CA2263662A1 - Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes - Google Patents
Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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- C01G51/54—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]-, e.g. Li(CoxMn2-x)04, Li(MyCoxMn2-x-y)O4
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Abstract
The cycling stability and capacity of li-ion rechargeable batteries are improved by the use of lithium manganese oxy-fluoride electrode component intercalation materials having the general formula Li1+xMyMn2-x-yO4-zFz, where M is a metal, e.g., Co, Cr, or Fe, and x0.4, y0.3 and 0.05z1Ø
Description
W O 98/10476 rCTfUS97115588 LITHIUM MANGANESE OXY-FLUORIDES FOR
LI-ION RECHARGEABLE BATTERY ELECTRODES
BACKGR~UND OF THE INVENTION
The present invention relates to lithium manganese oxide intercalation compounds useful as active electrode materials in Li-ion rechargeable batteries and, particularly, to oxy-fluoride complexes of such compounds and their use to improve the cycling stability and capacity of such batteries.
Litllium ma1.lcJanese oxide intercalatioll compounds, nominally LiMn204, have been increasingly proven to be effective and economical materials for the fabrication of secondary, rechargeable Li-ion electrolytic cells and composite batteries.
Successful batteries of this type are described in U.S. Pat.
Nos. 5,296,31g and 5,~60,904. These batteries exhibit an a~mirable level of electrical storage capacity and recharge cycling stability over a wide range of voltages; however, these properties have not been considered entirely satisfactory to meet the increasingly stringent requirements of modern electronic equipment and applications.
Extensive investigations have been undertaken to improve the noted properties, and such works have resulted in determinations that variations in the structural parameters of the LiMn204 spinel, for example, the a-axis lattice dimension of the compound, contribute significantly to ultimate cell ... . , ~
W O 98/1047~ rCTAUS97/15588 performance. Such structural parameters have in turn been found to depend to a great extent upon the constitution of the intercalation compound and upon the conditions of its synthesis. In this respect, it has been generally agreed, for instance, that an a-axis parameter of less than 8.23 A promotes desirable recharging stability over extended cycles.
Approaches to achieve this advantageous parameter range have included close control of synthesis conditions, such as described by Tarascon in U.S. Pat. No. 5,425,932, to gain the advantage of smaller a-axis dimensions exhibited by higher Mn valence levels; and cationic substitutions, such as noted by Tarascon et al., ~. Electrochem. Soc., Vol. 138, No. 10, pp. 2~3S9-2864, Oc~:ober 1991, or by re~lacement of a portion of tLle Mn atoms Wit].l Co, Cr, or Fe, such as suggested in Europeax Patent 390,185. A number of other investigators have recommended an increased level of lithium insertion to obtain a similar efEect from a replacement of Mn, according to the representative structural formul~, (Li)tet[Mh2-~Li]oct~4~ a~ an effec~ ive mei:lll,5 of improving cycling stability, bu~ this pl-aCt:iCe ha5 been found to result in a sacrifice of cell capacity, as was observed with the earlier Mn replacement approach.
In contrast to these previously implemented expedients, the present invention utilizes anionic substitution to provide a means for achieving concurrent improvements in both cycling stability and cell capacity and enables the fabrication of batteries capable of long-lasting and high-powered operation.
WO 98tlO476 PCT/U~97tlSS88 SU~A~Y QF THF INVENTION
We have discovered that -he inadequacies of prior practices may be remedied by anlonic substi~ution of a portion of the nominal LiMn2O4 oxygen a-oms with flu,orine. Although such substitutions alone were initially observed to result in expansion of the a-axis parameter beyond the preferred range, apparently due to Mn valence reduction, we found, upon further investigation, that a contemporary increase in Li substitution for Mn surprisingly achieved a dramatic shift of a-axis dimension into the optimum range below 8.23 A. Electrolytic battery cel~s comprising these fluoro-substituted electrode materials thexeafter exhibited remarkable cell capacity, as lS well as cyclin~ s~abili~y.
