FI128461B - Rechargeable sodium cells for use in high-energy battery - Google Patents

Rechargeable sodium cells for use in high-energy battery Download PDF

Info

Publication number
FI128461B
FI128461B FI20165184A FI20165184A FI128461B FI 128461 B FI128461 B FI 128461B FI 20165184 A FI20165184 A FI 20165184A FI 20165184 A FI20165184 A FI 20165184A FI 128461 B FI128461 B FI 128461B
Authority
FI
Finland
Prior art keywords
sodium
electrolyte
salt
cell
cathode
Prior art date
Application number
FI20165184A
Other languages
Finnish (fi)
Swedish (sv)
Other versions
FI20165184A7 (en
Inventor
Andras Kovacs
Débora Ruiz-Martínez
Roberto Gómez-Torregrosa
Tapani Alasaarela
David P Brown
Original Assignee
Broadbit Batteries Oy
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 to FI20165184A priority Critical patent/FI128461B/en
Application filed by Broadbit Batteries Oy filed Critical Broadbit Batteries Oy
Priority to CA3016202A priority patent/CA3016202A1/en
Priority to AU2017225241A priority patent/AU2017225241B2/en
Priority to BR112018067758-2A priority patent/BR112018067758B1/en
Priority to EP17759327.4A priority patent/EP3449525A4/en
Priority to RU2018133261A priority patent/RU2742351C2/en
Priority to CN201780015040.5A priority patent/CN108780917B/en
Priority to KR1020187028728A priority patent/KR102506303B1/en
Priority to JP2018546599A priority patent/JP6986515B2/en
Priority to MX2018010637A priority patent/MX2018010637A/en
Priority to US16/082,101 priority patent/US20200058958A1/en
Priority to TW106106982A priority patent/TWI777943B/en
Priority to PCT/FI2017/050139 priority patent/WO2017149204A2/en
Priority to IL261506A priority patent/IL261506B/en
Priority to PE2018001605A priority patent/PE20181946A1/en
Publication of FI20165184A7 publication Critical patent/FI20165184A7/en
Application granted granted Critical
Publication of FI128461B publication Critical patent/FI128461B/en

Links

Classifications

    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/582—Halogenides
    • 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
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Sustainable Energy (AREA)
  • Transportation (AREA)
  • Mechanical Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Keksintö koskee sähkökemiallista kennoa energiatiheää uudelleenladattavaa akkua varten. Kenno käsittää kiinteän natriummetallianodin, joka on päällystetty sopivan virrankerääjän päälle kennon lataamisprosessin aikana. Esiin tuodaan useita muunnelmia sopivista elektrolyyteistä sekä uusia katodimateriaaleja valmiin suurenergisen akkukennon muodostamiseksi.The invention relates to an electrochemical cell for an energy-dense rechargeable battery. The cell comprises a solid sodium metal anode coated on a suitable current collector during the charging process of the cell. Several variations of suitable electrolytes are disclosed, as well as new cathode materials to form a finished high-energy battery cell.

