EP1084515A1 - Lithiated manganese oxide - Google Patents
Lithiated manganese oxideInfo
- Publication number
- EP1084515A1 EP1084515A1 EP99922890A EP99922890A EP1084515A1 EP 1084515 A1 EP1084515 A1 EP 1084515A1 EP 99922890 A EP99922890 A EP 99922890A EP 99922890 A EP99922890 A EP 99922890A EP 1084515 A1 EP1084515 A1 EP 1084515A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- degree
- manganese oxide
- percent
- lithium
- cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 147
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 52
- 238000006386 neutralization reaction Methods 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- -1 for example Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910006648 β-MnO2 Inorganic materials 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 210000000352 storage cell Anatomy 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- a battery includes one or more galvanic cells (i.e., cells that produce a direct current of electricity) in a finished package.
- Cells of this type generally contain two electrodes separated by a liquid capable of transporting ions, called an electrolyte.
- Typical electrolytes include liquid organic electrolyte or a polymeric electrolyte.
- the cell produces electricity from chemical reactions through oxidation at one electrode, commonly referred to as the negative electrode, and reduction at the other electrode, commonly referred to as the positive electrode.
- Completion of an electronically conducting circuit including the negative and positive electrodes allows ion transport across the cell and discharges the battery.
- a primary battery is meant to be discharged to exhaustion once, and then discarded.
- a rechargeable battery can be charged and discharged multiple times.
- a primary battery is a primary lithium cell.
- a lithium electrochemical cell is a galvanic cell using lithium, a lithium alloy or other lithium containing material as one electrode in the cell.
- the other electrode of the cell can include, for example; a metal oxide, such as a manganese dioxide (e.g., ⁇ , ⁇ -MnO 2 ).
- the metal oxide used in the electrode can be processed prior to use in a lithium battery.
- manganese dioxide can be prepared by chemical methods or electrochemical methods. The resulting materials are known as chemically produced manganese dioxide (CMD) and electrochemically produced (e.g., electrolytic) manganese dioxide (EMD), respectively.
- a rechargeable battery such as a lithium ion battery, can include a lithiated carbon electrode.
- Manganese dioxide-based lithium cells are described, for example, in Ikeda, et al. "Manganese Dioxide as Cathodes for Lithium Batteries," in Manganese Dioxide Symposium, Vol. 1, The Electrochemical Society, Cleveland Section, 1975, p. 384-401, incorporated herein by reference.
- the invention relates to a lithiated manganese oxide for use in electrochemical cells.
- the lithiated manganese oxide can be prepared by exposure to a lithium source under conditions that results in the formation of a modified manganese oxide phase.
- the modified phase is used in a primary lithium cell, the operating voltage of an electrochemical cell containing the lithiated manganese oxide increases relative to the operating voltage of a cell containing a manganese dioxide that is not exposed to the lithium source.
- the invention features a manganese oxide composition that includes a lithiated manganese oxide.
- the lithiated manganese oxide can have an x-ray diffraction pattern including a 31 degree 2-Theta peak intensity of at least 35 percent and a 24 degree 2-Theta peak intensity of at least 35 percent.
- the 31 degree 2-Theta peak intensity can be at least 36 percent. In other embodiments, the 24 degree 2-Theta peak intensity can be at least 38 percent.
- the 31 degree 2-Theta peak can be between 31 degrees and 32 degrees.
- the 24 degree 2-Theta peak can be between 24 degrees and 24.8 degrees.
- the lithiated manganese oxide can have a discharge voltage of greater than 2.9V when tested in a CR 2430 coin cell (e.g, a primary lithium cell) at 1 mA/cm 2 continuous discharge at room temperature. It also can include greater than about 0.7 weight percent (e.g., greater than 1.0 weight percent) lithium in MnO 2 and less than 59 weight percent Mn 4+ .
- the invention features a method of preparing a lithiated manganese oxide.
- a manganese oxide is placed in a liquid to provide a suspension.
- the manganese oxide can be an electrochemically produced manganese dioxide (EMD).
- EMD electrochemically produced manganese dioxide
- the liquid can be water.
- a lithium salt is added to the suspension.
- the lithium salt can be lithium hydroxide.