Preparation of these advan~ageous oxy-fluoride spinel derivatives may most simply follow the usual practice, such as noted in Tarascon, U.S. 5,425,932, of anneallng at about 800~C
~oi.chiome~ric mixtures of appropriate precursor compounds, t~f1i.cally 1,i.~CO3, I.iF, ancl MnO2. These derivatives may al50 include precursors for cationic substitutions as earlier-noted in EP 390,185. The resulting intercalation materials that may be ef~ectively employed to achieve an improvement in prior electrolytic cells are therefore represented in the general formula, Li1~X ~ n2 x yO4 zFz, where M is a metal, such as Co, Cr, or Fe, and x S 0.4, y < 0.3, and 0.05 S z < 1Ø
Series of battery cell positive electrode compositions prepared with the oxy-fluoride compounds varying primarily in x and z formula components, i.e., Li and F, were examined by x-ray WO98/10476 PCT~S~7/15S88 diffraction analysis to determine the resulting a-axis lattice parameters and were then incorporated into test cells in the usual-manner, as described in the above-mentioned patents. The cells were subjected to repeated charge/discharge cycling to determine the effect of compola~.d constitution on the level of electrical storage capacity exnibited by the cells, generally as mAhr/g of electrode compound, as well as on the cycling stability, i.e., the ability to maintain the initial level of capacity over extended cycling.
BRIEF DESCRIPT~ N OF THE DRAWING
The present invention will be described wi~h reference to the accompanying drawing of which:
FIG. 1 is the x-ray diffraction pattern of an invention compound, LiltxMyMn2 x yO~ zFz~ .~.here x = O.1, y = O, and z = O.l;
FIG. 2 is a graph of a-axis lattice dimensions v. z of invention compounds, Lil+xMyMn2-x-yoa-zFz~ where x = O.05, y - O, and z S 0.5;
FIG. 3 is a graphic comparison of capacity and cycling stability v. number of charginy cycles for ba~tery cells comprising positive electrode compounds of FIG. 2;
FIG. 4 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising prior ~il+xMn20~ electrode compounds and a compound of the present invention;
WO g8110476 rCT/USg7/15588 FIG. 5 is a graphic comparison of a-axis lattice dimension v. z of invention compounds, Lil+xMyMn2 x yO~_zFz, where x < 0.~, y = O, and z < 0.4;
FIG. 6 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising invention compounds, Lil,xMyMn~.~y04 zFz, where x = O, y = O, and z < 0.4;
FIG. 7 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising invention compounds, Lil+xMyMn~ cyO4 zFz, where x = 0.1, y = O, a~d z < 0.4;
FIG. 8 is a graphic comparison of capacity and cyclin~
stability v. number of charging cycles for cells comprising invention compounds, Lil+xMyMn2 x yO4 zFz, where x = O.2, y = O, and z S 0.4; and F~G. 9 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising invention compounds, Lil+,cMyMn2 x yO4 zFz~ where x - O, y = 0.2, and z S 0.1.
DESCRIPTION OF THE INVENTION
Lil+xMn204 intercalation materials employed in prior practices (according to present formula designation, Lil+X ~ n2_x_yO4_zFz, where y = O and z = O) were prepared for use W098tlO476 PCT~Sg7tl5588 as performance control samples in the manner described in t~e aforementioned U.S. 5,425,932, ~Isins stoichiometric mixtures of the primary precursor compounds, for example, 9.23 parts by weight of Li2CO3 to 43.46 parts of MnO2 to obtain the nominal LiMn204. Test cells of these control samples, as well as samples of the present invention materials to be described later, were likewise prepared and tested in galvanostatic and potentiostatic studies, generally as described in that patent specification. Such test cells comprised lithium foil negative electrodes as a practical expedient, since experience has confirmed that performance results achieved in this manner are objectively comparable to those obtained with Li-ion cell compositions described in the other above-noted patent specifications. .~ clltional tests, as indicated below, were nonetheless conducted with Li-ion compositions comprising the present materials to obtain further confirmation of this correlation in results.