Description

RECHARGEABLE SODIUM CELLS FOR HIGH ENERGY DENSITY BATTERY USE
FIELD OF THE INVENTION Generally the invention relates to rechargeable electrochemical cells, batteries and supercapacitors. In particular, the present invention concerns the aforesaid devices utilizing metallic sodium anodes, a novel class of organic electrolyte composition compatible with the use of metallic sodium anodes, novel cathodes supporting high energy density, and solutions for electrolytes compatible with the disclosed electrodes.
BACKGROUND Intensive research is being conducted in the field of battery technology to find a more cost-effective and better performing battery technology than the presently dominant Li-ion technology. A recently introduced Sodium-based battery technology [1] sets a new high standard in terms of battery energy density, power density, and cost-efficiency. While progress beyond the battery aualities achieved in [1] is very challenging, O the aim of the present invention is twofold. On the one > hand, it aims to disclose a solution to the long- 0 standing challenge of working with metallic Sodium based = 30 anodes in organic electrolyte containing cells, which 7 are assembled in the discharged state. Resolving this = challenge allows retaining the current organic 3 electrolyte based cell architecture and the utilization io of existing cell production machinery and processes, Oo 35 thus resulting in a new battery technology which could N be manufactured without a need for significantmodification to the production machinery or processes. Additionally, the present invention aims to progress even further in terms of energy density. Achieving even higher energy density at reasonable production costs would be advantageous for many battery applications requiring high energy density. Several new battery applications, such as commercial electric airplanes, may be enabled by such energy-dense battery technology. The reversible use of metallic sodium anodes in certain ether-based organic electrolytes has been described in
[2], however that cell architecture only allows sodium- over-sodium cycling and does not support sodium deposition from a discharged state. The sodium deposition from discharged state and the reversible use of metallic sodium anodes has been described in [1] for certain nitrogen-containing concentrated electrolytes, which requires a highly concentrated electrolyte salt and has a limited electrolyte voltage window. Some recent publications, such as [4] and [5], describe cathode structures based on the high-capacity LioS material, which is slowly activated during the first charging cycle. Construction of cathodes from NaS material has not been previously reported. The slow charging of NaS based electrodes has been attempted, with the in-situ deposited ©polypyrrole conductive O additive prepared according to the procedure described > in [5], but the electrodes have apparently failed to 0 activate. In the lithium battery context, non-breathing = 30 lithium-oxygen battery formulations have recently been 9 described [3]. The present invention is advantageous in = several aspects with respect to the battery cell 3 described in [3], such as the use of sodium instead of io lithium, simpler cathode material synthesis, and higher Oo 35 Capacity and operating voltage capability. Reversible N sodium-over-sodium cycling of metallic sodium anodes incertain ether-based organic electrolytes has been described in [2], and this publication identified NaPF6c salt in diglyme as a particularly effective electrolyte composition for this purpose. The observed anode qualities have been attributed in [2] to the Solid Electrolyte Interface (SEI) layer being comprised of mainly Na»O and NaF, originating from the ether solvent and NaPFs salt decomposition respectively.
Additionally, in order to make the best utilization of the sodium anode capacity, new high-capacity cathode materials are needed which are at the same time able to facilitate discharged-state cell assembly. The metallic sodium anode and novel cathode material based battery cell inventions disclosed herein are therefore of high industrial importance and open up a new approach to the building of cost-effective yet high-performance batteries.
It would be advantageous to industry and commerce to provide a means to achieve higher cell-level energy density and to improve cost-efficiency through the use of Sodium-based battery cells.
SUMMARY OF THE INVENTION © I In the current invention, the limitations relating to 0 the use of certain nitrogen-containing concentrated = 30 electrolytes, requiring a highly concentrated S electrolyte salt and having a limited electrolyte E voltage window are overcome, and the advantages of the 3 use of metallic sodium on the anode side are expanded to io allow the use of its very high (1100 mAh/g) anodic Oo 35 capacity, which may be cycled with a very high N longevity. In order to make the best utilization of thisanode capacity, new high-capacity cathode materials are disclosed, which are, at the same time, able to facilitate discharged-state cell assembly. The metallic sodium anode and novel cathode material based battery cell inventions disclosed herein are therefore of high industrial importance and open up a new approach to the building of cost-effective yet high-performance batteries. An objective of the present invention is to disclose high-performance electrochemical cells for secondary (i.e. rechargeable) high-energy and high-power batteries, based on anodes comprising metallic sodium. In a preferred embodiment, the cell is provided with a metallic anode, preferably a solid metallic anode, which is electrodeposited during the cell's first charging cycle, a cathode selected from the electrode structures disclosed in this invention, and an electrolyte selected from the electrolytes disclosed in this invention.
One aspect of the invention relates to disclosing organic solvent based electrolytes that support the stable deposition and cycling of a metallic sodium anode, and are capable of supporting a high voltage window of the battery cell. Another aspect relates to disclosing a current collector material supporting O electrochemical deposition of sodium and preferably an > essentially smooth, dendrite-free and/or preferably O well-adhering electrochemical deposition of sodium. The = 30 electrochemical deposition of sodium is a practical 7 requirement for an effective implementation of the a. present invention.
D io Smooth is here defined to be having a surface roughness Oo 35 of below 100 micron and more preferably below 10 micron N and most preferably below 1 micron. Dentrite-free ishere defined as having preferably less than 20% and more preferably less than 50% and more preferably less than 203 and more preferably less than 10% and more preferably less than 5% and most preferably less than 2% 5 of the total mass of the sodium deposit as dendrites or dendritic structures. Well adhering is here defined to be maintained in contact with the substrate either by direct adhesion or by the application of a force pressing the deposit against its substrate. Stable cycling is here defined to be consumption of preferably less than 50% and more preferably less than 25% and more preferably less than 10% and most preferably less than 5% consumption of the electrolyte in the course of at least 100 cycles, and more preferably at least 1000 cycles, and most preferably at least 10000 cycles. This electrochemical sodium deposition takes place during the first charging cycle for cells assembled in the discharged state, thereby alleviating the need for working with or handling metallic sodium during the cell production process. The identification of a suitable current collector substrate for such sodium deposition and a suitable electrolyte for deposition over this substrate are interrelated and only a subset of those electrolytes supporting sodium over sodium deposition also support sodium deposition over current collector © substrates. The use of matching electrolyte - current > collector substrate couples, based on organic solvent 0 precursors, is therefore a main disclosure of the = 30 present invention. o
I a. In a further aspect, the invention relates to disclosing 3 novel high-capacity cathode materials, which are io compatible with these newly discovered metallic anode- > 35 electrolyte structures.
In a still further aspect, the invention relates to the use of electrochemical batteries, preferably electrochemical secondary batteries, comprising a number of cells according to any of the embodiments thus provided. The term “cell” refers in this disclosure to an electrochemical cell as a smallest, packed form of a battery. The term “battery” refers to a group of one or more of the abovesaid cells (a stack of cells, for example), unless otherwise indicated.
The utility of the present invention arises from a variety of reasons depending on each particular embodiment thereof, such as increased energy density per mass unit, increased cell voltage, or increased longevity or durability. Cost-effective implementation of the battery disclosed herewith will positively affect many battery-powered products. Sodium-based metal anodes provide some of the highest theoretical gravimetric capacities of any anode material: the gravimetric capacity of sodium is over 1100 mAh/g, along with a potential of -2.7 V vs. Standard Hydrogen Electrode (SHE) for the Na+/Na couple. For comparison, current graphite anodes for lithium-ion batteries have a gravimetric capacity of around 400 mAh/g. Furthermore, metallic anodes do not require O solid-state diffusion of ions to transfer material from > the charged to the discharged state, but merely the O successful deposition/dissolution of the ions on/from = 30 the surface of the metal. o
I a. Different embodiments of the present invention will 3 become apparent by consideration of the detailed io description and accompanying drawings. S 35
N
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the electrochemical behavior for sodium deposition over sodium in the diglyme solvent based electrolyte, containing 1.2 molar Na-Triflate salt and
0.02 mole fraction of SO, additive. The experiments were performed in a three-electrode cell at a sweep rate of 20 mV/s using sodium metal as a reference and counter electrode. The geometric exposed area of the working electrode is 1 cm”. FIG. 2 shows the electrochemical behavior of sodium deposition over sodium in the DOL:DME solvent based electrolyte, containing 2 molar Na-Triflate salt and
