WO2000023380A1 - Oxyde de lithium-manganese, et procedes de fabrication correspondants - Google Patents

Oxyde de lithium-manganese, et procedes de fabrication correspondants Download PDF

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WO2000023380A1
WO2000023380A1 PCT/NZ1999/000175 NZ9900175W WO0023380A1 WO 2000023380 A1 WO2000023380 A1 WO 2000023380A1 NZ 9900175 W NZ9900175 W NZ 9900175W WO 0023380 A1 WO0023380 A1 WO 0023380A1
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compound
composition according
lithium
manganese
oxide
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PCT/NZ1999/000175
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Paul Jason Pickering
David Jonathan Hassell
Rudolf Steiner
Zhen-Yu Liu
James Bernard Metson
Wei Gao
Brett Graeme Ammundsen
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Pacific Lithium Limited
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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

  • This invention relates to metal doped lithium manganese oxide and methods of its production.
  • the trivalent manganese compound LiMn0 2 has been identified as a possible cathode material for lithium ion batteries.
  • monoclinic (m-) LiMn0 2 space group C2/m
  • having a layered rock salt structure similar to LiCo0 2 and LiNi0 2 exhibits promising electrochemical properties.
  • Li_vln0 2 obtained via conventional solid state reaction usually has an orthorhombic (o-LiMn0 2 ) structure (space group Pmnm). since m-LiMnOi is not usually stable under these synthesis conditions.
  • m-LiMn0 2 has been obtained by an ion exchange reaction of lithium salts with NaMn0 2 as precursor, or by a mixed alkaline-hydrothermal reaction (Armstrong & Bruce, Nature 38 . 499 (1996); Tabuchi et. al. J. Electrochem. Soc.145. L49 (1998)..
  • compositions having a general formula Li x M y N x 0 2 , and including the compound LiAlo. 2 5Mno.75O 2 , being a layered monoclinic structure.
  • the added aluminium apparently stabilises the layered monoclinic modification and allows direct synthesis of the compound.
  • Chiang et al., in Electrochem. Solid State Lett. I, 13 (1998) describe the preparation of both LiAlo._5Mno . 75O 2 and LiAlo.0 5 Mno. 95 O 2 in the layered monoclinic structure.
  • This synthesis method is complex and expensive and the nitrates of aluminium and manganese may be carcinogens and mutagens. Thus, the method may not be appropriate for commercial production.
  • a combination of dopants used to stabilise a layered monoclinic phase of LiMn0 2 may facilitate the synthesis procedure and/or provide electrochemical advantages over the prior art compounds using only aluminium or chromium as the dopant.
  • a metal-doped lithium manganese oxide composition having the formula LiM 1 m iM 2 m2 ...M x mx Mn-O 2 wherein M 1 , M 2 ...M X are each different metal ions, ml+m2+...mx+z is substantially equal to 1, ml+m2+...mx is greater than zero but less than 0.75 and z and at least mi are each greater than zero, providing that where m2...mx are zero M 1 is Cr and 0 ⁇ ml ⁇ 0.05 or M 1 is Ga.
  • M 1 , M 2 ...M X are each selected to have an ionic radius in their relevant oxidation state, similar to or less than that of Mn 3+ .
  • M 1 , M ⁇ ...M X are each selected from the group consisting of Al, Ga, Cr, Co, Fe, B, V, Ti and Ru.
  • M 1 may be Al.
  • M 2 may be selected from Cr, Co, Fe, B, V, Ti and Ru and is most preferably Cr.
  • M 1 , M 2 ...M each has the property of existing in a minimally distorted octahedral sphere of co-ordination.
  • M 1 , M " ...M x each has a formal oxidation state of 3 + .
  • m ⁇ +m 2 +...m x may be greater than zero but less than about 0.25.
  • composition is in predominantly monoclinic form.