Example 1 In a typical preparation of an intercalation material of the present invention, stoichiometric proportions of the precursors, MnO2 (EMD-type), Li2CO3, and LiF, were thoroughly mixed in an agate mortar and pestle in a weight ratio of 60.94:12.82:1, and the mixture was annealed in air in an alumina crucible in the manner of the control samples to obtain a test composition of Lil+xMyMn2 x yO4 zFz, where x = 0.1, y = O, and z = 0.1 ~Lil lMnl 903 gFo ~)- Specifically, the mixture was heated at a regular rate over a period of about 12 hours to a temperature of 800~C a~ which it was maintained for about 12 hours. The sample was then cooled to room temperature at a W O 98/1047~ rcT~us~7/l5s88 regular rate over a period of about 24 hours. After a mix/grinding, the sample was reheated over a period of 5 hours to 80~~C where it was held for about 12 hours before being finally cooled to room temperature over a period of about 24 hours. The resulting oxy-fluoride compound was characterized by CuKa x-ray diffraction (XRD) examination to obtain the graphic pattern shown in FIG. 1. The clearly-defined peaks of the pattern confirmed the well-cr~stallized, single-phase product of the synthesis.
Example 2 A series of oxy-fluoride compounds of the present :invellt:i.orl was similarly prepared with appropriate combinations of precursor compounds to yield Li1~xMyMn2 x yO4 zFz, where x = 0.05, y = 0, and z = 0, 0.05, 0.10, 0.15, 0.20, 0.35, and 0.50. The resulting samples were characterized by XRD and the respective a-axis lattice parameters were calculated. A plot of these parameter dimensions as shown in FIG. 2 indicates the reg3ular i.ncrease which trac]cs and is indicative of the increase in fluorine substitution.
Portions of the same samples were individually incorporated with about 10~ conductive carbon and 5~
polyvinylidene fluoride binder and formed as a layer on an aluminum foil substrate to provide positive test cell electrodes. Arranged in the usual manner with a lithium foil electrode and intervening glass fiber separator saturated with a 1 M electrolyte solution of LiPF6 in a 2:1 mixture of ethylene carbonate:dimethylcarbonate, the sample electrodes formed test cells which were subjected to charge/discharge cycling over the WO98/1047G P~ bs~/15588 range o~ 3.4 - 4.5 V at a C/5 rate (full cycle over 5 hours).
The capacity of each cell was traced during a period of up to 35 cycles to provide an indic~tion, as seen in FIG. 3, of the rate of change of that property, i.e., the c~cling stability of the cell, with extended recharging. Traces,31-36 reflect the above-stated increasing levels of fluorine substitution, z, from 0.05 to 0.5. A comparison of the results depicted in FIG.s 2 and 3 graphically confirms the general tendency toward loss of both capacity and cycling stability with an increase in a-axis dimension above the preferred limit of about 8.23 A.
Exam~le 3 ~ series o~ unsubstituted intercalation compounds of ~he prior art varying only in Li, i.e., Lil~xM~Mn2 x_yO4_zFz, where x = 0.05, 0.075, and 0.1, y - 0, and z = 0, was prepared and tested in similar manner to provide an indication of the effect of that variable on the capaclty and cycling stability of resulting cells. ~s may be seen in FIG. 4 as traces 41-43 of increasing Li con~ent, ~hat variance alone improves cycling stability, but significantly reduces cell capacity. The performance of an additional cell prepared with the oxy-fluoride (x = 0.1, z = 0.1) compound of Example 1 is also represented in FIG. 4, at trace 44, and reflects the surprising e~fect achieved by the present invention. In particular, a comparison of traces 43 and 44 having like Li content reveals the outstanding improvement in both capacity and cycling stability resulting from this combination with fluorine substitution.
W098/104~6 PCT~S97115588 Example 4 Series of oxy-fluoride compounds were prepared varying in both Li and F, i.e., Ll ~M~Mn c.~0~ 7Fz, where x = O, O.l, and 0.2, y = O, and z = O, 0.05, ~.l, 0.2, and G.4. The variations of a-axis lattice parameter for each series are shown in FIG. 5 as traces 52-56 of increasing Li and indicate the remarkable effect of the combination of Li and F content on achieving an optimum range of this parameter.
Exam~le 5 The series of compounds of Example 4 comprising x = O was used to pr.epar~.? batteL-y cells which were tested in the manner described above. The results shown in FIG. 6 as traces 61-65 of increasing fluorine content indicate the effect on capacity and cycling stability of a compound favoring F in the Li:F ratio.
