EP0063129A1 - Lithium-batterien - Google Patents

Lithium-batterien

Info

Publication number
EP0063129A1
EP0063129A1 EP81902829A EP81902829A EP0063129A1 EP 0063129 A1 EP0063129 A1 EP 0063129A1 EP 81902829 A EP81902829 A EP 81902829A EP 81902829 A EP81902829 A EP 81902829A EP 0063129 A1 EP0063129 A1 EP 0063129A1
Authority
EP
European Patent Office
Prior art keywords
acetonitrile
cathode
propylene carbonate
lithium
electrochemical cell
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP81902829A
Other languages
English (en)
French (fr)
Inventor
Alan James Parker
Pritam Singh
Eric John Frazer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anumin Pty Ltd
Original Assignee
Anumin Pty Ltd
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
Application filed by Anumin Pty Ltd filed Critical Anumin Pty Ltd
Publication of EP0063129A1 publication Critical patent/EP0063129A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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
    • 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

Definitions

  • the present invention relates to lithium batteries. BACKGROUND AND PRIOR ART
  • Lithium batteries typically have an anode comprising lithium as the electro-chemically active component, a cathode and a liquid electrolyte solution in which the anode and cathode are immersed. It is known to have lithium batteries with a liquid electrolyte solution containing a mixture of lithium perchlorate or lithium hexafluoroarsenate and propylene carbonate. However such systems suffer from low conductance and high polarisation. Lithium is a reactive material and reacts readily with a wide range of organic materials. Those skilled in the art of lithium batteries are faced with a choice of solvents from an enormous number of solvents and solvent mixtures.
  • acetonitrile One solvent which is in principle desirable for lithium batteries is acetonitrile.
  • Acetonitrile has a high dielectric constant, an extremely low viscosity (0.35 cp) and is a moderately good solvator of lithium cations.
  • Many lithium salts dissolve in acetonitrile to give highly conducting solutions.
  • acetonitrile reacts rapidly with lithium and previously known lithium batteries containing acetonitrile have proved totally impractical because of the reaction between the lithium and the acetonitrile.
  • U.S. Patent No. 3658592 disloses cells containing a particular type of positive electrode, a negative electrode comprised of any of the light metals such as Li , Na , K , Ca , Mg and Al , said electrodes being disposed in an electrolyte comprising an organic solvent selected from the group consisting of tetrahydrofuran, N-nitroso, dimethyl amine, dimethyl sulphite, propylene carbonate, gamma butyrolactone, dimethyl carbonate, dimethoxy ethane, acetonitrile, dimethyl sulphoxide, dimethyl formamide and the mixtures thereof; and having dissolved therein soluble salts of the light metals; for example, the perchlorates, hexafluorophosphates, tetrafluoroborates, tetrach
  • an electro chemical battery comprising a substantially ahydrous electrolyte, consisting of a highly conducting organic liquid in the form of a non-aqueous solvent in which an inorganic compound constituting a Lewis acid in relation to the solvent, has been dissolved, and a set of compatible positive and negative electrodes constituting an effective electrochemical couple.
  • the anhydrous electrolyte may be acetonitrile or a mixture thereof with a ketone.
  • the negative electrode may be lithium.
  • U.S. Patent No. 3829330 discloses a cell comprising a lithium anode and a Mo03 cathode, and offers a very wide choice of solvents, salts and mixtures, of unspecified composition.
  • One combination given as an example is acetonitrile and propylene carbonate saturated with SO 2 and having dissolved therein LiBr.
  • Lithium hexafluoroarsenate is mentioned as an alternative to the lithium haiide.
  • the SO 2 is essential and plays two roles, one as a depolariser, the other to protect the lithium against attack by solvent.
  • the combination of SO 2 and acetonitrile is used in some lithium batteries and the SO 2 is essential to prevent reaction of acetonitrile with lithium.
  • U.S. Patent No. 3468716 discloses an electrochemical system comprising an anode, a cathode and a substantially anhydrous electrolyte for electrolytic conduction between said anode and cathode, said electrolyte comprising a pentacyclic ester and at least one solvent selected from the group consisting of aliphatic ethers, cyclic ethers, nitroparaffins, cyclic ketones and aliphatic nitriles.
  • the electrolyte may comprise a solute to improve the conductivity thereof said solute being preferably a Lewis acid and may additionally comprise a lithium halide.
  • the anode may be lithium.
  • the pentacyclic ester may be propylene carbonate.
  • 3829330 and 3098770 disclose workable systems containing a lithium anode and acetonitrile.
  • the former relies on the presence of SO 2 which makes the cells of that invention non-recyclable and the latter relies on the presence of Lewis acids.
  • an electrochemical cell having an anode containing lithium as the electrochemically active material, and a cathode, said anode and cathode being immersed in a substantially anhydrous electrolyte free from Lewis acids and sulphur dioxide and containing from 0.1M to saturation LiAsF 6 dissolved in a solvent mixture of propylene carbonate and acetonitrile said acetonitrile forming from 10 to 80% by volume of the combined volume of propylene carbonate and acetonitrile and the solvent mixture consisting of at least 80% by volume, preferably at least 90% by volume, more preferably at least 95% by volume, acetonitrile and propylene carbonate with the balance, if any, being in the form of inert liquid material
  • the electrolyte contains as liquids only acetonitrile and propylene carbonate.
  • the solvent preferably contains from 20 to 60% by volume acetonitrile and at least 0.5M LiAsF 6 .
