USH1721H - Aqueous rechargeable battery - Google Patents

Aqueous rechargeable battery Download PDF

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Publication number
USH1721H
USH1721H US08/772,464 US77246496A USH1721H US H1721 H USH1721 H US H1721H US 77246496 A US77246496 A US 77246496A US H1721 H USH1721 H US H1721H
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US
United States
Prior art keywords
aqueous
battery
electrolyte
batteries
rechargeable battery
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Abandoned
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US08/772,464
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English (en)
Inventor
David Stanley Wainwright
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NEC Moli Energy Canada Ltd
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NEC Moli Energy Canada Ltd
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Assigned to MOLI ENERGY (1990) LIMITED reassignment MOLI ENERGY (1990) LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WAINWRIGHT, DAVID STANLEY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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 invention pertains to aqueous rechargeable batteries and particularly to aqueous rechargeable batteries which employ insertion compounds as the electrode materials.
  • NiMH batteries are relatively expensive compared to other conventional systems (eg. Pb acid or NiCd) and do not perform well at elevated temperature (eg. above 45° C.). Lithium ion batteries also have very attractive energy density characteristics but they are markedly more expensive than NiMH batteries.
  • aqueous rechargeable battery systems which operate much like conventional lithium ion batteries except that aqueous electrolytes are employed. That is, two different insertion compounds are employed respectively as the cathode and anode electrodes and an alkali metal (eg. lithium) or alkaline earth metal species is ⁇ rocked ⁇ during charge and discharge of the battery (ie. species insertion takes place at one electrode with simultaneous species extraction taking place at the other electrode).
  • an alkali metal eg. lithium
  • alkaline earth metal species ⁇ rocked ⁇ during charge and discharge of the battery (ie. species insertion takes place at one electrode with simultaneous species extraction taking place at the other electrode).
  • species insertion takes place at one electrode with simultaneous species extraction taking place at the other electrode.
  • the typical aqueous electrolyte and typical aqueous battery construction are markedly less expensive than their non-aqueous counterparts. (The latter results from the typical non-aqueous rechargeable battery needing much thinner electrode constructions than its aqueous counterpart to compensate for the lower ionic conductivity of non-aqueous electrolytes.)
  • Non-aqueous electrochemical systems that not only have absolute potentials for insertion which are compatible with aqueous electrolytes, but which also have greater capacities for insertion of an alkali metal or alkaline earth metal species and which are also more stable in basic solutions.
  • lithium is particularly desirable for use as an inserted species.
  • Conventional non-aqueous lithium ion battery cathodes such as LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 have absolute potentials in a range compatible for use as a cathode in an aqueous lithium ion battery. LiNiO 2 is attractive because it is characterized by a large reversible capacity for lithium insertion.
  • LiMn 2 O 4 exhibits less reversible capacity but advantageously exhibits a relatively flat or constant voltage over this reversible range (thereby resulting in a battery with almost constant voltage during operation and consequently making it easier to engineer electrolyte stability over the reversible range) and the raw materials used in its preparation are less expensive.
  • the invention represents an improvement over those embodiments disclosed in Canadian Patent application Serial No. 2,114,902, Wainwright, filed Feb. 3, 1994.
  • the improvement involves the use of a polymer for at least one of the insertion compounds.
  • Improved energy density characteristics can be obtained by using certain polymers as insertion compounds for the electrodes and more options can become available for the selection of electrolyte salts and pH.
  • polymers were not previously considered as alternatives, polymer electrodes exhibiting large reversible capacities for inserted alkali or alkaline earth metals can be particularly useful as electrode materials in aqueous rechargeable insertion compound batteries.
  • Polymers generally can be less prone to dissolution or decomposition in basic aqueous electrolytes.