ExamPle 6 ~,0 The series of compounds of Example 4 comprising x = O.l was used to prepare battery cells which were tested in the manner described above. The results shown in FIG. 7 as traces 71-75 of increasing fluorine content indicate the improvement on capacity and cycling stability of a closer balance of F in the Li:F ratio.
Example 7 The series of compounds of Example 4 comprising x = 0.2 was used to prepare battery cells which were tested in the manner described above. The results shown in FIG. 8 as traces WO98/10476 PCT~S~7115588 81-85 of increasing fluorine content indicate the further effect, particularly on cycling stability of a still closer balance of F in the Li:F ratio.
Exam~le 9 A series of compounds of the present invention with both cationic (Cr) and anionic substitutions, Lil+x~Mn2_x_yO4_z~z, where x = 0, y = 0.2, and z = 0, 0.05, and O.l, was prepared in the above manner by combining appropriate stoichiometric amounts of precursors, for example, lO.3:2.31:l.0:0.086 weight ratio of MnO2, Li2Co3, Cr2O3, and LiF (LiCrO 2Mnl 8~3 gFo 05). The resulting materials were used to prepare test cells whose performance improvemellt was comparable to the foregoing results, as shown at FIG. 9 in traces 92-96 of increasing fluorine content. Similar results may be obtained with cationic Co and Fe substitutions.
Exam~le lO
A series of Li-ion battery cells was prepared with the positive electrode materials of Example 6, and employing petroleum coke negative electrodes and polyvinylidene copolymer matrix electrolyte/separator elements, as described in above-noted ~.S. 5,460,904. Tests of repeated charge cycling showed cell capacities and cycling stability comparable to those of Example 6.
It is expected that other embodiments of the present invention will become apparent to the skilled artisan in light of the foregoing description, and such variations are intended to be included within the scope of this invention as recited in the appended claims.
.... . . . . . . ...
LI-ION RECHARGEABLE BATTERY ELECTRODES
BACKGR~UND OF THE INVENTION
The present invention relates to lithium manganese oxide intercalation compounds useful as active electrode materials in Li-ion rechargeable batteries and, particularly, to oxy-fluoride complexes of such compounds and their use to improve the cycling stability and capacity of such batteries.
Litllium ma1.lcJanese oxide intercalatioll compounds, nominally LiMn204, have been increasingly proven to be effective and economical materials for the fabrication of secondary, rechargeable Li-ion electrolytic cells and composite batteries.
Successful batteries of this type are described in U.S. Pat.
Nos. 5,296,31g and 5,~60,904. These batteries exhibit an a~mirable level of electrical storage capacity and recharge cycling stability over a wide range of voltages; however, these properties have not been considered entirely satisfactory to meet the increasingly stringent requirements of modern electronic equipment and applications.
Extensive investigations have been undertaken to improve the noted properties, and such works have resulted in determinations that variations in the structural parameters of the LiMn204 spinel, for example, the a-axis lattice dimension of the compound, contribute significantly to ultimate cell ... . , ~
W O 98/1047~ rCTAUS97/15588 performance. Such structural parameters have in turn been found to depend to a great extent upon the constitution of the intercalation compound and upon the conditions of its synthesis. In this respect, it has been generally agreed, for instance, that an a-axis parameter of less than 8.23 A promotes desirable recharging stability over extended cycles.
Approaches to achieve this advantageous parameter range have included close control of synthesis conditions, such as described by Tarascon in U.S. Pat. No. 5,425,932, to gain the advantage of smaller a-axis dimensions exhibited by higher Mn valence levels; and cationic substitutions, such as noted by Tarascon et al., ~. Electrochem. Soc., Vol. 138, No. 10, pp. 2~3S9-2864, Oc~:ober 1991, or by re~lacement of a portion of tLle Mn atoms Wit].l Co, Cr, or Fe, such as suggested in Europeax Patent 390,185. A number of other investigators have recommended an increased level of lithium insertion to obtain a similar efEect from a replacement of Mn, according to the representative structural formul~, (Li)tet[Mh2-~Li]oct~4~ a~ an effec~ ive mei:lll,5 of improving cycling stability, bu~ this pl-aCt:iCe ha5 been found to result in a sacrifice of cell capacity, as was observed with the earlier Mn replacement approach.