- the pH of the suspension can be increased so that it is basic, such as to a pH greater than about 7, preferably greater than about 9, and more preferably greater than about 11.
- the pH of the suspension can be increased by adding a solution including lithium hydroxide to the suspension.
- the liquid After adding the lithium salt, the liquid is removed to provide a solid.
- the liquid can be removed by filtering the suspension, centrifuging the suspension, or evaporating the liquid, or combinations thereof.
- the solid can be a sediment, a particle or group of particles collected from a colloid, or a combination thereof.
- the invention features an electrochemical cell including a first electrode and a second electrode.
- the second electrode can be a lithium electrode or a lithiated carbon electrode.
- the electrode can include a lithiated manganese oxide.
- the cell can have a discharge voltage of greater than 2.9V.
- the invention features a method of manufacturing a lithium cell.
- the method includes preparing an electrode including a lithiated manganese oxide.
- the lithiated manganese oxide of the electrode can be prepared by placing a manganese oxide in a liquid to provide a suspension, adding a lithium salt to the suspension to provide a suspension at a pH greater than about 11 , removing the liquid from the suspension to provide a solid, and heating the solid to provide the lithiated manganese oxide.
- the lithiated manganese oxide can have the following advantages.
- the battery load voltage suppression can be improved by increasing the lithium content of the MnO 2 .
- the battery load voltage can be suppressed. Accordingly, the uses of the battery can be limited by the performance of the material, e.g., the suppressed load voltage does not meet the requirements for photographic camera applications.
- the lithium content of the manganese oxide can be increased by carrying out the neutralization step to higher pH levels (e.g., greater than about 9).
- the additional lithium can react with MnO 2 to form the lithiated manganese oxide.
- the lithiated manganese oxide can lead to an increase of the load voltage, especially at heavy discharge rates and at low temperatures.
- FIG. 1 is a graph depicting an x-ray diffraction pattern of a lithiated
- FIG. 2 is a graph depicting an x-ray diffraction pattern of a lithiated MnO,.
- FIG. 3 is a graph depicting the shifts in peak locations in the x-ray diffraction patterns of lithiated MnO 2 neutralized to various pH levels.
- FIG. 4 is a graph depicting the changes in intensities of peaks in the x-ray diffraction patterns of lithiated MnO 2 neutralized to various pH levels.
- FIG. 5 is a graph depicting the cyclic voltammograms of MnO 2 neutralized to various pH levels.
- FIG. 6 is a graph depicting capacity and lithium content in MnO 2 neutralized to various pH levels.
- FIG. 7 is a graph depicting the operating voltage dependance on lithium content in a lithiated MnO 2 .
- FIG. 8 is a graph depicting the operating voltage and discharge capacity of lithiated MnO 2 having different lithium contents.
- FIG. 9 is a graph depicting the operating voltage and discharge capacity of lithiated MnO 2 obtained at pH 11 and an EMD.
- EMD electrochemically produced manganese dioxide
- a strong acid such as sulfuric acid
- a base such as lithium hydroxide
- EMD electrochemically produced manganese dioxide
- a lithium grade MnO 2 is produced which has a low sodium content and can be used in primary lithium cells.
- EMD is commercially available from, for example, Delta E.M.D. (Pty) Ltd., Nelspruit, South Africa, and Kerr-McGee Chemical Co., Oklahoma City, Oklahoma.
- Neutralization of EMD with lithium hydroxide to a pH higher than about 7, preferably to a pH higher than about 9, and more preferably to a pH higher than about 11, can produce a lithiated manganese oxide with desirable electrochemical properties for use in electrochemical cells.
- LiOH is added to a MnO 2 (e.g., EMD) suspension in water until a saturation level is reached. This typically occurs at pH greater than 7 (e.g., greater than 11).
- the MnO 2 is isolated from water and heat treated to a temperature between about 350 and 400°C. The new crystallographic phase of lithiated manganese oxide is produced by this procedure.
- the lithiated manganese oxide generated by lithiation to a pH greater than 7 leads to an increase in operating voltage of lithium cells containing the material, an increased lithium content of the material, a decrease in the Mn 4+ content of the material, and a higher reversibility as a recyclable cathode.
- the lithiated manganese oxide can be identified by cyclic voltammetry and x-ray diffraction.