0.01 mole fraction of SO, additive. The DOL:DME solvent is composed of a 1:1 mixture between 1,3-Dioxolane and 1,2-Dimethoxyethane. The experiments were performed in a three-electrode cell at a sweep rate of 20 mV/s using sodium metal as a reference and counter electrode. The geometric exposed area of the working electrode is 1 cm”. FIG. 3 shows the electrochemical behavior of sodium deposition over copper in the diglyme solvent based electrolyte, containing 0.64 molar NaPF6 salt, with and without the use of SO, additive. The experiments were © performed in a three-electrode cell at a sweep rate of > 20 mV/s using sodium metal as a reference and counter O electrode. The geometric exposed area of the working = 30 electrode is 1 cm”. o
I = FIG. 4 shows the electrochemical behavior of sodium 3 deposition over copper in the DOL:DME solvent based io electrolyte, containing 2 molar Na-Triflate salt and Oo 35 0.01 mole fraction of 50, additive. The experiments were N performed in a three-electrode cell at a sweep rate of
20 mV/s using sodium metal as a reference and counter electrode. The geometric exposed area of the working electrode is 1 cm”.
FIG. 5 shows the comparative visual aspect of sodium deposition over copper in DOL:DME solvent based electrolytes, containing 2 molar Na-Triflate salt and varying mole fractions of SO, additive. The DOL:DME solvent is composed of a 1:1 mixture between 1,3- Dioxolane and 1,2-Dimethoxyethane. From left to right, the employed mole fractions of SO, additive are 0.1,
0.05, 0.01, and 0.
FIG. 6 shows the cell voltage evolution and initial cell capacity evolution during charge/discharge cycling of polypyrrol covered NaS active material in the DME solvent based electrolyte. The capacity is indicated with respect to the Na;S mass.
FIG. 7 shows the molecular structure of the Triazine- Quinone co-polymer cathode material, which can be described by the [C:HN;0,Na;>], formula.
DETAILED DESCRIPTION OF THE EMBODIMENTS Detailed embodiments of the present invention are O disclosed herein with reference to accompanying S drawings. S The following paragraphs firstly describe a novel type S 30 of organic electrolyte composition and corresponding E current collector substrate-electrolyte couples for the < deposition and cycling of the metallic sodium anode. = Subsequently, matching cathode compositions are © disclosed.
N
The disclosed electrochemical cells are implemented so as to allow reversible redox interaction of metal ions with the cathode electrode during charge-discharge cycles. The term "reversible redox interaction" refers to the ability of an ion to both get inserted into or onto and to depart from the electrode material, preferably while not causing significant degradation of the latter and therefore not exerting significant negative effect on the performance characteristics of said electrode over repeated cycling. A reversable redox interaction preferably allows greater than 1 and more preferably greater than 10 and more preferably greater than 100 and more preferably greater than 1000 and most preferably greater than 10000 charge-discharge cycles while degrading cell performance preferably less than 80% and more preferably less than 40% and more preferably less than 20% and more preferably less than 10% and most preferably less than 5%. Other ranges are possible according to the invention.
It has been surprisingly discovered that reversible sodium-over-sodium cycling of metallic sodium anodes can be achieved in a wide class of non-agueous solvents, which are characterized by a slow reactivity towards metallic sodium. A slow reactivity may generally be characterized as having a solvent reduction potential of o less than 1.1 V vs Na/Na+, and more preferably of less > than 0.9 V vs Na/Na+, and more preferably less than 0.7 0 V vs Na/Na+, and most preferably less than 0.5 V vs = 30 Na/Na+. Other ranges are possible according to the © invention. = a 3 In one embodiment, such stable cycling can be achieved io when the electrolyte salt contains sodium- Oo 35 trifluoromethanesulfonate (Na-Triflate), and the N electrolyte contains an 50, additive. Without intendingto be bound by theory, the stable cycling capability in this case is thought to result from the Solid Electrolyte Interface (SEI) layer being comprised of mainly NazS:04, Na0, Nas, and/or NaF, originating from the SO, additive and Na-Triflate salt, without a significant contribution to the SEI by the solvent decomposition products.
Thus, the SEI is believed to form synergistically with the 50, additive.
In an other embodiment, it is surprisingly found that such stable cycling can be achieved with any electrolyte salt that is not reduced by sodium, provided that it dissolves in the electrolyte to at least 1 molar concentration, and more preferably to at least 1.2 molar concentration, , and more preferably to at least 1.5 molar concentration, and most preferably to at least 2 molar concentration, and that the electrolyte contains dissolved 50, in at least a 0.05 mole fraction, and more preferably in at least a 0.1 mole fraction, and most preferably contains dissolved SO, in at least 0.2 mole fraction.
Other ranges are possible according to the invention.
Without intending to be bound by theory, the stable cycling capability in this case is thought to result from the SEI layer being comprised of mainly Na,S,04 , Na»O0 and/or NaoS, originating from the SO; component and without a significant contribution to the O SEI from the solvent decomposition products.
Thus, the > SEI is again believed to form synergistically with the 0 SO, additive. <Q x 30
Therefore, these discoveries enable the range cf E: applicable solvents to be any non-agueous solvent which 3 has a slower reactivity towards metallic sodium than SO; io and Na-Triflate in particular and to a wide range of Oo 35 electrolytic salts that are not reduced by sodium and N yet dissolve in the solvent.
Figures 1 and 2 show the sodium deposition/stripping voltammograms for the abovesaid electrolyte compositions, with diglyme solvent and with DOL:DME solvent mixture respectively. Beyond sodium-over-sodium cycling stability, it is desired for the electrolyte to also support metallic sodium deposition capability over a current collector substrate, in order to facilitate discharged state cell assembly. Considering the electrolytes investigated in
[2], it is found that they do not support metallic sodium deposition over any substrate. As shown in Figure 3, even the addition of up to 0.05 $S0, additive mole fraction has not improved their deposition capability, as the anodic processes remained virtually absent. Surprisingly, it has been discovered that the above- disclosed new classes of electrolytes facilitates a non- dendritic/dendrite-free deposition of metallic sodium when the anodic current collector is comprised of copper or some copper-based alloy. Figure 4 shows the sodium deposition/stripping voltammograms over a copper current collector foil, with DOL:DME solvent based electrolyte. © I The range of electrolyte compositions facilitating both 0 sodium deposition and its stable cycling has been = 30 investigated. According to the invention, the 7 electrolyte solvent may be selected from any solvent & which has a slower reactivity towards metallic sodium 3 than the 50, additive and a salt, preferably the Na- io Triflate salt, though other salts are possible according Oo 35 to the invention. The range of feasible electrolyte N solvents includes, but is not limited to, ether, amine,
and oxadiazole type solvents. Examples of particularly useful solvents are disclosed further below. When sodium deposition and stable cycling are achieved through the combined effects of the electrolyte salt and the 50, additive, the range of particularly effective salts includes fluorinated sulfonate and/or fluorinated carboxylate and/or fluorinated sulfonylimide and/or acetate type electrolyte salts. Fluorinated sulfonate and/or fluorinated carboxylate and/or fluorinated sulfonylimide and/or acetate type/based salts usable according to the invention include, but are not limited to, sodium-trifluoromethanesulfonate (Na-Triflate) and similar salts: including but not limited to sodium- pentaluoroethanesulfonate (Na-C>F5S03) , sodium bis (trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(flourosulfonyl)imide (NaFSI), and sodium- trifluoroacetate (Na-CF3CO>). In order to improve the electrolyte conductivity, these salts may be used in combination with other electrolyte salt types. The concentration of the Na-Triflate type electrolyte salt component is preferably between 0.5 molar and 3 molar, and more preferably between 1 molar and 2.5 molar. The mole fraction of the SO, additive may range between
0.001 and 0.2, and is preferably between 0.01 and 0.15, and more preferably between 0.05 and 0.1. Other ranges O are possible according to the invention. Figure 5 shows > the comparative visual aspect of sodium deposition over 0 a copper current collector foil, with different mole = 30 fraction values of the 50, additive. o
I a. In one of the embodiments, namely when sodium deposition 3 and stable cycling are achieved through the effect of a io significant mole fraction of dissolved S0,, it has been DO 35 found that the concentration of electrolyte salts is N correlated with the smoothness of the deposited metallicsodium surface. The abovesaid minimum salt concentration is needed for creating a sufficient smoothness of the deposited metallic surface. The use of NaSCN salt is particularly preferred because of its high solubility in ether based solvents and its cost-effectiveness, though other salts are possible according to the invention. The concentration of the electrolyte salts is preferably between 1.2 molar and 10 molar, and more preferably between 1.3 and 5 molar and more preferably between 1.4 and 3 molar and most preferably between 1.5 molar and
2.5 molar. The mole fraction of the dissolved $S0, may preferably range between 0.02 and 0.5, and more preferably between 0.02 and 0.3, and most preferably between 0.05 and 0.1. Other ranges are possible according to the invention. Particularly preferred electrolyte formulations are disclosed in the following paragraphs. In one embodiment, namely for batteries having a moderate operating voltage range of up to approximately 3.5 V, the use of DOL:DME solvent, is preferred, with SO; additive employed preferably in the 0.001 to 10 mole fraction range and more preferably in the 0.01 to 0.2 mole fraction range, more preferably at 0.02 mole fraction. A corresponding preferred electrolyte salt is Na-Triflate : NaSCN, Na-Triflate : NaNO, Na-Triflate : O NaTFSI, or Na-Triflate : NaPFs composition, where the > Na-Triflate part ensures the anode stability while the O optional NaSCN, NaN0;,, NaTFSI, or NaPFs part may improve = 30 ionic conductivity. The employed Na-Triflate 7 concentration is preferably in the 0.5 to 2 molar range, a. and the employed NaSCN, NaN03, NaTFSI, or NaPFe 3 concentration is preferably in the 1 to 2 molar range, io altogether resulting in 2 to 3 molar salt concentration. > 35 Other molar ranges are possible according to the invention, e.g. Na-Triflate molar concentration canrange from 0.1 to 10, the NaSCN, NaTFSI, NaN03, or NaPFgs. molar concentration can range from 0.2 to 20 and the total molar salt concentration can range from 0.3 to