In contrast to these previously implemented expedients, the present invention utilizes anionic substitution to provide a means for achieving concurrent improvements in both cycling stability and cell capacity and enables the fabrication of batteries capable of long-lasting and high-powered operation.
WO 98tlO476 PCT/U~97tlSS88 SU~A~Y QF THF INVENTION
We have discovered that -he inadequacies of prior practices may be remedied by anlonic substi~ution of a portion of the nominal LiMn2O4 oxygen a-oms with flu,orine. Although such substitutions alone were initially observed to result in expansion of the a-axis parameter beyond the preferred range, apparently due to Mn valence reduction, we found, upon further investigation, that a contemporary increase in Li substitution for Mn surprisingly achieved a dramatic shift of a-axis dimension into the optimum range below 8.23 A. Electrolytic battery cel~s comprising these fluoro-substituted electrode materials thexeafter exhibited remarkable cell capacity, as lS well as cyclin~ s~abili~y.
Preparation of these advan~ageous oxy-fluoride spinel derivatives may most simply follow the usual practice, such as noted in Tarascon, U.S. 5,425,932, of anneallng at about 800~C
~oi.chiome~ric mixtures of appropriate precursor compounds, t~f1i.cally 1,i.~CO3, I.iF, ancl MnO2. These derivatives may al50 include precursors for cationic substitutions as earlier-noted in EP 390,185. The resulting intercalation materials that may be ef~ectively employed to achieve an improvement in prior electrolytic cells are therefore represented in the general formula, Li1~X ~ n2 x yO4 zFz, where M is a metal, such as Co, Cr, or Fe, and x S 0.4, y < 0.3, and 0.05 S z < 1Ø
Series of battery cell positive electrode compositions prepared with the oxy-fluoride compounds varying primarily in x and z formula components, i.e., Li and F, were examined by x-ray WO98/10476 PCT~S~7/15S88 diffraction analysis to determine the resulting a-axis lattice parameters and were then incorporated into test cells in the usual-manner, as described in the above-mentioned patents. The cells were subjected to repeated charge/discharge cycling to determine the effect of compola~.d constitution on the level of electrical storage capacity exnibited by the cells, generally as mAhr/g of electrode compound, as well as on the cycling stability, i.e., the ability to maintain the initial level of capacity over extended cycling.
BRIEF DESCRIPT~ N OF THE DRAWING
The present invention will be described wi~h reference to the accompanying drawing of which:
FIG. 1 is the x-ray diffraction pattern of an invention compound, LiltxMyMn2 x yO~ zFz~ .~.here x = O.1, y = O, and z = O.l;
FIG. 2 is a graph of a-axis lattice dimensions v. z of invention compounds, Lil+xMyMn2-x-yoa-zFz~ where x = O.05, y - O, and z S 0.5;
FIG. 3 is a graphic comparison of capacity and cycling stability v. number of charginy cycles for ba~tery cells comprising positive electrode compounds of FIG. 2;
FIG. 4 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising prior ~il+xMn20~ electrode compounds and a compound of the present invention;
WO g8110476 rCT/USg7/15588 FIG. 5 is a graphic comparison of a-axis lattice dimension v. z of invention compounds, Lil+xMyMn2 x yO~_zFz, where x < 0.~, y = O, and z < 0.4;
FIG. 6 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising invention compounds, Lil,xMyMn~.~y04 zFz, where x = O, y = O, and z < 0.4;
FIG. 7 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising invention compounds, Lil+xMyMn~ cyO4 zFz, where x = 0.1, y = O, a~d z < 0.4;
FIG. 8 is a graphic comparison of capacity and cyclin~
stability v. number of charging cycles for cells comprising invention compounds, Lil+xMyMn2 x yO4 zFz, where x = O.2, y = O, and z S 0.4; and F~G. 9 is a graphic comparison of capacity and cycling stability v. number of charging cycles for cells comprising invention compounds, Lil+,cMyMn2 x yO4 zFz~ where x - O, y = 0.2, and z S 0.1.
