CA2221738C - An improved process for making a lithiated lithium manganese oxide spinel - Google Patents
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- C01G45/12—Complex oxides containing manganese and at least one other metal element
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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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- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
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- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/125—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3
- C01G45/1257—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3 containing lithium, e.g. Li2MnO3 or Li2(MxMn1-x)O3
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Abstract
Disclosed is a process for making a lithiated lithium manganese oxide spinet of the formula: Li(1+x)Mn2O4 comprising contacting a lithium manganese oxide spinet of the formula: LiMn2O4 with a lithium carboxylate compound, at a temperature and for a time sufficient to decompose the carboxylate compound and free the lithium to form said lithiated spinel.
Description
WO 96/40590 PCT~US~6/09~61 AN IMPROVED PROCESS FOR MAKING A
~ITHIATED LITHIUM MANGANESE OXIDE SPINEL
The present invention relates to an improved process for making a lithiated spinel compound. In particular, the invention relates to a process for lithiating a lithium manganese oxide spinel to form a spinel featuring excess lithium, which is useful as an electrochemically active component in a secondary electrochemical cell.
Lithium secondary, electrochemical cells, or rechargeable cells, typically include a Li-bearing intercalation compound as the positive electrode and a carbon, typically graphite, negative electrode, separated by a non-aqueous lithium-ion electrolyte. A lithium manganese oxide spinel of the general form~la LiMnlo~ Co~monl y has been employed as the electrochemically active cathode component. Studies of lithium intercalation into graphite have shown, however, that when the lithium manganese oxide spinel is used in a lithium-ion rechargeable cell in which the anode or negative electrode is graphi.te, there is a marked, detrimental irreversible loss in capaci.ty during the first recharging cycle. The initial appr~ach to overcome this problem was simply to use a larger mass of positive electrode [(l+x)LiMn20~] to compensa~e for the loss of lithium on the graphite anode during the first cycle.
However, increasing the mass of the cathode is not an effective remedy when taking performance efficiency into consideration.
In order to offset the lithium loss without, undesirably, seriously impacting massic or volumetric performance characteristics of the cell, lithiated lithium manganese oxide spinel. structures have been developed which feature excess lithium (Li(l,x~Mn20~). This excess lithium in the spinel compound CA 02221738 1997-ll-20 WO 96/40590 PCT~US96/09461 i8 available to compensate for the initial loss of lithium associated with the negative electrode, while reserving an amount of lithium needed to balance the reversible capacity of the graphite and maintain a useful energy level in the cell.
While such lithiated lithium manganese oxide spinel compounds have proven to be a useful and effective cathode material in secondary or rechargeable electrochemical cells, presently known methods for producing the Li(l~x)Mn20~ spinel are expensive and difficult to scale up from laboratory size to commercial volume. One such method of production, for example, includes subjecting LiMn20~ to a reducing reaction with a heated solution of lithium iodide (LiI) in acetonitrile; another involves a reduction of the lithium manganese oxide spinel with a solution of n-butyl lithiate ~n-BuLi) in h~An~. Both of these lithium-contA;n;ng reactants are prohibitively expensive, the production processes involve organic solvents, and, in addition, the n-BuLi features hazardous, pyrophoric properties.
Accordingly, there is a need for a viable method for commercial production of the lithiated lithium manganese oxide spinel.
It now has been discovered that a lithiated lithium manganese oxide spinel of the formula Lit1,x~Mn20~ can economically be made by a simple method which comprises contacting a lithium manganese oxide spinel of the formula LiMn20~ with a lithium carboxylate compound, at a temperature and for a time sufficient to decompose the carboxylate compound and free the lithium to form said lithiated, Li~1~x,Mn20~ spinel. This lithiated spinel compound has been found to be particularly useful as the positive electrode of a lithium-ion secondary electrochemical cell.
WO 9~/40590 PCTAJS96/09461 The present process produces a lithiated lithium manganese oxide spinel of the formula Li(l,x~Mn20~, wherein O<x<1;
preferably, the value of x ranges from about .05 to about 1.0;
most preferably, x ranges ~rom about .05 to about .3.
The process is carried at a reaction temperature sufficient to decompose the lithium carboxylate reactant and form the lithiated spinel compound, but, below about 350~C, to avoid decol~position of the spinel compound. Above about 300~C the spinel compound begins to decompose into non-spinel decomposition products such as ~ x~MnO3 and MnO2, which are not useful as cathode components in a lithium secondary electrochemical cell. The reaction temperature generally ranges from about 150~C to about 300~C; preferably, the reaction temperature ranges from about 230~C to about 250~C.
Reaction time is dependent upon choice of reactants and reaction temperature. In general, reaction time ranges from about 10 minutes to about 15 hours; preferably about 2 to about 8 hour reaction times are employed, since such times have been found to provide favorable results.
Preferably, the synthesis is conducted in an inert atmosphere to avoid oxidation reactions resulting in the formation of by products undesirable for electrochemical cathode utility, such as Li,CB3 and/or Li2MnO3. Suitable inert atmospheres include the noble gases (He, Ne, Ar, Kr, Xe, and Rn), vacuum, and combinations thereof, and the like. An argon atmosphere is preferred.