  • a method of synthesising a metal-doped lithium manganese oxide composition having the formula LiM' m i M 2 m2 ...M x mx Mn z 0 2 wherein M 1 , M 2 ...M are each different metal ions, m l+m2+...mx + z is substantially equal to 1, ml+m2+...mx is greater than zero but less than 0.75 and z and at least ml are each greater than zero, providing that where m2...mx are zero and M 1 is Cr then 0 ⁇ ml ⁇ 0.05, in stable form by solid state reaction.
  • the solid state reaction includes:
  • mixing reagents including a lithium compound, a manganese compound and at least one additional metal compound, each compound selected from an oxide, a hydroxide and/or a carbonate, and
  • the lithium compound may be lithium carbonate.
  • the manganese compound may be manganese oxide.
  • the or each metal of the at least one additional metal compound may be selected to have an ionic radius in its relevant oxidation state, similar to or less than that of Mn 3+ .
  • the or each metal of the at least one additional metal compound may be selected from the group consisting of Al, Ga, Cr, Co, Fe, B, V, Ti and Ru.
  • the at least one additional metal compound includes aluminium oxide.
  • a transitional alumina is preferable used.
  • the at least one additional metal compound alternatively, or in addition, includes chromium oxide.
  • the method may further include ball milling the mixed reagents.
  • the mixture may be heated to a temperature in the range substantially 900°C to 1080°C. More preferably substantially 1000°C to 1080°C for a period of at least 5 hours.
  • the inert atmosphere may have a sufficiently low p0 2 to facilitate the formation of manganese in its 3+ oxidation state.
  • the p0 2 may be substantially 10 "5 atm or less.
  • the mixture may be heated in a reactor having a high temperature stable lining.
  • - mixing reagents including a lithium compound, a manganese compound and at least one additional metal compound, each compound selected from an oxide, a hydroxide and/or a carbonate,
  • the heating in air may be at a temperature in the range 600 to 850°C. Most preferably substantially 700°C.
  • the heating under inert atmosphere may be at a temperature of substantially 1000 to 1080°C.
  • Figures 3 A-F X-ray diffraction patterns showing the effects of temperature on the production and phase of LiMn0 2 from a high temperature solid state reaction with metal doping in an alumina-lined reactor in accordance with Example II:
  • Figures 4 A-D X-ray diffraction patterns showing the effects of chromium doping on the production and phase of LiMn0 2 from a high temperature solid state reaction with metal doping in an alumina-lined reactor, in accordance with Example IV:
  • Figure 7 Schematic representation of the cell construction as used in Examples VI, VII, VIII and X.
  • Figures 9A-D X-ray diffraction patterns of (A) LiAlo.0 5 Cro .01 Mno.9 4 O 2 ,
  • Figures 10A&B X-ray diffraction patterns of (A) Lio.5Cro.05Mno .95 O 2 and (B) LiCro.05Mno.95O 2 prepared according to Example IX.
  • the basic reaction underlying the synthesis method and compositions of the present invention involves the conversion of, for example, lithium carbonate and manganese oxide to lithium manganese oxide.
  • One possible reaction scheme would be:
  • the invention involves methods of synthesising stable forms of metal-doped LiMn0 2 , in layered monoclinic form, by solid state reaction.
  • the invention also relates to specific stable compositions formed by these methods.
  • LiMn0 2 lithium carbonate
  • Mn0 2 manganese oxide
  • AI 2 O 3 aluminium oxide
  • the formation of LiMn0 2 in monoclinic form, may be facilitated by raising the temperature to between about 950°C and 1080°C, and using a transitional alumina as the source of aluminium.
  • compositions were produced with the starting reagents lithium carbonate (L_ 2 C0 3 ), manganese (IV) oxide (Mn ⁇ 2 ), aluminium oxide (A1 2 0 3 ) and chromium oxide (Cr 2 0 3 ) heated in a reactor under inert atmosphere to a temperature in the range 800°C to 1080°C for a period of at least 2 hours.
