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WO1996029750A1 - Additifs organiques a base de carbonate pour electrolyte non aqueux dans les piles electrochimiques a metaux alcalins - Google Patents

Additifs organiques a base de carbonate pour electrolyte non aqueux dans les piles electrochimiques a metaux alcalins Download PDF

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Publication number
WO1996029750A1
WO1996029750A1 PCT/US1996/003118 US9603118W WO9629750A1 WO 1996029750 A1 WO1996029750 A1 WO 1996029750A1 US 9603118 W US9603118 W US 9603118W WO 9629750 A1 WO9629750 A1 WO 9629750A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
anode
carbonate
group
electrolyte
Prior art date
Application number
PCT/US1996/003118
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English (en)
Inventor
Hong Gan
Esther S. Takeuchi
Original Assignee
Wilson Greatbatch 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 Wilson Greatbatch Ltd. filed Critical Wilson Greatbatch Ltd.
Priority to AU54198/96A priority Critical patent/AU5419896A/en
Publication of WO1996029750A1 publication Critical patent/WO1996029750A1/fr

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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
    • H01M10/05—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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • 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
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • 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 a nonagueous electrolyte alkali metal electrochemical cell, and in particular, a lithium cell designed for high current pulse discharge applications.
  • anode surface film plays a very important role in the discharge performance of either a primary or a secondary alkali metal electrochemical cell, and in particular, a lithium cell.
  • SEI solid-electrolyte interphase
  • a good SEI benefits cell performance, including high discharge capacity, long useful life, better rechargeability for secondary cells and little or no voltage delay during high current pulse applications. Since the formation of a surface film is unavoidable for alkali metal, and in particular, lithium metal anodes, and for lithium intercalated carbon anodes, due to their low potential and high reactivity towards organic electrolytes, much effort has been focused on modification of the chemical composition and morphology of the anode surface film.
  • the ideal anode surface film should be electrically insulating and ionically conducting. While most alkali metal, and in particular, lithium electrochemical systems meet the first requirement, the second requirement is difficult to achieve. As a result, higher impedance builds up inside the cell due to this surface layer formation which often results in lower discharge voltage and lower cell capacity. In the case of a cell subjected to high current pulse discharge, large voltage delay and voltage drop may occur and limit the effectiveness of the cell under these conditions.
  • the surface film also affects the efficiency and cyclability of secondary alkali metal cells.
  • the present invention is directed to dissolving organic additives in the electrolyte to change the anode surface film.
  • the carbonate additives have weak 0-X bonds, which when dissolved in the activating electrolyte effect the anode surface film to desirably change its ionic conductivity.
  • the object of the present invention is to improve the performance of a primary alkali metal electrochemical cell, and more particularly, a lithium electrochemical cell by dissolving in the nonaqueous electrolyte solution a combination of organic additives.
  • a further object of this invention is to provide the present electrolyte solution in operative association with an electrochemical system incorporated in a defibrillator battery to minimize or eliminate voltage delay under high current pulse discharge conditions.
  • the concept of this invention is likewise applicable to secondary alkali metal electrochemical cells.
  • the aforementioned objects are achieved by the addition of organic additive, preferably carbonate additives dissolved in the electrolyte solution of an alkali metal electrochemical cell.
  • the present invention uses solid organic additives which provide ease in handling and in electrolyte preparation.
  • the additives are designed to interact with the alkali metal anode, and particularly with a lithium anode to form a protective anode surface layer which improves the discharge performance of the cell, and minimizes or even eliminates voltage delay in high current discharge conditions.
  • Fig. l is a graph showing the pulse discharge curve 10 of a control electrochemical cell activated with an electrolyte comprising an alkali metal salt dissolved in an aprotic organic solvent devoid of an organic additive according to the present invention.