  • Preferred cathodes are titanium sulphides, copper sulphides, niobium sulphides, titanium selenides, copper selenides, niobium selenides, vanodium oxides and molybdenum oxides.
  • the lithium anode can contain lithium itself as active material or the lithium can.be alloyed with suitable other metals such as magnesium or aluminium in which case the alloy is the electrochemically active material.
  • the lithium material is typically supported on an inert electrically conductive material such as nickel.
  • an inert electrically conductive material such as nickel.
  • lithium batteries containing acetonitrile as solvent were totally impractical unless large amounts of SO 2 were present. They were not considered by those skilled in the art because of the rapid reaction of lithium with acetonitrile.
  • lithium reacts with acetonitrile containing a variety of soluble lithium salts including LiNO 3 , LiCl, LiClO 4 and LiAsF 6 and also in the absence of any salt.
  • Acetonitrile reacts with lithium metal when mixed in equal proportions with propylene carbonate containing LiClO 4 and when mixed in equal proportions with tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxy ethane or dimethylformamide all containing 1M LiAsF 6 .
  • Table 2 shows the polarisations for cycling lithium between Li/Al alloys at 1 mA cm -2 in propylene carbonate (PC) and in solvents containing acetonitrile. In all cases the polarisations are less in the presence of acetonitrile than in pure PC, even after iR corrections.
  • Polarisations are least for LiAsF 6 , in pure acetonitrile.
  • Figure 1 is a graph of the discharge of Li/MnO 2 , Li/Cus, Li/NbSe 3 and Li/MoO 3 cells at 1 mA cm -2 in various electrolyte solutions at ambient temperatures (discharge voltage versus utilization as coulombs per kg active cathodic material, electrolytes at 1M, mixtures are 50% by volume);
  • Figure 2 is a graph of the discharge of Li/V2O 5 and Li/Cu 2 S cells at 2 mA cm -2 and of a Li/TiS 2 cell at 1 mA cm -2 in various electrolyte solutions at ambient temperatures (discharge voltage versus utilisation as coulombs per kg of active cathodic material, electrolytes are 1M and mixtures are 50% by volume);
  • Figure 3 is a graph of the discharge of Li/V 6 O 1 3 cells at
  • Figure 4 is a graph of the discharge of Li/NbSe 3 cells at 1 mA cm -2 in 1M LiAsF 6 in propylene carbonate and in 50/50 propylene carbonate/acetonitrile mixture at ambient conditions (expanded voltage scale over Figure 1) .
  • the cells used comprised a lithium anode pressed onto nickel gauze of area about 1 cm 2 , the cellhaving a glass filter paper separator.
  • the cathode was a powder of the active material (0.1 - 0.5 g) mixed with 5% teflon powder and 10% nickel powder and pressed between two nickel gauze discs.
  • the cell was contained in a cylinder of polypropylene and electrical contact was via 2 brass screws.
  • FIG. 1 shows the voltage of lithium batteries having cathodes containing various active materials which do not show especially great advantages in voltage when discharged at 1 mA cm -2 of lithium anode in our new solvent mixture.
  • cathodic material The utilisation of the cathodic material is recited as coulombs/kg and is better for some cathodes in the new solvent.
  • the preferred electrolyte of the present invention of 1M to saturation LiAsF 6 in 50% V/V propylene carbonate-acetonitrile is compared with other electrolytes.
  • Cathodes used in Figure 1 are Mn O 2 , MoO 3 , NbSe 3 , and CuS. It can be seen that with the cathodes used in Figure 1 that LiAsF 6 /PC/AN on discharge at 1mA cm -2 does not provide a marked improvement in voltage discharge characteristics over certain other solvent mixtures.
  • MnO 2 cathode it is an inferior electrolyte to LiClO 4 PC/DME or LiAsF 6 /PC.
  • utilisation with MnO 2 and CuS as cathodes is better for the new electrolyte.
  • the electrolyte of the present invention has clear advantages over LiAsF 6 /PC or LiCIO 4 .
  • PC/DME when discharging at 1mA cm -2 or 2mA cm -2 .
  • the advantages include a markedly higher open current and discharge voltage with V 2 O 5 and V 6 O 13 and more effective utilisation of cathode material, especially with Cu 2 S as cathode.
  • the electrolyte of the present invention is particularly effective with V 6 O 13 , on all counts, as shown in Figure 3.
  • Figure 4 shows the behaviour of an Li/NbSe 3 cell in PC and in 50% PC/AN containing 1M LiAsF 6 .
  • the electrolyte of the present invention again has some advantage but it is not as marked as with V 2 O 5 and V 6 O 13 .
  • the new electrolyte has extremely advantageous conductance at 25° C as shown below: -
  • preferred cathodes for use in the present invention are Cu 2 S, V 2 O 5 , V 6 O 13 , TiS 2 or NbSe 3 .
  • Acetonitrile is an extremely good solvator of copper (I) ions, and, while we do not wish to be bound by any theory, it is believed that the acetonitrile assists the cathodic process at a Li (I) /Cu 2 S cathode.
  • Acetonitrile is a small and mobile molecule and it is believed that intercalation of acetonitrile solvated Li (I) has less polarisation at certain intercalation cathodes such as TiS 2 , V 2 O 5 and V 6 O 13 than with large solvent molecules such as propylene carbonate.
  • the advantages of acetonitrile over most solvents i.e. low viscosity, high dielectric onstant and good lithium solvating power are particularly advantageous in conjunction with certain cathode types, e.g. Cu 2 S, TiS 2 , V 2 O 5 and V 6 O 13 .
  • the higher conductance of LiAsF 6 PC/AN mixtures and the stability of lithium mean that the new electrolyte is in general preferable to LiClO 4 /PC for all lithium batteries, e.g. Li/MoO 3 , Li/NbSe 3 ) at high current density, but as noted, batteries with the preferred cathodes exhibit special advantages when the new electrolyte is used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
EP81902829A 1980-10-22 1981-10-21 Lithium-batterien Withdrawn EP0063129A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU616780 1980-10-22
AU6167/80 1980-10-22

