Chemistry: electrical current producing apparatus – product – and – Current producing cell – elements – subcombinations and... – Include electrolyte chemically specified and method
Reexamination Certificate
2000-12-18
2002-11-19
Ryan, Patrick (Department: 1745)
Chemistry: electrical current producing apparatus, product, and
Current producing cell, elements, subcombinations and...
Include electrolyte chemically specified and method
C429S231950, C429S231100, C429S188000, C429S320000, C429S321000, C429S322000
Reexamination Certificate
active
06482548
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to a high voltage, high capacity rechargeable electrochemical battery cell which comprises a positive electrode, a negative electrode, and an interposed separator with an electrolyte comprising, during operation of the cell, a pair of different mobile cation species which individually participate in redox activity at the respective electrodes. More particularly, the invention relates to the preparation and use of a rechargeable battery cell comprising an electrode material which participates predominantly, during cycling of the cell, in a redox reaction with the first of a pair of cation species, of which one is polyvalent, present in the cell electrolyte while the second of the cation species reacts predominantly at the opposite electrode of the cell. These contemporary redox reactions enable multiple electron per ion transfer during cell operation with a resulting significant increase in cell capacity without loss of high voltage output.
The present market for compact, light-weight rechargeable batteries is served in great measure by lithium intercalation batteries, particularly Li-ion cells, which, by virtue of the light weight of the lithium electrode and electrolyte component materials, provide a significant level of specific capacity, i.e., the amount of energy per unit of cell weight that can be stored and transferred from a cell. The high reactivity of lithium yields an additional benefit in providing an exceptionally low electrical potential in an incorporating negative cell electrode, which may comprise lithium metal or alloy, or a lithium-intercalating material. As a further advantage, a wide variety of metal oxide, sulfide, or fluoride materials are available which react with lithium at high electrical potential, thereby enabling their use as positive electrode components in resulting high-voltage battery cells.
The advantageous composite effect of the light weight and high voltage operation of Li-ion cells on the resultant specific energy density of these rechargeable batteries is marred, however, by the limitation that the mobile lithium cation upon which cell operation depends is monovalent and therefore capable of accounting for the operative transfer of only a single electron per available Li
+
ion.
Considering the dependence of cell capacity upon the valence of the charge transfer ion, an alternative means of increasing the capacity of an electrochemical cell would logically appear to involve the use of polyvalent reactive components. Such an approach has been considered, as in U.S. Pat. No. 5,601,949; however, the substitution of polyvalent cations for the monovalent lithium in an attempt to achieve higher capacity intercalation battery cells has met with little actual success. The failure of such cells appears to be attributable to a number of causes, not the least of which is the significantly greater size of the polyvalent ion which prevents effective intercalation into negative electrode compositions, such as the graphite or other carbonaceous materials proposed in that patent specification.
An additional deterrent to the effective operation of a polyvalent ion cell is the passivation layer of reaction materials, referred to as a solid/electrolyte interface (SEI), typically of reduction byproducts, e.g., electrolyte cation oxides, fluorides, carbonates, and the like, which form at the surface of the negative cell electrode during the first cycle charging period. While Li
+
ions of a common Li-ion intercalation cell are able to diffuse through the SEI layer in order to contact and be reduced at the negative electrode, polyvalent cations cannot diffuse in this manner and are significantly deterred from participating in the essential redox reaction at the negative electrode. Although some reduction of the polyvalent cation may transpire, the reaction occurs at the invariably higher potential of the passivation layer reaction products, thus decreasing the potential difference between the electrodes with a resulting decrease in the operating cell voltage.
The practical utilization of polyvalent electrochemical cell components in order to increase cell capacity has been found to require the implementation of a mechanism other than the simple transmission of a species of mobile polyvalent cation between cell electrodes. Co-pending U.S. patent application 09/577,643, filed May 24, 2000, the disclosure of which is incorporated herein by reference, describes such a novel and effective mechanism which enables the capacity improving use of such polyvalent cell components. In addition to a negative electrode member comprising a material source of highly reactive, negative-acting cation species, typically of an alkali metal, e.g., Li
+
, the described cell comprises a non-aqueous solution of a solute providing polyvalent yttrium, lanthanum, or alkaline earth metal cation species, along with a positive electrode member comprising a transition metal compound capable of reversibly taking up and releasing such polyvalent ions in reactions complementary to the reversible release and intercalation of the alkali metal ions between the negative electrode and the electrolyte.
In the course of further investigations into such dual cation electrolytic cells, it was discovered in the present invention that a remarkable and extraordinary improvement in the performance and practical economy of such cells can be effected through the use of electrolyte compounds of polyvalent aluminum cation species entirely unrelated to the alkaline earth metal compounds contemplated in the earlier work.
SUMMARY OF THE INVENTION
A rechargeable electrochemical cell prepared according to the present invention comprises a positive electrode member, a negative electrode member, and an interposed separator member which is ion-transmissive and electron-insulative. Also interposed and contained between the electrode members is an electrolyte comprising a non-aqueous solution of a solute providing polyvalent aluminum cations, viz., Al
3+
. Electrolyte solute compounds suitable for this purpose have been found to be those which, unlike aluminum halide and hydride salts commonly utilized in aluminum electrolysis operations, do not readily support the electrolytic plating of aluminum. Particularly useful are such solutes as aluminum triflate, perchlorate, tetrafluoroborate, and hexafluorophosphate salts
The positive electrode member comprises an active material, such as a transition metal oxide, sulfide, fluoride, or carbon fluoride, which can take up and release the polyvalent aluminum cations in a reversible reduction reaction of intercalation, alloying, adsorption, or the like during operation of the cell. The negative electrode member comprises an active material which provides a source of a second, highly reactive, negative-acting cation species, preferably of an alkali metal, such as Li
+
, Na
+
, K
+
, Rb
+
, or Cs
+
, capable of being reversibly released into and taken up from the electrolyte solvent during operation of the cell. Such a negative electrode active material may be the alkali metal, an alloy of the alkali metal, or a carbonaceous material, e.g., coke, hard carbon, or graphite, capable of intercalating the alkali metal cation.
One embodiment of a cell of the present invention comprises a positive electrode member of V
2
O
5
, a negative electrode member of Li
x
Si, and an electrolyte of 0.5 M Al(ClO
4
)
3
in a 2:1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) saturating a borosilicate glass fiber separator membrane. During the initial discharge of the cell, Al
3+
ions from the electrolyte move to the reversible reaction at the positive electrode while Li
+
ions from the negative electrode are released into the EC:DMC solvent of the electrolyte. Due primarily to the physical proximity to the positive electrode of the relatively high concentration of Al
+
ions and the higher overall potential of intercalation, these reactions predominate at their respe
Hey David A.
Martin Angela J
Ryan Patrick
Telcordia Technologies Inc.
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