CN1305644A - Lithiated manganese oxide - Google Patents

Lithiated manganese oxide Download PDF

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CN1305644A
CN1305644A CN99807317.2A CN99807317A CN1305644A CN 1305644 A CN1305644 A CN 1305644A CN 99807317 A CN99807317 A CN 99807317A CN 1305644 A CN1305644 A CN 1305644A
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manganese oxide
peaks
lithium
battery
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P·R·摩西
W·L·鲍登
N·艾特切夫
K·布兰特
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Duracell Inc USA
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Duracell Inc USA
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    • 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

Abstract

A lithiated manganese oxide for use in primary lithium cells is described. The lithiated manganese oxide can be prepared by exposure to a lithium source under conditions that result in the formation of a modified manganese oxide phase. When 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.

Description

Lithiated manganese oxide
The present invention relates to lithium electrochemical cells.
Battery pack contains the one or more primary cells (promptly producing galvanic battery) in the encapsulation in the end.This battery generally contains two electrodes that separated by the liquid that can transmit ion (being called electrolyte).Typical electrolyte comprises liquid organic bath or polymer dielectric.Described battery produces electricity by chemical reaction, oxidation reaction takes place being commonly referred on the electrode of negative pole, reduction reaction takes place being commonly referred on another anodal electrode.Complete formation comprises that negative pole and anodal conducting channel make ion by the battery transmission, and makes described battery power discharge.Primary cell is meant once to discharge into and exhausts, abandons then.Rechargeable battery can repeatedly charge and discharge.
An example of primary cell is a disposable lithium-battery.Lithium electrochemical cells is to use lithium, lithium alloy or other lithium-containing materials primary cell as an electrode in the battery.Another electrode of described battery can comprise, for example, metal oxide is as manganese dioxide (γ for example, β-MnO 2).The metal oxide that uses in the electrode can be processed before being used for lithium battery.In general, manganese dioxide can pass through chemical method or electrochemical production.The material of gained is called manganese dioxide (CMD) that chemical method produces and electrochemical process production (for example electrolysis) manganese dioxide (EMD).Rechargeable battery as lithium ion battery, can comprise the carbon electrode of a lithiumation.
For example, people such as Ikeda at the manganese dioxide proceeding, Vol.1, ECS, manganese dioxide base lithium battery has been described in " as the manganese dioxide of lithium cell cathode " of 1975, the 384-401 pages or leaves by Cleveland branch, this paper is incorporated by reference.
The present invention relates to be used for lithiumation (lithiated promptly the mixes lithium) manganese oxide of electrochemical cell.Described lithiated manganese oxide can prepare by being exposed in the lithium source under the condition that causes modified oxidized manganese to form mutually.When described modification was used for disposable lithium-battery mutually, with respect to the operating voltage of the battery that contains the manganese dioxide that is not exposed to the lithium source, the operating voltage that contains the electrochemical cell of lithiated manganese oxide increased.
On the one hand, the present invention is characterised in that the manganese oxide composition that comprises lithiated manganese oxide.The X-ray diffraction spectrogram of the manganese oxide of described lithiumation can comprise 2 θ peaks of one 31 degree, 2 θ peaks of intensity at least 35% and one 24 degree, intensity at least 35%.
In certain embodiments, 2 θ peak intensities of 31 degree can be at least 36%.In other embodiments, 2 θ peak intensities of 24 degree can be at least 38%.2 θ peaks of described 31 degree can be between 31 degree and 32 degree.2 θ peaks of described 24 degree can be between 24 degree and 24.8 degree.
Using CR2430 coin shape battery (for example a kind of disposable lithium-battery) at room temperature at 1mA/cm 3When following continuous discharge was tested, the manganese oxide of described lithiumation can have the discharge voltage greater than 2.9V.At MnO 2In also can contain greater than the lithium of about 0.7 weight % (for example greater than 1.0 weight %) with less than the Mn of 59 weight % 4+
Another aspect, the present invention is characterised in that a kind of method for preparing lithiated manganese oxide.
In described method, manganese oxide is placed in a kind of liquid, obtain a kind of suspension.Described manganese oxide can be the manganese dioxide (EMD) of electrochemical production.Described liquid can be water.
