WO2020174496A1 - A high-power density sodium-ion battery - Google Patents

A high-power density sodium-ion battery Download PDF

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Publication number
WO2020174496A1
WO2020174496A1 PCT/IN2020/050178 IN2020050178W WO2020174496A1 WO 2020174496 A1 WO2020174496 A1 WO 2020174496A1 IN 2020050178 W IN2020050178 W IN 2020050178W WO 2020174496 A1 WO2020174496 A1 WO 2020174496A1
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Prior art keywords
anode
electrode
cathode
carbon
ion battery
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PCT/IN2020/050178
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French (fr)
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Satishchandra Ogale
S. B. Pandit (Ravi)
Tejas KSHATRIYA
Sarika KELKAR
Anil SURYAWANSHI
Yogesh GAWLI
Dhanya PUTHHUSSERI
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Kpit Technologies Limited
Indian Institute Of Science Education And Research (Iiser), Pune
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Publication of WO2020174496A1 publication Critical patent/WO2020174496A1/en

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    • 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
    • H01M10/54—Reclaiming serviceable parts of waste 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • H01M4/621—Binders
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2300/0025—Organic electrolyte
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to the battery technology, and in particular relates to a high-power density and long-life cycle Sodium-ion battery system and method for designing the same.
  • the present invention further relates to method for formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode to prevent the irreversible loss of the capacity of the counter electrode.
  • SEI Solid Electrolyte Interface Layer
  • lithium-ion batteries are largely used in various devices like laptops, mobile phones, vehicles, etc.
  • Due to the limited availability of lithium it would be difficult to meet the ever-growing demand of energy storage system for various applications.
  • the cost would also increase in future. Mining and refining of lithium also adds to the cost of the battery.
  • lithium ion batteries take time to charge and discharge which is not convenient in todays’ fast-moving world.
  • sodium-ion is looked at as an alternative solution to the currently commercialized lithium-ion battery.
  • Sodium ion batteries requires materials that are abundantly available and are much cheaper.
  • SEI Solid Interface Layer
  • Xiaoxiao Liu et al reported Electrode-Level Chemical Presodiation Route by Solution Spraying to Improve the Energy Density of Sodium-Ion Batteries, in Advanced Functional Materials (https://d0i.0rg/l 0 1002/adfm.201903795).
  • the electrode-level presodiation strategy reported in this article comprises spraying a sodium naphthaline solution onto a carbon electrode to compensate the initial sodium loss and improves the energy density of Sodium-Ion Batteries.
  • An object of the present invention is to provide a high-power density sodium ion battery which provides for quick charging and discharging.
  • Another object of the present invention is to provide a long-life cycle sodium ion battery.
  • Another objective of the present invention is to provide an economical, convenient, pre-sodiation process to prevent the irreversible loss of the capacity of the counter electrode in sodium ion battery.
  • Yet another object of the present invention is to provide for a sodium ion battery that can be used for various applications, like, but not limited to consumer devices, gadget, industrial devices, electric vehicles, etc.
  • the present invention in one aspect provides a sodium ion battery of a high-power density with a capability of charging at rate of 3C to 6C and giving a cycle life of up to 5000.
  • the sodium ion battery according to the present invention comprises a positive electrode - cathode and a negative electrode- anode, a sodium-ion electrolyte composition along with electrolyte additives.
  • the cathode of the sodium ion battery according to the present invention comprises of a NASICON family member, a binder and a conducting carbon.
  • the cathode comprises of a carbon coated, Sodium Vanadium Phosphate (NVP) electrode.
  • the anode of the sodium ion battery according to present invention is an electrode selected from a group comprising of graphite, hard carbon or soft carbon or a combination of any of these.
  • composition of the electrolytes for the sodium ion battery of the present invention comprises salts selected from Sodium perchlorate (NaC104) or sodium hexafluorophate (NaPF6), dissolved in Ester/carbonate family of solvents selected from a group consisting of Ethylene Carbonate, Dimethyl Carbonate, Diethyl carbonate (DEC), Propylene carbonate (PC), or Ether family of solvents selected from the group consisting of diglyme, triglyme, tetraglyme.
  • the electrolyte additives are selected from a group comprising of Fluoroethylene carbonate, VC (vinylene carbonate) and Propane Sultone.
  • the present invention provides a sodium ion battery with a specific mass balance, for example, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5).
  • This mass balance of the present invention ensures the capacity balance between cathode electrode and anode electrode and has a strong correlation with final cell capacity and stability. Excess mass balance of anode gives better cycle life while excess mass balance of cathode provides for irreversible capacity loss during initial cycles. So, tuning the mass balance is very crucial for a targeted energy and power performance and cycle life of the battery.
  • the present invention further provides for a process for pre-alkalization/presodation of the anode electrode.
  • multiple batteries can be pre-alkalized simultaneously.
  • the mass balance is cathode excessive.
  • the ratio of the cathode electrode to anode electrode is in the range of cathode: anode, 1 : 1.3 to 1 :2.5.
  • the cathode is not excessive, hence, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5).
  • the sodium-ion battery of the present invention may be synthesized with or without presodiation of the anode electrode to provide a high-power density and long cycle life battery.
  • FIG. 1 illustrates a sodium-ion type battery designed according to the method of the present invention.
  • FIG. 2 illustrates an exemplary pre-sodiation of the carbon electrode according to an embodiment of the present invention.
  • FIG. 3 illustrates a pre-sodiation assembly according to an embodiment of the present invention.
  • FIG. 4 Illustrates performance of coin cell batteries for different presodiation time/shorting time with the pre-sodiation assembly according to an embodiment of the present invention.
  • FIG. 5 illustrates performance of coin cell batteries for different mass balance according to an embodiment of the present invention.
  • FIG. 6 illustrates the performance of the full cell (coin cell) representing capacity versus cycle life for hard carbon-based anode and carbonate-based electrolyte, according to an embodiment of the present invention.
  • FIG. 7 illustrates the performance of the full cell (coin cell) representing capacity versus cycle life for soft carbon-based anode and carbonate based electrolyte according to an embodiment of the present invention.
  • FIG. 8 illustrates the performance of the full cell (coin cell) battery representing capacity versus cycle life for soft carbon-based anode and ether based electrolyte according to an embodiment of the present invention.
  • the present invention provides a high-power density sodium ion battery, which comprises:
  • a positive electrode, cathode comprising of a NASICON family member, a binder and a conducting carbon, wherein, the cathode to binder to conducting carbon weight percentage is in the range of 90-5-5 to 70-10-20 wt%;
  • a negative electrode, anode comprising of a carbon material, a binder and a conducting carbon, wherein, the anode to binder to conducting carbon weight percentage is in the range of 95-3-2 to 80-10-10 wt%; and c) an electrolyte selected from either a carbonate or ether family of solvents and additives selected from the group consisting of a carbonate family or PS (propane sultone), wherein, the amount of electrolyte fill is in the range of 2 to 20gm/Ah.
  • the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5).
  • the said cathode electrode has a mass loading in the range of 4-30mg/cm3 and porosity in the range of 20-55%, while, the said anode electrode has a mass loading in the range of 6 to 40mg/cm3 and porosity in the range of 15-55%.
