CN1261330A - Method for producing lithium-manganese mixed oxides and their use - Google Patents

Method for producing lithium-manganese mixed oxides and their use Download PDF

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CN1261330A
CN1261330A CN98806502A CN98806502A CN1261330A CN 1261330 A CN1261330 A CN 1261330A CN 98806502 A CN98806502 A CN 98806502A CN 98806502 A CN98806502 A CN 98806502A CN 1261330 A CN1261330 A CN 1261330A
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electrode
nitrate
lithium manganese
manganese oxide
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U·黑德
V·希拉里乌斯
D·劳林
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Merck Patent GmbH
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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
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/52—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]2-, e.g. Li2(NixMn2-x)O4, Li2(MyNixMn2-x-y)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
    • 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
    • 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)
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    • 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
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    • 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
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a method for producing mixed oxides with slightly variable electrochemical properties and spinel-type structures of formula (I): LixMeyMn2-yO4, in which Me is a metal cation from the II, III, IV, V and VI main groups or from the I, II, IV, V, VII or VIII subgroups of the periodic table of the elements, in particular a cation from the group of elements Al, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, W, Zn, and 0<=x<=2 and 0<=y<=2. The invention also relates to their use in producing manganese dioxide electrodes for galvanic cells, electrochemical cells, secondary batteries, in particular for prismatic and round cells.