  • L_ 2 C0 3 lithium carbonate
  • IV oxide Mn ⁇ 2
  • aluminium oxide A1 2 0 3
  • Cr 2 0 3 chromium oxide
  • compositions were produced in a two-stage reaction by firstly reacting lithium carbonate (Li 2 C0 3 ) and manganese carbonate (MnCC ) with one or more of aluminium oxide (A1 2 0 3 ), chromium oxide (Cr 2 0 ), gallium oxide (Ga 2 ⁇ 3) and boric acid (H 3 B0 3 ) in air at a temperature of 600-850 °C to produce oxygen-rich lithium manganese oxides, followed by a second heating step under nitrogen at 800-1080 °C.
  • Li 2 C0 3 lithium carbonate
  • MnCC manganese carbonate
  • aluminium oxide Al 2 0 3
  • Cr 2 0 chromium oxide
  • Ga 2 ⁇ 3 gallium oxide
  • boric acid H 3 B0 3
  • M may be one or more dopant elements.
  • the reagents in the first stage can be combined in the appropriate ratios to give a product with a lithium/(manganese + dopant) ratio of approximately 0.5.
  • the product of the reaction in air will then be a single-phase doped spinel oxide. This can then be combined with additional Li reactant in the second stage under N 2 to give doped LiMn0 2 , e.g.:
  • An advantage of the two-stage method is that the dopant precursor compounds are reacted with the manganese precursor compound in air, which provides more reactive conditions for the decomposition of some metal salts than an inert atmosphere such as N 2 . This may allow the selection of metal salts as starting compounds which may be difficult to react together to give a single-phase product under an inert atmosphere.
  • Spinel LiMn 2 ⁇ 4 can be prepared with a large number of different dopants at a range of concentrations. Many of these doped LiMn 2 0 4 compounds are known and have been well characterised in terms of the effects of the dopant element on the crystal structure. This allows for ready identification of the doped spinel intermediate phase by techniques such as X-ray powder diffraction.
  • the relatively facile formation of doped spinel phases in air then provides an atomic-level dispersion of the dopant element in the manganese oxide lattice before proceeding to the conversion step under N 2 .
  • the conversion step under N 2 therefore involves essentially lithium diffusion into the spinel phase from the Li 2 Mn0 3 phase or additional Li reactant, some reduction of Mn 4+ to Mn 3+ , and an accompanying crystal phase transformation.
  • lithium, manganese and dopant compounds may also be employed as the starting reagents, but generally selected from carbonates, oxides and hydroxides.
  • the metal ions most preferred for doping of the LiMn0 2 should be selected by several criteria, firstly ionic radius, and secondly appropriate charge state.
  • the incorporation of a metal ion with an ionic radius similar to or less than that of Mn 3+ is likely to mitigate the distortion of the octahedral geometry around the Mn 3+ .
  • the metal ion or ions should have an ionic radius, in their relevant oxidation state, similar to or less than that of Mn " .
  • the dopants may be selected from, for example, B, Ga, Cr, Co, Fe, V, Ti and Ru.
  • the metal ion or ions may also have the property of existing in a minimally distorted octahedral sphere of co-ordination.
  • the other phases identified by XRD were orthorhombic 0-LiMnO 2 , tetragonal LiA10 2 , and rock salt Li 2 Mn0 3 .
  • the latter, and the spinel phase LiMn 2 0 were preferentially formed if the oxygen partial pressure in the reactor exceeded lO ⁇ atm.
  • the inert atmosphere should preferably involve a p ⁇ 2 of 10 "5 atm or less. This is sufficient to facilitate the formation of manganese in its 3+ oxidation state.
  • Example II More detailed temperature effect results, and X-ray diffraction data are included below under Example II.