  • the high-power density sodium ion battery according to the present invention encompasses a carbon coated, sodium vanadium phosphate, Na3V2((PO)4)3 (NVP) electrode as a cathode and an anode comprises of a hard carbon or a soft carbon or graphite or a combination of any of these.
  • the anode electrode according to the invention is pre-treated for formation of a solid electrolyte interface layer (SEI) on the surface of the anode electrode to prevent the first cycle irreversible losses.
  • SEI solid electrolyte interface layer
  • the binder used in high-power density sodium ion battery is a NMP soluble binder or an aqueous soluble binder, for example Polyvinylidene fluoride (PVDF).
  • PVDF Polyvinylidene fluoride
  • FIG. 1 illustrates a sodium-ion type battery designed according to the method of the present invention.
  • Fig. la illustrates a coin cell battery
  • Fig. lb illustrates a pouch cell battery.
  • the sodium ion battery of the present invention comprises of a positive electrode cathode, which is a carbon coated, Sodium Vanadium Phosphate (NVP) electrode.
  • the cathode of the sodium ion battery of the present invention is prepared by the process described herein below.
  • precursors selected from a group comprising of, vanadium(V) oxide, ammonium dihydrogen phosphate, sodium carbonate anhydrous, and oxalic acid dihydrate were mixed in a specific weight ratio of 14.7%, 27.8%, 12.8% and 43.7%, respectively and further heated in a gas environment comprising a mixture of argon and hydrogen gas at a specific temperature (e.g.
  • NVP Sodium Vanadium Phosphate
  • the cathode slurry was prepared by mixing NVP, conducting carbon and Polyvinylidene fluoride (PVDF) binder with N-methyl Pyridine (NMP) solvent in which the active material is in the range of 65-80% weight ratio.
  • the slurry viscosity was maintained around 5000-20000 millipascal-second.
  • the cathode slurry was drop casted onto either an aluminium foil or a carbon coated aluminium foil by a blade coater. Coating thickness was maintained at a particular range, for example, around 100-200 micron. The coating was dried in oven for about 6-8 hrs at a temperature of around 120° C.
  • the cathode material has a density of around 0.8-2 gm/cm3 or similar density as per the requirement.
  • the cathode to binder to conducting carbon weight percentage was maintained in the range of 90-5-5 to 70-10-20 wt%.
  • the cathode electrode thus obtained has a mass loading in the range of 4-30mg/cm3 and porosity in the range of 20-55%.
  • the anode electrode of the sodium ion battery of the present invention is selected from a group comprising of graphite, hard carbon, soft carbon or a combination of any of these. Depending upon the required performance the % of hard carbon and/or soft carbon and/or graphite can be decided. Hard carbon anode is better for higher energy density while soft carbon is good for better power density.
  • the charge storage mechanism of sodium ions in the above-mentioned carbon materials depends upon the micro structure, pore structure, surface area, and the type of electrolyte used. This was achieved in soft carbon material by heating the soft carbon source at a specific temperature, for example, around 600-1400°C and for a specific time frame, for example, about 2-8 hours, followed by ball milling and sieving.
  • Hard carbon was also synthesized by the same protocol.
  • the precursors for hard carbon are known sources of hard carbon, like, but not limited, to, bio-waste or agro-waste products such as sugarcane bagasse or rice straw. Different types of graphite, natural or synthetic may also be used.
  • Soft carbon was synthesized from known sources of soft carbon, like, but not limited to, coal, coke, coal tar pitch, etc.
  • the anode slurry was prepared by mixing active carbon (hard, soft, graphite or combination of any of these ) obtained as per the above processes, conducting carbon and PVDF binder in N-methyl Pyridine (NMP) solvent or a water soluble binder such as, but not limited to, Carboxymethyl cellulose (CMC) , polyacrylic acid (PAA), Polyvinyl Alcohol (PVA), in which the active material was maintained at 80-90 % weight ratio.
  • NMP N-methyl Pyridine
  • PAA polyacrylic acid
  • PVA Polyvinyl Alcohol
  • the slurry viscosity was maintained around 5000-15000 millipascal-second.
  • the anode slurry was drop casted onto either an aluminium foil or a carbon coated aluminium foil by a blade coater. The coating thickness was around 200-300 micron.
  • the coating was dried in oven for 6-8 hrs at 90-120° C. It was then hot pressed to give the anode material a density of around 0.8-1.8gm/cm3.
  • the anode to binder to conducting carbon weight percentage was maintained in the range of 95-3-2 to 80-10-10 wt%.
  • the anode electrode thus obtained has a mass loading in the range of 6 to 40mg/cm3 and porosity in the range of 15-55%.
  • the salts used in the composition may be selected from NaC104 or NaPF6, (0.5M- 2M).
  • the additives are selected from a group comprising of 2-5 wt % of Fluoroethylene carbonate, 1-5% of VC (vinylene carbonate), Propane Sultone in an amount of 1 to 10%.
  • the amount of electrolyte fill is in the range of 2 to 20gm/Ah.
  • the anode selected is either a soft carbon or a hard carbon or graphite or a combination of any of these and was subjected to a pre- sodiation treatment process by forming Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode, to prevent the irreversible loss of the capacity of the counter electrode.
  • SEI Solid Electrolyte Interface Layer
  • the Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode is achieved by pre-sodiation of the anodes.
  • FIG. 3 illustrates a pre-sodiation assembly according to an embodiment of the present invention.
  • the present invention further provides for a process for pre-alkalization/presodation of the anode electrode.
  • multiple batteries can be pre-alkalized simultaneously.
  • the mass balance is cathode excessive.
  • the ratio of the cathode electrode to anode electrode is in the range of cathode: anode, 1 : 1.3 to 1 :2.5.
  • the cathode is not excessive, hence, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5).
  • the method for formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode comprising the steps of a) mounting the carbon coated electrodes (101) on a stack (109) containing two vertical contact rods in such a way that all the carbon coated electrodes on the left-hand side are in electrical contact (117) with the left-hand side rod (115),
  • FIG. 2 illustrates an exemplary pre-sodiation of the carbon electrodes.
  • Fig. 2 provides comparison of the microstructure of the a) bare electrode with that of b) conventionally pre-sodiated (cycled over several charging discharging cycles at low rate) electrodes and c) spontaneously pre-sodiated electrodes.
  • the spontaneously pre-sodiated electrodes have been processed with electrically connecting the anode with sodium metal counter electrode and maintaining the connection for a certain amount of time (5 min to 18hr is shown in FIG. 2) to obtain d) prolonged pre-sodiated electrodes.
  • the electrolyte used for pre-sodiation assembly has similar composition and percentages as described above. In another embodiment of the present invention, the electrolyte used for pre-sodiation assembly has a different percentage of additives than the one described above.
  • the above pre-sodiation assembly can be conveniently assembled inside a glove box or any other inert environment so as to avoid exposure of alkali metal to the moisture and oxygen.
  • a very thin and uniform alkali metal coating can be obtained on any substrate- especially on a porous carbon-based substrate. This can be used to make an alkali metal battery or to incorporate excess alkali metal onto the electrode that serves to compensate the first cycle irreversible capacity loss of the battery.
