WO2007089980A2 - Electrolyte additive for performance stability of batteries - Google Patents

Electrolyte additive for performance stability of batteries Download PDF

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Publication number
WO2007089980A2
WO2007089980A2 PCT/US2007/060602 US2007060602W WO2007089980A2 WO 2007089980 A2 WO2007089980 A2 WO 2007089980A2 US 2007060602 W US2007060602 W US 2007060602W WO 2007089980 A2 WO2007089980 A2 WO 2007089980A2
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Prior art keywords
additive
electrolyte
organic
group
salicylate
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PCT/US2007/060602
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French (fr)
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WO2007089980A3 (en
Inventor
Kaimin Chen
Craig L. Schmidt
Donald R. Merritt
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Medtronic Inc
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Medtronic Inc
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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
    • 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
    • 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
    • H01M4/382—Lithium
    • 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of 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
    • H01M4/36—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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver

Definitions

  • FIG 1 is a cutaway perspective view of an implantable medical device (IMD);
  • Figure 3 is art enlarged view of a portion of the battery depicted in Figure 2 and designated by line 4.
  • FIGS. 2 and 3 depict details of an exemplary organic electrolyte battery 54.
  • Battery 54 includes a case 70, an anode 72, separators 74, a cathode 76, a liquid electrolyte 78, and a feed-through terminal SO, Cathode 76 is wound in a plurality of turns, with anode 72 interposed between the turns of the cathode winding. Separator 74 insulates anode 72 from cathode 76 windings.
  • Case 70 contains the liquid electrolyte 78 to create an iomcaUy conductive path between anode 72 and cathode 76.
  • Table 2 lists exemplary embodiments in which, the position of each group, represented by F l and F2. are placed m ' different positions relative to the carbon atom of a benzeae compound.
  • a benzene compound includes six carbon atoms that are represented by the symbols Cl, C2, C3, C4, CS, and C6, as shown below:
  • FIG. 5 graphically depicts the superiority of electrolyte 78 over a control electrolyte 88.
  • Electrolyte 78 includes lithium salicylate as the organic additive and the base electrolyte composition previously described.
  • Control electrolyte SS is the base electrolyte composition without any additive.
  • Passivation layer $2 initially possesses similar discharge to passivation layer formed by control electrolyte 88. However, beginning iti the discharge (BOL), the passivation iayer formed by control electrolyte SS exhibits resistance that substantially increases.
  • electrolyte 78 that includes the additive causes battery 54 to exhibit increased performance and resistance that remains substantially below the resistance of control electrolyte S8 late in discharge. For example s electrolyte 7S results in batter)' 54 having 30 ohms lower resistance than control electrolyte 8S, as show in Figure 5.
  • FIGSB illustrate the significant difference between a lithium anode of a control battery cell 100 to a lithium anode from a battery cell 110 containing an additive after one month of storage at 6 ⁇ ⁇ C, Lithium anode 110 with the additive is a lighter shade of gray than the lithium anode 100 of a control battery cell. A lighter shade indicates less oxidation occurred which, in turn y produces a decreased amount of a passivation layer S2 compared to a conventional lithium anode 100.
  • Figure 7 depicts a method for forming an organic additive composition, which is later added to an electrolyte composition, At operation 200, a first organic additive is selected. At operation 2.10, the first organic additive is combined with a second organic additive to create an organic additive composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

An organic additive to an electrolyte for a battery cell in an implantable medical device is presented. At least one organic additive is selected from a group comprising one of lithium salicylate, hydroxyphthalic anhydride, a hydroxybenzoic acid, salicylate ester, salicylamide, and salicylanilide.