  • reaction seems to be completed in approximately three hours. Reaction times of longer than 5 hours usually lead to a decrease of the LiMn0 2 -phases and the formation of spinel phase. Reaction time and temperature are likely to be dependent on particle size, and the required reaction may be achieved in a shorter time employing reagents, particularly manganese oxide, having a smaller particle size.
  • Samples resulting from processing for about 5 hours at 1040°C had average phase compositions of approximately 80% o-LiMn0 2 and 10% m-LiMn0 2 .
  • Elemental analysis revealed the presence of high amounts of iron and chromium in samples produced in the conventional steel reactors in comparison with the samples produced in alumina-lined reactors.
  • the Fe content of samples prepared in a steel reactor was generally in the range 1- 3%, with Cr in the range 0.05-0.2%. These figures were reduced by about a factor of 10 in the alumina reactor.
  • Example II The process of Example II was repeated in alumina boats in a tube furnace, with the addition of chromium (in the form of Cr 2 0 3 ) to the reaction mixture and subsequent firing at temperatures from 1050 to 1100°C for 3 to 7 hours, under an inert atmosphere. As in Example II, the mixture was first heated to about 200°C for about an hour before increasing the temperature to the selected level. The results are shown in Table 2.
  • chromium oxide Whilst these results were obtained using chromium oxide, it is anticipated that other metals (such as Co and Fe) or combinations of metals would similarly facilitate the formation of Al-doped m-LiMn ⁇ 2 - It is also considered that the chromium, or an alternative metal, may reduce the temperature at which Al- doped m-LiMn0 2 is formed.
  • LiMn0 2 was still predominantly in the orthorhombic form (45%), although there was a 35% proportion of monoclinic form contrasting with only 15% under the same conditions but without chromium doping (see Figure 3). With 5 wt% Cr 2 ⁇ 3 , LiMnC> 2 was predominantly in the monoclinic form (70%o). The higher proportion of chromium oxide required in this Example compared with Example III could indicate inadequate mixing of the starting materials. Pregrinding of the reaction mixture could significantly improve the effect of chromium.
  • the X-ray diffraction patterns of the products are shown in Figure 5.
  • the phase mixtures obtained, estimated from the ⁇ -ray diffraction analyses of the products, are given in Table 4.
  • x is between 0.05 and 0.20 the products are 100% single phase monoclinic LiCr_Mni_.0 , as indicated by the data of Davidson et al. in J. Power Sources 54, 205 (1995) and Dahn et al. in J. Electrochem. Soc. 145, 851 (1998).
  • the monoclinic layered structure (space group C2/m) of the LiCr.Mn 1 ._O 2 products was confirmed by Rietveld analysis of the X-ray diffraction data.
  • Chromium doping results in changes in the crystal unit cell dimensions consistent with substitution of Cr ions into Mn sites of the crystal structure.
  • LiMn ⁇ 2 the extent of the monoclinic crystal distortion resulting from the Jahn Teller distortion of the octahedral coordination environment around the Mn ions is reflected in the magnitude of the ratio between the a and b crystal axes.
  • the systematic decrease in the alb ratio with increasing amounts of Cr in the crystal is an effect of a minimally distorted octahedral sphere of coordination around the Cr ions.
  • the atomic positions of the cations in the crystal lattice were also refined using the Rietveld method. The results confirmed that Cr and Mn ions share the transition metal sites in the layered crystal structure. No Mn or Cr ions were detected in the interlayer (lithium) sites of the crystal.
  • the X-ray diffraction pattern of the product shown in Figure 6, shows that the product contains approximately 90% m-LiMn0 2 . and approximately 10% o-LiMn0 2 . No additional impurity phases were detected.
  • the unit cell parameters for the monoclinic phase obtained by performing a simultaneous Rietveld refinement of the crystal parameters for both the monoclinic and the orthorhombic phase from the X-ray diffraction data, are compared with those given by Capitaine et al. (Solid State Ionics 89, 197 (1996)) for non-doped monoclinic LiMn0 2 in Table 6.