  • FIG. 4 illustrates performance of coin cell batteries for different presodiation time/shorting time with the pre-sodiation assembly according to an embodiment of the present invention.
  • the presodiation time of 5mins to 18hours shows very low irreversible capacity loss (60mAhr/gm) and gives 500 cycles of stable performance.
  • the applied current and specific capacity is calculated w.r.t. mas of cathode and anode active material.
  • FIG. 5 illustrates performance of coin cell batteries for different anode to cathode mass ratio according to an embodiment of the present invention.
  • the anode to cathode mass ratio has been tested in the range of 0.65 to 2.5.
  • cathode to anode mass balance of 1 : 1.8 to 1 :2.5 shows a good cycle life of up to 500 cycles.
  • the pre-sodiation set up can be conveniently assembled inside a glove box or any other inert environment so as to avoid exposure of alkali metal to the moisture and oxygen.
  • the cathode and the pre-sodiated anodes are stacked together with a polypropylene separator (105) or any other similar characteristics material separator in between. Multiple layers of both are stacked together. This way the stacking density can be increased to a large number.
  • an extra separator is wound around the cell battery assembly to make it compact.
  • the anode and cathode tabs/connections are welded together and inserted inside a laminated aluminium pouch or a plastic hard casing or any other similar material known in the art.
  • a suitable amount of electrolyte is dispensed inside the pouch or the plastic hard casing. For example, for 6 layers of stacking with the mentioned electrode density (cathode density of 35% and anode density of 20%), about 6-9ml of electrolyte is dispensed inside the pouch. The pouch is then put under a diffusion chamber for proper soaking of electrodes. The pouch is then sealed, and the sodium-ion coin cell battery fabrication process is completed.
  • FIG. 6 illustrates the performance of the full cell (coin cell) representing capacity versus cycle life for hard carbon-based anode and carbonate-based electrolyte. These coin cells show 83 % retention after 12000 cycles of charge/discharge. These cells are charged and discharged initially at 2C rate (60mAhr/gm) and 6C rate (180mAhr/gm).
  • FIG. 7 illustrates the performance of the full cell (coin cell) battery representing capacity versus cycle life for soft carbon-based anode and carbonate-based electrolyte. As illustrated in the graph, it shows a stable performance of 500 cycles. These cells are charged and discharged initially at 2C rate (70mAhr/gm) and 6C rate (210mAhr/gm).
  • FIG. 8 illustrates the performance of the full cell (coin cell) battery representing capacity versus cycle life for soft carbon-based anode and ether-based electrolyte. As illustrated in the graph, it shows a stable performance of 4000 cycles. These cells are charged and discharged initially at 1C rate (lOOmAhr/gm) and 3C rate (300mAhr/gm).
  • the sodium ion battery system and method of the present invention can be used for various applications, like, but not limited to automotive, consumer devices, gadget, industrial devices, electric vehicles, etc.
  • the present invention discloses a simple and economical method for designing a high-power density (quick charging and discharging battery) and long cycle life sodium ion battery.
  • Planetary ball miller muffle furnace, vacuum slurry maker, blade coater, vacuum oven, glove box and charging discharging cycler. Examples:
  • the precursors selected from a group comprising of, vanadium(V) oxide, ammonium dihydrogen phosphate, sodium carbonate anhydrous, and oxalic acid dihydrate were mixed in a specific weight ratio of 14.7%, 27.8%, 12.8% and 43.7%, respectively and was further heated in a gas environment comprising a mixture of argon and hydrogen gas at temperature of 800C for 8 hours to obtain Sodium Vanadium Phosphate (NVP). Further, the NVP thus obtained was ball milled for 2-5 minutes to achieve the desired particle size. The particle size detected was in the range of 10-100 microns.
  • the cathode slurry was prepared by mixing NVP (42.5gm), conducting carbon (3.5gm), and Polyvinylidene fluoride (PVDF) binder (4 gm) with N-methyl Pyridine (NMP) solvent (100ml). The slurry viscosity was maintained at around 8000 millipascal-second.
  • NMP N-methyl Pyridine
  • Coating thickness was maintained at around 180 micron. The coating was dried in oven for about 6 hrs at a temperature of around 120° C.
  • the cathode material was then hot pressed to give the cathode material with a density of around 1.5 gm/cm3 or similar density as per the requirement.
  • the cathode to binder to conducting carbon weight percentage was maintained in the range of 85-7-8wt%.
  • the cathode electrode thus obtained has a mass loading in the range of 17mg/cm3 and porosity of 35%.
  • the soft carbon of the anode was synthesized from coal. This was done by heating the coal at a temperature range of around 1200°C and for about 4 hours, followed by ball milling and sieving. Hard carbon was also synthesized by the same protocol; however, the precursors are bio-waste or agro-waste products such as sugarcane bagasse or rice straw. Graphite may be used as it is commercially available and can be ball milled further if required.
  • the anode slurry was prepared by mixing active carbon (hard, soft, graphite or combination of two) obtained as per the above process, conducting carbon and PVDF binder in N-methyl Pyridine (NMP) solvent in which the specific weights for a 50ml slurry are 44gm, 3gm, 3gm, 42gm, respectively.
  • NMP N-methyl Pyridine
  • the slurry viscosity was maintained around 10000 millipascal-second.
  • the anode coating the anode slurry was drop casted onto an aluminium foil or a carbon coated aluminium foil by a blade coater. The coating thickness was around 220 micron. The coating was dried in oven for 4 hrs at 70° C. It was then hot pressed to give the anode material with a density of around 1.2gm/cm3.
  • the anode to binder to conducting carbon weight percentage was maintained in the range of 89-5-6 wt%.
  • the anode electrode thus obtained has a mass loading of 13 mg/cm3 (without presodiation) and 25mg/cm3 (with presodiation) and porosity in the range of 20%.
  • Electrolyte composition :
  • the cathode and the pre-sodiated anodes are stacked together with a polypropylene separator or any other similar characteristics material separator in between. Multiple layers of both anode and cathode are stacked together. At the end, an extra separator was wound around the cell battery assembly to make it compact. Once this is done, the anode and cathode tabs/connections are welded together and inserted inside a laminated aluminium pouch or a plastic hard casing. Once this is assembled, a suitable amount of electrolyte was dispensed inside the pouch or the plastic hard casing.
  • a carbon coated electrode and a counter electrode were arranged in an assembly and connected to two different rods. Between the carbon coated electrode and the counter electrode, the electrolyte was filled. The entire assembly was sealed with gasket layers inserted after the active electrode and clamped in the end with winged screws. In the end, the two rods are electrically connected for the controlled amount of time via a known resistor (to control the current) during which a thin layer of alkali metal gets electrochemically coated on the active electrode.
  • the battery constructed with the cathode and anode prepared in accordance with the examples 1 to 4 having different anode to cathode mass ratio in the range of 1 : 1.5 to 1 : 2.5 ratio can charge and discharge in a potential range of 3.6 to 2.3V, in which the electrolyte solution is stable and the cycle performance is excellent even after 500 cycles.