In described suspension, add lithium salts.Described lithium salts can be a lithium hydroxide.Can improve the pH value of described suspension, make its suspension that becomes alkalescence, for example, the pH value is greater than about 7, be preferably greater than about 9, more preferably greater than about 11.For example, can improve the pH value of described suspension by in described suspension, adding the solution that contains lithium hydroxide.
After adding described lithium salts, remove described liquid, obtain a kind of solid.Can be by filtering described suspension, centrifugal described suspension or evaporating described liquid, described liquid is removed in the perhaps combination of these methods.Particle or particle aggregate that described solid can be sediment, collect from colloid, perhaps their combination.
Described solid heating, obtain described lithiated manganese oxide.Heating can comprise to be brought up to the temperature of described solid between about 350 ℃ and 400 ℃.
On the other hand, the present invention is characterised in that a kind of electrochemical cell, comprises first electrode and second electrode.Second electrode can be the carbon electrode of a kind of lithium electrode or lithiumation.Described electrode can comprise a kind of lithiated manganese oxide.Described battery can have the discharge voltage greater than 2.9V.
On the other hand, the present invention is characterised in that a kind of method of making lithium battery.Described method comprises: prepare a kind of electrode that comprises lithiated manganese oxide.The lithiated manganese oxide of described electrode can be prepared as follows: promptly manganese oxide is placed in a kind of liquid and forms suspension, in described suspension, add lithium salts, obtain pH greater than about 11 suspension, from described suspension, remove liquid, obtain a kind of solid, heat described solid, obtain described lithiated manganese oxide.
Described lithiated manganese oxide can have following advantage.For example, increase MnO 2Lithium content can improve cell load voltage and suppress.At lithium level MnO 2The beginning of heavy load low temperature discharge curve, can suppress cell load voltage.Therefore, the use of described battery can be subjected to the restriction of material property, and for example, downtrod load voltage does not satisfy the requirement of camera application.By described neutralization procedure being proceeded to the lithium content that higher pH value (for example greater than about 9) can increase described manganese oxide.Subsequently to the processing of EMD and dry with the process that is applicable to lithium battery in, other lithium can with MnO 2Reaction, the manganese oxide of formation lithiumation.Described lithiated manganese oxide can cause the increase of load voltage, especially under big discharge rate and low temperature.
From the description of embodiment preferred and in the accessory rights requirement, other features and advantages of the present invention will be tangible.
Fig. 1 is a kind of lithiumation MnO of expression 2The X-ray diffraction spectrogram.
Fig. 2 is a kind of lithiumation MnO of expression 2The X-ray diffraction spectrogram.
Fig. 3 is the lithiumation MnO that is illustrated in the various pH values that neutralize 2The X-ray diffraction spectrogram in the figure of peak position displacement.
Fig. 4 is the lithiumation MnO that is illustrated in the various pH values that neutralize 2The X-ray diffraction spectrogram in the figure that changes of peak intensity.
Fig. 5 is the neutralize lithiumation MnO of various pH values of expression 2The figure of cyclic voltammetry curve (voltammograms).
Fig. 6 is the neutralize lithiumation MnO of various pH values of expression 2Capacity and the figure of lithium content.
Fig. 7 is expression operating voltage and lithiumation MnO 2The figure of the dependence of middle lithium content.
Fig. 8 is the lithiumation MnO that expression has different lithium content 2Operating voltage and the figure of discharge capacity.
Fig. 9 is the lithiumation MnO that obtains when being illustrated in pH=11 2With the operating voltage of EMD and the figure of discharge capacity.
The ion-exchange of manganese oxide surface proton and lithium ion causes forming the oxidation of lithiumation when heat treatment Manganese. The manganese oxide of lithiumation is a kind of new MnO2Phase. In general, the dioxy of electrochemical process production The preparation of changing manganese (EMD) relates to manganese dioxide is exposed in the strong acid (such as sulfuric acid), uses at last alkali (such as lithium hydroxide) neutralization. By washing EMD with lithium hydroxide, produce lithium level MnO2, its sodium contains Measure lowly, and can be used for disposable lithium-battery. For example, EMD can be from Delta E.M.D. (Pty) Ltd., Nelspruit, South Africa and Kerr-Megee Chemical Co., Oklahoma City, Oklahoma buys.
With lithium hydroxide EMD is neutralized the pH value greater than about 7, preferably arrive the pH value greater than about 9, more Be preferably greater than the pH value greater than about 11, can produce the desired electrical chemistry that has for electrochemical cell The lithiated manganese oxide of performance.