  • the monoclinic LiAlo.0 5 Mno.95O 2 phase of this example shows a contracted crystal lattice by comparison with the undoped compound. This is consistent with the presence of the Al ion, which has a smaller ionic radius than trivalent Mn, sharing the same crystallographic site as Mn.
  • the contraction is more significant along the a crystal axis than the b crystal axis, consistent with a minimally distorted octahedral sphere of co-ordination around the Al ions since the magnitude of the alb ratio is related to the average degree of distortion of the octahedron of oxygen ions around the cations in the Mn layer.
  • Electrodes were prepared by mixing 80 wt.%> of LiAlo.05Mno.95O 2 , 12 wt.% acetylene black and 8 wt.% poly(vinylidene fluoride) as a slurry in 1-methyl-
  • the electrodes were assembled into electrochemical cells within the argon- filled glove box using 2032 button cell hardware.
  • the cell assembly is schematically illustrated in Figure 7.
  • the electrode containing the LiAlo 05Mn 09 5O 2 was the cathode 1.
  • the anode 2 was a circular disk of lithium foil having a thickness of 0.38 mm, pressed into a stainless steel lid 3.
  • a polymeric gasket 4 was then positioned over the lip of the lid.
  • a porous glass fibre disk separator 5 wetted with 1M LiPF 6 in (50 wt.% ethylene carbonate + 50 wt.%) dimethylene carbonate) electrolyte solution was placed between the anode and cathode.
  • a stainless steel disk 6 and spring 7 were then positioned behind the cathode and the entire assembly hermetically closed within the stainless steel casing 8 by crimp sealing.
  • Example VII Cells prepared by this procedure were cycled more than 200 times between 2.0 and 4.4 V at ambient temperature and elevated temperature (55 °C). A constant charging current of 30 or 75 mA/g was applied until 4.4 V was reached, then the cell was held at 4.4 V until the current dropped below 3 mA/g. Cells were discharged at constant currents of 30 or 75 mA/g. Typical discharge capacities obtained by this procedure at the 30 mA g discharge rate are given for the 1 st , 16 th , and 200 th cycles in Table 8 in Example VIII. The discharge capacities at ambient temperature increase with cycling. At 55 °C the discharge capacities are particularly high and show good stability. Example VII
  • the X-ray diffraction pattern of the product shown in Figure 8, shows that the product contains approximately 95% m-LiMn0 2 , with the remainder being o-LiMn0 2 phase. No additional impurity phases were detected.
  • the LiAl 0. ⁇ oMno .9 o0 material of this example shows a contracted crystal lattice by comparison with the undoped compound.
  • Electrodes and electrochemical cells containing the LiAl 0. ⁇ oM ⁇ io .9 o0 2 material were prepared as described in Example VI, and the cells were charged and discharged following the same procedures.
  • Typical discharge capacities obtained at the 30 mA/g discharge rate are given for the 1 st , 16 th , and 200 th cycles at ambient and 55 °C in Table 8 in Example VIII.
  • the material shows slightly lower initial capacities than the LiAlo .05 Mno . O 2 compound of Example VI, but the capacity increases with cycling to values which are similar to those of the LiAlo . o 5 Mn 0.95 ⁇ 2 material.
  • Example VHI Example VHI
  • compositions LiAl Cr v Mn ⁇ . -y ⁇ 2 were prepared by reacting lithium carbonate (99.9% pure), Mn0 2 (99.0% pure), theta-Al 2 0 3 (99.95% pure) and Cr 2 0 3 (99.0% pure). Exact stoichiometric amounts of the reactants to give the compositions LiAlo o5Cr 0 oiMn 0 9 O 2 , LiAl 0 osCro 03Mn 0 9 2 0 2 , LiAlo osCro osMno 9 o0 2 .
  • the X-ray diffraction patterns of the products are shown in Figure 9(A-D).
  • the pro ⁇ cts were 80-90 % layered monoclinic phase, with the remaining phase being o-LiMn0 2 . No other impurity phases were observed.