  • the performance of coin cell fabricated using soft carbon anode was evaluated at a current density ranging at 70 to 210 mA/g.
  • the performance of coin cell as depicted in Figure 8 shows 90 to 100 % energy density retention even after 500 cycles of charge/discharge.
  • the above confirms that the battery constructed with soft carbon anode prepared in accordance with the example 2 can charge and discharge in a potential range of 3.6 to 2.3V, in which the electrolyte solution is stable and the cycle performance is excellent even after 500 cycles.

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Abstract

The present invention discloses a high-power density and long cycle life Sodium-ion battery system and method for designing the same. The present invention further relates to method for formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode to prevent the irreversible loss of the capacity of the counter electrode.

Description

A HIGH-POWER DENSITY SODIUM-ION BATTERY
TECHNICAL FIELD:
The present invention relates to the battery technology, and in particular relates to a high-power density and long-life cycle Sodium-ion battery system and method for designing the same. The present invention further relates to method for formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode to prevent the irreversible loss of the capacity of the counter electrode.
BACKGROUND OF THE INVENTION:
Background description includes information that may be useful in understanding of the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
Recently, due to the increasing demands of energy storage systems for various applications like consumer devices, gadgets, automotive, manufacturing, etc. the need for reliable and rechargeable batteries is growing. With the need for a green and clean technology, electric vehicles are in demand today. Electric vehicles are being looked at as a means of a clean and sustainable transport system.
Currently, lithium-ion batteries are largely used in various devices like laptops, mobile phones, vehicles, etc. However, due to the limited availability of lithium, it would be difficult to meet the ever-growing demand of energy storage system for various applications. Also, as the needs increase, with the limited supply of lithium available on the planet, the cost would also increase in future. Mining and refining of lithium also adds to the cost of the battery. Additionally, lithium ion batteries take time to charge and discharge which is not convenient in todays’ fast-moving world. To meet the growing demand of batteries for energy storage, sodium-ion is looked at as an alternative solution to the currently commercialized lithium-ion battery. Sodium ion batteries requires materials that are abundantly available and are much cheaper. There is a need for a sodium-ion battery which provides fast charging and discharging to meet the requirements of current fast paced applications. There is a need for a sodium-ion battery with a high energy density, a high-power density, a high performance, and a good life cycle. There is a need for a low cost and high efficiency sodium-ion battery that can be used for various applications. There is a need for a sodium ion battery that can store higher amount of charge and provide quick charging as per the requirement.
Current high-performance lithium ion batteries (NMC-graphite type) can be charged at maximum 1C (1 hour) rate. Charging them at higher rate compromises the cycle life. On the other hand, Lithium titanate type batteries can sustain faster charging, but are very expensive and require specialized post coating manufacturing steps. The current highest energy density lithium ion batteries give a cycle life of up to 2500 cycles. All existing Na-ion batteries are mostly suitable for charging at 0.5C to 1C rate, giving cycle life of up to 1000 cycles. Thus, there is a need for a battery technology, and in particular a system and method for designing a battery which provides a high-power density and long-life cycle Sodium-ion battery.
Most of the active materials for sodium-ion batteries suffer from the problem of low-energy efficiency in the first cycle because of the loss of active sodium ions consumed for the formation of a solid electrolyte interface (SEI). Therefore, one of the challenges with the sodium-ion battery is the formation of a Solid Interface Layer (SEI) on the surface of an anode during the first charging and discharging cycle. Due to this there is irreversible loss of the capacity of the counter electrode. This first cycle irreversible loss is different for different battery chemistries. In order to cater to this challenge, the SEI is formed on the surface of anode prior to the fabrication of full cell battery. Therefore, to make up for the lost sodium ion, presodiation treatments have been applied, which are effective ways to mitigate the low initial efficiency.
There is ample literature available on methods of presodiation treatment of the anodes, as described herein below.
Xiaoxiao Liu et al reported Electrode-Level Chemical Presodiation Route by Solution Spraying to Improve the Energy Density of Sodium-Ion Batteries, in Advanced Functional Materials (https://d0i.0rg/l 0 1002/adfm.201903795). The electrode-level presodiation strategy reported in this article comprises spraying a sodium naphthaline solution onto a carbon electrode to compensate the initial sodium loss and improves the energy density of Sodium-Ion Batteries.
Moeez I, et all reported (ACS Appl Mater Interfaces. 2019 Nov 6; 11(44):41394- 41401. doi: 10.1021/acsami.9bl4381. Epub 2019 Oct 28) a direct-contact method to achieve the presodiation for cathode and anode electrodes.
Yang Cao et al reported a pre-sodiation method by simply immersing the electrode in a liquid sodium source to reduce irreversible capacity loss for titanium-based materials (Chemical Communications, Issue 98, 2019).
However, the present methods used for such pre-alkalization/pre-sodiation are typically not efficient and convenient for industrial production. Thus, there is a need in the art to provide a convenient pre-alkalization process to prevent the irreversible loss of the capacity of the counter electrode. With the rapidly growing demands of battery for various applications, there is need for an economical, high-power density, and long life cycle Sodium-ion battery system and method for designing the same. OBJECTS OF THE INVENTION
An object of the present invention is to provide a high-power density sodium ion battery which provides for quick charging and discharging.
Another object of the present invention is to provide a long-life cycle sodium ion battery.
Another objective of the present invention is to provide an economical, convenient, pre-sodiation process to prevent the irreversible loss of the capacity of the counter electrode in sodium ion battery.
Yet another object of the present invention is to provide for a sodium ion battery that can be used for various applications, like, but not limited to consumer devices, gadget, industrial devices, electric vehicles, etc.
SUMMARY OF THE INVENTION:
Current high-performance lithium ion batteries (NMC-graphite type) can be charged at maximum 1C (1 hour) rate. Charging them at higher rate compromises the cycle life. On the other hand, Lithium titanate type batteries can sustain faster charging but are very expensive and require specialized post coating manufacturing steps. The current highest energy density lithium ion batteries give a cycle life of up to 2500 cycles. All existing Na-ion batteries are mostly suitable for charging at 0.5 to 1 C rate, giving cycle life of up to 1000 cycles.
In line with the above objectives, the present invention in one aspect provides a sodium ion battery of a high-power density with a capability of charging at rate of 3C to 6C and giving a cycle life of up to 5000. The sodium ion battery according to the present invention comprises a positive electrode - cathode and a negative electrode- anode, a sodium-ion electrolyte composition along with electrolyte additives. The cathode of the sodium ion battery according to the present invention comprises of a NASICON family member, a binder and a conducting carbon. In one preferred aspect, the cathode comprises of a carbon coated, Sodium Vanadium Phosphate (NVP) electrode. The anode of the sodium ion battery according to present invention is an electrode selected from a group comprising of graphite, hard carbon or soft carbon or a combination of any of these.
The composition of the electrolytes for the sodium ion battery of the present invention comprises salts selected from Sodium perchlorate (NaC104) or sodium hexafluorophate (NaPF6), dissolved in Ester/carbonate family of solvents selected from a group consisting of Ethylene Carbonate, Dimethyl Carbonate, Diethyl carbonate (DEC), Propylene carbonate (PC), or Ether family of solvents selected from the group consisting of diglyme, triglyme, tetraglyme. The electrolyte additives are selected from a group comprising of Fluoroethylene carbonate, VC (vinylene carbonate) and Propane Sultone.