Description

Manufacture method of lithium-manganese mixed oxides and uses thereof
The present invention relates to a kind of method of making mixed oxide, this mixed oxide has the electrochemical properties and the spinel structure formula (I) of easy variation
Li xMe yMn 2-yO 4(I) wherein Me is the metallic cation of main groups such as II in the periodic table of elements, III, IV, V and VI and subgroups such as I, II, IV, V, VII or VIII, particularly from element al, Co, Cr, Fe, Ge, Mg, Nb, a kind of positively charged ion among Ni, Sn, Ta, Te, V, W and the Zn etc.With 0≤x≤2 and 0≤y＜2 and relate to the manganese dioxide electrode that is used for galvanic cell, electrochemical cell and rechargeable battery with these oxide compound manufacturings, particularly make the electrode that is used for prismatic and circular batteries.
The negative electrode that the typical components of lithium battery is made up of the lithiumation metal oxide, preferably with the anode of carbon system, the transparent separator material of sprotic ionogen and ionogen.
The effect of the separator material between electrode is that two electrodes are carried out electronic isolation.
Cathode material commonly used is lithium-galaxite, and the electrochemical activity of this material is very high.In order to improve electroconductibility, this class manganese dioxide electrode mixes mutually with carbon granules, carbon black grain and granular graphite usually.Used caking agent is organic or inorganic additives.
The LiMn that DE-A1-41 19 944 mentions 2O 4And Li 4Mn 5O 12Be stoichiometric spinel, cathode material is by lithium salts, particularly lithium hydroxide under the temperature more than 750 ℃ with the manganese oxide prepared in reaction.
DE-A1-43 28 755 discloses a kind of corresponding cathode material, and this material has variable stoichiometric equation Li 1+xMn 2-xO 4+ δ, 0≤x＜0.33 and 0≤δ＜0.5 wherein, the selection of varying parameter x and δ should make material just keep cubic symmetry (spinel lattice) under common discharge condition, and the average oxidisability of Mn is not less than 3.5.
On the other hand, people such as M.N.Richard (Solid State Ionics (solid state ionics) 75 (1994) 81-91) have narrated the spinel of a kind of " hypoxgia ", and its formula is Li (Li 1/3/ Mn 5/3) 0 4-δThe increase of δ makes the average oxidisability of Mn drop to 3.5 from 4.Lithium can Mn 3+Simultaneous oxidation and removal of impurities, like this in addition the spinel of tolerable this " hypoxgia " as the cathode material of reversible action.
The accessible capacity of this class cathode material is between 10mAh/g-120mAh/g.This material depends on that their stoichiometric composition and crystalline structure more or less are sensitivity and unstable in air to humidity.In satisfied cyclical stability, improving high-temperature shelf property can only be just can reach under the acceptable prerequisite as a rule at lower capacity.
But disclosed preparation has the method for the lithium-Mn oxide of sharp crystal structure certain shortcoming is all arranged as a rule, and its powdered material can only prepare in batches, and will stand thermal treatment for a long time, and this is with regard to exigent energy input.
Therefore, the object of the present invention is to provide a kind of simple, fast and method for saving energy prepare suitable lithium manganese mixed oxides, this oxide compound has spinel structure, and has a superperformance of the negative electrode that is used for rechargeable electrochemical cell, this method provide a kind of may, promptly the performance of the powder that will prepare is carried out system's modification according to desired use.
The measure that reaches this purpose is to adopt a kind of method for preparing lithium manganese oxide, and this oxide compound has the electrochemical properties of easy change, and big surface-area and sharp crystalline structure are particularly arranged, and its general formula I is
Li xMe yMn 2-yO 4(4) wherein Me is the II of the periodic table of elements, III, IV, main group such as V and VI and I, II, IV, V, a kind of metallic cation of subgroup such as VII or VIII, particularly from element al, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, a kind of positively charged ion among W and the Zn etc. and 0≤x≤2 and 0≤y≤2 the method is characterized in that a) nitrate with the various metals of the stoichiometric ratio of required powder constituent is dissolved in water/alcohol mixture, the percentage ratio of water (in total mixture) can be 0-100% in this mixture, be preferably 5-50%, preferred 30-50%, b then) pyrolysis in the nitrate pyrolysis plant, the temperature out of reactor is 400-700 ℃.
According to the present invention, press material process under 500-750 ℃ of nitrate method for pyrolysis powdered and replenish annealing operation.
This annealing operation is carried out in oxygen-containing atmosphere, and preferred oxygen concn can reach 100%.
Simultaneously, the lithium manganese oxide that the present invention relates to according to said method to prepare is used for the application of the manganese dioxide electrode of galvanic cell and electrochemical cell in manufacturing.
Particularly, reaching heavy body and good cyclical stability simultaneously is purpose of the present invention, adopt powdered material with homogeneous phase and stoichiometric composition for this reason, cause possible doping agent homogeneous phase ground to be present in the material, this material directly has spinel structure after preparation, and very little granularity is uniformly arranged, its granularity should be less than 10 μ m.
Test shows, if prepare pulverous lithium manganese oxide with the spray pyrolysis method, can unexpectedly be met these high requests of material.In order to implement this method, can utilize the solution of various salt or the mixture of corresponding suspension, make its oxidation in thermal reaction area, the rapid evaporation solvent forms the lithium manganese oxide shown in the required formula (I) simultaneously.
Be particularly suitable for preparing that available nitrate pyrolysis characterizes on the methodological principle of above-mentioned lithium manganese mixed oxides.Can being implemented of this method by means of the aqueous solution of metal nitrate or the suspension of other component in its nitrate aqueous solution.Its advantage is and can adopts with the nitrate of stoichiometry use or the aqueous solution or the suspension of each component according to required the finished product.To 400-700 ℃, particularly in 475-650 ℃ air or the alternative definite atmosphere directly the solution or the suspension that prepare of spraying can directly obtain required spinel type product, this product be pure phase do not need any follow-up processing.
When implementing present method, preferably use the salts solution of those thermopositive reaction to obtain required mixed oxide.The advantage of this mode is, though initiation reaction requires reaction chamber to reach certain temperature at first, reaction thereafter will under the optimizing situation be control oneself and can keep temperature, if desired, also available igniting comes initiation reaction.
The used raw material of lithium manganese oxide that is used to form formula (I) is preferably the nitrate of required metal in the product.But the suitable salt of other comprises acetate, Citrate trianion, oxyhydroxide or other energy is water-soluble or the organic metal salt of water/positive alcohol mixture.