1'he lithium carboxylate reactant employed in the present process is any lithium salt of mono and polycarboxylic acids, which features a decomposition temperature below about 300~C, and which i8 effective to lithiate a LiMn20~ spinel when heated in contact with said spinel at a temperature below about 300~C.
Examples of suitable lithium carboxylates useful in the present process include lithium acetate, lithium citrate, lithium formate, lithium lactate, other lithium carboxylates in which the carboxylate group is attached to a group that is election-withdrawing relative to methyl (such as hydrogen, perfluoroalkyl, CF3S02CH2, and (CF3SO2)2N ), and the like. Lithium acetate is particularly preferred as the lithium carboxylate reactant.
The process of the present invention may be practiced using various techniques. In one embodiment, particulate LiMn20 spinel first is mixed with a solution, preferably an aqueous solution, of lithium carboxylate to form a paste. Then, the paste is dried to remove the solvent and the so-formed intimate admixture of spinel and carboxylate is heated to a temperature and for a time sufficient to decompose the carboxylate and initiate reaction to form the Li(lx~Mn~O~ spinel.
In another alternative embo~m~nt of the process, the particulate LiMn20~ spinel and the lithium carboxylate salt are dry-mixed to form an intimate mixture. The dry admixture then is heat treated to lithiate the spinel to form the desired Li(1,x~Mn20~ product. Any suitable dry mixing technique -may be used to form the reactant mixture; such techniques include drum mixers, ball mixers, rod mixers, and the like.
In a preferred process, lithium acetate; as the lithium carboxylate reactant, is dissolved in water, and lithium manganese oxide spinel is added to the solution to form a paste.
The LiOAc/LiMn20~ paste then is air dried at a temperature of CA 02221738 1997-ll-20 W 096/40~90 PCTAUS96/09461 about 50~C to about 150~C, preferably about 100~C. The dried admixture next is reacted by heating it in an argon atmosphere to a temperature from about 230~C to about 2s0~C for a period o~
about 2 to about 8 hours.
The following examples are provided to further illustrate the invention.
.
Example 1 Lithiated spinel of the formula Lil1Mn2O~ is prepared by dissolving 1.695 grams of lithium acetate (LioAc) in about 30ml of deionized (DI) water. A stoichiometric amount of particulate lithium manganese oxide LiMn2O~ spinel, 30 gram~, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants, while the slurry is heated at 80-90~C
for a~out 3 hours to remove excess water and convert the slurry into a paste. The paste then is vacuum dried at 80~C. The resu:Lting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and i8 held at that temperature for 2 hours to form a bluish black powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the tube furnace. Weight loss during the reaction is about 17-20~ of the comb:ined weight of the LiOAc and spinel reactants. The Lil.lMn20~
spinel powder product is analyzed by atomic absorption (AA) for Li and Mn concentration and characterized by X-ray powder diffraction (XRD) analysis.
W O 96/40590 PCTrUS96/09461 Example 2 Lithiated spinel of the formula Lil2Mn2O~ is prepared from lithium acetate by dissolving 3.39 grams of LiOAc in about 30ml of dionized (DI) water. A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants while heating at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and is held at that temperature for 2 hours to form the Li12Mn2O~ spinel product, a bluish black powder. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the tube furnace. The hil2Mn2O~ spinel powder is characterized by X-ray powder diffraction (XRD) analysis and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure.
le 3 Lithiated spinel of the formula Li2Mn2O~ is prepared by dissolving 16.95 grams of lithium acetate (LiOAc) in about 30ml of dionized (DI) water. A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LioAc solution and the resulting slurry is stirred to keep the spinel in suspension and the ensure homogeneity between the spinel and LiOAc reactants while the slurry is heated at 80-90~C for about 3 hours to remove wal 9~/40590 PCT~US96/09461 excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and held at that temperature for two hours. The powder is cooled to 110~C
over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the furnace. A color change from bluish black to brown is observed during the reac~ion and the Li2Mn2O~ spinel product has a brown color which is different from the bluish black color of the LiMn~0~ spinel reaclant. The Li2Mn20~ spinel powder is characterized by X-ray powder diffraction (XRD) analysis and analyzed ~y atomic absorption (AA) for Li and Mn concentration.
~ le 4 Lithiated spinel of the formula LillMn20~ is prepared by dissolving 3.482 grams of lithium citrate in about 30ml of deionized water. A stoichiometric amount of LiMnaO~, 30 grams, is added to the lithium citrate solution and ~he resulting slur~y is stirred to keep the spinel in suspension and to ensure homo~eneity between the spinel and lithium citrate reactants.
The slurry is heated at 80-90~C for about 3 hours while stirring to Lelll~UVe excesc water until the slurry turns into a paste. The paste then is vacuum dried by heating at 80~C for about 3 hours.