In another aspect, the present invention provides a sodium ion battery with a specific mass balance, for example, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5). This mass balance of the present invention ensures the capacity balance between cathode electrode and anode electrode and has a strong correlation with final cell capacity and stability. Excess mass balance of anode gives better cycle life while excess mass balance of cathode provides for irreversible capacity loss during initial cycles. So, tuning the mass balance is very crucial for a targeted energy and power performance and cycle life of the battery.
In an altemate/optional embodiment, the present invention further provides for a process for pre-alkalization/presodation of the anode electrode. According to the process of the present invention, multiple batteries can be pre-alkalized simultaneously. With the presodiation of the anode electrode, the mass balance is cathode excessive. Hence, the ratio of the cathode electrode to anode electrode is in the range of cathode: anode, 1 : 1.3 to 1 :2.5. As mentioned in the earlier embodiment, without presodiation, the cathode is not excessive, hence, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5). It is to be noted that, the sodium-ion battery of the present invention may be synthesized with or without presodiation of the anode electrode to provide a high-power density and long cycle life battery.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings are included to provide a further understanding of the present disclosure and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure.
FIG. 1 (and b) illustrates a sodium-ion type battery designed according to the method of the present invention.
FIG. 2 illustrates an exemplary pre-sodiation of the carbon electrode according to an embodiment of the present invention.
FIG. 3 illustrates a pre-sodiation assembly according to an embodiment of the present invention.
FIG. 4 Illustrates performance of coin cell batteries for different presodiation time/shorting time with the pre-sodiation assembly according to an embodiment of the present invention.
FIG. 5 illustrates performance of coin cell batteries for different mass balance according to an embodiment of the present invention.
FIG. 6 illustrates the performance of the full cell (coin cell) representing capacity versus cycle life for hard carbon-based anode and carbonate-based electrolyte, according to an embodiment of the present invention.
FIG. 7 illustrates the performance of the full cell (coin cell) representing capacity versus cycle life for soft carbon-based anode and carbonate based electrolyte according to an embodiment of the present invention. FIG. 8 illustrates the performance of the full cell (coin cell) battery representing capacity versus cycle life for soft carbon-based anode and ether based electrolyte according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION:
The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.
Accordingly, the present invention provides a high-power density sodium ion battery, which comprises:
a) a positive electrode, cathode, comprising of a NASICON family member, a binder and a conducting carbon, wherein, the cathode to binder to conducting carbon weight percentage is in the range of 90-5-5 to 70-10-20 wt%;
b) a negative electrode, anode, comprising of a carbon material, a binder and a conducting carbon, wherein, the anode to binder to conducting carbon weight percentage is in the range of 95-3-2 to 80-10-10 wt%; and c) an electrolyte selected from either a carbonate or ether family of solvents and additives selected from the group consisting of a carbonate family or PS (propane sultone), wherein, the amount of electrolyte fill is in the range of 2 to 20gm/Ah.
wherein, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5).,
wherein, the said cathode electrode has a mass loading in the range of 4-30mg/cm3 and porosity in the range of 20-55%, while, the said anode electrode has a mass loading in the range of 6 to 40mg/cm3 and porosity in the range of 15-55%.
Lower electrode porosity leads to poor electrolyte soaking, hence, hinders ionic transport, while, a high electrode porosity decreases electronic transport. Hence, for a high-power density battery, for a given mass loading of electrode, appropriate tuning of porosity is very crucial. In order to increase the specific energy density of a battery, active material mass loading has to be maximized. The mass balance, mass loading range and the porosity range of the present invention provides a specific energy density of upto 70Wh/Kg and a capability to be charged at a 3C (15 to 20mins).
In a preferred embodiment, the high-power density sodium ion battery according to the present invention encompasses a carbon coated, sodium vanadium phosphate, Na3V2((PO)4)3 (NVP) electrode as a cathode and an anode comprises of a hard carbon or a soft carbon or graphite or a combination of any of these.
The anode electrode according to the invention is pre-treated for formation of a solid electrolyte interface layer (SEI) on the surface of the anode electrode to prevent the first cycle irreversible losses.
The binder used in high-power density sodium ion battery is a NMP soluble binder or an aqueous soluble binder, for example Polyvinylidene fluoride (PVDF).
Detailed description of the preferred and optional embodiments with reference to the drawings is provided herein below.
FIG. 1 (and b) illustrates a sodium-ion type battery designed according to the method of the present invention. Fig. la illustrates a coin cell battery, while Fig. lb illustrates a pouch cell battery.
The sodium ion battery of the present invention comprises of a positive electrode cathode, which is a carbon coated, Sodium Vanadium Phosphate (NVP) electrode. The cathode of the sodium ion battery of the present invention is prepared by the process described herein below. In the first step, precursors, selected from a group comprising of, vanadium(V) oxide, ammonium dihydrogen phosphate, sodium carbonate anhydrous, and oxalic acid dihydrate were mixed in a specific weight ratio of 14.7%, 27.8%, 12.8% and 43.7%, respectively and further heated in a gas environment comprising a mixture of argon and hydrogen gas at a specific temperature (e.g. 700°C to 900°C) for a specific time frame, for example, 6 hours to 10 hours, to obtain Sodium Vanadium Phosphate (NVP). Further, the NVP thus obtained was ball milled for a specific time frame (2-5 minutes) to achieve the desired particle size in the range of 10-100 microns.
In the second step, the cathode slurry was prepared by mixing NVP, conducting carbon and Polyvinylidene fluoride (PVDF) binder with N-methyl Pyridine (NMP) solvent in which the active material is in the range of 65-80% weight ratio. The slurry viscosity was maintained around 5000-20000 millipascal-second. For the cathode coating, the cathode slurry was drop casted onto either an aluminium foil or a carbon coated aluminium foil by a blade coater. Coating thickness was maintained at a particular range, for example, around 100-200 micron. The coating was dried in oven for about 6-8 hrs at a temperature of around 120° C. It was then hot pressed to give the cathode material with a density of around 0.8-2 gm/cm3 or similar density as per the requirement. The cathode to binder to conducting carbon weight percentage was maintained in the range of 90-5-5 to 70-10-20 wt%. The cathode electrode thus obtained has a mass loading in the range of 4-30mg/cm3 and porosity in the range of 20-55%.
The anode electrode of the sodium ion battery of the present invention is selected from a group comprising of graphite, hard carbon, soft carbon or a combination of any of these. Depending upon the required performance the % of hard carbon and/or soft carbon and/or graphite can be decided. Hard carbon anode is better for higher energy density while soft carbon is good for better power density. The charge storage mechanism of sodium ions in the above-mentioned carbon materials depends upon the micro structure, pore structure, surface area, and the type of electrolyte used. This was achieved in soft carbon material by heating the soft carbon source at a specific temperature, for example, around 600-1400°C and for a specific time frame, for example, about 2-8 hours, followed by ball milling and sieving. Hard carbon was also synthesized by the same protocol. The precursors for hard carbon are known sources of hard carbon, like, but not limited, to, bio-waste or agro-waste products such as sugarcane bagasse or rice straw. Different types of graphite, natural or synthetic may also be used. Soft carbon was synthesized from known sources of soft carbon, like, but not limited to, coal, coke, coal tar pitch, etc.
