transition metal or a mixture of multiple transition metals.
  • the inorganic material for use as a cathode active material may be selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) a combination thereof.
  • the organic material or polymeric material is selected from poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 3,4,9, lO-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9, lO-tetraone (PYT), polymer- bound PYT, quino(triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,l0,l l-hexamethoxytriphenylene (HMTP), poly(5-amino- l,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS 2 ) 3 Jn), lithiated l,4,5,8-naphthale
  • HAT(CN) 6 hexaazatriphenylene hexacarbonitrile
  • HAT(CN) 6 5-benzylidene hydantoin
  • isatine lithium salt pyromellitic diimide lithium salt
  • tctrahydroxy- -hcnzoquinonc derivatives TQLi 4
  • PPP N,N’- diphenyl-2,3,5,6-tetraketopiperazine
  • AP N,N’-diallyl-2,3,5,6-tetraketopiperazine
  • PRP N,N’- dipropyl-2,3,5,6-tetraketopiperazine
  • PRP a thioether polymer
  • quinone compound 1,4- benzoquinone, 5,7,l2,l4-pentacenetetrone (PT), 5-amino-2, 3-dihydro- l,4-dyhydroxy
  • anthraquinone ADDAQ
  • 5-amino-l,4-dyhydroxy anthraquinone ADAQ
  • calixquinone L14C6O6, Li 2 C 6 0 6 , LieCeOe, or a combination thereof.
  • the thioether polymer in the above list may be selected from poly[methanetetryl- tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), a polymer containing poly(ethene-l,l,2,2-tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, poly(2-phenyl-l,3-dithiolane) (PPDT), poly(l,4-di(l,3-dithiolan-2- yljbcnzcnc) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[l,2,4,5- tetrakis(propylthio)benzene] (PTKPTB, or poly
  • the organic material contains a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium
  • phthalocyanine aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, or a combination thereof.
  • These compounds are preferably mixed with a conducting material to improve their electrical conductivity and rigidity so as to enable the peeling-off of graphene sheets from the graphitic material particles.
  • FIG. 1(A) Schematic of a rechargeable lithium metal battery containing a lithium metal anode and a lithium ion reservoir disposed between the anode and the porous separator
  • FIG. 1(B) Schematic of a lithium-ion battery containing an anode (comprising particles of an anode active material, such as Si and Sn0 2 , an optional conductive additive, and an optional resin binder) and a lithium ion reservoir disposed between the anode and the porous separator.
  • anode comprising particles of an anode active material, such as Si and Sn0 2 , an optional conductive additive, and an optional resin binder
  • FIG. 2 Lithium ion conductivity values in a solid polymer mixture of a sulfonated polymer (S- PEEK or S-PTFE) and a conventional electrolyte polymer (PEO or PPO) plotted as a function of the sulfonated polymer proportion (each containing 30% by weight of lithium salt).
  • FIG. 3 The actual charge storage capacity values of two cells each containing an anode of
  • lithiated natural graphite particles and a cathode of G0/Li x V 3 0 8 nanosheets are plotted as a function of the C rates.
  • One cell contains a lithium ion reservoir disposed between the anode and the porous separator, but the other cell does not have such a reservoir.
  • FIG. 4 The discharge capacity values of two Li-S cells (each featuring a Li foil as the anode active material and graphene-supported sulfur as the cathode active material) are plotted as a function of the number of charge/discharge cycles.
  • One cell contains a lithium ion reservoir disposed between the Li metal anode and the separator, but the other cell does not have such a reservoir.
  • the present disclosure provides a safe and high-performing rechargeable lithium battery, which can be any of the various types of lithium-ion cells (e.g. using graphite or Si as the main anode active material) or lithium metal cells (e.g. Li-metal oxide, Li-S, Li-air, and Li-Se cells, etc. using lithium metal as the main anode active material).
  • lithium metal cells e.g. Li-metal oxide, Li-S, Li-air, and Li-Se cells, etc. using lithium metal as the main anode active material.
  • the cathode active materials can be, for instance, a transition metal oxide (e.g. V 2 O 5 ) or sulfide (e.g. MoS 2 ), sulfur or polysulfide (e.g. lithium polysulfide), selenium, metal selenide, or just outside air (for a lithium-air cell).
  • the present disclosure provides a lithium secondary battery, as schematically illustrated in FIG. 1(A) for a lithium metal battery (e.g. having a lithium metal foil or lithium ahoy powder layer as the primary anode active material) or FIG. 1(B) for a lithium-ion battery (e.g. having a layer of particles of an anode active material, such as graphite, Si, Ge, Sn, Sn0 2 , and optional conductive additive and resin binder).
  • a lithium metal battery e.g. having a lithium metal foil or lithium ahoy powder layer as the primary anode active material
  • a lithium-ion battery e.g. having a layer of particles of an anode active material, such as graphite, Si, Ge, Sn, Sn0 2 , and optional conductive additive and resin binder.
  • the lithium secondary battery comprises an anode, a cathode, a porous separator disposed between the anode and the cathode, an electrolyte, and a lithium ion reservoir disposed between the anode and the porous separator and configured to receive lithium ions from the cathode through the porous separator when the battery is charged and enable the lithium ions to enter the anode in a time-delayed manner.
  • the lithium ion reservoir comprises an electron-conducting or lithium ion-conducting porous framework structure having pores, having a pore size from 1 nm to 500 pm, and lithium-capturing groups residing in the pores, wherein the lithium-capturing groups are selected from (a) redox forming species that reversibly form a redox pair with a lithium ion when the battery is charged; (b) electron-donating groups interspaced between non-electron-donating groups; (c) anions and cations wherein the anions are more mobile than the cations; or (d) chemical reducing groups that partially reduce lithium ions from Li +1 to Li +6 , wherein 0 ⁇ d ⁇ 1.
  • the term“in a time-delayed manner” means that (a) at least a portion (e.g. no less than 10%) of the lithium ions that enter the lithium ion reservoir does not immediately enter the anode layer (but being retained in the reservoir) when the battery is charged at a charging rate of 5C or higher; or (b) when the external battery charger is switched off or unplugged, at least a portion of the of the lithium ions that enter the lithium ion reservoir remains in the reservoir and continues to enter the anode and the anode active material (i.e. the internal charging procedure continues even though the external charger is off).