The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours and held at that temperature for 2 hours to form a bluish black powder product. The powder then is cooled to 110~C over a period of 3 hours in flowing argon. During the react:ion, water is seen con~Pn~ing at the downstream end of the W O 96/40590 PCTAJS96/09461flowing tube furnace. Weight loss during the reaction is about 40-45~ of the combined weight of the citrate and spinel reactants. The powder is characterized by XRD and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure as LillMn20~ spinel.
il ~m~le 5 Lithiated Lil2Mn20~ spinel is prepared by dissolving 6.964 grams of lithium citrate in about 30ml of deionized water. A
stoichiometric amount of LiMn20~, 30 grams, is added to the lithium citrate solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and lithium citrate reactants. The slurry then is heated at 80-90~C for about 3 hours while stirring to remove excess water until the slurry turns into a paste. The paste is vacuum dried by heating at 80~C for a few hours. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours and held at that temperature for 2 hours to form a powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water is seen con~n~ing at the downstream end of the flowing tube furnace. A
color change from bluish black to brown is observed during the reaction and the powder product has a brown color which is different from the bluish black color of the LiMn20~ spinel reactant. The powder product is characterized by XRD and analyzed for Li and Mn concentration to confirm its structure as Lil2Mn20~ spinel.
Example 6 Lithiated spinel of the ~ormula Li2Mn2O~ is prepared by dissolving 34.82 grams of lithium citrate in about 30ml of deionized water. A stoichiometric amount of particulate LiMn20~
spinel, 30 grams, is added to the lithium citrate solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and lithium citrate react:ants while the slurry is heated at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowl.y heated, in a tube ~urnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and held at that temperature for 2 hours to form a powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water is con~n~ed at the downstream end of the tube furnace. A color change from bluish black to brown is observed during the reaction and the powder product has a brown color which is different from the bluish black color of the LiMn2O~ spinel reactant. The powder product is characterized by X-ray powder di~fraction (XRD) analysis and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure as Li2Mn2O4 spinel.
~xam~le 7 hithiated LillMn20~ spinel is prepared by dissolving 1.591 grams of lithium lactate in about 30ml o~ deionized (DI) water.
A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is CA 0222l738 l997-ll-20 stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LioAc reactants while heating at 80-90C for about 3 hours to remove excess water until the slurry turns into a paste. The paste is vacuum dried at 80~C.
The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1 hour and held at that temperature for 2 hours to form a bluish black powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the tube furnace. Weight loss during the reaction is about 20~ of the combined weight of the lithium lactate and spinel reactants.
The powder product is characterized by X-ray powder diffraction (XRD) analy~is and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure as Lil1Mn2O~ spinel.
le 8 Lithiated Lil2Mn2O~ spinel is prepared from lithium lactate by dissolving 3.182 grams of lithium lactate in about 30ml of deionized (DI) water. A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants while the slurry is heated at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1 hour, and held at that temperature for 2 hours to form a bluish black powder product. The powder is cooled to 110~C over a period of 3 hours in ~lowing argon. During the reaction, water is condensed at the downstream end of the tube furnace. The powder product is characterized by X-ray powder diffraction (XRD) analysis and analyzed by atomic absorption (AA) for Li and Mn concentration to con~irm its structure as Lil2Mn2O~ spinel.
r ~7rAm,~Le 9 Lithiated Li2MnzO~ spinel is prepared by dissolving 15.91 gram~ of lithium lactate in about 30ml o~ deionized (DI) water.
A stoi.chiometric amount of particulate LiMn,O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants while the slurry is heated at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacullm, dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period o~ 1 hour, and held at that temperature for 2 hours to fonm a powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~ences at the downstream end of the tube furnace. A color change from bluish black to brown is observed during the reaction and the powder product has a brown color which is different from the bluish black color of ~he LiMn20~
spinel reactant. The powder product is characterized by X-ray powder diffraction (XRD) analysis and analyzed by atomic abso~tion (AA) for Li and Mn concentration to confirm its structure as Li2Mn2O~ spinel.
~ITHIATED LITHIUM MANGANESE OXIDE SPINEL
The present invention relates to an improved process for making a lithiated spinel compound. In particular, the invention relates to a process for lithiating a lithium manganese oxide spinel to form a spinel featuring excess lithium, which is useful as an electrochemically active component in a secondary electrochemical cell.
Lithium secondary, electrochemical cells, or rechargeable cells, typically include a Li-bearing intercalation compound as the positive electrode and a carbon, typically graphite, negative electrode, separated by a non-aqueous lithium-ion electrolyte. A lithium manganese oxide spinel of the general form~la LiMnlo~ Co~monl y has been employed as the electrochemically active cathode component. Studies of lithium intercalation into graphite have shown, however, that when the lithium manganese oxide spinel is used in a lithium-ion rechargeable cell in which the anode or negative electrode is graphi.te, there is a marked, detrimental irreversible loss in capaci.ty during the first recharging cycle. The initial appr~ach to overcome this problem was simply to use a larger mass of positive electrode [(l+x)LiMn20~] to compensa~e for the loss of lithium on the graphite anode during the first cycle.
However, increasing the mass of the cathode is not an effective remedy when taking performance efficiency into consideration.