The anode slurry was prepared by mixing active carbon (hard, soft, graphite or combination of any of these ) obtained as per the above processes, conducting carbon and PVDF binder in N-methyl Pyridine (NMP) solvent or a water soluble binder such as, but not limited to, Carboxymethyl cellulose (CMC) , polyacrylic acid (PAA), Polyvinyl Alcohol (PVA), in which the active material was maintained at 80-90 % weight ratio. The slurry viscosity was maintained around 5000-15000 millipascal-second. For the anode coating, the anode slurry was drop casted onto either an aluminium foil or a carbon coated aluminium foil by a blade coater. The coating thickness was around 200-300 micron. The coating was dried in oven for 6-8 hrs at 90-120° C. It was then hot pressed to give the anode material a density of around 0.8-1.8gm/cm3. The anode to binder to conducting carbon weight percentage was maintained in the range of 95-3-2 to 80-10-10 wt%. The anode electrode thus obtained has a mass loading in the range of 6 to 40mg/cm3 and porosity in the range of 15-55%.
The composition of electrolytes, as used for the sodium ion battery of the present invention comprises Ester/carbonate family of solvents such as Ethylene Carbonate,, Dimethyl Carbonate (50-50wt%), Diethyl carbonate (DEC), Propylene carbonate (PC), or Ether family of solvents such as diglyme, triglyme, tetraglyme. The salts used in the composition may be selected from NaC104 or NaPF6, (0.5M- 2M). The additives are selected from a group comprising of 2-5 wt % of Fluoroethylene carbonate, 1-5% of VC (vinylene carbonate), Propane Sultone in an amount of 1 to 10%. The amount of electrolyte fill is in the range of 2 to 20gm/Ah.
In an alternate embodiment wherein, the anode selected is either a soft carbon or a hard carbon or graphite or a combination of any of these and was subjected to a pre- sodiation treatment process by forming Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode, to prevent the irreversible loss of the capacity of the counter electrode. The Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode is achieved by pre-sodiation of the anodes. FIG. 3 illustrates a pre-sodiation assembly according to an embodiment of the present invention.
In an altemate/optional embodiment, the present invention further provides for a process for pre-alkalization/presodation of the anode electrode. According to the process of the present invention, multiple batteries can be pre-alkalized simultaneously. With the presodiation of the anode electrode, the mass balance is cathode excessive. Hence, the ratio of the cathode electrode to anode electrode is in the range of cathode: anode, 1 : 1.3 to 1 :2.5. As mentioned in the earlier embodiment, without presodiation, the cathode is not excessive, hence, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (cathode: anode, 1 :0.5 to 1 : 2.5).
Accordingly, as illustrated in Fig. 3, the method for formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode, comprising the steps of a) mounting the carbon coated electrodes (101) on a stack (109) containing two vertical contact rods in such a way that all the carbon coated electrodes on the left-hand side are in electrical contact (117) with the left-hand side rod (115),
b) inserting a counter electrode (107) between each carbon electrode in such a way that all the counter electrodes are in electrical contact (117) with the right-hand side rod (113),
c) filling the electrolyte (103) between the carbon coated electrodes (101) and the counter electrodes - sodium (107),
d) sealing the entire assembly with gasket layers (111) inserted after each carbon coated electrode to separate each stack and to avoid electrolyte leakage, and clamping the ends, and e) electrically connecting the two vertical contact rods for electrochemically coating a thin layer of alkali metal on the carbon coated electrode (SEI).
According to another embodiment of the present invention, with the presodiation of the anode electrode according to the process of the present invention, cathode electrode to anode electrode mass balance in the range of cathode: anode, 1 : 1.3 to 1 :2.5. is achieved. FIG. 2 illustrates an exemplary pre-sodiation of the carbon electrodes. Fig. 2 provides comparison of the microstructure of the a) bare electrode with that of b) conventionally pre-sodiated (cycled over several charging discharging cycles at low rate) electrodes and c) spontaneously pre-sodiated electrodes. The spontaneously pre-sodiated electrodes have been processed with electrically connecting the anode with sodium metal counter electrode and maintaining the connection for a certain amount of time (5 min to 18hr is shown in FIG. 2) to obtain d) prolonged pre-sodiated electrodes.
In an embodiment of the present invention, the electrolyte used for pre-sodiation assembly has similar composition and percentages as described above. In another embodiment of the present invention, the electrolyte used for pre-sodiation assembly has a different percentage of additives than the one described above.
The above pre-sodiation assembly can be conveniently assembled inside a glove box or any other inert environment so as to avoid exposure of alkali metal to the moisture and oxygen. With the assembly of the present invention, a very thin and uniform alkali metal coating can be obtained on any substrate- especially on a porous carbon-based substrate. This can be used to make an alkali metal battery or to incorporate excess alkali metal onto the electrode that serves to compensate the first cycle irreversible capacity loss of the battery.
FIG. 4 illustrates performance of coin cell batteries for different presodiation time/shorting time with the pre-sodiation assembly according to an embodiment of the present invention. As illustrated in the graph, the presodiation time of 5mins to 18hours shows very low irreversible capacity loss (60mAhr/gm) and gives 500 cycles of stable performance. The applied current and specific capacity is calculated w.r.t. mas of cathode and anode active material.
FIG. 5 illustrates performance of coin cell batteries for different anode to cathode mass ratio according to an embodiment of the present invention. The anode to cathode mass ratio has been tested in the range of 0.65 to 2.5. As illustrated in the graph, cathode to anode mass balance of 1 : 1.8 to 1 :2.5 shows a good cycle life of up to 500 cycles.
The pre-sodiation set up can be conveniently assembled inside a glove box or any other inert environment so as to avoid exposure of alkali metal to the moisture and oxygen. Once the anode is pre-sodiated, the cathode and the pre-sodiated anodes are stacked together with a polypropylene separator (105) or any other similar characteristics material separator in between. Multiple layers of both are stacked together. This way the stacking density can be increased to a large number. At the end, an extra separator is wound around the cell battery assembly to make it compact. Once this is done, the anode and cathode tabs/connections are welded together and inserted inside a laminated aluminium pouch or a plastic hard casing or any other similar material known in the art. Once this is assembled, a suitable amount of electrolyte is dispensed inside the pouch or the plastic hard casing. For example, for 6 layers of stacking with the mentioned electrode density (cathode density of 35% and anode density of 20%), about 6-9ml of electrolyte is dispensed inside the pouch. The pouch is then put under a diffusion chamber for proper soaking of electrodes. The pouch is then sealed, and the sodium-ion coin cell battery fabrication process is completed.