DESCRIPTION OF THE INVENTION
Lil+xMn204 intercalation materials employed in prior practices (according to present formula designation, Lil+X ~ n2_x_yO4_zFz, where y = O and z = O) were prepared for use W098tlO476 PCT~Sg7tl5588 as performance control samples in the manner described in t~e aforementioned U.S. 5,425,932, ~Isins stoichiometric mixtures of the primary precursor compounds, for example, 9.23 parts by weight of Li2CO3 to 43.46 parts of MnO2 to obtain the nominal LiMn204. Test cells of these control samples, as well as samples of the present invention materials to be described later, were likewise prepared and tested in galvanostatic and potentiostatic studies, generally as described in that patent specification. Such test cells comprised lithium foil negative electrodes as a practical expedient, since experience has confirmed that performance results achieved in this manner are objectively comparable to those obtained with Li-ion cell compositions described in the other above-noted patent specifications. .~ clltional tests, as indicated below, were nonetheless conducted with Li-ion compositions comprising the present materials to obtain further confirmation of this correlation in results.
Example 1 In a typical preparation of an intercalation material of the present invention, stoichiometric proportions of the precursors, MnO2 (EMD-type), Li2CO3, and LiF, were thoroughly mixed in an agate mortar and pestle in a weight ratio of 60.94:12.82:1, and the mixture was annealed in air in an alumina crucible in the manner of the control samples to obtain a test composition of Lil+xMyMn2 x yO4 zFz, where x = 0.1, y = O, and z = 0.1 ~Lil lMnl 903 gFo ~)- Specifically, the mixture was heated at a regular rate over a period of about 12 hours to a temperature of 800~C a~ which it was maintained for about 12 hours. The sample was then cooled to room temperature at a W O 98/1047~ rcT~us~7/l5s88 regular rate over a period of about 24 hours. After a mix/grinding, the sample was reheated over a period of 5 hours to 80~~C where it was held for about 12 hours before being finally cooled to room temperature over a period of about 24 hours. The resulting oxy-fluoride compound was characterized by CuKa x-ray diffraction (XRD) examination to obtain the graphic pattern shown in FIG. 1. The clearly-defined peaks of the pattern confirmed the well-cr~stallized, single-phase product of the synthesis.
Example 2 A series of oxy-fluoride compounds of the present :invellt:i.orl was similarly prepared with appropriate combinations of precursor compounds to yield Li1~xMyMn2 x yO4 zFz, where x = 0.05, y = 0, and z = 0, 0.05, 0.10, 0.15, 0.20, 0.35, and 0.50. The resulting samples were characterized by XRD and the respective a-axis lattice parameters were calculated. A plot of these parameter dimensions as shown in FIG. 2 indicates the reg3ular i.ncrease which trac]cs and is indicative of the increase in fluorine substitution.
Portions of the same samples were individually incorporated with about 10~ conductive carbon and 5~
polyvinylidene fluoride binder and formed as a layer on an aluminum foil substrate to provide positive test cell electrodes. Arranged in the usual manner with a lithium foil electrode and intervening glass fiber separator saturated with a 1 M electrolyte solution of LiPF6 in a 2:1 mixture of ethylene carbonate:dimethylcarbonate, the sample electrodes formed test cells which were subjected to charge/discharge cycling over the WO98/1047G P~ bs~/15588 range o~ 3.4 - 4.5 V at a C/5 rate (full cycle over 5 hours).
The capacity of each cell was traced during a period of up to 35 cycles to provide an indic~tion, as seen in FIG. 3, of the rate of change of that property, i.e., the c~cling stability of the cell, with extended recharging. Traces,31-36 reflect the above-stated increasing levels of fluorine substitution, z, from 0.05 to 0.5. A comparison of the results depicted in FIG.s 2 and 3 graphically confirms the general tendency toward loss of both capacity and cycling stability with an increase in a-axis dimension above the preferred limit of about 8.23 A.