  • the compositions LiAl 0 osCro os no 90O 2 and LiAl 0 o_Cr 0 o ⁇ Mn 093 ⁇ 2 were phase- pure layered monoclinic materials. Cell parameters for these phases are given in Table 7.
  • Electrodes and electrochemical cells containing the LiAlo 05 Cr 0 o 5 Mn 09 o0 2 , and LiAlo o 2 Cr 0 osMno 9 O 2 materials were prepared as described in Example VI, and the cells were charged and discharged following the same procedures.
  • Typical discharge capacities obtained at the 30 mA/g discharge rate are given for the 1 st , 16 th , and 200 th cycles at ambient temperature and 55 °C in Table 8.
  • the cells cycled at 55 °C showed similar excellent capacity retention over 200 cycles as the LiAl 0 osMno 95O 2 and LiAlo ⁇ oMn 0 9o0 2 materials of Examples VI and VII.
  • LiAl 0 o_Cr 0 osMn 093 O 2 materials showed increased overall capacity at both 55 °C and ambient temperature when compared with the LiAl 0 osMno 95O 2 and LiAl 0 ⁇ oMn 09 o ⁇ 2 . materials.
  • the co bination of chromium plus aluminium together in monoclinic layered LiMn0 2 therefore provides a material with improved cycling characteristics over monoclinic layered LiMn0 2 doped with aluminium alone.
  • the addition of chromium to the aluminium-doped LiMn0 2 also facilitated the obtaining of a single-phase monoclinic layered material.
  • Table 8 Discharge capacities for the monoclinic LiAl ⁇ Mn ⁇ -. 0 2 materials of Examples VI, VII & IX, and the LiAl v Cr,,Mn 1- ⁇ -v 0 2 materials of Example VHI.
  • This example shows that a two stage solid state process, in which a doped spinel phase is formed by reaction in air and then reacted with additional lithium under nitrogen, can be used to synthesise doped LiMn0 2 materials.
  • This reaction route provides an alternative to the single-step reaction, and may be useful when employing starting oxides or salts (as the source of lithium, manganese or dopant) which are difficult to react together to give a single- phase product under an inert atmosphere.
  • oxides or salts may react more easily in air to give a doped oxidised lithium manganese oxide product, which can then be converted into the doped LiMn0 2 in inert atmosphere in a second stage.
  • doped oxidised lithium manganese oxide compounds can be formed by solid state reactions at temperatures ranging from 200 °C up to 900 °C, and that a range of temperature conditions could therefore be used in the first stage of this process.
  • the second, conversion step in inert atmosphere should preferably be performed at a higher temperature than the first step.
  • the two stage reaction process was used to prepare Al-doped LiMn0 2 .
  • Exact stoichiometric amounts of lithium carbonate (99.9% pure), Mn ⁇ 2 (99.0% pure) and theta-Al ⁇ 3 (99.95%) pure) to give a product of formula LiAlo.05Mno.95O 2 were mixed and ball-milled for 30 minutes.
  • the resulting mixture was heated at 700°C in air for 8 hours, cooled, then fired at 1000 °C for 5 hours under a flow of zero grade nitrogen.
  • the product was cooled over a period of one hour, maintaining the nitrogen flow until the temperature dropped below 50 °C.
  • Electrodes and electrochemical cells containing the LiAlo.0 5 Mno .95 O 2 material of this example were prepared as described in Example V, and the cells were charged and discharged following the same procedures. Typical discharge capacities obtained at the 30 mA/g discharge rate are given for the 1 st , 16 th , and 200 th cycles at ambient and 55 °C in Table 8 in Example VIII. The electrochemical characteristics are almost identical to those of the LiAlo .05 Mno .95 O 2 product of Example VI.