  • the presently invented lithium ion reservoir strategy enables the charging process to be conducted in a time-delayed manner to allow most of the available lithium ions to eventually get charged into the anode active material. Without such a lithium ion reservoir, fast charging can lead to either a significantly lower amount of lithium ions that actually get intercalated or inserted into the anode active material or the formation of lithium metal plating and dangerous lithium dendrite formation.
  • the lithium-capturing group is selected from a molecule having a core or backbone structure and at least a side group that is ionic or electron-rich in nature.
  • the core or backbone structure may contain an aryl, heterocycloalkyl, crown etheryl, cyclamyl, cyclenyl, l,4,7-triazacyclononayl, hexacyclenyl, cryptandyl, naphtalenyl, antracenyl, phenantrenyl, tetracenyl, chrysenyl, tryphenylenyl, pyrenyl, pentacenyl, single-benzene or cyclic structure, double-benzene or bi-cyclic structure, or multiple-cyclic structure having 3-10 benzene rings.
  • the side group may contain C0 2 H, CO 2 M 1 , C0 2 R, SO 3 H, SO 3 M 1 , Rq 3 3 ⁇ 4, PCLM 1 ⁇ P0 3 M1H, PO 4 H 2 , PO 4 M 1 2 , P0 4 M1H, P0 4 M 2 , C(0)NHOH, NH 2 , NHR, N(R) 2 , N0 2 , COOR, CHO, CH 2 OH, OH, OR, SH, SR, C(0)N(R) 2 , C(0)NHR, C(0)NH 2 , halide, tosylate, mesylate, S0 2 NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano, CF 3 , or Si(OR) 3 ; wherein R is independently selected from methyl, ethyl, isopropyl, n-propyl, alkyl, haloalkyl, cycloalkyl,
  • the redox pair with lithium is selected from lithium 4- methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium 2,6-dimethylbenzene- 1, 4-disulfonate, 3,3'-((l,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3'-((4- mercapto-l,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate, poly(lithium-4-styrenesulfonate, lithium sulfate, lithium phosphate, lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium 1,1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8- heptadecafluorooctane-l- sulfonate, lithium 2, 6-di-tert-butylbenzene-l, 4-
  • Electron-donating groups may be selected from those molecules having one to 10 benzene rings or cyclic structure as the core/backbone portion having conjugated double bonds, acidic groups, etc. Examples include sodium 4-methylbenzenesulfonate, sodium 3,5- dicarboxybenzenesulfonate, sodium 2, 6-dimethylbenzene-l, 4-disulfonate, and sodium aniline sulfonate. These molecules in the lithium ion reservoir appear to be capable of partially reducing the incoming lithium ions that pass through the porous separator from the cathode.
  • the lithium ion-capturing group may contain a salt that is dissociated into an anion and a cation in a liquid medium (typically an organic solvent).
  • a salt that is dissociated into an anion and a cation in a liquid medium (typically an organic solvent).
  • the liquid medium to dissolve these salts may contain a solvent selected from l,3-dioxolane (DOL), l,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (g-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (
  • TTSPi tris(trimethylsilyl)phosphite
  • TEP triallyl phosphate
  • DTD ethylene sulfate
  • PS propene sultone
  • DEC diethyl carbonate
  • alkylsiloxane Si-O
  • alkyylsilane Si-C
  • liquid oligomeric silaxane -Si-O-Si-
  • TEGDME tetraethylene glycol dimethylether
  • the lithium ion-capturing groups may contain ionic liquids, which are low melting temperature salts that are in a molten or liquid state when above a desired temperature.
  • a salt is considered as an ionic liquid if its melting point is below l00°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 desired ionic liquids for use in the presently invented lithium ion reservoir preferably have a melting point lower than 60°C, more preferably lower than 0°C, and further more preferably lower than -20°C.
  • the IL 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).
  • the anions of the ionic liquid may be selected to be more mobile than the c
  • a typical and well-known ionic liquid is formed by the combination of a l-ethyl-3- methylimidazolium (EMI) cation and an /V,/V-bis(trifluoromethane) sulfonamide (TFSI) anion.
  • EMI l-ethyl-3- methylimidazolium
  • TFSI /V,/V-bis(trifluoromethane) sulfonamide
  • Ionic liquids are basically composed of organic ions that come in an essentially 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(trifluoromethanesulfonyl) imide, bis(fluorosulfonyl)imide, and hexafluorophosphate as anions. Based on their
  • compositions, ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.
  • RTILs room temperature ionic liquids
  • RTILs include, but not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl- pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium.
  • RTILs include, but not limited to, BF 4 , B(CN) 4 , CH3BF3 , CH2CHBF3 , CF3BF3 , C2F5BFT, ft-C 3 F 7 BF 3 , ft-C 4 F 9 BF 3 , PF 6 , CF 3 C0 2- , CF3SO3-, N(S0 2 CF 3 ) 2- , N(C0CF 3 )(S0 2 CF 3 )-, N(S0 2 F) 2 , N(CN) 2- , C(CN) 3 , SCN-, SeCN , CuCl 2 _ , AlCLf, F(HF) 23 , etc.
  • the pores preferably contain mesoscaled pores having a pore size from 2 nm to 100 nm, preferably from 2 nm to 50 nm. These mesopores are particularly effective in holding the lithium-capturing groups inside the pores to perform their intended functions.
  • the electron-conducting porous structure has pore walls comprising an electron-conducting material selected from carbon nanotubes, carbon nanofibers, graphene sheets, expanded graphite platelets, carbon fibers, graphite fibers, graphite particles, needle coke, mesocarbon microbeads, carbon particles, carbon black, acetylene black, activated carbon particles, or a combination thereof.
  • the electron-conducting material is made into a fabric (woven or non-woven), paper, or foam structure.
  • the foam structure may be a closed-cell foam, but preferably an open-cell foam. The construction or production of these electron-conducting materials in a fabric, paper, or foam structure is well- known in the art.
  • the electron-conducting porous structure contains a graphene foam.
  • a foam or foamed material
  • the pores can be interconnected to form an open-cell foam.
  • a graphene foam is composed of pores and pore walls that contain a graphene material.
  • the first method is the hydrothermal reduction of graphene oxide hydrogel that typically involves sealing graphene oxide (GO) aqueous suspension in a high-pressure autoclave and heating the GO suspension under a high pressure (tens or hundreds of atm) at a temperature typically in the range from l80-300°C for an extended period of time (typically 12-36 hours).
  • GO graphene oxide
  • a useful reference for this method is given here: Y. Xu, et al.“Self-Assembled Graphene Hydrogel via a One-Step Hydrothermal Process,” ACS Nano 2010, 4, 4324-4330.
  • the second method is based on a template-assisted catalytic CVD process, which involves CVD deposition of graphene on a sacrificial template (e.g. Ni foam).
  • a sacrificial template e.g. Ni foam