  • Fig. 2 is a graph showing the pulse discharge curve 20 of an electrochemical cell activated with an electrolyte comprising an alkali metal salt dissolved in an aprotic organic solvent including an organic additive according to the present invention.
  • Fig. 3 is a graph showing the pulse discharge curve 30 of an electrochemical cell similar to that discharged to generate the graph shown in Fig. 2 but without the organic additive.
  • Figs. 4 to 6 are graphs showing discharge curves of electrochemical cells having 800 mAh of capacity removed before testing and including no additive, 0.01M BSC additive and 0.03M DBC additive, respectively.
  • Figs. 7 to 9 are graphs showing discharge curves of electrochemical cells having 1200 mAh of capacity removed before testing and including no additive, 0.01M BSC additive and 0.03M DBC additive, respectively.
  • the electrochemical cell of the present invention includes an anode selected from Group IA of the Periodic Table of Elements, including lithium, sodium, potassium, etc., and their alloys and intermetallic compounds including, for example Li-Si, Li-B and Li-Si-B alloys and intermetallic compounds.
  • the preferred anode comprises lithium, and the more preferred anode comprises a lithium alloy, the preferred lithium alloy being lithium-aluminum with the aluminum comprising from between about 0% to about 50% by weight of the alloy.
  • the form of the anode may vary, but preferably the anode is a thin metal sheet or foil of the anode metal, pressed or rolled on a metallic anode current collector, i.e., preferably comprising nickel, to form an anode component.
  • the anode component has an extended tab or lead of the same material as the anode current collector, i.e., preferably nickel, integrally formed therewith such as by welding and contacted by a weld to a cell case of conductive metal in a case-negative electrical configuration.
  • the anode may be formed in some other geometry, such as a bobbin shape, cylinder or pellet to allow an alternate low surface cell design.
  • the electrochemical reaction at the cathode involves conversion of ions which migrate from the anode to the cathode in atomic or molecular forms.
  • the solid cathode material may comprise a metal element, a metal oxide, a mixed metal oxide, a metal sulfide or carbonaceous compounds, and combinations thereof. Suitable cathode materials include silver vanadium oxide, copper silver vanadium oxide, manganese dioxide, titanium disulfide, copper oxide, copper sulfide, iron sulfide, iron disulfide, carbon and fluorinated carbon.
  • the solid cathode exhibits excellent thermal stability and is generally safer and less reactive than a non-solid cathode.
  • the solid cathode material comprises a mixed metal oxide formed by the chemical addition, reaction or otherwise intimate contact or by a thermal spray coating process of various metal sulfides, metal oxides or metal oxide/elemental metal combinations.
  • the materials thereby produced contain metals and oxides of Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements, which includes the noble metals and/or their oxide compounds.
  • an exemplary cathode active material comprises silver vanadium oxide having the general formula Ag x V 2 O y in any one of its many phases, i.e.
  • the cell of the present invention includes a separator to provide physical separation between the anode and cathode active electrodes.
  • the separator is of electrically insulative material to prevent an internal electrical short circuit between the electrodes, and the separator material also is chemically unreactive with the anode and cathode active materials and both chemically unreactive with and insoluble in the electrolyte.
  • the separator material has a degree of porosity sufficient to allow flow therethrough of the electrolyte during the electrochemical reaction of the cell.
  • Illustrative separator materials include non-woven glass, polypropylene, polyethylene, glass fiber material, ceramics, polytetrafluorethylene membrane commercially available under the designations ZITEX (Chemplast Inc.), polypropylene membrane, commercially available under the designation CELGARD (Celanese Plastic Company Inc.) and DEXIGLAS (CH. Dexter, Div. , Dexter Corp.).
  • the form of the separator typically is a sheet which is placed between the anode and cathode electrodes and in a manner preventing physical contact therebetween.
  • the electrochemical cell of the present invention further includes a nonaqueous, ionically conductive electrolyte operatively associated with the anode and the cathode electrodes.
  • the electrolyte serves as a medium for migration of ions between the anode and the cathode during the electrochemical reactions of the cell and nonaqueous solvents suitable for the present invention are chosen so as to exhibit those physical properties necessary for ionic transport (low viscosity, low surface tension and wettability) .