  • Example IX The two-stage synthesis procedure described in Example IX was used to prepare a compound of stoichiometry LiGao. ⁇ oMn 0 .9o0 2 . Exact stoichiomefric amounts of lithium carbonate (99.9% pure), manganese carbonate (99.5%> pure) and gallium oxide Ga 2 ⁇ 3 (99.9% pure) to give a product of formula
  • Lio .5 Gao .10 Mno .90 O1 were mixed and ground in an acetone slurry using a mortar and pestle.
  • the mixture was loaded into a vessel formed from an inert metal alloy and fired in a furnace at 700 "G ⁇ for 20 hours in air.
  • This compound was ground in acetone with an equivalent of lithium carbonate to give a product of formula LiGao. ⁇ oMno.9o0 2 , and heated under a flow of zero grade nitrogen at 1000 °C for 15 hours.
  • Example IX The two- stage synthesis procedure described in Example IX was used to prepare compounds of stoichiometry LiCr 0 osGao osMn 0 9o0 2 and LiCr 0 05 B 0 osMno 9 o0 2 .
  • monoclinic layered LiMn0 2 may be formed during a high temperature solid state reaction involving metal doping, under specific conditions of time and temperature, and with appropriate starting reagents.
  • Zero grade nitrogen is sufficient to control the manganese oxidation state in the formation of the monoclinic LiMn ⁇ 2 material, as only very little Li 2 Mn0 3 and no spinel phases were usually formed in the reactions under zero grade nitrogen.
  • the temperature window for producing layered monoclinic LiMn0 2 is in the range 800 to 1080°C.
  • aluminium doped layered monoclinic LiMn0 2 from lithium carbonate, manganese oxide and aluminium oxide (or hydroxide) precursors by high temperature solid state reaction is facilitated by the inclusion of an additional metal, such as chromium.
  • the high temperature solid state reaction method of the invention can produce stable layered monoclinic LiMn0 2 doped with aluminium, chromium, gallium, or combinations of aluminium, chromium, gallium and boron. Combinations of aluminium and chromium result in improved electrochemical properties over materials doped with aluminium alone. It is anticipated that other combinations may also result in improvements.

Abstract

La présente invention concerne un oxyde de lithium-manganèse dopé par un métal, et ses procédés de production. L'invention concerne, en particulier, un oxyde de lithium-manganèse stable, sous forme monoclinique, dopé par un ou plusieurs ions métalliques, les dopants préférés étant l'aluminium, le chrome, voire les deux. Le procédé selon l'invention consiste à synthétiser l'oxyde de lithium-manganèse stable dopé par un métal, sous forme monoclinique, par une réaction à l'état solide haute température.
PCT/NZ1999/000175 1998-10-16 1999-10-15 Oxyde de lithium-manganese, et procedes de fabrication correspondants WO2000023380A1 (fr)

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EP1058325A2 (fr) * 1999-06-04 2000-12-06 Sony Corporation Batterie à électrolyte non-acqueux
WO2001041238A1 (fr) * 1999-12-03 2001-06-07 Ferro Gmbh Materiau d'electrode pour electrodes positives de piles au lithium rechargeables
US6677082B2 (en) * 2000-06-22 2004-01-13 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6680143B2 (en) 2000-06-22 2004-01-20 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6686096B1 (en) 2000-01-27 2004-02-03 New Billion Investments Limited Rechargeable solid state chromium-fluorine-lithium electric battery
US6964828B2 (en) 2001-04-27 2005-11-15 3M Innovative Properties Company Cathode compositions for lithium-ion batteries
US7648693B2 (en) 2005-04-13 2010-01-19 Lg Chem, Ltd. Ni-based lithium transition metal oxide
CN102664254A (zh) * 2012-05-25 2012-09-12 青岛乾运高科新材料股份有限公司 一步烧结固相反应制备复合掺杂锰酸锂的方法