  • the graphene material conforms to the shape and dimensions of the Ni foam structure.
  • the Ni foam is then etched away using an etching agent, leaving behind a monolith of graphene skeleton that is essentially an open-cell foam.
  • a useful reference for this method is given here: Zongping Chen, et ah,“Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition,” Nature Materials, 10 (June 2011) 424-428.
  • the fourth method of producing a graphene foam (Aruna Zhamu and Bor Z. Jang, “Highly Conductive Graphene Foams and Process for Producing Same,” U.S. Patent Application No. 14/120,959 (07/17/2014); U.S. Publication No. 20160019995 (01/21/2016)) comprises:
  • the solid graphene foam in the anode layer typically has a density from 0.01 to 1.7 g/cm
  • a specific surface area from 50 to 3,000 m /g (more typically from 200 to 2,000 m 2 /g, and most typically from 500 to 1,500 m 2 /g).
  • This optional blowing agent is not required if the graphene material has a content of non carbon elements (e.g. O, H, N, B, F, Cl, Br, I, etc.) no less than 5% by weight (preferably no less than 10%, further preferably no less than 20%, even more preferably no less than 30% or 40%, and most preferably up to 50%).
  • the subsequent high temperature treatment serves to remove a majority of these non-carbon elements from the graphene material, generating volatile gas species that produce pores or cells in the solid graphene material structure.
  • these non-carbon elements play the role of a blowing agent.
  • an externally added blowing agent is optional (not required).
  • blowing agent can provide added flexibility in regulating or adjusting the porosity level and pore sizes for a desired application.
  • the blowing agent is typically required if the non-carbon element content is less than 5%, such as pristine graphene that is essentially all-carbon.
  • the lithium ion-conducting porous structure comprises a polymer foam or polymer fabric having pores and pore walls.
  • the pore walls comprise a lithium ion- conducting polymer having a lithium ion conductivity from 10 -8 to 10 -2 S/cm when measured at 25°C.
  • the lithium ion-conducting polymer is selected from sulfonated polyaniline, sulfonated polypyrrole, a sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, or a combination thereof. These sulfonated polymers are found to be both electron-conducting and lithium ion-conducting.
  • the lithium ion-conducting polymer contains a sulfonated rubber or elastomer selected from sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated styrene-butadiene rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, metallocene-based sulfonated poly(ethylene-co-octene) elastomer, sulfonated poly(ethylene-co-butene) elastomer, sulfonated styrene- ethylene-butadiene -styrene elastomer
  • polyethylene polyethylene, sulfonated ethylene-vinyl acetate, sulfonated thermoplastic elastomer, sulfonated protein resilin, sulfonated protein elastin, sulfonated ethylene oxide-epichlorohydrin copolymer, sulfonated polyurethane, sulfonated urethane-urea copolymer, or a combination thereof.
  • the lithium ion-conducting polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride,
  • sulfonation polymers are well-known in the art.
  • a sulfonated polymer by polymerizing a sulfonated monomer or a monomer containing a sulfonyl group (e.g. T. G. Dang, et al. U.S. Publication No. 2005/0165213 (07/28/2005)).
  • a concentrated sulfuric acid e.g.
  • a desired polymer is made into fibers and then a fabric or paper structure, which is followed by a sulfonation treatment.
  • a chemical blowing agent or physical blowing agent to assist in forming a polymer foam structure (e.g. a film or sheet shape).
  • the resulting porous structure may then be soaked with the lithium ion-capturing molecules or ionic salt solution discussed above.
  • the lithium ion-conducting polymer is selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, and poly(vinylidene fluoride) -hexafluoropropylene (PVDF-HFP) copolymer, modified polyacrylic acid-based copolymer, polyester polyamine amide-based copolymer, polycarboxylic acid-based copolymer, polyalkylol amino amide-based copolymer, polysiloxane polyacryl-based copolymer, polysiloxane polycarboxylic acid-based copolymer, polyalkoxylate-based copolymer, a copolymer
  • lithium ion reservoir composed of a conducting framework porous structure (foam, paper, fabric, etc.) having pores filled with lithium ion-capturing molecules or ions.
  • these molecules or ions either have a low melting point (lower than l00°C or even ⁇ 25°C) and, thus, can be easily melted to become a highly flowable state, or can be dissolved in a liquid solvent to become solution.
  • these lithium ion-capturing species can be readily made to permeate into pores of the porous framework structure.
  • Such permeation can be accomplished by using, for instance, the following procedures:
  • Solution permeation This includes dispersion or dissolution of molecules or ions in water or a solvent to form a solution or suspension, followed by coating or spraying the solution onto the porous structure or by dipping the porous structure into this solution or suspension; or
  • the anode typically is composed of an anode active material, a conductive additive (e.g. carbon black, acetylene black, graphite platelets, carbon nanotubes, etc.), and a resin binder (e.g. the well-known SBR rubber, PVDF, CMC, etc.).
  • the anode electrode may comprise an anode active material comprising an element selected from Si, Ge, Sn, Cd, Sb, Pb, Bi, Zn, Al, Co, Ni, Ti, or an alloy thereof.
  • the anode comprises an anode active material selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, Mn, V, or Cd, and their mixtures, composites, or lithium
  • the anode of a lithium-ion battery may be made by using the well-known slurry coating method. For instance, one may mix particles of an anode active material (e.g. carbon-coated Si nanoparticles or nanowires), a resin binder (e.g. SBR rubber, CMC, polyacrylamide), and a conductive filler (e.g. particles of acetylene black, carbon black, or carbon nanotubes) in water or an organic solvent (e.g. NMP) to form a slurry. The slurry is then coated on one primary surface or both primary surfaces of a Cu foil and then dried to form an anode electrode. For the anode of a lithium metal battery, one may simply use a thin Li foil attached to a Cu foil or a graphene- based current collector.
  • an anode active material e.g. carbon-coated Si nanoparticles or nanowires
  • a resin binder e.g. SBR rubber, CMC, polyacrylamide
  • the particles of an anode active material preferably have a diameter from 5 nm to 1 pm, more preferably from 10 to 500 nm, and most preferably from 20 to 100 nm.
  • porous separator there is no restriction on the type of porous separator that can be used in the presently invented lithium battery.
  • a porous separator e.g. polyolefin-based, non-woven of electrically insulating fibers, etc.