In order to offset the lithium loss without, undesirably, seriously impacting massic or volumetric performance characteristics of the cell, lithiated lithium manganese oxide spinel. structures have been developed which feature excess lithium (Li(l,x~Mn20~). This excess lithium in the spinel compound CA 02221738 1997-ll-20 WO 96/40590 PCT~US96/09461 i8 available to compensate for the initial loss of lithium associated with the negative electrode, while reserving an amount of lithium needed to balance the reversible capacity of the graphite and maintain a useful energy level in the cell.
While such lithiated lithium manganese oxide spinel compounds have proven to be a useful and effective cathode material in secondary or rechargeable electrochemical cells, presently known methods for producing the Li(l~x)Mn20~ spinel are expensive and difficult to scale up from laboratory size to commercial volume. One such method of production, for example, includes subjecting LiMn20~ to a reducing reaction with a heated solution of lithium iodide (LiI) in acetonitrile; another involves a reduction of the lithium manganese oxide spinel with a solution of n-butyl lithiate ~n-BuLi) in h~An~. Both of these lithium-contA;n;ng reactants are prohibitively expensive, the production processes involve organic solvents, and, in addition, the n-BuLi features hazardous, pyrophoric properties.
Accordingly, there is a need for a viable method for commercial production of the lithiated lithium manganese oxide spinel.
It now has been discovered that a lithiated lithium manganese oxide spinel of the formula Lit1,x~Mn20~ can economically be made by a simple method which comprises contacting a lithium manganese oxide spinel of the formula LiMn20~ with a lithium carboxylate compound, at a temperature and for a time sufficient to decompose the carboxylate compound and free the lithium to form said lithiated, Li~1~x,Mn20~ spinel. This lithiated spinel compound has been found to be particularly useful as the positive electrode of a lithium-ion secondary electrochemical cell.
WO 9~/40590 PCTAJS96/09461 The present process produces a lithiated lithium manganese oxide spinel of the formula Li(l,x~Mn20~, wherein O<x<1;
preferably, the value of x ranges from about .05 to about 1.0;
most preferably, x ranges ~rom about .05 to about .3.
The process is carried at a reaction temperature sufficient to decompose the lithium carboxylate reactant and form the lithiated spinel compound, but, below about 350~C, to avoid decol~position of the spinel compound. Above about 300~C the spinel compound begins to decompose into non-spinel decomposition products such as ~ x~MnO3 and MnO2, which are not useful as cathode components in a lithium secondary electrochemical cell. The reaction temperature generally ranges from about 150~C to about 300~C; preferably, the reaction temperature ranges from about 230~C to about 250~C.
Reaction time is dependent upon choice of reactants and reaction temperature. In general, reaction time ranges from about 10 minutes to about 15 hours; preferably about 2 to about 8 hour reaction times are employed, since such times have been found to provide favorable results.
Preferably, the synthesis is conducted in an inert atmosphere to avoid oxidation reactions resulting in the formation of by products undesirable for electrochemical cathode utility, such as Li,CB3 and/or Li2MnO3. Suitable inert atmospheres include the noble gases (He, Ne, Ar, Kr, Xe, and Rn), vacuum, and combinations thereof, and the like. An argon atmosphere is preferred.
1'he lithium carboxylate reactant employed in the present process is any lithium salt of mono and polycarboxylic acids, which features a decomposition temperature below about 300~C, and which i8 effective to lithiate a LiMn20~ spinel when heated in contact with said spinel at a temperature below about 300~C.
Examples of suitable lithium carboxylates useful in the present process include lithium acetate, lithium citrate, lithium formate, lithium lactate, other lithium carboxylates in which the carboxylate group is attached to a group that is election-withdrawing relative to methyl (such as hydrogen, perfluoroalkyl, CF3S02CH2, and (CF3SO2)2N ), and the like. Lithium acetate is particularly preferred as the lithium carboxylate reactant.
The process of the present invention may be practiced using various techniques. In one embodiment, particulate LiMn20 spinel first is mixed with a solution, preferably an aqueous solution, of lithium carboxylate to form a paste. Then, the paste is dried to remove the solvent and the so-formed intimate admixture of spinel and carboxylate is heated to a temperature and for a time sufficient to decompose the carboxylate and initiate reaction to form the Li(lx~Mn~O~ spinel.
In another alternative embo~m~nt of the process, the particulate LiMn20~ spinel and the lithium carboxylate salt are dry-mixed to form an intimate mixture. The dry admixture then is heat treated to lithiate the spinel to form the desired Li(1,x~Mn20~ product. Any suitable dry mixing technique -may be used to form the reactant mixture; such techniques include drum mixers, ball mixers, rod mixers, and the like.
In a preferred process, lithium acetate; as the lithium carboxylate reactant, is dissolved in water, and lithium manganese oxide spinel is added to the solution to form a paste.
The LiOAc/LiMn20~ paste then is air dried at a temperature of CA 02221738 1997-ll-20 W 096/40~90 PCTAUS96/09461 about 50~C to about 150~C, preferably about 100~C. The dried admixture next is reacted by heating it in an argon atmosphere to a temperature from about 230~C to about 2s0~C for a period o~
about 2 to about 8 hours.
The following examples are provided to further illustrate the invention.
.