30. A particularly preferred composition is the employment of 1.5 M NaSCN + 1 M Na-Triflate salt mixture. This electrolyte formulation is particularly effective in the case of Sulfur-based cathodes, because the S50, additive is thought to generate a thin layer of sodium-dithionite on the cathode surface, which is conductive for Na+ ions but mitigates the dissolution of polysulfide species. Other salt compositions are possible according to the invention. In one embodiment, namely for batteries having a higher operating voltage range of up to approximately 4.5 V, the use of DX (1,4-dioxane) : DME (1,2-dimethoxyethane) ether solvent mixtures is preferred, with $S0, additive preferably employed 0.001 to 0.3 mole fraction range, and more preferably in the 0.02 to 0.2 mole fraction range, and more preferably at approximately 0.1 mole fraction. Other ranges are possible according to the invention. Any mixture of DX and DME solvents is possible according to the invention. The preferred volumetric DX : DME ratio is 1:2, in accordance with the melting point and viscosity optimization described in
[7]. The employed Na-Triflate concentration is o preferably in the 0.5 to 2.5 molar range. Pyridine may, > in some cases, be preferred over or in combination with 0 DX and/or DME because of its low cost, low viscosity, = 30 and very low reactivity towards sodiun. In order to S improve ionic conductivity with respect to using just E Na-Triflate salt, a mixture of salts may be used; one 3 preferred electrolyte salt composition being the Na- io Triflate : NaPF¢ mixture, where the Na-Triflate part > 35 ensures the anode stability while the NaPF6 partimproves ionic conductivity.
Other salt compositions arepossible according to the invention.
In one embodiment, namely for batteries requiring a very high operating voltage range, possibly up to approximately 5.7 V, the use of furazan (1,2,5- Oxadiazole) type solvents is preferred, with SO; additive employed in the 0.001 to 0.3 mole fraction range, and preferably in the 0.01 to 0.04 mole fraction range, and more preferably at approximately 0.02 mole fraction.
Other ranges are possible according to the invention.
Furazan type solvents have been discovered to possess a surprisingly high oxidation potential level in the range of 6 V vs Na/Na+, along with a reasonably high boiling point, good solvent properties, and low reactivity towards metallic sodium.
The group of furazan type solvents includes, but is not limited to, furazan, methyl-furazan, and dimethyl-furazan.
Corresponding preferred electrolyte salts are pure Na-Triflate or Na- Triflate : NaBF, compositions, where the Na-Triflate part may promote the anode stability while the NaBF, part may optionally improve ionic conductivity.
The employed Na-Triflate concentration is preferably in the lto 4 molar range and more preferably in the 1.2 to 2 molar range, when used without any additional salt.
Other ranges are possible according to the invention.
In O case of employing Na-Triflate : NaBF, composition, the > Na-Triflate concentration is preferably in the 0.5 to 4 O molar range and more preferably in the 1 to 2 molar = 30 range, and the employed NaBF, concentration is 7 preferably also 0.5 to 4 molar range and more preferably a. in the 1 to 2 molar range, altogether resulting in 1.5 3 to 8 and more preferably in the 2 to 4 molar salt io concentration.
Besides NaBF, and Na-Triflate, other > 35 possible high voltage possibilities salts include NaPFs, NaClOy, NaB (CN) 4, NaBF:CN, NaBF, (CN) 2, NaBF (CN) 3,
NaAl (BHy) 4. Other salt compositions are possible according to the invention. Other ranges are possible according to the invention.
The following paragraphs describe high-capacity and cost-effective cathode materials, which are compatible with the abovesaid new electrolytes formulations, and facilitate discharged state preparation of the sodium based cell.
It has been surprisingly discovered that partially oxidized NaS material can be activated. Electrodes constructed from oxidized NaoS particles, and with an in-situ deposited polypyrrole conductive additive have been prepared. The in-situ polypyrrole deposition has been achieved by dispersing the abovesaid Na,S particles in anhydrous methyl-acetate containing FeCl; as an oxidant and poly(vinyl acetate) as a stabilizing agent, followed by the addition of pyrrole. The polypyrrole deposition has taken place at room temperature after 12 hours reaction time. A stable capacity of approximately 220 mAh/g has been obtained with respect to the NaS mass in DME solvent based electrolyte. A practical means of carrying out partial NaS oxidation is to heat it under vacuum preferably in the 125-300 °C range, and more preferably in the 150-250 °C range, most preferably © at approximately 200 °C for some hours. The residual > Oxygen content of vacuum will gradually oxidize the NaoS 0 at that temperature. In one embodiment, this heat = 30 treatment may range between 0.5 and 10 hours, more 7 preferably between 1 and 5 hours and more preferably = between 1.5 and 3 hours and most preferably about 2 X hours. Other process temperatures and process times are io possible according to the invention. Other means of Oo 35 carrying out partial Na,S oxidation is possible N according to the invention. The production of cost-
effective Sodium-Sulfur batteries therefore becomes feasible, according to the process disclosed herein. As a well-matching cathode for the above-disclosed high voltage electrolytes, NaMg0, has been discovered to be chargeable to Magnesium-peroxide (MgO,) during the battery charging, surprisingly giving rise to a stable charge/discharge capacity and a charge/discharge voltage in the range of 4.6 V. According to the invention, an electrochemical cell, wherein the active cathode material material comprises NaMg0, ternary oxide materials, may also include its variations where the Na, Mg, and O constituents may be partially replaced by other elements.
Surprisingly, it has been discovered that NaBr salt or NaBr : NaCl salt mixture may be employed as an energy- dense cathode material with the abovesaid electrolytes, particularly in the case of using an electrolyte with at least 3.9 V voltage window. In a preferred embodiment, a carbon framework, preferably Ketjen-Black type carbon, is infused by the NaBr salt, whereby this type carbon is used as a conductive framework material. Upon cell charging, NaBr is oxidized into NaBrs salt. For best reversibility, further full oxidation into Br, catholyte is preferred to be avoided, and furthermore a cation- O conducting film, such as a Nafion-coated separator [8], > is preferred to be used to mitigate a cross-over of 0 dissolved Bra anions. Without intending to be bound by = 30 theory, it is believed that on the anode side the 9 operation of this simple Na-Br cell is made possible by = the electrically insulating qualities of the formed SEI 3 and the anion / Br, cross-over hindering capability of io the employed cation-conducting film. On the cathode DO 35 side, it is believed that the operation of the Na-Br N cell is made possible by the NaBr salt crystallizationaway from the carbon surface, thereby preventing the passivation of the electrode surface upon discharge. Despite not being in direct electric contact with the carbon surface, the NaBr is electrochemically active; a small amount of dissolved NaBr or NaBrs is oxidized to Br,, which initiates NaBr to NaBrs conversion of the NaBr active. Ether type solvents have a limited direct solubility of NaBr and NaBrs salts. Therefore the theoretical energy density of the 3 NaBr 6 2 Na + NaBr; reaction can be realized to nearly its full extent. Furthermore, NaBr may be partially replaced by NaCl for improving the energy density of the cathode; up to 1:2 NaCl : NaBr molar ratio may be used without gas evolution upon charging. The 1:2 NaCl : NaBr ratio results in the formation of NaBr,Cl oxidized salt. The NaBr and NaCl : NaBr cathode material may be used with electrolyte formulations supporting a voltage window of at least 3.9 V charging voltage. DX : DME mixture is a preferred solvent, because of its good Na anode compatibility, its high oxidation voltage (around 4.5 V vs Na/Na+), and its reasonably high ionic conductivity. Other solvents, and in particular solvents with low reactivity with respect to metallic sodium, high oxidation voltage, preferably above 4 and more preferably above 4.5 and most preferably above 4.6 V vs Na/Na+, and concentrations of solute NaBr is above 0.005 o Molar and more preferably above 0.05 Molar and most > preferably above 0.5 Molar are possible according to the 0 invention.
I x 30 I According to the invention, an electrochemical cell, a. wherein the active cathode material material comprises 3 NaBr, may include its variations where the Na, Br, and io Cl constituents may be partially replaced by other > 35 elements.
According to the invention, in references to carbon and carbon frameworks, the carbon may be in any suitable form.
Preferred forms of carbon include CNT, fullerene, CNB, graphene, graphite, Ketjen-Black, mesoporous carbon, activated carbon, Y-carbon, nanocarbon, carbon nanoparticle and/or porous carbon.
Other forms of carbon are possible according to the invention.
A new polymer type high-energy cathode material has been furthermore discovered, which complements well the above disclosed electrolyte formulations.
This cathode material is a co-polymer of triazine rings and quinone rings.
Its structure is shown in Figure 7. This material may be described by the [C:HN;0,Na,)], formula, and self- arranges during its synthesis into a micro-porous structure, where well-defined 1-2 nm wide channels facilitate the ion migration.
This material can be reversibly cycled down to the 1.3 V vs Na/Na low voltage limit.
Both the triazine and quinone rings contribute to its cycling capacity, resulting in a very high specific capacity, measured to be in excess of 300 mAh/g.
An exemplary procedure for the abovesaid Triazine- Quinone co-polymer synthesis may be based on the 2,5- dichloro-1,4-hydroguinone starting material.
This O precursor is firstly stirred in agueous or alcohol-based > NaOH solution for achieving H' to Na' ion exchange.
O After subsequent evaporation of the solvent, it is = 30 stirred in hot DMSO based solution of NaCN for achieving S Chloride to Cyanide ligand exchange.