  • Most of the commercially available lithium batteries make use of a polyolefin (e.g. polyethylene, polypropylene, PE/PP copolymer, etc.) as a separator.
  • the cathode active material in the cathode in this rechargeable alkali metal battery may be selected from sulfur, selenium, tellurium, lithium sulfide, lithium selenide, lithium telluride, sodium sulfide, sodium selenide, sodium telluride, a chemically treated carbon or graphite material having an expanded inter-graphene spacing doo 2 of at least 0.4 nm, or an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, nickel, or a combination thereof.
  • Preferred cathode active materials include non-lithiated and slightly lithiated compounds having relatively high lithium or sodium storage capacities, such as TiS 2
  • MXenes A novel family of 2D metal carbides or metal carbonides, now commonly referred to as MXenes, can be used as a cathode active material. MXenes can be 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 HF 2 was used at room temperature as the etchant for Ti 3 AlC 2 .
  • the MXene materials investigated include Ti 2 CT v , (Tio .
  • Nbo .5 2 CT A , Nb 2 CT A , V 2 CT V , Ti 3 C 2 T A , (Vo .5 , Cr 0.5 ) 3 C 2 T A , Ti 3 CNT A , Ta 4 C 3 T A , and Nb 4 C 3 T A .
  • the cathode layer contains an air cathode and the battery is a lithium- air battery.
  • the cathode active material is selected from sulfur or lithium polysulfide and the battery is a lithium-sulfur battery.
  • the cathode active material may be selected from an organic or polymeric material capable of capturing or storing lithium ions (e.g. via reversibly forming a redox pair with lithium ion).
  • the cathode active material may be selected from a metal oxide/phosphate/sulfide/halogenide, an inorganic material, an organic or polymeric material, or a combination thereof:
  • metal oxide, metal phosphate, and metal sulfides consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium transition metal oxide, lithium-mixed metal oxide (e.g. the well-known NCM, NCA, etc.), transition metal fluoride, transition metal chloride, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphates, transition metal sulfides, and combinations thereof.
  • the lithium vanadium oxide may be selected from the group consisting of V0 2 , Li x V0 2 , V 2 0 5 , Li x V 2 0 5 , V 3 0 8 , Li x V 3 0 8 , Li x V 3 0 7 , V 4 0 9 , Li x V 4 0 9 , V 6 0i 3 , u c n 6 0 13 , their doped versions, their derivatives, and combinations thereof, wherein 0.1 ⁇ x ⁇ 5;
  • Lithium transition metal oxide may be selected from a layered compound LiM0 2 , spinel compound LiM 2 0 4 , olivine compound LiMP0 4 , silicate compound Li 2 MSi0 4 , tavorite compound LiMP0 4 F, borate compound LiMB0 3 , or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.
  • an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b)
  • transition metal dichalcogenide or trichalcogenide (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) sulfur, sulfur compound, lithium polysulfide (f) a combination thereof.
  • TiS 2 , TaS 2 , MoS 2 , NbSe 3 , non-lithiated Mn0 2 , Co0 2 , iron oxide, vanadium oxide, or a combination thereof may be used as a cathode active material in a lithium metal cell.
  • the organic material or polymeric material may be selected from poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 3,4,9, lO-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4, 5, 9, lO-tetraone (PYT), polymer-bound PYT, quino(triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,l0,l l-hexamethoxytriphenylene (HMTP), poly(5- amino-l,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS 2 ) 3 ]H), lithiated l,4,5,8-naphthalenetetrao
  • HATN hexaazatrinaphtylene
  • HAT(CN) 6 hexaazatriphenylene hexacarbonitrile
  • 5- benzylidene hydantoin isatine lithium salt
  • pyromellitic diimide lithium salt isatine lithium salt
  • tetrahydroxy-p-benzoquinone derivatives TQLi 4
  • calixquinone Li 4 C 6 0 6 , Li 2 C 6 0 6 , Li 6 C 6 0 6 , or a combination thereof.
  • the thioether polymer is selected from poly[methanetetryl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), a polymer containing poly(ethene- l,l,2,2-tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, poly(2-phenyl-l,3-dithiolane) (PPDT), poly(l,4-di(l,3- dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[l,2,4,5-tetrakis(propylthio)benzene] (PTKPTB, or
  • the organic material may include a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, or a combination thereof.
  • a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthal
  • the cathode of a lithium-ion battery may be made by using the well-known slurry coating method. For instance, one may mix particles of a cathode active material (e.g. particles of NMC, NCA, LiCo0 2 , TiS 2 , graphene-protected S particles, etc.), a resin binder (e.g. PVDF), and a conductive filler (e.g. particles of acetylene black, carbon black, or carbon nanotubes) in an organic solvent (e.g. NMP) to form a slurry. The slurry is then coated on one primary surface or both primary surfaces of an Al foil and then dried to form a cathode electrode.
  • a cathode active material e.g. particles of NMC, NCA, LiCo0 2 , TiS 2 , graphene-protected S particles, etc.
  • a resin binder e.g. PVDF
  • a conductive filler e.g. particles of acet
  • the electrolytes that can be used in the lithium battery may be selected from any lithium metal salt that is dissolvable in a solvent to produce an electrolyte.
  • the metal salt is selected from lithium perchlorate (LiCl0 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (L1CF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3S0 2 ) 2 ), lithium
  • LiBOB bis(oxalato)borate
  • LiBF 2 C 2 0 4 lithium oxalyldifluoroborate
  • LiNO3 Li-fluoroalkyl-phosphate
  • LiBETI lithium bisperfluoro-ethylsulfonylimide
  • lithium bis(trifluoromethanesulfonyl)imide lithium bis(fluorosulfonyl)imide
  • lithium bis(fluorosulfonyl)imide lithium
  • LiTFSI trifluoromethanesulfonimide
  • the electrolytes used may contain a solvent selected from l,3-dioxolane (DOL), 1,2- dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (g-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylen
  • the ionic liquid may also be used as an electrolyte for the lithium battery.
  • the anode of a lithium-ion battery may contain anode active material particles selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (
  • the anode active material of a lithium metal battery may contain a layer of Li metal or alloy (> 70% by weight of Li, preferably > 80%, and more preferably >
  • the Li metal or alloy may be supported by a nanostructure composed of conductive nanofilaments.
  • a nanostructure composed of conductive nanofilaments.
  • multiple conductive nanofilaments 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 nanofilament may be selected from, as examples, a carbon nanofiber (CNF), graphite nanofiber (GNF), carbon nanotube (CNT), metal nanowire (MNW), conductive nanofibers obtained by electrospinning, conductive electrospun composite nanofibers, nanoscaled graphene platelet (NGP), or a combination thereof.