  • Suitable nonaqueous solvents are comprised of an inorganic salt dissolved in a nonaqueous solvent and more preferably an alkali metal salt dissolved in a mixture of aprotic organic solvents comprising a low viscosity solvent including organic esters, ethers and dialkyl carbonates, and mixtures thereof, and a high permittivity solvent including cyclic carbonates, cyclic esters and cyclic amides, and mixtures thereof.
  • Low viscosity solvents include tetrahydrofuran (THF) , methyl acetate (MA) , diglyme, triglyme, tetraglyme, dimethyl carbonate (DMC) , 1,2-dimethoxyethane (DME) and others.
  • High permittivity solvents include propylene carbonate (PC) , ethylene carbonate (EC) , acetonitrile, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, 7-butyrolactone (GBL) and N-methyl- pyrrolidinone (NMP) and others.
  • Suitable nonaqueous solvents are substantially inert to the anode and cathode electrode materials and a preferred solvent comprises a 50/50 mixture (by volume) of propylene carbonate (PC) and dimethoxyethane (DME) .
  • the preferred electrolyte comprises an inorganic salt having the general formula MMF 6 wherein M is an alkali metal similar to the alkali metal comprising the anode and M is an element selected from the group consisting of phosphorous, arsenic and antimony.
  • MMF 6 hexafluorophosphate
  • AsF 6 hexafluoroarsenate
  • SbF 6 hexafluoroantimonate
  • the electrolyte comprises at least one ion-forming alkali metal salt of hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate dissolved in a suitable organic solvent wherein the ion-forming alkali metal is similar to the alkali metal comprising the anode.
  • the alkali metal salt of the electrolyte of the present invention comprises lithium hexafluorophosphate, lithium hexafluoroarsenate or lithium hexafluoroantimonate dissolved in a suitable solvent mixture.
  • inorganic salts useful with the present invention include LiBF 4 , LiCI0 4 and LiCF 3 S0 3 , and mixtures thereof.
  • organic additives containing an O-X bond having a dissociation energy less than about 80 kcal/mol (X can be C, 0 or N) on either one or both sides of a carbonate group improves the high current pulse discharge performance of the alkali metal cells.
  • X can be C, 0 or N
  • di- (N-succinimidyl) carbonate, benzyl-N- succinimidyl carbonate and dibenzyl carbonate, and mixtures thereof are used as additives in the electrolyte.
  • the presence of a weak 0-X bond in these additives is crucial for improved performance of the alkali metal cells, and particularly lithium cells.
  • the anode is lithium metal and the cathode is preferably the transition mixed metal oxide AgV 2 0 5 . s (SVO) .
  • the preferred electrolyte is l.OM to 1.4M LiAsF 6 dissolved in an aprotic solvent mixture comprising at least one low viscosity solvent and one high permittivity solvent.
  • the low viscosity solvent is preferably selected from organic esters, ethers and dialkyl carbonates.
  • the high permittivity solvent is preferably selected from cyclic carbonates, cyclic esters and cyclic amides.
  • concentration of the above mentioned organic additives should preferably be in the range of between about 0.001M to about 0.1M.
  • the assembly of the cell described herein is preferably in the form of a wound element cell. That is, the fabricated cathode, anode and separator are wound together in a "jellyroll" type configuration or “wound element cell stack" such that the anode is on the outside of the roll to make electrical contact with the cell case in a case-negative configuration.
  • the wound cell stack is inserted into a metallic case of a suitable size dimension.
  • the metallic case may comprise materials such as stainless steel, mild steel, nickel-plated mild steel, titanium or aluminum, but not limited thereto, so long as the metallic material is compatible for use with components of the cell.
  • the cell header comprises a metallic disc-shaped body with a first hole to accommodate a glass-to-metal seal/terminal pin feedthrough and a second hole for electrolyte filling.
  • the glass used is of a corrosion resistant type having from between about 0% to about 50% by weight silicon such as CABAL 12, TA 23 or FUSITE 425 or FUSITE 435.
  • the positive terminal pin feedthrough preferably comprises titanium although molybdenum, aluminum, nickel alloy, or stainless steel can also be used.
  • the cell header comprises elements having compatibility with the other components of the electrochemical cell and is resistant to corrosion.
  • the cathode lead is welded to the positive terminal pin in the glass-to-metal seal and the header is welded to the case containing the electrode stack.
  • the cell is thereafter filled with the electrolyte solution described hereinabove and hermetically sealed such as by close-welding a stainless steel ball over the fill hole, but not limited thereto.
  • This above assembly describes a case-negative cell which is the preferred construction of the exemplary cell of the present invention.
  • the exemplary electrochemical system of the present invention can also be constructed in a case-positive configuration.