- the lithiated manganese oxide can be incorporated into an electrode of a primary storage cell, or battery.
- a primary storage cell includes a negative electrode in electrical contact with negative lead or contact, a positive electrode in electrical contact with positive lead or contact.
- the positive electrode includes the lithiated manganese oxide.
- the negative electrode includes lithium.
- the electrode material is mixed with a polymeric binding medium to produce a paste which can be applied to a highly porous sintered, felt, or foam substrate. Electrode pieces of the appropriate size can be cut from the substrate.
- a separator is located between the electrodes.
- the separator prevents the positive and negative electrodes from making electrical contact.
- the separator is a porous polymer film or thin sheet that serves as a spacer and is composed of relatively non-reactive polymers such as, for example, polypropylene, polyethylene, a polyamide (i.e., a nylon), a polysulfone, or polyvinyl chloride (PVC).
- the separator is porous and prevents contact between the electrodes while allowing the electrolyte to move through the pores.
- the preferred separator has a thickness between about 10 microns to 200 microns, more preferably between about 20 microns to 50 microns.
- the electrodes and the separator are contained within a case.
- the case can form a coin cell, button cell, prismatic cell, or other standard cell geometry.
- the case is closed to provide a gas-tight and fluid-tight seal.
- the case can be made of a metal such as nickel or nickel plated steel, or a plastic material such as PVC, polypropylene, a polysulfone, ABS, or a polyamide.
- the case containing the electrodes and separator is filled with an electrolyte.
- the electrolyte may be any electrolyte known in the art.
- a preferred electrolyte is a 0.6M solution of lithium trifluormethylsulfonate (CF 3 SO 3 Li; LITFS) in an ethylene carbonate (EC)/propylene carbonate (PC)/dimethoxyethane (DME) mixture.
- EC ethylene carbonate
- PC propylene carbonate
- DME diimethoxyethane
- Example 1 The lithiated manganese oxide was prepared by treating EMD with a lithium salt, such as lithium hydroxide, to high pH.
- a lithium salt such as lithium hydroxide
- Commercial lithium grade EMD e.g., less than 500 ppm Na
- EMD having an initial of pH 4.4 was used as a starting material.
- EMD can be prepared according to the method described, for example, in U.S. Pat. No. 5,698,176, incorporated herein by reference.
- the lithiated manganese oxide was recovered by filtration and was subsequently heated to about 380°C for about four hours.
- X-ray diffraction analysis of the heat treated lithiated manganese oxide samples prepared by neutralization to pH 11 and neutralization to pH 12.7 also suggest that the phase composition of the material leads to the different electrochemical properties of the materials.
- the lithiated manganese oxide prepared at pH 11 was composed of a mixture of phases, including ⁇ -MnO 2 .
- the material prepared by neutralization to pH 12.7 contained significantly less of the ⁇ -MnO 2 phase.
- a new second phase with x-ray diffraction peaks at 24 (2-Theta) and 31 (2-Theta) can be observed clearly in FIG. 2.
- the appearance of the new phase can be attributed, in part, to the increased lithium content of the lithiated manganese oxide.
- the presence of the new phase can be followed by a detailed x-ray diffraction analysis of the heat treated, e.g., 380°C for about 8 hours, manganese dioxide neutralized to different pH levels.
- the 2-Theta peak at 24 and the 2-Theta peak at 31 each shift position depending on the pH of processing.
- the 2-Theta peak at 24 can be found between about 25 and 24, shifting to lower angles as pH increases.
- the 2- Theta peak at 31 can be found between about 29.6 and 31.5, shifting to higher angles as pH increases. Referring to FIG. 4, the intensity of each of these two peaks also changes as the neutralization pH changes.
- the intensity of the 2-Theta peak at 24 increases from about 35 to about 40 percent as the pH increases from 7 to 12.7; the intensity of the 2-Theta peak at 31 increase from about 34.8 to about 37 over the same pH range.
- BET surface area analysis of the lithiated manganese oxide after heat treatment showed that both pore surface and pore volume decrease for the manganese dioxide that is neutralized at the higher pH levels.
- the new phase is not observed by x-ray diffraction or cyclic voltammetry when the manganese dioxide is heat treated prior to neutralization with lithium hydroxide.