  • the nanofilaments may be bonded by a binder material selected from a polymer, coal tar pitch, petroleum pitch, mesophase pitch, coke, or a derivative thereof.
  • Nanofibers may be selected from the group consisting of an electrically conductive electrospun polymer fiber, electrospun polymer nanocomposite fiber comprising a conductive filler, nanocarbon fiber obtained from carbonization of an electrospun polymer fiber, electrospun pitch fiber, and combinations thereof.
  • a nano structured electrode can be obtained by electro spinning of polyacrylonitrile (PAN) into polymer nanofibers, followed by
  • a possible lithium cell may be comprised of an alkali metal layer (e.g. Li foil, etc.) or an anode active material particle layer (e.g. particles of Si plus conductive additive and binder resin), an anode current collector (e.g. Cu foil and/or a nanostructure of an alkali metal layer (e.g. Li foil, etc.) or an anode active material particle layer (e.g. particles of Si plus conductive additive and binder resin), an anode current collector (e.g. Cu foil and/or a nanostructure of an alkali metal layer (e.g. Li foil, etc.) or an anode active material particle layer (e.g. particles of Si plus conductive additive and binder resin), an anode current collector (e.g. Cu foil and/or a nanostructure of an alkali metal layer (e.g. Li foil, etc.) or an anode active material particle layer (e.g. particles of Si plus conductive additive and binder resin), an anode current collector (e.
  • interconnected conductive filaments supporting the anode layer, a lithium ion reservoir layer, a porous separator and an electrolyte phase, a cathode, and an optional cathode current collector (e.g. Al foil and/or or a nanostructure of interconnected conductive filaments, such as graphene sheets and carbon nanofibers) to support the cathode layer.
  • cathode current collector e.g. Al foil and/or or a nanostructure of interconnected conductive filaments, such as graphene sheets and carbon nanofibers
  • S-PANi The chemical synthesis of the S-PANi polymers was accomplished by reacting polyaniline with concentrated sulfuric acid. The procedure was similar to that used by Epstein, et al. (U.S. Patent No. 5,109,070, April 28, 1992).
  • the lithium ion conductivity of these S0 3 or S0 3 H-based S-PANi compositions was in the range from 8.5 x 10 -5 S/cm to 4.6 x 10 -3 S/cm and their electron conductivity in the range from 0.1 S/cm to 0.5 S/cm when the degree of sulfonation was from approximately 30% to 75% (with y being approximately 0.4-0.6).
  • the porous framework for the lithium ion reservoir layer was obtained by dissolving S- PANi in water to form a polymer-water solution, which was freeze-dried to obtain a sponge-like foamed structure. A porosity level from approximately 20% to 85% was achieved.
  • the pores in several foam structures were impregnated with several different lithium ion-capturing species, respectively: including lithium 4-methylbenzenesulfonate, lithium aniline sulfonate, lithium sulfate, lithium phosphate, and an ionic liquid having a l-ethyl-3- methylimidazolium (EMI) cation and an /V,/V-bis(trifluoromethane)sulfonamide (TFSI) anion.
  • lithium 4-methylbenzenesulfonate lithium aniline sulfonate
  • lithium sulfate lithium phosphate
  • an ionic liquid having a l-ethyl-3- methylimidazolium (EMI) cation and an /V,/V-bis(trifluoromethane)sulfonamide (TFSI) anion.
  • EMI l-ethyl-3- methylimidazolium
  • TFSI /V,/V-bis(triflu
  • lithium-ion cells (“graphite anode + NCA cathode” and“anode of graphene -protected Si particles + NCM cathode”) and lithium metal cells (“Li metal foil anode + MOS 2 cathode” and“Li metal anode + graphene/S cathode).
  • PTFE Polytetrafluoroethylene
  • PSf polysulfone
  • PEEK poly (ether ether ketone)
  • PI polyimide
  • SB styrene-butadiene copolymers
  • Chopped graphite fibers with an average diameter of 12 pm and natural graphite particles were separately used as a starting material, which was immersed in a mixture of concentrated sulfuric acid, nitric acid, and potassium permanganate (as the chemical intercalate and oxidizer) to prepare graphite intercalation compounds (GICs).
  • the starting material was first dried in a vacuum oven for 24 h at 80°C. Then, a mixture of concentrated sulfuric acid, fuming nitric acid, and potassium permanganate (at a weight ratio of 4: 1:0.05) was slowly added, under appropriate cooling and stirring, to a three-neck flask containing fiber segments.
  • the acid-treated graphite fibers or natural graphite particles were filtered and washed thoroughly with deionized water until the pH level of the solution reached 6. After being dried at l00°C overnight, the resulting graphite intercalation compound (GIC) or graphite oxide fiber was re-dispersed in water and/or alcohol to form a slurry.
  • GIC graphite intercalation compound
  • the resulting suspension was then cast onto a stainless steel plate.
  • a wiper was used to exert shear stresses at a high shearing rate, inducing GO sheet orientations.
  • the wet GO suspension was then dried.
  • the GO suspension was then subjected to heat treatments that typically involve an initial thermal reduction temperature of 80°C -350°C for 1-8 hours, followed by heat-treating at a second temperature of l,500°C - 2,850°C for 0.5 to 5 hours.
  • the heat-treated sample was typically excessively porous with constituent graphene sheets in the pore walls being very poorly oriented and incapable of chemical merging and linking with one another. As a result, the thermal conductivity, electrical conductivity, and mechanical strength of the graphene foam were compromised.
  • the resulting graphene foam structures were then separately dipped in several lithium ion-capturing species in a liquid state, including sodium 4-methylbenzenesulfonate, sodium aniline sulfonate, sodium sulfate, sodium phosphate, and an ionic liquid having a tetra- alkylimidazolium cation and a BF 4 anion, to prepare various lithium ion reservoir layers.
  • lithium ion-capturing species including sodium 4-methylbenzenesulfonate, sodium aniline sulfonate, sodium sulfate, sodium phosphate, and an ionic liquid having a tetra- alkylimidazolium cation and a BF 4 anion
  • the graphene shapes were then subjected to heat treatments that involve an initial (first) thermal reduction temperature of 80°C -l,500°C for 1-5 hours. This first heat treatment generated a graphene foam structure. Some of the pristine foam samples were then subjected to a second temperature of l,500°C -2,850°C to further perfect the graphene foam structure (re- graphitized to become more ordered or having a higher degree of crystallinity). These foam structures were used as a framework porous structure for accommodating lithium ion-capturing species.