  • the "Handbook of Plastics and Elastomers" C. A. Harper, Editor-in-chief, 1975,McGraw-Hill, states "Generally speaking, inorganic salt solutions, weak aqueous alkaline solutions . . . do not have an adverse effect upon plastics, resins, or elastomers.”
  • Carbon-sulfur polymers such as those described in the aforementioned U.S. Pat. No. 5,441,831, can exhibit relatively constant voltages over a wide insertion range for alkali metals, especially lithium. Such carbon-sulfur polymers are particularly attractive for use, not only as cathode materials in non-aqueous batteries, but as anode materials in aqueous lithium ion batteries.
  • the anode polymer can be poly(carbon disulfide) having the formula (CS x ) n , wherein x is a number from about 1.2 to 2.33 and n is a number greater than or equal to 2.
  • a preferred embodiment of the invention combines a poly(carbon disulfide) anode with a lithium manganese oxide spinel cathode, denoted Li y Mn 2 O 4 , wherein lithium can, in principle, be reversibly inserted over a value of y ranging from 0 to about 2.
  • the aqueous electrolyte can comprise one or more lithium salts.
  • a basic electrolyte is preferred (ie. pH>7).
  • a very basic electrolyte may be preferred for a poly(carbon disulfide) anode/ lithium manganese oxide spinel cathode embodiment.
  • LiOH may be employed to adjust pH and other non-hydroxide salts of lithium may be used as a source of additional lithium ions in the electrolyte solution.
  • FIGURE illustrates certain non-optimized aspects of the invention, but should not be construed as limiting in any way.
  • FIG. 1 shows the overall voltage of the battery of Example 1 versus capacity and also shows the voltages of the individual electrodes therein versus Li/Li + .
  • insertion compounds are broadly defined as host materials into which a species can be inserted and extracted without irreversible effect on the structure of the host).
  • an aqueous electrolyte comprising a dissolved salt of the inserted species A of the battery.
  • ions of A migrate to and from each electrode through the aqueous electrolyte. Concurrently, electrons migrate to and from each electrode via an external circuit. (Note that some hydrogen insertion can inherently be expected to occur to some limited extent in both electrodes. Additionally therefore, some limited ⁇ rocking ⁇ of hydrogen may also occur between the electrodes.)
  • the electrode materials are preferably selected such that the largest operating voltage is obtained without decomposing the aqueous electrolyte into H 2 and O 2 by electrolysis.
  • practical batteries may be constructed that operate beyond the fundamental thermodynamic stability limits of the electrolyte. It is possible in principle to operate at significant overvoltages before significant gas evolution occurs.
  • the electrodes themselves must also not decompose or dissolve.
  • Polymer insertion compounds are generally more stable and less prone to dissolution in basic electrolytes than are typical inorganic insertion compounds. Thus, their use would generally provide for greater options with regards to electrolyte salts and pH selection in the aqueous electrolyte.
  • the electrolyte preferably has high ionic conductivity and has sufficient salt concentration to prevent electrolyte depletion during operation of the battery. This implies having a substantial cation concentration which may additionally help to bind the water to the dissociated salt ions (thereby preventing reaction with inserted lithium to some extent) and to prevent the water from decomposing into H 2 and O 2 . It may be desirable to use more than one dissolved salt in the electrolyte in order to meet all these conditions simultaneously.
  • Preferred embodiments will combine the advantages of both aqueous and non-aqueous battery constructions where possible.
  • typical aqueous electrolytes have much higher ionic conductivities than typical non-aqueous electrolytes, the thicker electrode constructions of aqueous batteries may be employed resulting in a simpler, less expensive construction than those of non-aqueous batteries.
  • the aqueous electrolyte in the battery of the invention does not substantially participate in its basic electrochemical operation.
  • relatively high loadings of active electrode can be expected in the battery.
  • the active electrode materials constitute about 50% by weight in today's typical small cylindrical non-aqueous lithium ion batteries in commercial use, and these batteries employ relatively large area, yet thin electrodes.
  • overcharge protection via oxygen recombination reactions can be preferred to provide for overcharge protection via oxygen recombination reactions as found in many conventional aqueous systems.