Description

ELECTROLYTE ABDITIVE FOR FERPOKMAlSfCE STABtLiTY OF
BATTERIES
RELATED APPLICATION
This application is related to, and claims the benefit of, U.S. Patent Application Ser. No. 10/876,003 filed February 13, 2003 entitled "Liquid Electrolyte For An Electrochemical Cell, Electrochemical Cell And Implantable Medical Device", which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention generally relates to an electrochemical eel) asd, .more particularly, to an additive in an electrolyte for a battery.
BACKGROUND OF THE INVENTION
.Implantable medical devices (3MDs) detect, diagnose, and deliver therapy for a variety of medical conditions in patients. IMDs include implantable pulse generators (IPGs) or implantable cardioverter-defibrillators (ICDs) that deliver electrical stimuli to tissue of a patient. ICDs typically eoit.ipr.be, inter alia, a control module, a capacitor, and a battery that are housed in a hermetically sealed container. When therapy is required by a patient, the corneal module signals the battery lo charge the capacitor, which in turn discharges electrical stimuli to tissue of a patient.
The batten^ includes a case, a liner, and an electrode assembly. The liner surrounds the electrode assembly to prevent the electrode assembly from contacting the inside of the case?, The electrode assembly comprises an anode and a cathode with a separator therebetween. In the case wall, or cover is a fill port or tube that allows introduction of electrolyte into the case. The electrolyte is a medium that facilitates ionic transport and forms a conductive pathway between the anode and cathode. An electrochemical reaction between the electrodes and the electrolyte causes charge to be stored, on each electrode. The electrochemical reaction also creates a solid electrolyte interphase (SEI) or passivation film on a surface of an anode such as a lithium anode. The passivation film is iomcaϊly conductive and prevents parasitic- loss of lithium. However, the passivation film increases internal resistance which reduces the power capability of the battery, ϊt is desirable to .reduce internal resistance associated with the passivation film for a battery.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
Figure 1 is a cutaway perspective view of an implantable medical device (IMD);
Figure 2 is a cutaway perspective view of a battery in the IMD of Figure I;
Figure 3 is art enlarged view of a portion of the battery depicted in Figure 2 and designated by line 4.
Figure 4 is a cross-sectional view of an anode and a passivation film;
Figure 5 is graph that, compares performance between a conventional, battery ceil and exemplary battery cell that includes an additive to an electrolyte;
Figure όA ϊ$ a lithium anode from a control cell after one month of storage at 600C;
Figure 6B is a lithium anode from a cell containing an additive after one month of storage at 600C; and
Figure 7 is a flow diagram for forming an electrolyte in a battery, DETAII-ED DESCRIPTION
The following description of embodiments is merely exemplary in nature and is in no way intended to limit the Invention, its application, or uses. For purposes of clarity t the same reference numbers are used in the drawings to identify similar elements. The present iϊϊvention is directed to an organic additive for an electrolyte in lithium carbon monofiuoride silver vanadium oxide (Li/ CFx-SVO) batteries. The additive stabilizes performance of the battery during storage, thermal processing, and throughout, discharge. In one embodiment, the organic additive is characterized by a hydroxy (-OH) and/or carboxy groups. Exemplary additives include lithiuna salicylate, hydroxyphthaiic anhydride, a hydroxybenzoie acid, salicylate ester, saϊioylamkfe, and salicyiaiύϊide. These- additives enable batteries to exceed certain performance and stability requirements.
Figure 1 depicts an implantable medical device (IMD) 10 such as implantable cardioverter-defibrillators. ϊMϋ 10 includes a case 50, a control module 52, a battery 54 (e.g. organic electrolyte battery) and caρacitor(s) 56. Control module 52 controls one or more sensing and/or stimulation processes from IMD 10 via leads (not shown). Battery 54 includes an insulator 58 disposed therearound. Battery 54 charges capaclior(s) 56 and powers control module 52.
Figures 2 and 3 depict details of an exemplary organic electrolyte battery 54. Battery 54 includes a case 70, an anode 72, separators 74, a cathode 76, a liquid electrolyte 78, and a feed-through terminal SO, Cathode 76 is wound in a plurality of turns, with anode 72 interposed between the turns of the cathode winding. Separator 74 insulates anode 72 from cathode 76 windings. Case 70 contains the liquid electrolyte 78 to create an iomcaUy conductive path between anode 72 and cathode 76. Electrolyte 78, which includes an additive, serves as a medium for migration of ions between anode 72 and cathode 76 during an electrochemical reaction with ihesβ electrodes. Electrolyte 78 includes, for example, LiPFs in propylene carbonate (PC) and dimefhøxyethane (DME),
Anode 72 is formed of a material selected from Group IA, HA. or JIIB of the periodic table of elements (e.g. lithium, sodium, potassium, etc.), alloys thereof or inteimetaJUc compounds (e.g, Li-Si., Ii-B5 Li-Si-B etc.). Anode 72 comprises an. alkali metal (e.g. lithium, etc.) in .metallic or ionic form.
Cathode 76 may comprise metal oxides (e.g. vanadium oxide, silver vanadium oxide (SVOX manganese dioxide (MnOa) , lithium vanadium oxide (Li V3O&)ete.), carbon nxmorluoride and hybrids thereof (e.g., CPx-rMπOa). combination silver vaaadiura oxide (CSVO) or other suitable compounds.