A suitable E: temperature range for this reaction is between 100 and 3 150 °C.
Subsequently, it is mixed with NaOH-NaCl salt io eutectic, and subjected to ionothermal heat treatment in Oo 35 the 300 to 400 °C temperature range.
The micro-porous N polymer structure is self-assembled during this heattreatment. The final polymer is then obtained after washing away the salts and filtration. According to the invention, the terms “x-cored”, “x- type” and “x-based” with regards to materials or material class x refers to materials having x as an essential or identifiable component of the material. The term "similar as”, according to the invention means materials having properties or characteristics relevant to the invention which are similar to the referred to material (s) and which can be readily substituted for the specific material(s) referenced. One embodiment of the invention comprises an electrochemical cell, comprising a cathode and an anode and a non-aqueous electrolyte which comprises an SO; additive and at least one electrolyte salt which participates in the anodic SEI formation together with the 50, additive positioned between the cathode and anode. One embodiment of the invention comprises an electrochemical cell, comprising a cathode and an anode and an electrolyte which comprises a sufficient amount of dissolved 50, for a stable SEI formation at least one electrolyte salt which is soluble to at least 1.2 molar O concentration positioned between the cathode and anode. & 0 In one embodiment of the invention, the salt = 30 participating in the SEI formation comprises fluorinated 7 sulfonate and/or fluorinated carboxylate and/or a. fluorinated sulfonylimide and/or acetate salt.
D io In one embodiment, the salt participating in the SEI Oo 35 formation is selected from sodium N trifluoromethanesulfonate (NaTriflate), sodium-
pentaluoroethanesulfonate (Na-C2F5S03) and sodium- trifluoroacetate (Na-CF3CO,) or other similar salts. In one embodiment, the non-agueous electrolyte solvent comprises one or more ether, amine, or oxadiazole type solvents, or any mixture thereof.
In one embodiment, the solvent is preferably selected from 1,3-Dioxolane, 1,2-Dimethoxyethane, 1,4-Dioxane, diglyme, glyme, pyridine, furazan, methyl-furazan, dimethyl-furazan or any mixture thereof.
In one embodiment, the electrolyte salt at least partially comprises NaBF4, NaSCN, NaPF6c, NaClQy, NaB (CN) 4, NaBF3CN, NaBF,(CN),, NaBF (CN); or NaAl (BH4)g4.
In one embodiment, the anodic current collector substrate is selected from copper or its alloys.
One embodiment of the invention comprises an electrochemical cell for a battery, wherein the active cathode material material comprises partially oxidized Nas.
One embodiment of the invention comprises an electrochemical cell, wherein the active cathode O material material comprises NaMg0, ternary oxide > material, including its variations where the Na, Mg, and O 0 constituents may be partially replaced by other
O <+ 30 elements.
O
I = One embodiment of the invention comprises an 3 electrochemical cell, wherein the active cathode io material material comprises NaBr or NaBr : NaCl salt Oo 35 mixture, including its variations where the Na, Br, and
N
Cl constituents may be partially replaced by other elements. One embodiment of the invention comprises an electrochemical cell, wherein the active cathode material] material comprises Triazine-Ouinone co-polymer. One embodiment of the invention comprises an electrochemical cell employing any of the electrolytes, anode structure and/or the cathodes of any embodiment of the invention.
One embodiment of the invention comprises a method of manufacturing an electrochemical cell, comprising providing a cathode and an anode and providing a non- aqueous electrolyte which comprises an SO, additive and at least one electrolyte salt which participates in the anodic SEI formation together with the SO, additive.
One embodiment of the invention comprises a method of manufacturing an electrochemical cell, comprising providing a cathode and an anode and providing an electrolyte which comprises a sufficient amount of dissolved SO, for a stable SEI formation at least one electrolyte salt which is soluble to at least 1.2 molar concentration.
© I One embodiment of the invention comprises the method of 0 any embodiment of the invention wherein the salt = 30 participating in the SEI formation comprises fluorinated 7 sulfonate and/or fluorinated carboxylate and/or a. fluorinated sulfonylimide and/or acetate salt.
D io In one embodiment of the invention, the salt Oo 35 participating in the SEI formation is selected from N sodium trifluoromethanesulfonate (NaTriflate), sodium-
pentaluoroethanesulfonate (Na-C2F5S03) and sodium- trifluoroacetate (Na-CF3CO,) or other similar salts.
In one embodiment, the non-agueous electrolyte solvent comprises one or more ether, amine, or oxadiazole type solvents, or any mixture thereof.
In one embodiment, the electrolyte salt at least partially comprises NaBF,, NaSCN, NaPF6, NaC1l0,, NaB (CN) 4, NaBF:CN, NaBF>,(CN),, NaBF(CN)3 or NaAl (BH4)4. One embodiment of the invention comprises a rechargeable battery comprising of a single or plurality of electrochemical cells as described in any embodiment of the invention or made by any of the methods of any embodiment of the invention.
One embodiment of the invention comprises an electric vehicle, an electrical or electronic device, a power unit, a backup energy unity or a grid storage or stabilization unit utilizing an electrochemical cell, battery or supercapacitor according to any embodiment of the invention or an electrochemical cell, battery or supercapacitor made according to the method of any embodiment of the invention.
O Conseguently, a skilled person may on the basis of this > disclosure and general knowledge apply the provided O teachings in order to implement the scope of the present = 30 invention as defined by the appended claims in each 7 particular use case with necessary modifications, & deletions, and additions.
The fulcrum will substantially 3 remain the same. 2 > 35
EXAMPLES Preparation of electrolytes. Example 1 The DOL:DME electrolyte has been prepared from different volumetrics mixtures of DOL and DME by cooling down to - 20 °C and, a suitable volume of condensed SO, was added in order to reach 0.02 S50, mole fraction. After letting the mixture to warm up to room temperature, 1 M Na- Triflate and 1.5 M NaSCN salts have been dissolved into it. Example 2 Furazan has been cooled to -20 %, then a suitable volume of condensed SO; has been added into it, in order to reach 0.02 SO, mole fraction. After letting the mixture to warm up to room temperature, 2 M Na-Triflate salt has been dissolved into it.
Example 3 DME has been cooled to -20 °C. A suitable volume of condensed SO, has been added into it, in order to reach
0.02 SO; mole fraction. After letting the DME to warm up to room temperature, the DX:DME based solvent has been prepared by adding DX solvent to reach 1:2 volumetric O mixture of DX and DME. 2 M Na-Triflate salt has been > dissolved into this mixture. g x 30 Preparation of the active material i 3 Example 4 io Na,S-PPY was obtained by firstly removing the hydration > 35 water from Na,S -9H,0 through drying in several steps: first, the Nas :9H,0 was heated at 50 °C for 240minutes, then the temperature was increased to 80 °C for 240 minutes. In the third step, the temperature was 120 °C during 2 hours. In the last step, the temperature was increased to 200 °C for 2 hours to obtain the partially oxidized dry Na;S. Finally, polypyrrole was polymerized onto Nas according to the procedure described in [5], yielding the Na,S-PPY material. Preparation of the positive electrode Example 5 80wt% of NaoS-PPY from Example 4, 15wt% of carbon nanotubes and 5wt% of PVDF (polyvinilidenefluoride) were dispersed in N-methylpyrrolidone under magnetic stirring at room temperature to form a slurry. Then the slurry was coated onto carbon-coated aluminum foil. Finally, the electrode was dried at 80 °C under vacuum overnight. Example 6 The electrode framework was prepared from a mixture of 94wt% Ketjen-Black carbon and 6wt% of PTFE. This mixture was dry-pressed onto carbon-coated aluminum current collector, according to the dry-pressing procedure of
[6]. NaBr was dissolved in anhydrous methanol, and the solution was drop-cast onto the electrode in sufficient O amount to obtain approximately 3.7 : 1 mass ratio > between the NaBr and carbon. Finally, the electrode was 0 dried at 80 °C overnight in vacuun. 3 30 I Example 7 a. The electrode framework was prepared from a mixture of 3 94wt% Ketjen-Black carbon and 6wt% of PTFE. This mixture io was dry-pressed onto carbon-coated aluminum current Oo 35 collector, according to the dry-pressing procedure of N [6]. 1:2 molar ratio of NaCl : NaBr was dissolved inanhydrous methanol, and the solution was drop-cast onto the electrode in sufficient amount to obtain approximately 4 : 1 mass ratio between these salts and carbon.
Finally, the electrode was dried at 80 °C overnight in vacuum.
Preparation of the rechargeable batteries
Example 8 A rechargeable sodium battery was prepared having a copper foil negative electrode, a porous polyethylene separator of 15 micron of thickness, and the Na,S-PPY based positive electrode from Example 5. The cell was filled with the electrolyte from example 1. The battery prepared for this example exhibited a capacity of 220 mAh/g respect to the Na,S mass.
Example 9 A rechargeable sodium battery was prepared having a copper foil negative electrode, a Nafion-coated porous polyethylene separator of 15 micron of thickness, which has been prepared according to [8], and the NaBr based positive electrode from Example 6. The cell was filled with the electrolyte from example 3. The battery O prepared for this example exhibited a rechargeable > capacity of 160 mAh/g respect to the NaBr mass. g + 30 Example 10 7 A rechargeable sodium battery was prepared having a a. copper foil negative electrode, a Nafion-coated porous 3 polyethylene separator of 15 micron of thickness, which io has been prepared according to [8], and the NaBr:NaCl o 35 based positive electrode from Example 7. The cell was N filled with the electrolyte from example 3. The batteryprepared for this example exhibited a rechargeable capacity of 185 mAh/g respect to the NaBr:NaCl mass.
REFERENCES
1. Patent application FI 20150270.
2. Seh et al. ACS Cent. Sci. (2015); 1: 449-455
3. Kobayashi et al. Journal or Power Sources (2016); 306: 567-572
4. Seh et al. Nature Comm. (2014); 5 : 5017.
5. Seh et al. Energy Environ. Sci. (2014); 10 : 1039.
6. Patent number DE 10 2012 203 019 Al
7. Miao et al. Nature Scientific Reports (2016); 6 : 21771
8. Bauer et al. Chem. Commun. (2014); 50:3208-3210. ©
O N
O <Q <
O
I jami a < 0
LO ©
O N