FIG. 6 illustrates the performance of the full cell (coin cell) representing capacity versus cycle life for hard carbon-based anode and carbonate-based electrolyte. These coin cells show 83 % retention after 12000 cycles of charge/discharge. These cells are charged and discharged initially at 2C rate (60mAhr/gm) and 6C rate (180mAhr/gm).
FIG. 7 illustrates the performance of the full cell (coin cell) battery representing capacity versus cycle life for soft carbon-based anode and carbonate-based electrolyte. As illustrated in the graph, it shows a stable performance of 500 cycles. These cells are charged and discharged initially at 2C rate (70mAhr/gm) and 6C rate (210mAhr/gm).
FIG. 8 illustrates the performance of the full cell (coin cell) battery representing capacity versus cycle life for soft carbon-based anode and ether-based electrolyte. As illustrated in the graph, it shows a stable performance of 4000 cycles. These cells are charged and discharged initially at 1C rate (lOOmAhr/gm) and 3C rate (300mAhr/gm).
Thus, the sodium ion battery system and method of the present invention can be used for various applications, like, but not limited to automotive, consumer devices, gadget, industrial devices, electric vehicles, etc. The present invention discloses a simple and economical method for designing a high-power density (quick charging and discharging battery) and long cycle life sodium ion battery.
The present invention is exemplified by the following examples which are provided for illustration only and, should not be construed to limit the scope of the invention.
Instrumentation:
Planetary ball miller, muffle furnace, vacuum slurry maker, blade coater, vacuum oven, glove box and charging discharging cycler. Examples:
Example 1:
Synthesis of cathode active material for sodium-ion battery
The precursors, selected from a group comprising of, vanadium(V) oxide, ammonium dihydrogen phosphate, sodium carbonate anhydrous, and oxalic acid dihydrate were mixed in a specific weight ratio of 14.7%, 27.8%, 12.8% and 43.7%, respectively and was further heated in a gas environment comprising a mixture of argon and hydrogen gas at temperature of 800C for 8 hours to obtain Sodium Vanadium Phosphate (NVP). Further, the NVP thus obtained was ball milled for 2-5 minutes to achieve the desired particle size. The particle size detected was in the range of 10-100 microns.
Fabrication of cathode:
The cathode slurry was prepared by mixing NVP (42.5gm), conducting carbon (3.5gm), and Polyvinylidene fluoride (PVDF) binder (4 gm) with N-methyl Pyridine (NMP) solvent (100ml). The slurry viscosity was maintained at around 8000 millipascal-second. For the cathode coating, the cathode slurry was drop casted onto an aluminium foil or a carbon coated aluminium foil by a blade coater. Coating thickness was maintained at around 180 micron. The coating was dried in oven for about 6 hrs at a temperature of around 120° C. It was then hot pressed to give the cathode material with a density of around 1.5 gm/cm3 or similar density as per the requirement. The cathode to binder to conducting carbon weight percentage was maintained in the range of 85-7-8wt%. The cathode electrode thus obtained has a mass loading in the range of 17mg/cm3 and porosity of 35%.
Example 2:
Synthesis of anode material for sodium-ion battery
The soft carbon of the anode was synthesized from coal. This was done by heating the coal at a temperature range of around 1200°C and for about 4 hours, followed by ball milling and sieving. Hard carbon was also synthesized by the same protocol; however, the precursors are bio-waste or agro-waste products such as sugarcane bagasse or rice straw. Graphite may be used as it is commercially available and can be ball milled further if required.
Fabrication of anode
The anode slurry was prepared by mixing active carbon (hard, soft, graphite or combination of two) obtained as per the above process, conducting carbon and PVDF binder in N-methyl Pyridine (NMP) solvent in which the specific weights for a 50ml slurry are 44gm, 3gm, 3gm, 42gm, respectively. The slurry viscosity was maintained around 10000 millipascal-second. For the anode coating, the anode slurry was drop casted onto an aluminium foil or a carbon coated aluminium foil by a blade coater. The coating thickness was around 220 micron. The coating was dried in oven for 4 hrs at 70° C. It was then hot pressed to give the anode material with a density of around 1.2gm/cm3.
The anode to binder to conducting carbon weight percentage was maintained in the range of 89-5-6 wt%. The anode electrode thus obtained has a mass loading of 13 mg/cm3 (without presodiation) and 25mg/cm3 (with presodiation) and porosity in the range of 20%.
Example 3
Electrolyte composition:
Carbonate based electrolyte - 1 Molar NaC104 in EC + DEC in the ratio of 50:50 Ether based electrolyte - 1 Molar NaPF6 in diglyme
Example 4:
Fabrication of coin cell/ pouch cell battery:
For the fabrication of coin cell battery, the cathode and the pre-sodiated anodes are stacked together with a polypropylene separator or any other similar characteristics material separator in between. Multiple layers of both anode and cathode are stacked together. At the end, an extra separator was wound around the cell battery assembly to make it compact. Once this is done, the anode and cathode tabs/connections are welded together and inserted inside a laminated aluminium pouch or a plastic hard casing. Once this is assembled, a suitable amount of electrolyte was dispensed inside the pouch or the plastic hard casing. For example, for 6 layers of stacking with the cathode density of 35% and anode density of 20%; about 6ml/Ah of electrolyte was dispensed inside the pouch. The pouch was then put under a diffusion chamber to proper soaking of electrodes. The pouch was then sealed, to obtain the sodium-ion coin cell/pouch cell battery.
Example 5:
Method of formation of a Solid Electrolyte Interface (SEP layer on anode in sodium-ion battery
In a pre-sodiation assembly, a carbon coated electrode and a counter electrode were arranged in an assembly and connected to two different rods. Between the carbon coated electrode and the counter electrode, the electrolyte was filled. The entire assembly was sealed with gasket layers inserted after the active electrode and clamped in the end with winged screws. In the end, the two rods are electrically connected for the controlled amount of time via a known resistor (to control the current) during which a thin layer of alkali metal gets electrochemically coated on the active electrode.
Example 6
Performance of coin cell batteries for different presodiation/shorting time
The performance of full coin cell battery prepared in accordance with Example 4 with hard carbon as anode, for different shorting time ranging from 5 mins to 18 hrs within the pre-sodiation assembly, was evaluated at current density of 60 to 240 mA/g. The applied current and specific capacity is calculated w.r.t. mas of cathode and anode active material. With the pre-sodiation assembly and process of the present invention, the SEI is formed in a very short time, for example, within 5 minutes. Figure 5 confirms that the anode pre-sodiated for different shoring times, as mentioned above still exhibits 90 to 100 % energy density retention even after 500 cycles of charge/discharge.
Example 7:
Performance of coin cell batteries for different anode to cathode mass ratio
The performance of coin cell battery prepared in accordance with example 4 for different anode to cathode mass ratio of 1 : 1.5; 1 : 1.8 and 1 : 2.5 was evaluated at 250 mA/g. The three coin cells (having different anode to cathode mass ratio) as depicted in Figure 6 (the plot of specific capacity Vs number of cycles) individually shows 90 to 100 % energy density retention even after 500 cycles of charge/discharge. The above confirms that the battery constructed with the cathode and anode prepared in accordance with the examples 1 to 4 having different anode to cathode mass ratio in the range of 1 : 1.5 to 1 : 2.5 ratio can charge and discharge in a potential range of 3.6 to 2.3V, in which the electrolyte solution is stable and the cycle performance is excellent even after 500 cycles.