- Neutralization can lead to a sediment phase and a colloidal phase of lithiated manganese oxide.
- a sediment phase and a colloidal phase of lithiated manganese oxide For example, when the EMD was neutralized to a pH between about 5 and about 11 by the addition of lithium hydroxide, a sediment and colloidal suspension of particles formed. The colloidal suspension included the lithiated manganese oxide.
- the neutralization pH increased, there was a corresponding increase in the lithium content of the lithiated manganese oxide.
- the lithium content was determined by inductively coupled plasma atomic emission spectroscopy. Referring to FIG.
- Example 2 Coin cells were prepared, including the lithiated manganese oxide.
- CR 2430 SS coin cells were prepared by pressing 600 mg of a mixture containing 75% KS6 graphite and 25% PTFE into the bottom of the coin cell, followed by pressing a cathode mixture (60% MnO 2 , 35% KS6 and 5% PTFE) containing 100 mg of the lithiated manganese oxide on top of the KS6/PTFE layer.
- the separator (Celgard 2400) was placed on top of the cathode mixture.
- a Li metal anode was placed on top of the separator and the electrolyte (0.57M LiTFS in DME/EC/PC in a 70/10/20 volume percent ratio) was added to the cell.
- the modified lithiated manganese oxide prepared to a pH higher than 7, and particularly to a pH higher than 11, can have an increased operating voltage.
- Cells containing the lithiated manganese oxide that was neutralized to a pH higher than 9, had an operating voltage at C/10 of at least 2.8V.
- the neutralization pH increased to above 11, the operating voltage at C/10 was greater than 2.85V.
- the operating voltage increased to about 2.95V.
- the increased operating voltage correlates to the lithium content of the lithiated manganese oxide.
- the lithium content of the lithiated manganese oxide increases as the neutralization pH increases.
- the lithium content of the lithiated manganese oxide can be determined by ICP.
- the Mn 4+ content of the lithiated manganese oxide neutralized to a pH greater than 11 was less than 59 percent (e.g., about 57.7 percent) after heat treatment.
- Example 3 Flooded cells were used for electrochemical measurements of the lithiated manganese oxides.
- a flooded cell is a cell containing excess electrolyte in which electrolyte access does not limit the current of the cell.
- a three electrode flooded cell was used, as described in N. Iltchev, J Power Sources 35:175-181 (1991).
- the test cathode was 100 mg of a 60/40 MnO/Teflonized Acetylene Black (TAB-2) mix pressed on a nickel current collector.
- the counter and reference electrodes were lithium metal.
- discharge of flooded cells at a C/10 discharge rate also showed an increase in operating voltage when the neutralization pH was increased. Similar results were observed with three other batches of EMD from Delta (Delta E.M.D. (Pty) Ltd., Nelspruit, South Africa) that were neutralized to high pH with LiOH.
- 2/3A cells were prepared using EMD from Delta (Delta E.M.D. (Pty) Ltd., Nelspruit, South Africa) (control or comparative cell) and the lithiated manganese oxide prepared at pH 11 (pH 11). All other aspects of the control 2/3 A cell and pH 11 2/3 A cell were the same. The cells were discharged at 0.9A by pulsing 3 seconds on and 27 seconds off at -10°C. Referring to FIG. 9, the operating voltage of the pH 11 2/3 A cell was consistently higher than the output voltage of the control or comparative 2/3 A cell.