Publications (1)

Publication Number Publication Date
EP0063129A1 true EP0063129A1 (de) 1982-10-27

Family

ID=3696675

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81902829A Withdrawn EP0063129A1 (de) 1980-10-22 1981-10-21 Lithium-batterien

Country Status (2)

Country Link
EP (1) EP0063129A1 (de)
WO (1) WO1982001442A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPS119502A0 (en) * 2002-03-19 2002-04-18 Energy Storage Systems Pty Ltd An electrolyte for an energy storage device

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2139714C3 (de) * 1971-08-07 1975-08-14 Rheinisch-Westfaelisches Elektrizitaetswerk Ag, 4300 Essen Galvanisches Sekundärelement mit auf Graphitbasis durch anodische Oxidation aufgebauter positiver Elektrode
US3877988A (en) * 1973-03-21 1975-04-15 Mallory & Co Inc P R Lithium-metal telluride organic electrolyte cell
US4091152A (en) * 1973-08-16 1978-05-23 P.R. Mallory & Co. Inc. Lithium SO2 cell
US3969139A (en) * 1974-10-07 1976-07-13 Rockwell International Corporation Lithium electrode and an electrical energy storage device containing the same
US4228226A (en) * 1978-10-10 1980-10-14 Bell Telephone Laboratories, Incorporated Nonaqueous secondary cell using vanadium oxide positive electrode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8201442A1 *

Also Published As

Publication number Publication date
WO1982001442A1 (en) 1982-04-29

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19821220

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Inventor name: PARKER, ALAN JAMES

Inventor name: FRAZER, ERIC JOHN

Inventor name: SINGH, PRITAM