More specifically, the MnO that LiOH is added to the water2(as, EMD) in the suspension, until Reach capacity. This typically takes place down greater than 7 (as greater than 11) in the pH value. After improving the pH value, MnO2From water, separate, and heat treatment under the temperature between about 350-400 ℃. By this mistake Journey has been produced the lithiated manganese oxide of new crystalline phase.
The operating voltage that causes containing the lithium battery of this material by the lithiated manganese oxide that produces greater than 7 lithiumation to the pH value improves, this material lithium content improves, the Mn of this material4+Content, And has higher invertibity as circulating electrode. Described lithiated manganese oxide can be by circulation Voltammetry and X-ray diffraction characterize.
Described lithiated manganese oxide can be incorporated into a battery (primary storage cell) Or in the electrode in the battery pack. Battery comprises that one electrically contacts with negative wire or contact Negative pole, a positive pole that electrically contacts with positive wire or contact. Described positive pole comprises described lithium Change manganese oxide. Described negative pole comprises lithium. Described electrode material mixes with polymer-bonded medium, Form a kind of cream, can be coated on the sintering pad or foam matrix of porous. Can be from described base The electrode slice of cutting suitable dimension on the matter.
Dividing plate is between described electrode. Described dividing plate prevents that described positive pole from contacting with negative electricity. Described dividing plate is porous polymer film or thin slice, as spacer, and by relatively nonactive Polymer form, for example polypropylene, polyethylene, polyamide (being nylon), polysulfones or Polyvinyl chloride (PVC). Described dividing plate is porous, and prevents the contact between the electrode, simultaneously So that electrolyte can pass through described hole. Preferred block board thickness between the 10-200 micron, More preferably between the 20-50 micron.
Electrode and dividing plate are contained in the battery case. Battery case can form coin shape battery, button cell, The cell shapes of prismatic battery or other standard. Seal described battery case, air-tightness is provided With the Fluid Sealing performance. Described battery case can be used the metal manufacturing, the steel of nickel or nickel plating for example, Perhaps use the plastic material manufacturing, such as PVC, polypropylene, polysulfones, ABS or polyamide.
The battery case that described electrode and dividing plate are housed is filled with electrolyte. Described electrolyte can be this Any known electrolyte in the field. Preferred electrolyte is the trifluoromethyl sulfonic acid lithium of 0.6M (CF3SO 3Li; LITFS) at ethylene carbonate (EC)/propylene carbonate (PC)/dimethoxy-ethane (DME) solution in the mixture. Behind the filling electrolyte, seal described battery case. By using lithium salts (such as lithium hydroxide) processes high pH value to manganese dioxide, can improve lithium battery or Li/MnO2The operating voltage of battery.
The following example has illustrated the present invention.
Embodiment 1
By EMD being handled high pH value, prepare the manganese oxide of described lithiumation with lithium salts (as lithium hydroxide).Using initial pH value is that 4.4 industrial lithium level EMD (for example, less than 500ppm Na) is as raw material.EMD for example can be according at United States Patent (USP) 5,698, the method preparation described in 176, and this patent is incorporated by reference in this article.
In described EMD, add entry and form slurry.By continuing to add the pH value that LiOH improves described EMD,, reach the pH value and be about 12.7 up to degree of saturation.When the pH value stabilization, stir described mixture a whole night, make lithium sneak in the manganese oxide fully.Second day, the pH value reduced, and adds more LiOH again, meets the requirements of the pH value.In case the pH value stabilization stirred described mixture 1 hour.Prepare the pH value simultaneously and be 7,9 and 11 charge.The LiOH that adds various amounts regulates the pH value.For example, use the Li level EMD of 2kg, the LiOH that adds about 27g makes the pH value reach 9, and it is 12 that the LiOH of the about 100g of adding makes the pH value.By the manganese oxide of filtered and recycled lithiumation, be heated to subsequently about 380 ℃ about 4 hours.