  • Lithium anode material and silver vanadium oxide cathode material were each pressed on titanium current collector screens connected to nickel leads.
  • a prismatic cell stack assembly of a single anode and a single cathode with two layers of polypropylene separator sandwiched between the two electrodes was prepared.
  • the thusly constructed electrode assembly was placed in a glass vessel sealed with a rubber septum and activated with a nonaqueous electrolyte.
  • the electrochemical cell assemblies were then divided into ten cell groups.
  • the nonaqueous electrolyte was prepared by dissolving LiAsF6 salt in each of the solvent mixtures listed in Table 1.
  • Electrolyte Solvent Conductivity [LiAsF 6 ] (Ratio) (mmho/cm)
  • PC propylene carbonate
  • DME 1,2-dimethoxyethane
  • DMC dimethyl carbonate
  • MA methyl acetate
  • GBL 7-butyrolactone
  • NMP -methyl-pyrrolidinone
  • DSC di- (N-succinimidyl) carbonate
  • BSC benzyl-N-succinimidyl carbonate
  • DBC dibenzyl carbonate
  • All the cells i.e., those having the organic additives of the present invention dissolved in the respective electrolytes and the reference test cells, . were discharged under a IK ohm load for l hour and then discharged under a 2K ohm load.
  • These cells received once every two days an application of a pulse train consisting of four 17.7 mA/cm 2 , 10 second pulses with 15 seconds rest between each pulse. Four pulse trains were applied to each cell.
  • voltage delay in the first pulse can be observed for all of the above reference test cells in the third and fourth pulse trains. Voltage delay is defined as pulse one end potential minus pulse one minimum potential as shown in Fig.
  • Lithium anode material was pressed on nickel current collector screen and silver vanadium oxide cathode material was pressed on titanium current collector screen.
  • a prismatic cell stack assembly configuration with two layers of icroporous membrane propylene separator sandwiched between the anode and cathode was prepared.
  • the electrode assembly was then hermetically sealed in a stainless steel casing in a casenegative configuration and activated with an electrolyte comprising l.OM LiAsF 6 dissolved in a 50/50 mixture (by volume) of propylene carbonate and 1,2-dimethoxyethane.
  • Li/SVO defibrillator cells were constructed similar to those described in Example II and activated with an electrolyte comprising l.OM LiAsF 6 dissolved in a 50/50 mixture (by volume) of propylene carbonate and 1,2-dimethoxyethane. Some of the cells were provided with 0.01M BSC dissolved in the electrolyte while some of the cells were provided with 0.03M DBC additive dissolved in the electrolyte. Reference cells for the two cell groups were built without organic additives in the electrolyte. These cells were further divided into two sub-groups. One group was partially discharged under 200 ohm for about 56 hours to remove 800 mAh capacity.
  • the second sub-group cells were discharged under 200 ohm for about 87 hours to remove 1200 mAh capacity. After storing on open circuit at 37°C for 8 weeks, they received an application of a pulse train consisting of four 18.4 mA/cm 2 , 10 second pulses with 15 second rest between each pulse at 37°C. The voltage delay results are listed in Table 6 and are graphically shown in Figs. 4 to 9. Thus, the pulse discharge curve 40 (Fig.
  • Fig. 5 was constructed from a Li/SVO cell activated with an electrolyte of l.OM LiAsF 6 dissolved in a 50/50 mixture (by volume) of propylene carbonate and 1.2-dimethoxyethane without any additive therein and after 800 mAh of capacity was removed, wherein the pulse one end potential is indicated at 42 and the pulse one minimum potential is indicated at 44.
  • the pulse discharge curve 50 in Fig. 5 was constructed from a cell similar to that used in Fig.
  • the pulse discharge curve 60 in Fig. 6 was constructed from a similar electrochemical system as that used in Fig. 5 except that the electrolyte contained 0.03M DBC additive dissolved therein and after 800 mAh of capacity was removed, wherein the pulse one end potential is indicated at 62 and the pulse one minimum potential is indicated at 64.
  • the pulse discharge curve in Fig. 2 was constructed from a Li/SVO cell activated with an electrolyte of l.OM, LiAsF 6 dissolved in a 50/50 mixture (by volume) of PC/DME without any additive therein and after 1200 mAh of capacity was removed, wherein the pulse one end potential is indicated at 72 and the pulse one minimum potential is indicated at 74.
  • the pulse discharge curve 80 in Fig. 8 was constructed from a similar electrochemical system as that used in Fig. 7 except that the electrolyte contained 0.01M BSC additive dissolved therein and after 1200 mAh of capacity was removed, wherein the pulse one end potential is indicated at 82 and the pulse one minimum potential is indicated at 84.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
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Abstract