Example 8:
Performance of the coin cell fabricated using soft carbon anode
The performance of coin cell fabricated using soft carbon anode was evaluated at a current density ranging at 70 to 210 mA/g. The performance of coin cell as depicted in Figure 8 (the plot of specific capacity Vs number of cycles) shows 90 to 100 % energy density retention even after 500 cycles of charge/discharge. The above confirms that the battery constructed with soft carbon anode prepared in accordance with the example 2 can charge and discharge in a potential range of 3.6 to 2.3V, in which the electrolyte solution is stable and the cycle performance is excellent even after 500 cycles.

Claims

We claim.
1. A high-power density sodium ion battery, comprising:
a positive electrode, cathode, comprising of a NASICON family member, a binder and a conducting carbon, wherein, the cathode to binder to conducting carbon weight percentage is in the range of 90-5-5 to 70-10-20 wt%; a negative electrode, anode, comprising of a carbon material, a binder and a conducting carbon, wherein, the anode to binder to conducting carbon weight percentage is in the range of 95-3-2 to 80-10-10 wt%;
an electrolyte selected from either a carbonate family or ether family of solvents and additives comprising of a carbonate family or PS (propane sultone),
wherein, the cathode electrode to anode electrode has a mass balance ratio in the range of 0.5 to 2.5 (i.e. cathode: anode, 1 :0.5 to 1 :2.5) and
wherein, the said cathode electrode has a mass loading in the range of 4- 30mg/cm3 and porosity in the range of 20-55%, while, the said anode electrode has a mass loading in the range of 6 to 40mg/cm3 and porosity in the range of 15-55%.
2. The high-power density sodium ion battery as claimed in Claim 1, wherein, the cathode comprises of a carbon coated, sodium vanadium phosphate - Na3 V2((PO)4)3 (NVP) electrode and the anode comprises of a hard carbon or a soft carbon or a graphite or a combination of any of these.
3. The high-power density sodium ion battery of Claim 1, wherein, the anode electrode is pre-treated for formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode to prevent the first cycle irreversible losses, and wherein the cathode electrode to anode electrode has a mass balance ratio in the range of 1.3 to 2.5 (i.e. cathode: anode, 1 : 1.3 to 1 :2.5).
4. The high-power density sodium ion battery of Claim 1, wherein, the binder is a NMP soluble binder or an aqueous soluble binder.
5. The high-power density sodium ion battery of Claim 1, wherein, the said mass balance of the cathode electrode to anode electrode provides a high- power density and a long-life cycle at a higher charging and discharging rate.
6. The high-power density sodium ion battery of Claim 3, wherein, the said electrochemical pre-treatment comprises of electrically shorting the anode and counter electrodes for a controlled amount of time during which a thin and uniform layer of alkali metal ions gets electrochemically coated on the active anode electrode.
7. A method of producing the cathode electrode of the high-performance sodium ion battery, as claimed in claim 2, wherein, the method comprising; a) mixing precursors comprising of vanadium(V) oxide, ammonium dihydrogen phosphate, sodium carbonate anhydrous, and oxalic acid dehydrate;
b) heating the mixture in a gas environment comprising a mixture of argon and hydrogen gas, and ball milling the final product for obtaining the particle size in the range of 10-100 microns;
c) preparing a cathode slurry by mixing NVP, conducting carbon and PVDF binder with N-methyl Pyridine (NMP) solvent or aqueous solvent and
d) drop-casting the cathode slurry onto an aluminium foil for cathode coating, drying the coating and hot pressing the cathode electrode.
8. A method of producing the anode electrode of the high-performance sodium ion battery, as claimed in Claim 2, wherein, the method comprising; a) selecting precursors from a group of soft carbon, hardon carbon, or graphite, or a combination of any of these, and heating the precursors, followed by ball milling and sieving,
b) preparing an anode slurry by mixing carbon, conducting carbon and binder in N-methyl Pyridine (NMP) solvent or aqueous solvent, c) drop-casting the anode slurry onto an aluminium foil for anode coating, drying the coating and hot pressing the anode electrode.
9. The high-performance sodium ion battery as claimed in Claim 1, wherein the method of formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode, comprises;
a) mounting the carbon coated electrodes (101) on a stack (109) containing two vertical contact rods in such a way that all electrodes on the left- hand side are in electrical contact (117) with the left-hand side rod (115), b) inserting a counter electrode (107) between each carbon electrode in such a way that all counter electrodes are in electrical contact (117) with the right-hand side rod (113),
c) filling the electrolyte (103) between the carbon coated electrodes (101) and the counter electrode (107),
d) sealing the entire assembly with gasket layers (111) inserted after each carbon coated electrode and clamping the ends, and
e) electrically connecting the two vertical contact rods for electrochemically coating a thin layer of alkali metal on the carbon coated electrode.
10. The high-power density Na-ion battery as claimed in any one of the preceding claims, wherein, the construction of the battery comprising a) stacking multiple layers of the cathode and the pre-treated anode together with a separator (105), b) welding the anode and cathode tabs/connections together followed by inserting in a laminated battery casing along with a suitable amount of electrolyte and sealing the battery casing.
PCT/IN2020/050178 2019-02-28 2020-02-27 A high-power density sodium-ion battery WO2020174496A1 (en)

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CN112919434A (en) * 2021-02-09 2021-06-08 复旦大学 Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof
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CN112635709A (en) * 2020-12-15 2021-04-09 合肥工业大学 SEI film forming agent for negative electrode of sodium-ion battery, pre-sodium treatment method and sodium-ion battery
CN112635709B (en) * 2020-12-15 2022-06-28 合肥工业大学 SEI film forming agent for negative electrode of sodium ion battery, pre-sodium treatment method and sodium ion battery
CN112919434A (en) * 2021-02-09 2021-06-08 复旦大学 Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof
CN112952037A (en) * 2021-02-25 2021-06-11 武汉大学 Pre-sodium-modified sodium ion battery positive electrode and pre-sodium-modification method and application thereof
CN112952037B (en) * 2021-02-25 2022-11-11 深圳珈钠能源科技有限公司 Pre-sodium-modified sodium ion battery positive electrode and pre-sodium-modification method and application thereof
CN113135561A (en) * 2021-04-13 2021-07-20 河北农业大学 Preparation method of sodium ion battery positive electrode material and prepared material
CN113135561B (en) * 2021-04-13 2022-06-21 河北农业大学 Preparation method of sodium ion battery positive electrode material and prepared material
CN115020643A (en) * 2021-09-09 2022-09-06 中南大学 Biomass-based hard carbon, preparation method thereof and application thereof in sodium-ion battery
CN114464953A (en) * 2021-12-27 2022-05-10 国联汽车动力电池研究院有限责任公司 Pre-sodium treatment method of diaphragm for sodium ion battery
CN115020637A (en) * 2022-07-05 2022-09-06 湖州超钠新能源科技有限公司 Sodium supplement pole piece, sodium ion battery and preparation method thereof

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