Claims (20)

1.An electrochemical cell, comprising: a) a cathode and a rechargeable metallic sodium anode; and b) a non-aqueous electrolyte which comprises an SO, additive and at least one electrolyte salt which participates in the anodic SEI (Solid Electrolyte Interface) formation together with the SO; additive positioned between the cathode and the anode.
2. An electrochemical cell, comprising: a) a cathode and a rechargeable metallic sodium anode; and b) an electrolyte which comprises a sufficient amount of dissolved SO? for a stable SEI (Solid Electrolyte Interface) formation and at least one electrolyte salt which is soluble to at least 1.2 molar concentration positioned between the cathode and anode.
3. The cell of any of claims 1) - 2) wherein the salt participating in the SEI formation comprises fluorinated sulfonate and/or fluorinated carboxylate salt and/or fluorinated sulfunylimide and/or acetate salt.
4. The cell of claim 3) wherein the salt participating in the SEI formation is selected from sodium trifluoromethanesulfonate — (NaTriflate), sodium- pentaluoroethanesulfonate (Na-C2F5SO3), sodium bis (trifluoromethanesulfonyl)imide —(NaTFSTI), sodium = bis(flourosulfonyl)imide (NaFSI), and sodium-trifluoroacetate (Na-CF3CO)>) or other similar salts.
5. The cell of any claims 1), 3) and/or 4) wherein the non-agueous electrolyte solvent comprises one or more ether, amine, or oxadiazole type solvents, or any mixture thereof.
6. The cell of claim 5) wherein the solvent is preferably selected from 1,3- Dioxolane, 1,4-Dioxane, 1,2-Dimethoxyethane, diglyme, glyme, pyridine, furazan, methyl-furazan, dimethyl-furazan or any mixture thereof.
7. The cell of any of claims 1) to 6) wherein the electrolyte salt at least partially Q comprises NaBF4, NaSCN, NaPFs, NaClO4, NaB(CN)4, NaBF;CN, NaBF (CN), S NaBF(CN); or NaAl(BH4)4.
O <Q 8. The cell of any of claims 1) to 7) wherein the anodic current collector substrate O 40 is selected from copper or its alloys.
I = 9. An electrochemical cell, wherein the active cathode material comprises partially < oxidized NaS. co 2 45 10. The electrochemical cell employing the electrolyte of any of claims 1) to 7), the DO anode structure of claim 8), and/or the cathode of claim 9).
N
11. A method of manufacturing an electrochemical cell, comprising: a) providing a cathode and a rechargeable metallic sodium anode; andb) providing a non-aqueous electrolyte which comprises an SO; additive and at least one electrolyte salt which participates in the anodic SEI (Solid Electrolyte Interface) formation together with the SO, additive.
12. A method of manufacturing an electrochemical cell, comprising: a) providing a cathode and a rechargeable metallic sodium anode; and b) providing an electrolyte which comprises a sufficient amount of dissolved SO, for a stable SEI (Solid Electrolyte Interface) formation and at least one electrolyte salt which is soluble to at least 1.2 molar concentration.
13. The method of any of claims 11) - 12) wherein the salt participating in the SEI formation comprises fluorinated sulfonate and/or fluorinated carboxylate salt and/or fluorinated sulfonylimide and/or acetate salt.
14. The method of any of claims 11) - 13) wherein the salt participating in the SEI formation is selected from sodium trifluoromethanesulfonate (NaTriflate), sodium- pentaluoroethanesulfonate (Na-C2FsSOs) and sodium-trifluoroacetate (Na-CF3CO)), sodium bis (trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(flourosulfonyl)imide (NaFSI), or other similar salts.
15. The method of any claims 11), 13) and/or 14) wherein the non-aqueous electrolyte solvent comprises one or more ether, amine, or oxadiazole type solvents, or any mixture thereof.
16. The method of claim 15) wherein the solvent is preferably selected from 1,3- Dioxolane, 1,4-Dioxane, 1,2-Dimethoxyethane, diglyme, glyme, pyridine, furazan, methyl-furazan, dimethyl-furazan or any mixture thereof.
17. The method of any of claims 11) to 16) wherein the electrolyte salt at least partially comprises NaBF4, NaSCN, NaPF¢, NaClO4s, NaB(CN),, NaBF:CN, NaBF2(CN)2, NaBF(CN); or NaAl(BH4)4.
18. The method of any of claims 11) to 17) wherein the anodic current collector substrate is selected from copper or its alloys.
o
19. A rechargeable battery comprising of a single or plurality of electrochemical S cells as described in any of claims 1) - 9) or made by any of the methods of any of N claims 11) - 17).
3 © 40
20. An electric vehicle, an electrical or electronic device, a power unit, a backup N energy unity or a grid storage or stabilization unit utilizing: E a) an electrochemical cell, battery or supercapacitor according to any of claims 1)-9)or 19): or > b) an electrochemical cell, battery or supercapacitor made according to io 45 the method any of claims 11) to 18).
R
FI20165184A 2016-03-04 2016-03-04 Rechargeable sodium cells for use in high-energy battery FI128461B (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
FI20165184A FI128461B (en) 2016-03-04 2016-03-04 Rechargeable sodium cells for use in high-energy battery
US16/082,101 US20200058958A1 (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use
BR112018067758-2A BR112018067758B1 (en) 2016-03-04 2017-03-03 RECHARGEABLE SODIUM ELECTROCHEMICAL CELLS FOR USE IN HIGH ENERGY DENSITY BATTERY, METHOD OF MANUFACTURE THEREOF, RECHARGEABLE BATTERY, ELECTRIC VEHICLE, POWER UNIT, RESERVE POWER UNIT AND STORAGE OR NETWORK STABILIZATION UNIT
EP17759327.4A EP3449525A4 (en) 2016-03-04 2017-03-03 RECHARGEABLE SODIUM CELLS FOR BATTERIES WITH HIGH ENERGY DENSITY
RU2018133261A RU2742351C2 (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use
CN201780015040.5A CN108780917B (en) 2016-03-04 2017-03-03 Rechargeable Sodium Cells for High Energy Density Batteries
CA3016202A CA3016202A1 (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use
JP2018546599A JP6986515B2 (en) 2016-03-04 2017-03-03 Rechargeable sodium battery for use with high energy density batteries
MX2018010637A MX2018010637A (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use.
AU2017225241A AU2017225241B2 (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use
TW106106982A TWI777943B (en) 2016-03-04 2017-03-03 Electrochemical cell, method of manufacturing electrochemical cell, rechargeable battery and battery
PCT/FI2017/050139 WO2017149204A2 (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use
IL261506A IL261506B (en) 2016-03-04 2017-03-03 Rechargeable sodium cells for high energy density battery use
PE2018001605A PE20181946A1 (en) 2016-03-04 2017-03-03 RECHARGEABLE SODIUM CELLS FOR USE IN HIGH ENERGY DENSITY BATTERIES
KR1020187028728A KR102506303B1 (en) 2016-03-04 2017-03-03 Rechargeable sodium cell for use in high energy density batteries