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JP2013100197A (ja) * 2011-11-08 2013-05-23 National Institute Of Advanced Industrial Science & Technology リチウムマンガン系複合酸化物およびその製造方法
US8450013B2 (en) 2005-04-13 2013-05-28 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8540961B2 (en) 2005-04-13 2013-09-24 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
CN112678875A (zh) * 2020-12-25 2021-04-20 中国科学院青海盐湖研究所 一种尖晶石型Li1.6Mn1.6O4微球粉体的制备方法
WO2023067360A1 (fr) * 2021-10-22 2023-04-27 Johnson Matthey Public Limited Company Matériaux actifs de cathode

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EP1058325A2 (fr) * 1999-06-04 2000-12-06 Sony Corporation Batterie à électrolyte non-acqueux
EP1058325A3 (fr) * 1999-06-04 2003-12-03 Sony Corporation Batterie à électrolyte non-acqueux
WO2001041238A1 (fr) * 1999-12-03 2001-06-07 Ferro Gmbh Materiau d'electrode pour electrodes positives de piles au lithium rechargeables
US6998069B1 (en) 1999-12-03 2006-02-14 Ferro Gmbh Electrode material for positive electrodes of rechargeable lithium batteries
US6686096B1 (en) 2000-01-27 2004-02-03 New Billion Investments Limited Rechargeable solid state chromium-fluorine-lithium electric battery
US6677082B2 (en) * 2000-06-22 2004-01-13 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6680143B2 (en) 2000-06-22 2004-01-20 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US7135252B2 (en) 2000-06-22 2006-11-14 Uchicago Argonne Llc Lithium metal oxide electrodes for lithium cells and batteries
US6964828B2 (en) 2001-04-27 2005-11-15 3M Innovative Properties Company Cathode compositions for lithium-ion batteries
US7078128B2 (en) 2001-04-27 2006-07-18 3M Innovative Properties Company Cathode compositions for lithium-ion batteries
US8795897B2 (en) 2005-04-13 2014-08-05 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8574541B2 (en) 2005-04-13 2013-11-05 Lg Chem, Ltd. Process of making cathode material containing Ni-based lithium transition metal oxide
US7939203B2 (en) 2005-04-13 2011-05-10 Lg Chem, Ltd. Battery containing Ni-based lithium transition metal oxide
US7943111B2 (en) 2005-04-13 2011-05-17 Lg Chem, Ltd. Process of making cathode material containing Ni-based lithium transition metal oxide
US9590243B2 (en) 2005-04-13 2017-03-07 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8426066B2 (en) 2005-04-13 2013-04-23 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US9590235B2 (en) 2005-04-13 2017-03-07 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8450013B2 (en) 2005-04-13 2013-05-28 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8540961B2 (en) 2005-04-13 2013-09-24 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
US7939049B2 (en) 2005-04-13 2011-05-10 Lg Chem, Ltd. Cathode material containing Ni-based lithium transition metal oxide
US8784770B2 (en) 2005-04-13 2014-07-22 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US7648693B2 (en) 2005-04-13 2010-01-19 Lg Chem, Ltd. Ni-based lithium transition metal oxide
US8815204B2 (en) 2005-04-13 2014-08-26 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
US9412996B2 (en) 2005-04-13 2016-08-09 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US9416024B2 (en) 2005-04-13 2016-08-16 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
JP2013100197A (ja) * 2011-11-08 2013-05-23 National Institute Of Advanced Industrial Science & Technology リチウムマンガン系複合酸化物およびその製造方法
CN102664254A (zh) * 2012-05-25 2012-09-12 青岛乾运高科新材料股份有限公司 一步烧结固相反应制备复合掺杂锰酸锂的方法
CN112678875A (zh) * 2020-12-25 2021-04-20 中国科学院青海盐湖研究所 一种尖晶石型Li1.6Mn1.6O4微球粉体的制备方法
WO2023067360A1 (fr) * 2021-10-22 2023-04-27 Johnson Matthey Public Limited Company Matériaux actifs de cathode

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