Exam~le 3 ~ series o~ unsubstituted intercalation compounds of ~he prior art varying only in Li, i.e., Lil~xM~Mn2 x_yO4_zFz, where x = 0.05, 0.075, and 0.1, y - 0, and z = 0, was prepared and tested in similar manner to provide an indication of the effect of that variable on the capaclty and cycling stability of resulting cells. ~s may be seen in FIG. 4 as traces 41-43 of increasing Li con~ent, ~hat variance alone improves cycling stability, but significantly reduces cell capacity. The performance of an additional cell prepared with the oxy-fluoride (x = 0.1, z = 0.1) compound of Example 1 is also represented in FIG. 4, at trace 44, and reflects the surprising e~fect achieved by the present invention. In particular, a comparison of traces 43 and 44 having like Li content reveals the outstanding improvement in both capacity and cycling stability resulting from this combination with fluorine substitution.
W098/104~6 PCT~S97115588 Example 4 Series of oxy-fluoride compounds were prepared varying in both Li and F, i.e., Ll ~M~Mn c.~0~ 7Fz, where x = O, O.l, and 0.2, y = O, and z = O, 0.05, ~.l, 0.2, and G.4. The variations of a-axis lattice parameter for each series are shown in FIG. 5 as traces 52-56 of increasing Li and indicate the remarkable effect of the combination of Li and F content on achieving an optimum range of this parameter.
Exam~le 5 The series of compounds of Example 4 comprising x = O was used to pr.epar~.? batteL-y cells which were tested in the manner described above. The results shown in FIG. 6 as traces 61-65 of increasing fluorine content indicate the effect on capacity and cycling stability of a compound favoring F in the Li:F ratio.
ExamPle 6 ~,0 The series of compounds of Example 4 comprising x = O.l was used to prepare battery cells which were tested in the manner described above. The results shown in FIG. 7 as traces 71-75 of increasing fluorine content indicate the improvement on capacity and cycling stability of a closer balance of F in the Li:F ratio.
Example 7 The series of compounds of Example 4 comprising x = 0.2 was used to prepare battery cells which were tested in the manner described above. The results shown in FIG. 8 as traces WO98/10476 PCT~S~7115588 81-85 of increasing fluorine content indicate the further effect, particularly on cycling stability of a still closer balance of F in the Li:F ratio.
Exam~le 9 A series of compounds of the present invention with both cationic (Cr) and anionic substitutions, Lil+x~Mn2_x_yO4_z~z, where x = 0, y = 0.2, and z = 0, 0.05, and O.l, was prepared in the above manner by combining appropriate stoichiometric amounts of precursors, for example, lO.3:2.31:l.0:0.086 weight ratio of MnO2, Li2Co3, Cr2O3, and LiF (LiCrO 2Mnl 8~3 gFo 05). The resulting materials were used to prepare test cells whose performance improvemellt was comparable to the foregoing results, as shown at FIG. 9 in traces 92-96 of increasing fluorine content. Similar results may be obtained with cationic Co and Fe substitutions.
Exam~le lO
A series of Li-ion battery cells was prepared with the positive electrode materials of Example 6, and employing petroleum coke negative electrodes and polyvinylidene copolymer matrix electrolyte/separator elements, as described in above-noted ~.S. 5,460,904. Tests of repeated charge cycling showed cell capacities and cycling stability comparable to those of Example 6.
It is expected that other embodiments of the present invention will become apparent to the skilled artisan in light of the foregoing description, and such variations are intended to be included within the scope of this invention as recited in the appended claims.
.... . . . . . . ...
Claims (12)
1. A lithium manganese oxy-fluoride compound having the general formula, Li1+x M y Mn2-x-y O4-z F z, where M is a metal and x ~ 0.4, y ~ 0.3, and 0.05 ~ z ~ 1Ø
2. A compound according to claim 1 where M is Co, Cr, or Fe.
3. A compound according to claim 2 where x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.4.
4. A compound according to claim 2 where 0 0.1 ~ x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.4.
5. A compound according to claim 2 where 0.1 ~ x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.2.
6. A compound according to claim 2 where 0.05 ~ x ~ 0.2, y ~ 0.3, and 0.05 ~ z ~ 0.2.
7. A rechargeable battery cell comprising a positive electrode, a negative electrode, and a separator disposed therebetween characterized in that said positive electrode comprises an intercalation compound having the general formula, Li1+x M y Mn2-x-y O4-z F z, where M is a metal and x ~ 0.4, y ~ 0.3, and 0.05 ~ z ~ 1Ø
8. A rechargeable battery cell according to claim 7 where M is Co, Cr, or Fe.
9. A rechargeable battery cell according to claim 8 where x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.4.
10. A rechargeable battery cell according to claim 8 where 0.1 ~
x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.4.
x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.4.