Example 1 Lithiated spinel of the formula Lil1Mn2O~ is prepared by dissolving 1.695 grams of lithium acetate (LioAc) in about 30ml of deionized (DI) water. A stoichiometric amount of particulate lithium manganese oxide LiMn2O~ spinel, 30 gram~, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants, while the slurry is heated at 80-90~C
for a~out 3 hours to remove excess water and convert the slurry into a paste. The paste then is vacuum dried at 80~C. The resu:Lting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and i8 held at that temperature for 2 hours to form a bluish black powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the tube furnace. Weight loss during the reaction is about 17-20~ of the comb:ined weight of the LiOAc and spinel reactants. The Lil.lMn20~
spinel powder product is analyzed by atomic absorption (AA) for Li and Mn concentration and characterized by X-ray powder diffraction (XRD) analysis.
W O 96/40590 PCTrUS96/09461 Example 2 Lithiated spinel of the formula Lil2Mn2O~ is prepared from lithium acetate by dissolving 3.39 grams of LiOAc in about 30ml of dionized (DI) water. A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants while heating at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and is held at that temperature for 2 hours to form the Li12Mn2O~ spinel product, a bluish black powder. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the tube furnace. The hil2Mn2O~ spinel powder is characterized by X-ray powder diffraction (XRD) analysis and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure.
le 3 Lithiated spinel of the formula Li2Mn2O~ is prepared by dissolving 16.95 grams of lithium acetate (LiOAc) in about 30ml of dionized (DI) water. A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LioAc solution and the resulting slurry is stirred to keep the spinel in suspension and the ensure homogeneity between the spinel and LiOAc reactants while the slurry is heated at 80-90~C for about 3 hours to remove wal 9~/40590 PCT~US96/09461 excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and held at that temperature for two hours. The powder is cooled to 110~C
over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the furnace. A color change from bluish black to brown is observed during the reac~ion and the Li2Mn2O~ spinel product has a brown color which is different from the bluish black color of the LiMn~0~ spinel reaclant. The Li2Mn20~ spinel powder is characterized by X-ray powder diffraction (XRD) analysis and analyzed ~y atomic absorption (AA) for Li and Mn concentration.
~ le 4 Lithiated spinel of the formula LillMn20~ is prepared by dissolving 3.482 grams of lithium citrate in about 30ml of deionized water. A stoichiometric amount of LiMnaO~, 30 grams, is added to the lithium citrate solution and ~he resulting slur~y is stirred to keep the spinel in suspension and to ensure homo~eneity between the spinel and lithium citrate reactants.
The slurry is heated at 80-90~C for about 3 hours while stirring to Lelll~UVe excesc water until the slurry turns into a paste. The paste then is vacuum dried by heating at 80~C for about 3 hours.
The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours and held at that temperature for 2 hours to form a bluish black powder product. The powder then is cooled to 110~C over a period of 3 hours in flowing argon. During the react:ion, water is seen con~Pn~ing at the downstream end of the W O 96/40590 PCTAJS96/09461flowing tube furnace. Weight loss during the reaction is about 40-45~ of the combined weight of the citrate and spinel reactants. The powder is characterized by XRD and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure as LillMn20~ spinel.
il ~m~le 5 Lithiated Lil2Mn20~ spinel is prepared by dissolving 6.964 grams of lithium citrate in about 30ml of deionized water. A
stoichiometric amount of LiMn20~, 30 grams, is added to the lithium citrate solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and lithium citrate reactants. The slurry then is heated at 80-90~C for about 3 hours while stirring to remove excess water until the slurry turns into a paste. The paste is vacuum dried by heating at 80~C for a few hours. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours and held at that temperature for 2 hours to form a powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water is seen con~n~ing at the downstream end of the flowing tube furnace. A
color change from bluish black to brown is observed during the reaction and the powder product has a brown color which is different from the bluish black color of the LiMn20~ spinel reactant. The powder product is characterized by XRD and analyzed for Li and Mn concentration to confirm its structure as Lil2Mn20~ spinel.
Example 6 Lithiated spinel of the ~ormula Li2Mn2O~ is prepared by dissolving 34.82 grams of lithium citrate in about 30ml of deionized water. A stoichiometric amount of particulate LiMn20~
spinel, 30 grams, is added to the lithium citrate solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and lithium citrate react:ants while the slurry is heated at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowl.y heated, in a tube ~urnace in the presence of flowing argon, from room temperature to 250~C over a period of 1.5 hours, and held at that temperature for 2 hours to form a powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water is con~n~ed at the downstream end of the tube furnace. A color change from bluish black to brown is observed during the reaction and the powder product has a brown color which is different from the bluish black color of the LiMn2O~ spinel reactant. The powder product is characterized by X-ray powder di~fraction (XRD) analysis and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure as Li2Mn2O4 spinel.
~xam~le 7 hithiated LillMn20~ spinel is prepared by dissolving 1.591 grams of lithium lactate in about 30ml o~ deionized (DI) water.
A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is CA 0222l738 l997-ll-20 stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LioAc reactants while heating at 80-90C for about 3 hours to remove excess water until the slurry turns into a paste. The paste is vacuum dried at 80~C.