  • Another group of presently invented lithium ion-conducting framework porous structures to retain lithium ion-capturing species therein typically comprises a mixture of a conventional lithium ion-conducting electrolyte polymer (e.g. PEO, PPO, etc.) and a sulfonated polymer.
  • a conventional lithium ion-conducting electrolyte polymer e.g. PEO, PPO, etc.
  • sulfonated polymer e.g. PEO, PPO, etc.
  • the lithium ion conductivity values of a polymer mixture containing a conventional solid electrolyte polymer (PEO or PPO) and a sulfonated polymer exhibit unexpected synergistic effect.
  • Some electron-conducting fillers e.g. carbon nanotubes (CNF), carbon nanofibers (CNT), carbon black (CB), expanded graphite flakes (EGF), etc.
  • CNF carbon nanotubes
  • CNT carbon nanofibers
  • CB carbon black
  • Such a material appears to be more effective in capturing lithium ions during the fast battery charge operations, retaining more lithium ions in the resulting reservoir and continuing to send lithium ions into the anode layer even after the external charger unit is switched off.
  • Table 2 Lithium ion conductivity of various conducting framework porous structure materials.
  • Ultra-thin MoS 2 /RGO hybrid was synthesized by a one-step solvothermal reaction of (NH 4 ) 2 MOS4 and hydrazine in an /V, N-d ⁇ methyl formamidc (DMF) solution of graphene oxide (GO) at 200°C.
  • 22 mg of (NH 4 ) 2 MoS 4 was added to 10 mg of GO dispersed in 10 ml of DMF.
  • the mixture was sonicated at room temperature for approximately 10 min until a clear and homogeneous solution was obtained. After that, 0.1 ml of N 2 H 4 ⁇ H 2 0 was added.
  • reaction solution was further sonicated for 30 min before being transferred to a 40 mL Teflon-lined autoclave.
  • the system was heated in an oven at 200°C for 10 h.
  • Product was collected by centrifugation at 8000 rpm for 5 min, washed with DI water and recollected by centrifugation. The washing step was repeated for at least 5 times to ensure that most DMF was removed. Finally, product was dried and made into a cathode.
  • V 2 Os 99.6%, Alfa Aesar
  • LiOH 99+%, Sigma- Aldrich
  • Graphene oxide GO, 1% w/v obtained from Taiwan Graphene Co., Taipei, Taiwan
  • V 2 Os and LiOH in a stoichiometric V/Li ratio of 1:3 were dissolved in actively stirred de-ionized water at 50°C until an aqueous solution of Li x V 3 0 8 was formed.
  • the values of Ret for the vanadium oxide alone and graphene-enhanced composite electrodes are about 50.0 and 350.0 W for NLVO-l and LVO- 2, respectively.
  • the Ret of the composite electrode is much smaller than that of the LVO electrode. Therefore, the presence of graphene ( ⁇ 2% by weight in this case) in the vanadium oxide composite has dramatically reduced the internal charge transfer resistance and improved the battery performance upon extended cycling.
  • NLVO-l was subsequently used in two Li-ion cells (one featuring a Li ion reservoir layer and the other not) for evaluation of the effect of a lithium ion reservoir layer on the maximum amount of charges that can be stored in the anode.
  • the NLVO-based cathode material was formed into a cathode and then combined with a layer of lithiated natural graphite particles (as an anode), a lithium ion reservoir layer and a porous separator layer (Celgard 2400) to prepare a lithium-ion battery.
  • a corresponding cell containing no lithium ion reservoir layer was also prepared for comparison purpose.
  • the electrolyte was a conventional PEO gel electrolyte containing LiPF 6 in PC-EC solvent.
  • the cathode electrode was prepared following the following procedure.
  • Li-S lithium- sulfur battery cell
  • the anode, the electrolyte, and the integral layer of porous graphene structure (serving as a cathode layer) are positioned in an external container outside of a lithium-sulfur cell.
  • the needed apparatus was similar to an electroplating system, which is well-known in the art.
  • a metal polysulfide (L12S9 and Nai 2 S6) was dissolved in a solvent (e.g. mixture of DOL/DME at a volume ratio from 1:3 to 3:1) to form an electrolyte solution.
  • a solvent e.g. mixture of DOL/DME at a volume ratio from 1:3 to 3:1
  • the electrolyte solution was then poured into a chamber or reactor under a dry and controlled atmosphere condition (e.g. He or Nitrogen gas).
  • a metal foil was used as the anode and a layer of the porous graphene foam structure as the cathode; both being immersed in the electrolyte solution.
  • This configuration constitutes an electrochemical deposition system.
  • the step of electrochemically depositing nanoscaled sulfur particles or coating on the graphene surfaces was conducted at a current density preferably in the range from 1 mA/g to 10 A/g, based on the layer weight of the porous graphene structure.
  • the precipitated S is preferentially nucleated and grown on massive graphene surfaces to form nanoscaled coating or nanoparticles.
  • the coating thickness or particle diameter and the amount of S coating/particles was controlled by the specific surface area, electrochemical reaction current density, temperature and time. In general, a lower current density and lower reaction temperature lead to a more uniform distribution of S and the reactions are easier to control.
  • a longer reaction time leads to a larger amount of S deposited on graphene surfaces and the reaction is ceased when the sulfur source is consumed or when a desired amount of S is deposited.
  • Li-S cells were produced wherein lithium metal foil was used as an anode active material and lithium trifluoromethane-sulfonimide (LiTFSI), dissolved in l,3-dioxolane (DOL), was used as the electrolyte.
  • LiTFSI lithium trifluoromethane-sulfonimide
  • DOL l,3-dioxolane
  • a lithium ion reservoir layer obtained in Example 1 was implemented between a porous PE-PP separator and a lithium foil anode layer.
  • the discharge capacity values of two Li-S cells are plotted as a function of the number of charge/discharge cycles (FIG. 4).
  • One cell contains a lithium ion reservoir disposed between the Li metal anode and the separator, but the other cell does not have such a reservoir. It is quite unexpected to observe that the implementation of such a lithium ion reservoir layer also results in a significantly more stable cycling behavior. Examination of post cycling specimens led to the observation of a significant amount of dead lithium particles separated from the lithium foil anode of the cell containing no lithium ion reservoir.
  • the lithium metal anode surface of the cell featuring a lithium ion reservoir appeared relatively smooth and very few dead Li particles were observed.
  • Such a reservoir layer seems capable of helping to stabilize the lithium metal-electrolyte interface zone and prevent dendrite formation, leading to a much longer cycle-life for a safer rechargeable lithium metal battery.
  • Such a lithium ion reservoir strategy also enables the normally slow-charging lithium metal battery (including Li-S cell) to become fast chargeable.