In addition, the suitable oxyhydroxide that uses with nitrate also can be used for reaction.For example, stoichiometric lithium hydroxide, manganous nitrate and other from periodic table of elements main group II, III, IV, V, with VI or subgroup I, II, IV, V, the metal-salt of VII or VIII, metal-salt from elements such as Al, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, W and Zn also can be used for method of the present invention especially, and this other salt is preferably water-soluble nitrate equally.
Before spray pyrolysis process of the present invention was carried out, above-mentioned various salt added solution according to the stoichiometric ratio of required powder constituent.Good especially character appear at salt in total concn with 5-50%, 30-50% situation about existing particularly.
Suitable salts solution comprise pure water solution and not Dan Yishui make solution and comprise a kind of solution of organic solvent.Particularly, appropriate organic solvent is the solvent that can mix with water, can be used for this purpose such as alcohols such as ethanol, methyl alcohol or propyl alcohol.But can adopt other solvent equally, these solvents can play coordination agent, for example glycol ether simultaneously.But preferred alcohols, since their solubleness height in water, special preferred alcohol.
Particularly, organic solvent works to keep temperature in the spray pyrolysis reaction.If the employing organic solvent, then the selection of concentration and temperature of reaction should make carbon compound that thermopositive reaction completely takes place, and make noresidue carbon in the mixed oxide that is generated, otherwise the generation of spinel structure can be hindered.Say in essence, can adopt the solution that only contains organic solvent, that is to say that the concentration of organic solvent in the solvent total amount can rise to 100%.
Be the purpose of the new type lithium manganese oxide that reaches preparation formula (I), the salts solution that makes sprays in the NPA reactor (NPA nitrate pyrolysis installation) that is heated to service temperature.This reactor is the reactor of the special development of applicant, and spraying realizes to twin nipple with pump.The reaction soln that sprays into reactor in this way also is converted into finely divided free-pouring powder during the course by pyrolysis.
According to later purposes, the character of powder can be with subsequent heat treatment modification in addition, and this can make physical properties and electrochemistry-physical properties by system's modification, so that satisfy application requiring.
With the relevant character of preparation battery, for example granularity, specific surface area, oxygen level and lattice parameter can easily be carried out the subsequent heat treatment change in the atmosphere of determining.
Another advantage of novel method is, can select to prepare the doping type mixed oxide of above-mentioned general formula in simple mode.Even under the very little situation of the precursor quality of used doping agent, also can guarantee to distribute at the homogeneous phase of the prepared precursor substance that is used for electrode.
Superior especially is that method of the present invention can simply and fast be carried out, even also is like this on sizable scale.In addition, because self-sustaining reaction, this preparation method's unique distinction is that energy input is low.
Suitably the control reaction can make the powder that makes directly be required spinel phase, and is appropriate as long as the temperature out of nitrate pyrolysis installation is selected.It is that a kind of granularity is lower than 10 μ m and the finely divided powder of high bulk density is arranged.
The carrying out of the annealing operation of back can change electrochemistry and physicochemical property.
The subsequent disposal of this powder particularly can influence crystallinity, lattice parameter, granularity, specific surface area and capacity.
What certainly, play a decisive role during the course is determined temperature, heating and cooling speed and annealing phase.Other important parameters comprises the atmosphere of selected stove and the full level of crucible.
In order to prepare actual cathode material, powder-product and other component of gained are carried out intense mixing, go back suspended substance.These must component example can enumerate the organic or inorganic caking agent and electricity is led additive.Addible organic adhesive comprises PTFE, and PVDF and other those skilled in the art know is used for the relevant caking agent of this purpose.That suitable especially is PTFE.Suitable electricity is led additive and is comprised carbon black, graphite, steel wool and other electro-conductive fiber.Interpolation quantity is 5-50, and particularly the carbon black of (in total amount) and graphite can give especially good results about 15% (weight).
Fusion the powder of various additives be converted into electrode then, its transform mode itself is known.This can be used on and contains a kind of inert material, and for example applying very between the wire cloth of aluminium, high pressure realizes.If desired, can carry out hyperthermic treatment thereafter, products obtained therefrom is dried during the course.
The electrode that makes like this can be used to make the secondary galvanic cell by known way, carbon dioxide process carbon electrode wherein, to sprotic electrolytical in the presence of, usually as counter electrode.But corresponding galvanic cell also can have other design.For example can add various additives, example gel agent, silica gel or other additive itself are the electrolytical viscosity of water to increase.Suitable polymer blend fabric or adherent fabric can place do between the electrode dividing plate and, can insert partition if desired.The material form that the polymer bonding fabric can be made up of PVA, polypropylene or other inert polymer.The known partition that is used for existing commercially available battery, can be corrugated and by, for example PVC forms.
In order to test, make electrode with the mixture of lithium/manganese dioxide of the present invention, with homogenize in the mixing tank of each component, all add conductive additive and caking agent under the various conditions.The mixture of preparation is like this added and is pressed into the negative electrode that is used for button cell, and make its drying.
Provide some examples below, attempt the present invention is illustrated, and make it be easier to understand with these examples, but this and do not mean that restriction range of application of the present invention.
Embodiment
Preparing stoichiometric formula is Li 1.045Mn 2O 4 ± 8Precursor:
Experiment is described
Stoichiometric lithium nitrate of weighing and manganous nitrate, and under agitation be dissolved in the deionized water.
The spray pyrolysis condition:
Nozzle pressure: 2.5bar
Burner temperature: 600 ℃
Air ratio: 2
Flow: 4.95kg/h
Adopt the Schlick twin nipple, 970/4 type, between the aperture 0.8mm reaction period, reactor is cooled.
Theoretical yield: 5244g
Thick productive rate: 5155g
This transformation efficiency that is equivalent to basic material is 98.3%
Product analysis provides following content:
Empirical theory
Li 3.928％ 3.879％
Mn 60.465％ 60.72％
O 35.607％ 35.40％
Li 1.029Mn 2O 4.044
Under different condition, calcine:
First experimental arrangement: 750 ℃, 10h, heating rate 3K/min in the air
Second experiment condition: 750 ℃, 24h, heating rate 3K/min table 1 in the air:
Two kinds of calcining result of experiment reach with comparative characteristic precursor substance calcining experiment 1 calcining of precursor mixture tests 2 particle size (d 50) [μ] 9.2 5.9 5.7 surface-area (BET) [m 2/ g] 13.2 3.4 2.9 lattice parameters [], 8.205 8.210 8.215 electrochemistry capacitances [mAh/g] 94 113 117