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FI20165184A FI128461B (en) 2016-03-04 2016-03-04 Rechargeable sodium cells for use in high-energy battery

Publications (2)

Publication Number Publication Date
FI20165184A7 FI20165184A7 (en) 2017-09-05
FI128461B true FI128461B (en) 2020-05-29

Family

ID=59743411

Family Applications (1)

Application Number Title Priority Date Filing Date
FI20165184A FI128461B (en) 2016-03-04 2016-03-04 Rechargeable sodium cells for use in high-energy battery

Country Status (14)

Country Link
US (1) US20200058958A1 (en)
EP (1) EP3449525A4 (en)
JP (1) JP6986515B2 (en)
KR (1) KR102506303B1 (en)
CN (1) CN108780917B (en)
AU (1) AU2017225241B2 (en)
CA (1) CA3016202A1 (en)
FI (1) FI128461B (en)
IL (1) IL261506B (en)
MX (1) MX2018010637A (en)
PE (1) PE20181946A1 (en)
RU (1) RU2742351C2 (en)
TW (1) TWI777943B (en)
WO (1) WO2017149204A2 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI130182B (en) * 2017-03-17 2023-03-31 Broadbit Batteries Oy Electrolyte for supercapacitor and high-power battery use
US11387450B2 (en) 2017-04-05 2022-07-12 Massachusetts Institute Of Technology Electrolytes for lithium metal electrodes and rechargeable batteries using same
US11316199B2 (en) * 2018-01-16 2022-04-26 International Business Machines Corporation Rechargeable metal halide battery
WO2019236550A1 (en) * 2018-06-04 2019-12-12 Massachusetts Institute Of Technology Electrolytes for lithium metal electrodes and rechargeable batteries using same
FI129862B (en) 2018-10-24 2022-10-14 Broadbit Batteries Oy An improved anode material and anode for a rechargeable battery, a method of making them, and an electrochemical cell made therefrom
US12288877B2 (en) 2020-07-13 2025-04-29 International Business Machines Corporation Rechargeable metal halide battery with intercalation anode
US20240297343A1 (en) * 2021-06-23 2024-09-05 Central Glass Co., Ltd. Nonaqueous electrolyte solution, nonaqueous sodium ion battery, nonaqueous potassium ion battery, method for producing nonaqueous sodium ion battery, and method for producing nonaqueous potassium ion battery
CN113451546B (en) 2021-06-26 2022-05-06 宁德时代新能源科技股份有限公司 Sodium metal batteries, electrochemical devices
KR102797793B1 (en) * 2021-07-21 2025-04-17 컨템포러리 엠퍼렉스 테크놀로지 (홍콩) 리미티드 Electrolyte, secondary battery, battery module, battery pack and electrical device
GB202204201D0 (en) * 2022-03-24 2022-05-11 Faradion Ltd Electrolyte compositions
JP2025511543A (en) * 2022-06-13 2025-04-16 香港時代新能源科技有限公司 Electrolyte, secondary battery, battery module, battery pack, and power consuming device
CN118104024B (en) * 2022-06-24 2025-07-29 宁德时代新能源科技股份有限公司 Electrolyte and sodium ion secondary battery, battery pack, battery module and power utilization device comprising same
CN115084652B (en) * 2022-07-25 2024-12-06 广东省国研科技研究中心有限公司 A composite rechargeable magnesium battery electrolyte and preparation method thereof