Abstract

L'invention concerne une batterie secondaire au lithium contenant une anode, une cathode, un séparateur poreux disposé entre l'anode et la cathode, un électrolyte, et un réservoir d'ions lithium disposé entre l'anode et le séparateur poreux et conçu pour recevoir des ions lithium de la cathode lorsque la batterie est chargée et permettre aux ions lithium d'entrer dans l'anode d'une manière retardée, le réservoir comprenant une structure d'ossature poreuse conductrice ayant des pores (taille de pore de 1 nm à 500 µm) et des groupes de capture de lithium se trouvant dans les pores, les groupes de capture de lithium étant choisis parmi (a) des espèces formant redox qui forment de manière réversible une paire redox avec un ion lithium ; (b) des groupes donneurs d'électrons espacés entre des groupes non donneurs d'électrons ; (c) des anions et des cations, les anions étant davantage mobiles que les cations ; ou (d) des groupes de réduction chimique qui réduisent partiellement des ions lithium de Li+1? à Li+δ, où 0 < δ < 1. L'invention concerne également un procédé d'amélioration de la capacité de charge rapide d'une batterie secondaire au lithium.
PCT/US2019/036051 2018-06-12 2019-06-07 Batterie au lithium à charge rapide WO2019241065A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US16/006,131 2018-06-12
US16/006,138 2018-06-12
US16/006,131 US11024849B2 (en) 2018-06-12 2018-06-12 Fast-chargeable lithium battery
US16/006,138 US11171388B2 (en) 2018-06-12 2018-06-12 Method of improving fast-chargeability of a lithium battery