The X-ray diffraction analysis through heat treated lithiated manganese oxide sample by the neutralize pH=11 and the pH=12.7 preparation that neutralizes shows that also the phase composition of described material causes described material to have different chemical properties.With reference to figure 1, the lithiated manganese oxide for preparing when pH=11 is made up of the mixture of some phases, comprises β-MnO 2With reference to figure 2, by contrast, the material of the pH=12.7 that neutralizes preparation contains significantly less β-MnO 2Phase.In Fig. 2, can clearly observe at 24 ° (2 θ) and 31 ° (2 θ) and locate new second mutually the X-ray diffraction peak.The appearance part of described cenotype increases owing to the lithium content of described lithiated manganese oxide.
By the detailed X-ray diffraction analysis through the manganese dioxide of heat treatment (for example 380 ℃ of heat treatments 8 hours) of the different pH values that neutralize, can follow the tracks of the existence of cenotype.With reference to figure 3,2 θ peaks of 24 degree and at 2 θ peaks of 31 degree all along with the pH value generation position excursion of handling.The pH value that depends on neutralization, the 2 θ peaks that can find 24 degree float to lower angle along with pH increases between about 25 and 24 degree.The 2 θ peaks that can find 31 degree float to higher angle along with the pH value increases between about 29.6 and 31.5.With reference to figure 4, the intensity at each peak at these two peaks is also along with the pH value of neutralization changes and changes.Along with pH increases to 12.7 from 7, the intensity at 2 θ peaks of 24 degree is increased to about 40% from about 35%; In identical pH scope, the intensity at the 31 2 θ peaks of spending is increased to about 37% from about 34.8%.
After the heat treatment, the BET surface area of lithiated manganese oxide the analysis showed that for the manganese dioxide of neutralization under higher pH value, hole surface and pore volume all reduce.
With in the lithium hydroxide and during preceding heat treatment, do not observe described cenotype at described manganese dioxide by X-ray diffraction or cyclic voltammetry.Neutralization can form the precipitated phase and the gel phase of lithiated manganese oxide.For example, by adding lithium hydroxide when described EMD is neutralized pH value between about 5 and 11, the precipitation and the colloidal suspension of formation particle, described colloidal suspension comprises described lithiated manganese oxide.
Along with the pH increase of neutralization, the lithium content of the manganese oxide of described lithiumation increases thereupon.Determine lithium content by the inductively coupled plasma atomic emission spectrum.With reference to figure 6, neutralizing produces lithium content greater than 0.5% lithiated manganese oxide greater than 9 pH value; Neutralize and produce lithium content greater than 0.7% lithiated manganese oxide greater than 11 pH value; Neutralize and produce lithium content greater than 1.2% lithiated manganese oxide greater than 12.7 pH value.
Embodiment 2
Preparation comprises the coin shape battery of lithiated manganese oxide.Be pressed into the bottom of described coin shape battery by the mixture that 600mg is contained 75%KS6 graphite and 25%PTFE; Cathode mix (the 60%MnO that contains the 100mg lithiated manganese oxide then in the compacting of described KS6/PTFE layer top 2, 35%KS6 and 5%PTFE), preparation CR2430 SS coin shape battery.Dividing plate (Celgard2400) is placed at top at cathode mix.The Li metal anode is placed on above the dividing plate, and in described battery, adds electrolyte (0.57M's is LiTFS among 70/10/20 the DME/EC/PC in percent by volume).
Described coin shape battery under C/10, discharge (i.e. the speed of in 10 hour time, discharging) with described battery capacity.With reference to figure 7, greater than 7, particularly the pH value can have the operating voltage of raising greater than the improved lithiated manganese oxide of 11 preparations with the pH value.Contain the pH value that neutralizes and be at least 2.8V at the operating voltage under the C/10 greater than the battery of 9 lithiated manganese oxide.Along with the pH value that neutralizes increases to more than 11, the operating voltage under C/10 is greater than 2.85V.Under about 12.7 neutralization reaction pH value, described operating voltage is increased to about 2.95V.By in the handle and the pH value bring up to 12.7 from original 4.4, described operating voltage increment is about-150mV.
With reference to figure 7, the operating voltage of raising is relevant with the lithium content of described lithiated manganese oxide.With reference to figure 6 and 7, along with in and the increase of pH value, the lithium content increase of described lithiated manganese oxide.The lithium content of described lithiated manganese oxide can be measured by ICP.After the heat treatment, the Mn of pH greater than the lithiated manganese oxide of 11 (for example pH=12.7) neutralizes 4+Content is less than 59% (for example about 57.7%).