Electrolyte 78 chemically reacts with anode 72 to form an ionically conductive passivation film 82 on anode 72? as shown in Figure 4. Electrolyte 78 includes a base liquid electrolyte compositioa and at least oae peribmaace e&haaeϊng additive selected from Table 1 presented below. Ln another embodiment, electrolyte 78 includes a base liquid electrolyte composition and at least oae perfomaace enhancing additive selected from Table 2. The base electrolyte composition typically comprises LQ molar (M) lithium hexafluαr ©phosphate (1 -20% by weight), propylene carbonate (40-70% by weight), and 1,2-dimethoxyethane (30-50% by weight), A small amount (e,g. 0.05 M) of organic additive is combined with eleirolyte 78.
Table 1 List of exemplary organic additives
Figure imgf000006_0001
Figure imgf000007_0001
Skilled artisans understand that additive compositions may be mixed with the base electrolyte composition to increase performance of battery 54. Additive compositions are formed by selecting at least two additives from Table 1 and/or Table 2. Effective additive compositions are based upon additives that exhibit superior performance stabilizing characteristics of battery 54. Generally, each additive is combined with, electrolyte 7S through dissolution or other suitable means. The additives are based upon a chemical class referred to as aromatic hydroxcarboxylates. There are two base compounds that form the performance enhancing additives. The chemical structure for the first base compound is as follows:
Unregistered PLT
Figure imgf000008_0001
where F l represents a first group such as a hydroxy group (OH).
The chemical structure for the secoαd base compound is as follows;
Figure imgf000008_0002
where F2 represents a second group. The second group comprises ZA. Z is defined as O5 N, B, F, Si. A is defined as M, H, R where M represents metals such as LL Na, K and other suitable metals.
The present invention also includes derivatives of the first or second base compounds. For example, one or more carboxy groups may be added to oøe of the base compounds. Additionally, one or more hydroxy groups may be added to one of the base compounds. Ftsrthermøre, a combination of at least one or more carboxy groups and at least one or more hydroxy groups may be added to one of the base compounds. Still yet another derivative relates to condensation products. Bis~(3-hydroxy benzoic anyhydride) is an exemplary condensation product.
Table 2 lists exemplary embodiments in which, the position of each group, represented by F l and F2. are placed m ' different positions relative to the carbon atom of a benzeae compound. A benzene compound includes six carbon atoms that are represented by the symbols Cl, C2, C3, C4, CS, and C6, as shown below:
Figure imgf000009_0001
Skilled artisans understand that a variety of other combinations exist in. which Fl and F2 are repositioned. Table 2 may be interpreted in at least two ways. First, a skilled artisan selects a compound such as com pound 1. For compound I, Fl is located at Co and F2 is located at Cl. Alternatively, a skilled artisan may select the position of Fi. and F2 to determine the type of compound.
Table 2- -•••-Exemplary performance enhancing additives m which, groups Fl and F2 change their positions along a benzene ring
Figure imgf000009_0002
Figure imgf000010_0001
Figure 5 graphically depicts the superiority of electrolyte 78 over a control electrolyte 88. Electrolyte 78 includes lithium salicylate as the organic additive and the base electrolyte composition previously described. Control electrolyte SS is the base electrolyte composition without any additive. Passivation layer $2 initially possesses similar discharge to passivation layer formed by control electrolyte 88. However, beginning iti the discharge (BOL), the passivation iayer formed by control electrolyte SS exhibits resistance that substantially increases. In contrast, electrolyte 78 that includes the additive causes battery 54 to exhibit increased performance and resistance that remains substantially below the resistance of control electrolyte S8 late in discharge. For examples electrolyte 7S results in batter)' 54 having 30 ohms lower resistance than control electrolyte 8S, as show in Figure 5.
Figures 6 A-SB illustrate the significant difference between a lithium anode of a control battery cell 100 to a lithium anode from a battery cell 110 containing an additive after one month of storage at 6ϋϋC, Lithium anode 110 with the additive is a lighter shade of gray than the lithium anode 100 of a control battery cell. A lighter shade indicates less oxidation occurred which, in turny produces a decreased amount of a passivation layer S2 compared to a conventional lithium anode 100.
Figure 7 depicts a method for forming an organic additive composition, which is later added to an electrolyte composition, At operation 200, a first organic additive is selected. At operation 2.10, the first organic additive is combined with a second organic additive to create an organic additive composition.
The following patent application is incorporated by reference in its entirety. Co-pending U.S. patent application Ser, No, XXKXXXXX, entitled "RESISTANCE-STABΪLΪZIKG ADDITIVES FOR ELECTROLYTE", filed on January 3 L 2006 by Donald Merritt and Craig Schmidt and assigned to the same Assignee of the present invention,, describes resistance-stabilizing additives for electrolyte. Although various embodiments of the invention have been described and illustrated with reference to specific embodiments thereof, it is not intended that the invention be limited to such illustrative embodiments, For example, while an additive composition is described as a combination of two additives, it may also include two or more additives selected from Table .1 , The description of the invention is merely exemplary in nature and, thus, variations that do not depart, from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention.