Publications (1)

Publication Number Publication Date
WO2019241065A1 true WO2019241065A1 (fr) 2019-12-19

Family

ID=68843124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2019/036051 WO2019241065A1 (fr) 2018-06-12 2019-06-07 Batterie au lithium à charge rapide

Country Status (1)

Country Link
WO (1) WO2019241065A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113594540A (zh) * 2021-09-29 2021-11-02 中南大学 一种复合固态电解质及其制备方法和应用
CN114740063A (zh) * 2022-02-16 2022-07-12 陕西化工研究院有限公司 采用电化学检测肼的方法
WO2023081532A1 (fr) * 2021-11-08 2023-05-11 Advanced Cell Engineering, Inc. Empilement d'électrodes à fentes et cellules électrochimiques et batteries contenant un empilement d'électrodes à fentes
CN114740063B (zh) * 2022-02-16 2024-05-17 陕西化工研究院有限公司 采用电化学检测肼的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090088405A (ko) * 2006-11-14 2009-08-19 포투 인텔렉츄얼 프로퍼티 아게 재충전 가능한 전기화학 배터리 셀
US8859143B2 (en) * 2011-01-03 2014-10-14 Nanotek Instruments, Inc. Partially and fully surface-enabled metal ion-exchanging energy storage devices
US8895189B2 (en) * 2012-02-03 2014-11-25 Nanotek Instruments, Inc. Surface-mediated cells with high power density and high energy density
KR20150004358A (ko) * 2012-04-10 2015-01-12 캘리포니아 인스티튜트 오브 테크놀로지 전기화학 시스템들용 신규 세퍼레이터들
US20150050561A1 (en) * 2013-08-16 2015-02-19 Uchicago Argonne, Llc High voltage lithium ion batteries having fluorinated electrolytes and lithium-based additives

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090088405A (ko) * 2006-11-14 2009-08-19 포투 인텔렉츄얼 프로퍼티 아게 재충전 가능한 전기화학 배터리 셀
US8859143B2 (en) * 2011-01-03 2014-10-14 Nanotek Instruments, Inc. Partially and fully surface-enabled metal ion-exchanging energy storage devices
US8895189B2 (en) * 2012-02-03 2014-11-25 Nanotek Instruments, Inc. Surface-mediated cells with high power density and high energy density
KR20150004358A (ko) * 2012-04-10 2015-01-12 캘리포니아 인스티튜트 오브 테크놀로지 전기화학 시스템들용 신규 세퍼레이터들
US20150050561A1 (en) * 2013-08-16 2015-02-19 Uchicago Argonne, Llc High voltage lithium ion batteries having fluorinated electrolytes and lithium-based additives

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113594540A (zh) * 2021-09-29 2021-11-02 中南大学 一种复合固态电解质及其制备方法和应用
WO2023081532A1 (fr) * 2021-11-08 2023-05-11 Advanced Cell Engineering, Inc. Empilement d'électrodes à fentes et cellules électrochimiques et batteries contenant un empilement d'électrodes à fentes
WO2023081530A1 (fr) * 2021-11-08 2023-05-11 Advanced Cell Engineering, Inc. Anodes et éléments au lithium-ion à haute capacité et batteries contenant des anodes au lithium-ion
CN114740063A (zh) * 2022-02-16 2022-07-12 陕西化工研究院有限公司 采用电化学检测肼的方法
CN114740063B (zh) * 2022-02-16 2024-05-17 陕西化工研究院有限公司 采用电化学检测肼的方法

Similar Documents

Publication Publication Date Title
US11024849B2 (en) Fast-chargeable lithium battery
CN110268573B (zh) 用于锂二次电池的混合固态电解质
US11374254B2 (en) Solid state electrolyte for lithium secondary battery
KR102493304B1 (ko) 불연성 준고체 전해질 및 이를 함유한 리튬 이차 배터리
US10840565B2 (en) Method of improving power density and fast-chargeability of a lithium secondary battery
US10734671B2 (en) High-power and fast-chargeable lithium battery
US11289731B2 (en) Fire-resistant lithium battery containing an electrode-protecting layer
US11171388B2 (en) Method of improving fast-chargeability of a lithium battery
US9882238B2 (en) Lithium-sulfur secondary battery containing gradient electrolyte
US11394058B2 (en) Method of producing shape-conformable alkali metal-sulfur battery
US11870051B2 (en) Method of improving fast-chargeability of a lithium-ion battery
WO2019005298A1 (fr) Électrolyte ininflammable contenant un gaz liquéfie et batteries secondaires au lithium contenant ce dernier
US11335946B2 (en) Shape-conformable alkali metal-sulfur battery
WO2017123544A1 (fr) Accumulateurs métal alcalin-soufre à hautes densités d&#39;énergie volumique et massique
US20200028205A1 (en) Fast-chargeable lithium battery electrodes
WO2018222349A1 (fr) Batterie métal alcalin-soufre de forme adaptable
WO2020050895A1 (fr) Batterie secondaire au lithium-métal contenant deux couches de protection d&#39;anode
WO2020018731A1 (fr) Électrodes de batterie au lithium à chargement rapide
WO2019236371A2 (fr) Batterie au lithium résistant au feu contenant une couche de protection d&#39;électrode
WO2019005299A1 (fr) Batterie à métal alcalin-soufre à forme adaptable dotée d&#39;une électrode polymère quasi-solide conductrice et déformable
WO2020055470A1 (fr) Batterie lithium-soufre contenant deux couches de protection d&#39;anode
WO2020036781A1 (fr) Batterie au lithium à haute puissance et à charge rapide
WO2019241065A1 (fr) Batterie au lithium à charge rapide
US20190372174A1 (en) Method of improving fire-resistance of a lithium battery

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19820068

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19820068

Country of ref document: EP

Kind code of ref document: A1