With reference to figure 8, test coin shape battery under the speed of high C/2.Lithiated manganese oxide with high lithium content has the highest load voltage.The raising of load voltage causes the small size reduction (mAh/g) of described battery capacity.
Embodiment 3
The electrochemical measurement that battery (flooded cell) carries out described lithiated manganese oxide is overflowed in use.Overflowing battery is a kind of excessive electrolytical battery that contains, and wherein, electrolytical use is the electric current of limit battery not.As N.Iltchev, described in the J.Powder Sources 35:175-181 (1991), use a kind of three electrodes to overflow battery.The test negative electrode is a kind of 60/40 MnO that is compressed on the 100mg on the nickel collector body 2/ contain (Teflonized) acetylene black (TAB-2) mixture of teflon.To electrode and reference electrode is the lithium metal.At-10 ℃, overflow the discharge of battery under the velocity of discharge of C/10 and also show, when in and pH when increasing, operating voltage improves.Use from Delta (Delta E.M.D. (Pty) Ltd., Nelspruit, South Afica), observed similar result with neutralize three crowdes of other EMD of high pH value of LiOH.
Each batch manganese oxide for the various pH values that neutralize by the adding lithium hydroxide overflows battery with slow-scanning rates (for example, about 0.03mV/min) use and carries out the cyclic voltammetric test.With reference to figure 5, along with in and pH value increase the discharge voltage raising of maximum discharge current.In described and the pH value greater than 11 the time, described increase is the most remarkable.Be not restricted to any theory, when the drift of piezoelectric voltage can be owing to β-MnO in described lithiated manganese oxide mixture 2The content of phase is lower.
Embodiment 4
Use is from Delta (Delta E.M.D. (Pty) Ltd., Nelspruit, EMD SouthAfica) (reference or control cell) and lithiated manganese oxide (pH11) the preparation 2/3A battery for preparing under pH=11.Reference 2/3A battery all is identical with all others of the 2/3A battery of pH11.At-10 ℃, described battery discharges by opening in 3 seconds with the pulse of closing in 27 seconds under 0.9A.With reference to figure 9, the consistent output voltage that is higher than the 2/3A battery of described reference or contrast of the operating voltage of the 2/3A battery of pH11.
Other embodiment is in the appended claims scope.For example, except improving the pH value of handling, can improve the lithium content of lithiated manganese oxide by improving described ion exchange process with following several modes: (1) uses the vacuum backfill of process chamber to increase the enter degree of lithium salt solution for the aperture (for example radius is less than those apertures of 20 dusts) of manganese dioxide; (2) use by manganese dioxide is exposed to H 2SO 4Sour drop go out process; (3) in N-process, use the high processing temperature boiling point of water (for example near); Perhaps (4) use alcohol as surfactant, improve the manganese dioxide wettability of the surface.

Claims (37)

1. manganese oxide composition that contains lithiated manganese oxide, the X-ray diffraction spectrogram of described lithiated manganese oxide comprise one 31 degree 2 θ peaks, and intensity is at least 2 θ peaks of 35% and one 24 degree, and intensity is at least 35%.
2. according to the composition of claim 1, wherein, 2 θ peak intensities of described 31 degree are at least 36%.
3. according to the composition of claim 1, wherein, 2 θ peak intensities of described 24 degree are at least 38%.
4. according to the composition of claim 1, wherein, 2 θ peaks of described 31 degree are between 31 degree and 32 degree.
5. according to the composition of claim 1, wherein, 2 θ peaks of described 24 degree are between 24 degree and 24.8 degree.
6. according to the composition of claim 1, wherein, described lithiated manganese dioxide comprises the lithium greater than about 7% in MnO2.
7. according to the composition of claim 1, wherein, described lithiated manganese oxide comprises the Mn less than 59 weight % 4+
8. an electrochemical cell comprises first electrode that contains lithiated manganese dioxide, and described lithiated manganese dioxide is at MnO 2In contain lithium greater than about 0.7 weight %; With
Second electrode.
9. battery according to Claim 8, wherein, described second electrode is lithium electrode.
10. battery according to Claim 8, wherein, described second carbon electrode that electrode is a lithiumation.
11. battery according to Claim 8, wherein, described battery has the operating voltage greater than 2.9V.
12. battery according to Claim 8, wherein, the X-ray diffraction spectrogram of the manganese dioxide of described lithiumation has 2 θ peaks of one 31 degree, and intensity is at least 2 θ peaks of 35% and one 24 degree, and intensity is at least 35%.