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397921A (en) * 1981-08-13 1983-08-09 Dnepropetrovsky Khimiko-Tekhnologichesky Institut Imeni F.E. Dzerzhinskogo Electrochemical cell containing sulphur dioxide as cathodic depolarizer
GB8927274D0 (en) * 1989-12-01 1990-01-31 Lilliwyte Sa Electrode holder
JP3048899B2 (en) * 1995-09-06 2000-06-05 キヤノン株式会社 Lithium secondary battery
RU2121727C1 (en) * 1997-04-18 1998-11-10 Санкт-Петербургский государственный технический университет High-value capacitor
US6187479B1 (en) * 1998-03-06 2001-02-13 Changle Liu Ambient temperature, rechargeable cells with metal salt-based electrodes and a system of cell component materials for use therein
KR100330151B1 (en) * 1999-08-03 2002-03-28 김순택 A electrolyte for a lithium secondary battery
JP2002175837A (en) * 2000-12-06 2002-06-21 Nisshinbo Ind Inc Polymer gel electrolyte, secondary battery and electric double layer capacitor
US6632573B1 (en) * 2001-02-20 2003-10-14 Polyplus Battery Company Electrolytes with strong oxidizing additives for lithium/sulfur batteries
WO2006077380A2 (en) * 2005-01-18 2006-07-27 Oxis Energy Limited Improvements relating to electrolyte compositions for batteries using sulphur or sulphur compounds
KR101101001B1 (en) * 2005-01-19 2011-12-29 아리조나 보드 오브 리전트스, 아리조나주의 아리조나 주립대 대행법인 Current generating device having sulfone electrolyte
US20060222945A1 (en) * 2005-04-01 2006-10-05 Bowden William L Battery cathodes
US8313866B2 (en) * 2007-05-22 2012-11-20 Tiax Llc Non-aqueous electrolytes and electrochemical devices including the same
US8715865B2 (en) * 2007-07-11 2014-05-06 Basf Corporation Non-aqueous electrolytic solutions and electrochemical cells comprising the same
CN102598389B (en) * 2009-06-24 2015-04-01 丰田自动车工程及制造北美公司 High voltage electrolyte
EP2360772A1 (en) * 2010-02-12 2011-08-24 Fortu Intellectual Property AG Rechargeable and electrochemical cell
JP6086467B2 (en) * 2011-03-28 2017-03-01 日産自動車株式会社 Sodium ion secondary battery
CN103219542A (en) * 2012-01-19 2013-07-24 中国科学院物理研究所 High-salinity non-aqueous electrolyte and use thereof
JP2013157088A (en) * 2012-01-26 2013-08-15 Sony Corp Battery and battery pack, electronic apparatus, electric vehicle, power storage device and power system
DE102012203019A1 (en) 2012-02-28 2013-08-29 Technische Universität Dresden Cathode for lithium-containing batteries and solvent-free process for their preparation
CN104350631B (en) * 2012-04-10 2019-02-22 加州理工学院 Novel separators for electrochemical systems
EP2954588B1 (en) * 2013-02-07 2017-04-12 Alevo International S.A. Electrolyte for electrochemical battery cell and battery cell containing the same
US9059481B2 (en) * 2013-08-30 2015-06-16 Nanotek Instruments, Inc. Non-flammable quasi-solid electrolyte and non-lithium alkali metal or alkali-ion secondary batteries containing same
KR101520606B1 (en) * 2013-10-08 2015-05-15 전자부품연구원 Sodium-Sulfur Dioxide Secondary Battery and Manufacturing Method thereof
JP6420252B2 (en) * 2013-11-18 2018-11-07 住友化学株式会社 Sodium secondary battery
KR102356880B1 (en) * 2014-08-13 2022-02-03 에스케이이노베이션 주식회사 Sodium Secondary Battery
CN104201339B (en) * 2014-09-18 2016-08-17 厦门大学 Anode and preparation method thereof and the application in lithium-sulfur cell
FI126390B (en) 2015-09-30 2016-11-15 Broadbit Batteries Oy Electrochemical accumulators for high energy or high power battery use

Also Published As

Publication number Publication date
KR102506303B1 (en) 2023-03-06
WO2017149204A2 (en) 2017-09-08
RU2018133261A (en) 2020-04-06
TWI777943B (en) 2022-09-21
AU2017225241A1 (en) 2018-10-04
AU2017225241B2 (en) 2022-06-02
MX2018010637A (en) 2019-06-13
PE20181946A1 (en) 2018-12-13
KR20180118770A (en) 2018-10-31
EP3449525A2 (en) 2019-03-06
RU2742351C2 (en) 2021-02-05
CA3016202A1 (en) 2017-09-08
RU2018133261A3 (en) 2020-07-20
BR112018067758A2 (en) 2019-01-15
IL261506A (en) 2018-10-31
CN108780917A (en) 2018-11-09
IL261506B (en) 2022-08-01
CN108780917B (en) 2022-03-15
FI20165184A7 (en) 2017-09-05
JP6986515B2 (en) 2021-12-22
WO2017149204A3 (en) 2017-12-21
TW201801389A (en) 2018-01-01
US20200058958A1 (en) 2020-02-20
EP3449525A4 (en) 2020-04-22
JP2019508856A (en) 2019-03-28

Similar Documents

Publication Publication Date Title
FI128461B (en) Rechargeable sodium cells for use in high-energy battery
Guerfi et al. High cycling stability of zinc-anode/conducting polymer rechargeable battery with non-aqueous electrolyte
TW200305174A (en) Material for electrolytic solutions and use thereof
Manoj et al. Sulfur-polyaniline coated mesoporous carbon composite in combination with carbon nanotubes interlayer as a superior cathode assembly for high capacity lithium-sulfur cells
Zhu et al. A high-performance aqueous iron–hydrogen gas battery
Cheng et al. Electrostatic trapping of polysulfides enabled by imidazolium-based ionic polymers for high-energy-density lithium–sulfur batteries
US9742027B2 (en) Anode for sodium-ion and potassium-ion batteries
Guerfi et al. High rechargeable sodium metal-conducting polymer batteries
Thamizhselvan et al. Redox flow batteries: Pushing the cell voltage limits for sustainable energy storage
CN115548263A (en) Sodium nitrate-containing sodium ion battery negative electrode piece and preparation method and application thereof
Chen et al. Redox reactions of halogens for reversible electrochemical energy storage
CN111244560B (en) Double metal electrode secondary battery
CN113871698B (en) Electrolyte and lithium battery containing same
JP2025505886A (en) Polyaniline-based batteries with lean electrolytes
CN111757903A (en) Poly(ketone)-based polymer electrolytes for high-voltage lithium-ion batteries
CN105098187A (en) Battery
TW200830606A (en) Electrolyte for lithium ion batteries
BR112018067758B1 (en) RECHARGEABLE SODIUM ELECTROCHEMICAL CELLS FOR USE IN HIGH ENERGY DENSITY BATTERY, METHOD OF MANUFACTURE THEREOF, RECHARGEABLE BATTERY, ELECTRIC VEHICLE, POWER UNIT, RESERVE POWER UNIT AND STORAGE OR NETWORK STABILIZATION UNIT
HK1262998A1 (en) Rechargeable sodium cells for high energy density battery use
HK1262998B (en) Rechargeable sodium cells for high energy density battery use
CN118589020A (en) Antimony sulfide-based sodium ion battery
JP2007149533A (en) Electrode, and electrochemical cell using it
Nehra et al. 15 Advanced Organic
Nehra et al. Advanced Organic Materials for Zinc Batteries
KR20250159683A (en) Air and sulfur batteries

Legal Events

Date Code Title Description
FG Patent granted

Ref document number: 128461

Country of ref document: FI

Kind code of ref document: B