  • Batteries are usually assembled somewhat electrolyte starved such that it is easier and hence faster for the evolved oxygen to migrate back to the anode where recombination can occur. Hydrogen evolution at the anode is preferably avoided as much as is possible. Additives or inhibitors may be used to increase the hydrogen over-potential at the anode and hence suppress generation of hydrogen gas. Batteries may also be slightly cathode limited to avoid evolving hydrogen at the anode. (Otherwise, the capacities of both electrodes would generally be balanced in order to maximize overall battery capacity.) The voltages at which both oxygen and hydrogen are evolved will of course strongly depend on the electrolyte pH selected.
  • Hardware requirements for the batteries of the invention can also be expected to share similarities to other aqueous systems. Consideration with regards to possible chemical and/or electrochemical corrosion must be made in the choice of this hardware, particularly if strongly basic electrolytes are employed. As with some Pb acid batteries, it may be desirable to adopt a design that allows for replenishment of the electrolyte over time in order to compensate for losses due to electrolysis.
  • a preferred embodiment of the invention is an aqueous battery wherein lithium is the inserted species.
  • a class of carbon-sulfur polymer insertion compounds is preferred as their voltage characteristics can be fairly constant over a wide insertion range for lithium, and their voltages (typically about 2.5 V versus Li/Li + ) are at an absolute potential near that for hydrogen evolution in the electrolyte.
  • the polymer poly(carbon disulfide) described in the aforementioned U.S. Pat. No. 5,441,831 is particularly preferred as an anode since it is characterized by a very large reversible capacity for lithium over a voltage range of from about 2.1 to 2.7 V versus Li/Li + .
  • poly(carbon disulfide) is characterized by repeating units having C-S bonds in the chain and branches having C ⁇ S bonds.
  • the following example illustrates the possible capacity advantages that might be achieved by employing poly(carbon disulfide) as an anode material in an aqueous lithium ion battery.
  • FIG. 1 The voltage and capacity characteristics for an aqueous rechargeable battery are illustrated in FIG. 1 for an electrochemical couple comprising a lithium manganese oxide spinel cathode (denoted Li y Mn 2 O 4 ) and a poly(carbon disulfide) anode.
  • the lithium manganese oxide spinel cathode is considered as cycling with a 115 mAh/g reversible capacity at voltages versus Li/Li + ranging from 3.8 to 4.2 V (see for instance, J. Electrochem. Soc., Vol. 143, No.1, p109, FIG. 9, sample A-1).
  • the poly(carbon disulfide) anode is considered as cycling with a 460 mAh/g reversible capacity at voltages versus Li/Li + ranging from 2.8 to 2.1 V (see for instance, aforementioned U.S. Pat. No. 5,441,831).
  • the battery is assumed to comprise 4 g of spinel cathode material and 1 g of poly(carbon disulfide) anode material and the total active electrode weight (5 g) amounts to 60% of the overall battery weight.
  • FIG. 1 shows the approximate individual cathode and anode voltages versus Li/Li+ (based on low rate discharge data given in the cited references) as well as the expected overall battery voltage during a discharge (given by the difference in cathode and anode voltages).
  • the battery delivers 460 mAh at an average voltage of about 1.5 V (ranging over about 1.0-2.1 V) and therefore has a gravimetric energy density of about 83 Whr/kg, which is competitive with commercial nickel metal hydride batteries.
  • hysteresis between charge and discharge voltage curves and/or operation at high rate implies that either the charge voltage will have to be somewhat higher than that shown in FIG. 1 or that the achieved capacity will be somewhat lower.!
  • the aqueous electrolyte salt and pH are selected such that hydrogen evolution does not occur. Ideally, the electrolyte also allows for full recharge followed shortly after by the onset of oxygen evolution on OC for recombination purposes. From thermodynamic principles, a fairly basic electrolyte seems preferred, and can be obtained by using LiOH as a salt. Other Li salts (eg. nitrate, chloride, etc.) may also be used to provide for more cations if desired.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US08/772,464 1996-09-20 1996-12-23 Aqueous rechargeable battery Abandoned USH1721H (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA002186099A CA2186099A1 (fr) 1996-09-20 1996-09-20 Pile rechargeable a electrolyte aqueux
CA2186099 1996-09-20