The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1 hour and held at that temperature for 2 hours to form a bluish black powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~n~es at the downstream end of the tube furnace. Weight loss during the reaction is about 20~ of the combined weight of the lithium lactate and spinel reactants.
The powder product is characterized by X-ray powder diffraction (XRD) analy~is and analyzed by atomic absorption (AA) for Li and Mn concentration to confirm its structure as Lil1Mn2O~ spinel.
le 8 Lithiated Lil2Mn2O~ spinel is prepared from lithium lactate by dissolving 3.182 grams of lithium lactate in about 30ml of deionized (DI) water. A stoichiometric amount of particulate LiMn2O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants while the slurry is heated at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacuum dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period of 1 hour, and held at that temperature for 2 hours to form a bluish black powder product. The powder is cooled to 110~C over a period of 3 hours in ~lowing argon. During the reaction, water is condensed at the downstream end of the tube furnace. The powder product is characterized by X-ray powder diffraction (XRD) analysis and analyzed by atomic absorption (AA) for Li and Mn concentration to con~irm its structure as Lil2Mn2O~ spinel.
r ~7rAm,~Le 9 Lithiated Li2MnzO~ spinel is prepared by dissolving 15.91 gram~ of lithium lactate in about 30ml o~ deionized (DI) water.
A stoi.chiometric amount of particulate LiMn,O~ spinel, 30 grams, is added to the LiOAc solution and the resulting slurry is stirred to keep the spinel in suspension and to ensure homogeneity between the spinel and LiOAc reactants while the slurry is heated at 80-90~C for about 3 hours to remove excess water until the slurry turns into a paste. The paste then is vacullm, dried at 80~C. The resulting powder is slowly heated, in a tube furnace in the presence of flowing argon, from room temperature to 250~C over a period o~ 1 hour, and held at that temperature for 2 hours to fonm a powder product. The powder is cooled to 110~C over a period of 3 hours in flowing argon. During the reaction, water con~ences at the downstream end of the tube furnace. A color change from bluish black to brown is observed during the reaction and the powder product has a brown color which is different from the bluish black color of ~he LiMn20~
spinel reactant. The powder product is characterized by X-ray powder diffraction (XRD) analysis and analyzed by atomic abso~tion (AA) for Li and Mn concentration to confirm its structure as Li2Mn2O~ spinel.
Claims (9)
1. A process for preparing a lithiated lithium manganese.
dioxide spinel compound of the formula Li(1+x)Mn2O4 wherein 0<x~1, comprising reacting lithium manganese dioxide spinel compound of the formula LiMn2O4 with a lithium carboxylate at a temperature and for a time sufficient to decompose said carboxylate and form the lithiated spinel.
dioxide spinel compound of the formula Li(1+x)Mn2O4 wherein 0<x~1, comprising reacting lithium manganese dioxide spinel compound of the formula LiMn2O4 with a lithium carboxylate at a temperature and for a time sufficient to decompose said carboxylate and form the lithiated spinel.
2. The process of Claim 1 wherein the lithium carboxylate is selected from the group consisting of lithium acetate, lithium citrate, lithium lactate, and other lithium carboxylates an which the carboxylate group is attached to a group that is electron-withdrawing relative to methyl.