Claims (7)

1. method for preparing lithium manganese oxide, this oxide compound has the electrochemical properties and the spinel structure of malleable, and its general formula (I) is
Li xMe yMn 2-yO 4(I) wherein Me is the main group II of the periodic table of elements, III, IV, V and VI or subgroup I, II, IV, V, a kind of metal of VII or VIII, particularly from element al, Co, Cr, Fe, Ge, Mg, Nb, Ni, Sn, Ta, Te, V, a kind of positively charged ion among W and the Zn etc. and 0≤x≤2 and 0≤y≤2 is characterized in that a) being dissolved in water/alcohol mixture with the nitrate of the various metals of the stoichiometric ratio of required powder constituent, the percentage ratio of water (in total mixture) can be 0-100% in this mixture, be preferably 5-50%, preferred 30-50%, b then) pyrolysis in the nitrate pyrolysis plant, the temperature out of reactor is 400-700 ℃.
2. the method for claim 1 is characterized in that, by the additional annealing operation of powdered material warp under 500-750 ℃ of nitrate method for pyrolysis gained.
3. claim 1 and 2 method is characterized in that, this annealing is to carry out in a kind of oxygen concn can reach 100% oxygen-containing atmosphere.
4. be used for the application of the manganese dioxide electrode of galvanic cell in manufacturing according to the lithium manganese oxide of one of claim 1-3 or several method preparation.
5. be used for the application of cathodes for electrochemical cells in manufacturing according to the lithium manganese oxide of one of claim 1-4 or several method preparation, wherein as negative electrode, used anode then is preferably carbon dioxide process carbon electrode to manganese dioxide electrode in the presence of having sprotic ionogen.
6. be used for the application of the manganese dioxide electrode of prismatic and circular batteries in manufacturing according to the lithium manganese oxide of one of claim 1-4 or several method preparation.
7. be used for the application of the manganese dioxide electrode of rechargeable battery in manufacturing according to the lithium manganese oxide of one of claim 1-4 or several method preparation.
CN98806502A 1997-06-28 1998-06-18 Method for producing lithium-manganese mixed oxides and their use Pending CN1261330A (en)

Applications Claiming Priority (2)

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DE19727611A DE19727611A1 (en) 1997-06-28 1997-06-28 Process for the preparation of lithium manganese mixed oxides and their use
DE19727611.3 1997-06-28

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KR (1) KR20010014235A (en)
CN (1) CN1261330A (en)
CA (1) CA2295175A1 (en)
DE (1) DE19727611A1 (en)
WO (1) WO1999000329A1 (en)
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US6322744B1 (en) 1999-02-17 2001-11-27 Valence Technology, Inc. Lithium manganese oxide-based active material
JP2000331682A (en) * 1999-05-21 2000-11-30 Mitsui Mining & Smelting Co Ltd Positive electrode material for lithium secondary battery and battery using the same
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KR101272042B1 (en) * 2010-11-08 2013-06-07 주식회사 포스코이에스엠 Lithuium manganese complex oxide and the manufacturing method thereof
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EP0563988B1 (en) * 1992-04-02 1997-07-16 Fuji Photo Film Co., Ltd. Nonaqueous secondary battery
JP3221352B2 (en) * 1996-06-17 2001-10-22 株式会社村田製作所 Method for producing spinel-type lithium manganese composite oxide
JP3047827B2 (en) * 1996-07-16 2000-06-05 株式会社村田製作所 Lithium secondary battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100391855C (en) * 2005-07-08 2008-06-04 中南大学 Method for preparing manganiferous oxide
CN102337046A (en) * 2010-07-15 2012-02-01 星铂联制造公司 Manganese vanadium tantalum oxide and pigments having a black metallic effect coated with the same
CN102337046B (en) * 2010-07-15 2014-12-10 星铂联制造公司 Manganese vanadium tantalum oxide and pigments having a black metallic effect coated with the same

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JP2002506560A (en) 2002-02-26
CA2295175A1 (en) 1999-01-07
KR20010014235A (en) 2001-02-26

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