Claims

~i0~CLAIMS
L An additive for an electrolyte of a battery cell in an implantable medical device (IMD) comprising:
Unregistered PLT
Figure imgf000012_0001
where F 1 represents a first group such as a hydroxy group (OH).
2. An additive for an electrolyte of a battery cell in an implantable medical device (IMD) comprising:
Figure imgf000012_0002
where F2 represents a. second group comprising ZA such that Z being defined as O, N, B, P5 Si and A being defined as M, H, R where M. represents metals selected from the group consisting essentially of Li, Na, and K,
3. An additive for an. electrolyte of a battery ceil in an implantable medical device (1MB) comprising: an organic compound which includes one of a hydroxy (-OH) group and a carbøxy group.
4. The additive of claim 3 wherein the organic compound selected from a group consisting of lithium salicylate, hydrαxyphthaϋc anhydride, a hydroxybe.nzo.ic acid^ salicylate ester, sal ieyl amide, and salicylanilide.
5. An additive composition for an electrolyte in a battery cell for an IMD comprising: a first organic- additive; and a second organic additive combined with the first organic additive.
6. The additive composition of claim 5, the first organic additive being at least one of lithium salicylate, hydroxyphthalic anhydride, a hydroxybenzoic acid, salicylate ester, sslicyiajBs.de, and saiicylaailide.
7. The additive composition of claim. 5, the second second additive being at teast one of lithium salicylate, hydroxyphthalic anhydride, a hydroxybenzoic acid, salicylate ester, s&licyiamide, and salicyiartilide.
8. The additive composition of claim 5, .further cømprising; a third organic additive combined with the first and the second organic additives, the third organic additive being at least one of lithium salicylate, hydrαscypbthalic anhydride, a hydroxybenzoic acid, salicylate ester, saiϊcylamide, and salieylanilide.
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