3. The process of Claim 2 wherein the lithium carboxylate is lithium acetate.
4. The process of Claim 1 wherein the reaction takes place at a temperature between about 150°C to below about 350°C.
5. The process of Claim 4 wherein the temperature ranges from about 150°C to below about 300°C.
6. The process of Claim 1 wherein the time of reaction ranges from about 10 minutes to about 15 hours.
7. The process of Claim 5 wherein the time of reaction ranges from about 2 to about 8 hours.
8. The process of Claim 1 wherein the reaction is conducted in an inert atmosphere.
9. The process of Claim 1 wherein the lithium manganese dioxide spinel compound is reacted with lithium acetate at a temperature of about 230°C to about 250°C for a period of about to about 8 hours in an inert argon atmosphere.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US474,806 | 1995-06-07 | ||
| US08/474,806 US5693307A (en) | 1995-06-07 | 1995-06-07 | Process for making a lithiated lithium manganese oxide spinel |
| PCT/US1996/009461 WO1996040590A1 (en) | 1995-06-07 | 1996-06-05 | An improved process for making a lithiated lithium manganese oxide spinel |
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| CA2221738A1 CA2221738A1 (en) | 1996-12-19 |
| CA2221738C true CA2221738C (en) | 2001-02-27 |
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| CA002221738A Expired - Fee Related CA2221738C (en) | 1995-06-07 | 1996-06-05 | An improved process for making a lithiated lithium manganese oxide spinel |
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| Country | Link |
|---|---|
| US (1) | US5693307A (en) |
| EP (1) | EP0842120B1 (en) |
| JP (1) | JPH11507320A (en) |
| KR (1) | KR19990022253A (en) |
| CN (1) | CN1084305C (en) |
| AT (1) | ATE231823T1 (en) |
| AU (1) | AU716975B2 (en) |
| BG (1) | BG62395B1 (en) |
| BR (1) | BR9609184A (en) |
| CA (1) | CA2221738C (en) |
| CZ (1) | CZ371797A3 (en) |
| DE (1) | DE69626023T2 (en) |
| NZ (1) | NZ310242A (en) |
| PL (1) | PL324489A1 (en) |
| RO (1) | RO115348B1 (en) |
| RU (1) | RU2152355C1 (en) |
| TW (1) | TW362090B (en) |
| WO (1) | WO1996040590A1 (en) |
| ZA (1) | ZA963655B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0797263A2 (en) * | 1996-03-19 | 1997-09-24 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary cell |
| IT1283968B1 (en) * | 1996-03-29 | 1998-05-07 | Consiglio Nazionale Ricerche | RECHARGEABLE LITHIUM OR LITHIUM-ION BATTERY ABLE TO SUSTAIN PROLONGED CYCLING. |
| US6869547B2 (en) * | 1996-12-09 | 2005-03-22 | Valence Technology, Inc. | Stabilized electrochemical cell active material |
| US6183718B1 (en) * | 1996-12-09 | 2001-02-06 | Valence Technology, Inc. | Method of making stabilized electrochemical cell active material of lithium manganese oxide |
| US6110442A (en) * | 1997-05-30 | 2000-08-29 | Hughes Electronics Corporation | Method of preparing Lix Mn2 O4 for lithium-ion batteries |
| US6455198B1 (en) | 1997-11-10 | 2002-09-24 | Ngk Insulators, Ltd. | Lithium secondary battery with a lithium manganese oxide positive electrode |
| US5939043A (en) * | 1998-06-26 | 1999-08-17 | Ga-Tek Inc. | Process for preparing Lix Mn2 O4 intercalation compounds |
| US6468695B1 (en) | 1999-08-18 | 2002-10-22 | Valence Technology Inc. | Active material having extended cycle life |
| JP2001266874A (en) * | 2000-03-16 | 2001-09-28 | Toho Titanium Co Ltd | Lithium ion secondary battery |
| KR101352836B1 (en) * | 2010-10-27 | 2014-01-20 | 전남대학교산학협력단 | Process for Preparing Lithium Manganese-Based Oxide of Li-excess Content and Lithium Secondary Battery Comprising the Same |
| JP5765179B2 (en) * | 2011-10-14 | 2015-08-19 | 日産自動車株式会社 | Positive electrode material for electrochemical device and electrochemical device using the same |
| KR101383681B1 (en) * | 2011-11-15 | 2014-04-10 | 전남대학교산학협력단 | Method for preparing lithium manganese oxides electrode materials, lithium manganese oxides electrode materials prepared thereby and rechargeable battery comprising the electrode materials |
| RU2591154C1 (en) * | 2015-09-03 | 2016-07-10 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Method of producing lithiated double lithium and manganese oxide with spinel structure |
| CN105977471A (en) * | 2016-07-06 | 2016-09-28 | 福建师范大学 | Method for improving performance of spinel lithium-rich lithium manganate positive electrode material by use of acid salt |
| CN112960814A (en) * | 2021-02-03 | 2021-06-15 | 中环国投(重庆)环保产业开发有限公司 | Harmless treatment method for leachate of electrolytic manganese slag |
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| US4070529A (en) * | 1976-07-07 | 1978-01-24 | Agence Nationale De Valorisation De La Recherche (Anvar) | Solid electrolyte |
| US4246253A (en) * | 1978-09-29 | 1981-01-20 | Union Carbide Corporation | MnO2 derived from LiMn2 O4 |
| US4312930A (en) * | 1978-09-29 | 1982-01-26 | Union Carbide Corporation | MnO2 Derived from LiMn2 O4 |
| AU532635B2 (en) * | 1979-11-06 | 1983-10-06 | South African Inventions Development Corporation | Metal oxide cathode |