Publications (1)

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USH1721H true USH1721H (en) 1998-04-07

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CA (1) CA2186099A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140308581A1 (en) * 2013-04-10 2014-10-16 University Of Houston System Aqueous Energy Storage Devices with Organic Electrode Materials
US10218005B2 (en) 2016-09-16 2019-02-26 Kabushiki Kaisha Toshiba Secondary battery, battery pack, and vehicle
US10243212B2 (en) * 2013-06-03 2019-03-26 Lg Chem, Ltd. Electrode assembly for sulfur-lithium ion battery and sulfur-lithium ion battery including the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2134052A1 (fr) * 1993-10-22 1995-04-23 Yoshio Idota Batterie secondaire non aqueuse
CA2114902A1 (fr) * 1994-02-03 1995-08-04 David S. Wainwright Batterie rechargeable aqueuse
US5441831A (en) * 1992-12-17 1995-08-15 Associated Universities, Inc. Cells having cathodes containing polycarbon disulfide materials
US5604057A (en) * 1995-11-27 1997-02-18 General Motors Corporation Secondary cell having a lithium intercolating manganese oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441831A (en) * 1992-12-17 1995-08-15 Associated Universities, Inc. Cells having cathodes containing polycarbon disulfide materials
CA2134052A1 (fr) * 1993-10-22 1995-04-23 Yoshio Idota Batterie secondaire non aqueuse
CA2114902A1 (fr) * 1994-02-03 1995-08-04 David S. Wainwright Batterie rechargeable aqueuse
US5604057A (en) * 1995-11-27 1997-02-18 General Motors Corporation Secondary cell having a lithium intercolating manganese oxide

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
"Safer Rechargeable Lithium Ion Batteries Use Aqueous Electrolyte", Materials Technology, vol. 11, No. 1, Jan./Feb. 1996, pp. 9-12.
Deutscher, et al., "Investigations on an aqueous lithium secondary cell", Journal of Power Sources, 55 (1995) pp. 41-46. No month.
Deutscher, et al., Investigations on an aqueous lithium secondary cell , Journal of Power Sources, 55 (1995) pp. 41 46. No month. *
Li, et al., "Lithium-Ion Cells with Aqueous Electrolytes", J. Electrochem. Soc., vol. 142, No. 6, Jun. 1995, pp. 1742-1746.
Li, et al., Lithium Ion Cells with Aqueous Electrolytes , J. Electrochem. Soc., vol. 142, No. 6, Jun. 1995, pp. 1742 1746. *
Plichta, et al., "Lithium Ion Aqueous Cells", Army Research Lab Report No. ARL-TR-422, Feb. 1995.
Plichta, et al., Lithium Ion Aqueous Cells , Army Research Lab Report No. ARL TR 422, Feb. 1995. *
Review of the 13th International Seminar on Primary and Secondary Battery Technology and Applications, Mar. 4 7, 1996 Boca Raton, FL, USA (as presented by ITE Newsletter No. 2 (Mar. Apr.) 1996). *
Review of the 13th International Seminar on Primary and Secondary Battery Technology and Applications, Mar. 4-7, 1996 Boca Raton, FL, USA (as presented by ITE Newsletter No. 2 (Mar.-Apr.) 1996).
Safer Rechargeable Lithium Ion Batteries Use Aqueous Electrolyte , Materials Technology, vol. 11, No. 1, Jan./Feb. 1996, pp. 9 12. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140308581A1 (en) * 2013-04-10 2014-10-16 University Of Houston System Aqueous Energy Storage Devices with Organic Electrode Materials
CN106463781A (zh) * 2013-04-10 2017-02-22 休斯敦大学体系 具有有机电极材料的水性能量存储装置
US10411262B2 (en) * 2013-04-10 2019-09-10 University Of Houston System Aqueous energy storage devices with organic electrode materials
US10243212B2 (en) * 2013-06-03 2019-03-26 Lg Chem, Ltd. Electrode assembly for sulfur-lithium ion battery and sulfur-lithium ion battery including the same
US10218005B2 (en) 2016-09-16 2019-02-26 Kabushiki Kaisha Toshiba Secondary battery, battery pack, and vehicle

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Publication number Publication date
CA2186099A1 (fr) 1996-11-18

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