L'invention concerne une pile électrochimique non aqueuse à métal alcalin et cathode solide, pouvant produire des impulsions de courant élevé et retrouver rapidement sa tension à vide, et présentant une capacité de courant élevé. On obtient ces avantages en dissolvant des additifs organiques, de préférence à base de carbonate, dans l'électrolyte. Les additifs à base de carbonate ont une liaison O-X et une énergie de dissociation inférieure à 80 kcal/molécule environ sur un côté ou bien sur les deux côtés à la fois d'un groupe carbonyle, dans lequel X est choisi dans le groupe constitué de C, O et N.
PCT/US1996/003118 1995-03-17 1996-03-06 Additifs organiques a base de carbonate pour electrolyte non aqueux dans les piles electrochimiques a metaux alcalins WO1996029750A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54198/96A AU5419896A (en) 1995-03-17 1996-03-06 Organic carbonate additives for nonaqueous electrolyte in alkali metal electrochemical cells

Applications Claiming Priority (2)

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US40569995A 1995-03-17 1995-03-17
US08/405,699 1995-03-17

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WO1996029750A1 true WO1996029750A1 (fr) 1996-09-26

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998026467A1 (fr) * 1996-12-09 1998-06-18 Valence Technology, Inc. Additif de stabilisation de cellule electrochimique
EP0803924A3 (fr) * 1996-04-25 1998-12-09 Wilson Greatbatch Ltd. Carbonates organiques comme additifs dans l'électrolyte nonaqueux de piles électrochimiques contenant un métal alcalin
EP0951085A1 (fr) * 1998-04-16 1999-10-20 Wilson Greatbatch Ltd. Additifs du type dicarbonate pour électrolyte non-aqueux de piles électrochimiques contenant un métal alcalin
US6221534B1 (en) * 1998-11-25 2001-04-24 Wilson Greatbatch Ltd. Alkali metal electrochemical cell having an improved cathode activated with a nonaqueous electrolyte having a carbonate additive
US6605385B2 (en) 2001-03-22 2003-08-12 Wilson Greatbatch Ltd. Electrochemical cell having an electrode with a carbonate additive in the electrode active mixture
US6759170B2 (en) 1998-10-22 2004-07-06 Wilson Greatbatch Technologies, Inc. Organic carbonate additives for nonaqueous electrolyte rechargeable electrochemical cells

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260148A (en) * 1991-05-27 1993-11-09 Fuji Photo Film Co., Ltd. Lithium secondary battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260148A (en) * 1991-05-27 1993-11-09 Fuji Photo Film Co., Ltd. Lithium secondary battery

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0803924A3 (fr) * 1996-04-25 1998-12-09 Wilson Greatbatch Ltd. Carbonates organiques comme additifs dans l'électrolyte nonaqueux de piles électrochimiques contenant un métal alcalin
WO1998026467A1 (fr) * 1996-12-09 1998-06-18 Valence Technology, Inc. Additif de stabilisation de cellule electrochimique
US5846673A (en) * 1996-12-09 1998-12-08 Valence Technology, Inc. Additive to stabilize electrochemical cell
EP0951085A1 (fr) * 1998-04-16 1999-10-20 Wilson Greatbatch Ltd. Additifs du type dicarbonate pour électrolyte non-aqueux de piles électrochimiques contenant un métal alcalin
US6759170B2 (en) 1998-10-22 2004-07-06 Wilson Greatbatch Technologies, Inc. Organic carbonate additives for nonaqueous electrolyte rechargeable electrochemical cells
US6221534B1 (en) * 1998-11-25 2001-04-24 Wilson Greatbatch Ltd. Alkali metal electrochemical cell having an improved cathode activated with a nonaqueous electrolyte having a carbonate additive
US6605385B2 (en) 2001-03-22 2003-08-12 Wilson Greatbatch Ltd. Electrochemical cell having an electrode with a carbonate additive in the electrode active mixture

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