| US4507371A (en) * | 1982-06-02 | 1985-03-26 | South African Inventions Development Corporation | Solid state cell wherein an anode, solid electrolyte and cathode each comprise a cubic-close-packed framework structure |
| US4959282A (en) * | 1988-07-11 | 1990-09-25 | Moli Energy Limited | Cathode active materials, methods of making same and electrochemical cells incorporating the same |
| CA1331506C (en) * | 1988-07-12 | 1994-08-23 | Michael Makepeace Thackeray | Method of synthesizing a lithium manganese oxide |
| GB2234233B (en) * | 1989-07-28 | 1993-02-17 | Csir | Lithium manganese oxide |
| CA2022898C (en) * | 1989-08-15 | 1995-06-20 | Nobuhiro Furukawa | Non-aqueous secondary cell |
| JP2933645B2 (en) * | 1989-08-28 | 1999-08-16 | 日立マクセル株式会社 | Manufacturing method of lithium secondary battery |
| JPH03225750A (en) * | 1990-01-30 | 1991-10-04 | Bridgestone Corp | Positive electrode sheet for lithium battery |
| GB2242898B (en) * | 1990-04-12 | 1993-12-01 | Technology Finance Corp | Lithium transition metal oxide |
| US5166012A (en) * | 1990-05-17 | 1992-11-24 | Technology Finance Corporation (Proprietary) Limited | Manganese oxide compounds |
| JP3028582B2 (en) * | 1990-10-09 | 2000-04-04 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| JPH04169065A (en) * | 1990-10-31 | 1992-06-17 | Mitsubishi Electric Corp | Manufacture of positive electrode material for lithium battery |
| US5244757A (en) * | 1991-01-14 | 1993-09-14 | Kabushiki Kaisha Toshiba | Lithium secondary battery |
| US5196279A (en) * | 1991-01-28 | 1993-03-23 | Bell Communications Research, Inc. | Rechargeable battery including a Li1+x Mn2 O4 cathode and a carbon anode |
| US5266299A (en) * | 1991-01-28 | 1993-11-30 | Bell Communications Research, Inc. | Method of preparing LI1+XMN204 for use as secondary battery electrode |
| US5262255A (en) * | 1991-01-30 | 1993-11-16 | Matsushita Electric Industrial Co., Ltd. | Negative electrode for non-aqueous electrolyte secondary battery |
| US5135732A (en) * | 1991-04-23 | 1992-08-04 | Bell Communications Research, Inc. | Method for preparation of LiMn2 O4 intercalation compounds and use thereof in secondary lithium batteries |
| JP3145748B2 (en) * | 1991-11-14 | 2001-03-12 | 富士写真フイルム株式会社 | Organic electrolyte secondary battery |
| US5192629A (en) * | 1992-04-21 | 1993-03-09 | Bell Communications Research, Inc. | High-voltage-stable electrolytes for Li1+x Mn2 O4 /carbon secondary batteries |
| ZA936168B (en) * | 1992-08-28 | 1994-03-22 | Technology Finance Corp | Electrochemical cell |
| 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 |
| US5478672A (en) * | 1993-12-24 | 1995-12-26 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery, positive-electrode active material |
-
1995
- 1995-06-07 US US08/474,806 patent/US5693307A/en not_active Expired - Lifetime
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1996
- 1996-05-08 ZA ZA963655A patent/ZA963655B/en unknown
- 1996-05-24 TW TW085106148A patent/TW362090B/en active
- 1996-06-05 CN CN96195030A patent/CN1084305C/en not_active Expired - Fee Related
- 1996-06-05 CA CA002221738A patent/CA2221738C/en not_active Expired - Fee Related
- 1996-06-05 BR BR9609184A patent/BR9609184A/en not_active Application Discontinuation
- 1996-06-05 KR KR1019970708732A patent/KR19990022253A/en not_active Ceased
- 1996-06-05 NZ NZ310242A patent/NZ310242A/en unknown
- 1996-06-05 PL PL96324489A patent/PL324489A1/en unknown
- 1996-06-05 AU AU61004/96A patent/AU716975B2/en not_active Ceased
- 1996-06-05 DE DE69626023T patent/DE69626023T2/en not_active Expired - Fee Related
- 1996-06-05 CZ CZ973717A patent/CZ371797A3/en unknown
- 1996-06-05 EP EP96918315A patent/EP0842120B1/en not_active Expired - Lifetime
- 1996-06-05 RU RU98100422/12A patent/RU2152355C1/en not_active IP Right Cessation
- 1996-06-05 RO RO97-02251A patent/RO115348B1/en unknown
- 1996-06-05 WO PCT/US1996/009461 patent/WO1996040590A1/en not_active Ceased
- 1996-06-05 AT AT96918315T patent/ATE231823T1/en not_active IP Right Cessation
- 1996-06-05 JP JP9501775A patent/JPH11507320A/en active Pending
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Also Published As
| Publication number | Publication date |
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| RO115348B1 (en) | 2000-01-28 |
| CN1084305C (en) | 2002-05-08 |
| KR19990022253A (en) | 1999-03-25 |
| BR9609184A (en) | 1999-05-11 |
| CA2221738A1 (en) | 1996-12-19 |
| RU2152355C1 (en) | 2000-07-10 |
| JPH11507320A (en) | 1999-06-29 |
| EP0842120A4 (en) | 1998-12-09 |
| TW362090B (en) | 1999-06-21 |
| CZ371797A3 (en) | 1998-06-17 |
| BG62395B1 (en) | 1999-10-29 |
| WO1996040590A1 (en) | 1996-12-19 |
| AU6100496A (en) | 1996-12-30 |
| DE69626023D1 (en) | 2003-03-06 |
| US5693307A (en) | 1997-12-02 |
| NZ310242A (en) | 1998-11-25 |
| AU716975B2 (en) | 2000-03-09 |
| HK1010866A1 (en) | 1999-07-02 |
| CN1189143A (en) | 1998-07-29 |
| BG102161A (en) | 1998-08-31 |
| EP0842120B1 (en) | 2003-01-29 |
| EP0842120A1 (en) | 1998-05-20 |
| ATE231823T1 (en) | 2003-02-15 |
| ZA963655B (en) | 1996-11-21 |
| PL324489A1 (en) | 1998-05-25 |
| DE69626023T2 (en) | 2003-10-16 |
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