13. battery according to Claim 8, wherein, 2 θ peak intensities of described 31 degree are at least 36%.
14. battery according to Claim 8, wherein, 2 θ peak intensities of described 24 degree are at least 38%.
15. battery according to Claim 8, wherein, 2 θ peaks of described 31 degree are between 31 degree and 32 degree.
16. battery according to Claim 8, wherein, 2 θ peaks of described 24 degree are between 24 degree and 24.8 degree.
17. a method of making electrochemical cell comprises:
Preparation comprises the electrode of lithiated manganese oxide, and the X-ray diffraction spectrogram of described lithiated manganese oxide comprises 2 θ peaks of one 31 degree, and intensity is at least 2 θ peaks of 35% and one 24 degree, and intensity is at least 35%; And
Form a battery that comprises described electrode and lithium electrode.
18. according to the method for claim 17, wherein, the process for preparing described electrode comprises:
The manganese oxide of described lithiumation is provided.
19., wherein, provide the process of the manganese oxide of described lithiumation to comprise according to the method for claim 18:
Manganese oxide is placed in the liquid, forms suspension;
In described suspension, add lithium salts, obtain a kind of pH value greater than about 7 suspension;
From described suspension, remove described liquid, obtain a kind of solid; And
Described solid heating, obtain the manganese oxide of described lithiumation.
20. according to the method for claim 19, wherein, in described suspension, add described lithium salts, obtain the pH value greater than about 11 suspension.
21. according to the method for claim 17, wherein, 2 θ peak intensities of described 31 degree are at least 36%.
22. according to the method for claim 17, wherein, 2 θ peak intensities of described 24 degree are at least 38%.
23. according to the method for claim 17, wherein, 2 θ peaks of described 31 degree are between 31 degree and 32 degree.
24. according to the method for claim 17, wherein, 2 θ peaks of described 24 degree are between 24 degree and 24.8 degree.
25. according to the method for claim 17, wherein, the manganese dioxide of described lithiumation contains the lithium greater than about 0.7% in MnO2.
26. according to the method for claim 17, wherein, described battery has the operating voltage greater than 2.9V.
27. a method for preparing lithiated manganese dioxide comprises:
In the suspension of manganese oxide in liquid, add lithium salts;
From described suspension, remove described liquid, obtain a kind of solid; And
Heat described solid, obtain a kind of manganese dioxide of lithiumation, the X-ray diffraction spectrogram of described lithiated manganese dioxide comprises 2 θ peaks of one 31 degree, and intensity is at least 2 θ peaks of 35% and one 24 degree, and intensity is at least 35%.
28. according to the method for claim 27, wherein, described manganese oxide comprises the manganese dioxide that a kind of electrochemical process is produced.
29. according to the method for claim 27, wherein, described lithium salts comprises lithium hydroxide.
30. according to the method for claim 27, wherein, the step that adds a kind of lithium salts comprises add the solution that contains lithium hydroxide in described suspension.
31. according to the method for claim 27, wherein, described liquid comprises water.
32. according to the method for claim 27, wherein, heating steps comprises to be brought up to the temperature of described solid between about 350-400 ℃.
33. according to the method for claim 27, wherein, the manganese dioxide of described lithiumation is at MnO 2In comprise lithium greater than about 0.7 weight %.
34. according to the method for claim 27, wherein, the manganese dioxide of described lithiumation comprises the Mn less than 59 weight % 4+
35. according to the method for claim 27, wherein, the manganese dioxide of described lithiumation has the operating voltage greater than 2.9V.
36. a method for preparing lithiated manganese oxide comprises:
In the suspension of manganese oxide in a kind of liquid, add a kind of lithium salts, obtain a kind of pH value greater than about 11 suspension;
From described suspension, remove described liquid, obtain a kind of solid; And
Heat described solid, obtain described lithiated manganese oxide.
37. according to the method for claim 36, wherein, the X-ray diffraction spectrogram of described lithiated manganese dioxide comprises 2 θ peaks of one 31 degree, intensity is at least 2 θ peaks of 35% and one 24 degree, and intensity is at least 35%.
CN99807317.2A 1998-05-11 1999-05-10 Lithiated manganese oxide Pending CN1305644A (en)

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