- the lithium content of lithiated manganese oxide can also be increased by, in addition to raising the processing pH, modifying the ion-exchange process in ways including: (1) Using vacuum back fill of the processing chamber to increase accessibility of the lithium salt solution to small manganese dioxide pores (e.g., those with a radius of less than 20 Angstroms); (2) Using an acid leach process by exposing the manganese dioxide to H 2 SO 4 ; (3) Using elevated processing temperature (e.g., close to the water boiling point) during neutralization; or (4) Using alcohol as surfactant to improve the wettability of the manganese dioxide surface.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US75586 | 1998-05-11 | ||
US7558698A | 1998-09-03 | 1998-09-03 | |
PCT/US1999/010173 WO1999059215A1 (en) | 1998-05-11 | 1999-05-10 | Lithiated manganese oxide |
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EP1084515A1 true EP1084515A1 (en) | 2001-03-21 |
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Application Number | Title | Priority Date | Filing Date |
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EP99922890A Withdrawn EP1084515A1 (en) | 1998-05-11 | 1999-05-10 | Lithiated manganese oxide |
Country Status (6)
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EP (1) | EP1084515A1 (en) |
JP (1) | JP2002515638A (en) |
CN (1) | CN1305644A (en) |
AU (1) | AU3978599A (en) |
TW (1) | TW477085B (en) |
WO (1) | WO1999059215A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US6190800B1 (en) * | 1998-05-11 | 2001-02-20 | The Gillette Company | Lithiated manganese dioxide |
KR100433666B1 (en) * | 2001-06-09 | 2004-05-31 | 한국과학기술연구원 | Lithium primary battery comprising lithium metal oxide or lithium metal compound cathode and grid anode |
US6878489B2 (en) * | 2002-05-06 | 2005-04-12 | The Gillette Company | Lithium cell with improved cathode |
US20050048366A1 (en) | 2003-08-27 | 2005-03-03 | Bowden William L. | Cathode material and method of manufacturing |
US8003254B2 (en) | 2004-01-22 | 2011-08-23 | The Gillette Company | Battery cathodes |
US8137842B2 (en) | 2004-01-22 | 2012-03-20 | The Gillette Company | Battery cathodes |
US20050164085A1 (en) | 2004-01-22 | 2005-07-28 | Bofinger Todd E. | Cathode material for lithium battery |
US7771874B2 (en) * | 2005-06-29 | 2010-08-10 | Fmc Corporation | Lithium manganese compounds and methods of making the same |
CN105489879B (en) * | 2015-12-30 | 2018-05-25 | 河南师范大学 | Alkali metal ion modifies the preparation method of manganese series oxides negative material |
CN106744675B (en) * | 2017-01-22 | 2018-11-09 | 郑州大学 | A kind of nano material cutting off processing method |
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JPH0746608B2 (en) * | 1986-10-30 | 1995-05-17 | 三洋電機株式会社 | Non-aqueous secondary battery |
JPH07114125B2 (en) * | 1988-03-15 | 1995-12-06 | 三洋電機株式会社 | Non-aqueous secondary battery |
JPH01234329A (en) * | 1988-03-16 | 1989-09-19 | Mitsui Mining & Smelting Co Ltd | Manganese dioxide and its production |
JP2714092B2 (en) * | 1989-01-06 | 1998-02-16 | 三洋電機株式会社 | Manufacturing method of positive electrode for non-aqueous secondary battery |
FR2644295A1 (en) * | 1989-03-09 | 1990-09-14 | Accumulateurs Fixes | RECHARGEABLE ELECTROCHEMICAL GENERATOR WITH LITHIUM ANODE |
JPH03122968A (en) * | 1989-10-05 | 1991-05-24 | Mitsui Mining & Smelting Co Ltd | Manufacture of manganese dioxide for lithium primary battery |
EP0797263A2 (en) * | 1996-03-19 | 1997-09-24 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary cell |
EP0816292B1 (en) * | 1996-06-27 | 2000-01-05 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
US5747193A (en) * | 1996-07-11 | 1998-05-05 | Bell Communications Research, Inc. | Process for synthesizing lixmny04 intercalation compounds |
-
1999
- 1999-05-10 EP EP99922890A patent/EP1084515A1/en not_active Withdrawn
- 1999-05-10 WO PCT/US1999/010173 patent/WO1999059215A1/en not_active Application Discontinuation
- 1999-05-10 AU AU39785/99A patent/AU3978599A/en not_active Abandoned
- 1999-05-10 JP JP2000548930A patent/JP2002515638A/en not_active Withdrawn
- 1999-05-10 CN CN99807317.2A patent/CN1305644A/en active Pending
- 1999-05-11 TW TW088107616A patent/TW477085B/en active
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See references of WO9959215A1 * |
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JP2002515638A (en) | 2002-05-28 |
AU3978599A (en) | 1999-11-29 |
CN1305644A (en) | 2001-07-25 |
WO1999059215A9 (en) | 2000-03-16 |
TW477085B (en) | 2002-02-21 |
WO1999059215A1 (en) | 1999-11-18 |
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