11. A rechargeable battery cell according to claim 8 where 0.1 ~ x ~ 0.2, y = 0, and 0.05 ~ z ~ 0.2.
12. A rechargeable battery cell according to claim 8 where 0.05 ~ x ~ 0.2, y ~ 0.3, and 0.05 ~ z ~ 0.2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/706,546 US5674645A (en) | 1996-09-06 | 1996-09-06 | Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes |
| US08/706,546 | 1996-09-06 | ||
| PCT/US1997/015588 WO1998010476A1 (en) | 1996-09-06 | 1997-09-04 | Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2263662A1 true CA2263662A1 (en) | 1998-03-12 |
Family
ID=56289789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002263662A Abandoned CA2263662A1 (en) | 1996-09-06 | 1997-09-04 | Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0947012A4 (en) |
| JP (1) | JP2000514773A (en) |
| AU (1) | AU711516B2 (en) |
| CA (1) | CA2263662A1 (en) |
| WO (1) | WO1998010476A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100296877B1 (en) * | 1999-05-27 | 2001-07-12 | 김순택 | Positive active material for lithium secondary battery and lithium secondary by using the same |
| EP1119062A3 (en) * | 2000-01-21 | 2003-07-09 | New Billion Investments Limited | Rechargeable solid state chromium-fluorine-lithium electric battery |
| JP2001319653A (en) * | 2000-05-12 | 2001-11-16 | Hitachi Maxell Ltd | Non-aqueous secondary battery |
| JP2002151080A (en) * | 2000-11-15 | 2002-05-24 | Sony Corp | Positive pole active material, non-aqueous electrolyte battery, and those manufacturing method |
| US7556655B2 (en) | 2003-03-14 | 2009-07-07 | 3M Innovative Properties Company | Method of producing lithium ion cathode materials |
| JP5017010B2 (en) * | 2007-08-08 | 2012-09-05 | 株式会社日立製作所 | Lithium secondary battery |
| JP7065341B2 (en) * | 2017-01-19 | 2022-05-12 | パナソニックＩｐマネジメント株式会社 | Positive electrode active material and battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2098953A5 (en) * | 1970-07-31 | 1972-03-10 | Anvar | |
| JPH06243871A (en) * | 1993-02-16 | 1994-09-02 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
| US5460904A (en) * | 1993-08-23 | 1995-10-24 | Bell Communications Research, Inc. | Electrolyte activatable lithium-ion rechargeable battery cell |
| US5296318A (en) * | 1993-03-05 | 1994-03-22 | Bell Communications Research, Inc. | Rechargeable lithium intercalation battery with hybrid polymeric electrolyte |
| US5425932A (en) * | 1993-05-19 | 1995-06-20 | Bell Communications Research, Inc. | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
| US5370949A (en) * | 1993-07-09 | 1994-12-06 | National Research Council Of Canada | Materials for use as cathodes in lithium electrochemical cells |
| JPH07240200A (en) * | 1994-02-28 | 1995-09-12 | Fuji Photo Film Co Ltd | Nonaqueous secondary battery |
-
1997
- 1997-09-04 JP JP10512903A patent/JP2000514773A/en active Pending
- 1997-09-04 CA CA002263662A patent/CA2263662A1/en not_active Abandoned
- 1997-09-04 WO PCT/US1997/015588 patent/WO1998010476A1/en not_active Application Discontinuation
- 1997-09-04 AU AU47996/97A patent/AU711516B2/en not_active Ceased
- 1997-09-04 EP EP97910695A patent/EP0947012A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0947012A4 (en) | 2000-02-09 |
| WO1998010476A1 (en) | 1998-03-12 |
| AU711516B2 (en) | 1999-10-14 |
| JP2000514773A (en) | 2000-11-07 |
| EP0947012A1 (en) | 1999-10-06 |
| AU4799697A (en) | 1998-03-06 |
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