JP2002513198A - Insertion compound and battery electrode - Google Patents

Abstract

  (57) [Summary] Insertion compounds having improved properties for use in batteries, especially lithium insertion compounds. The compositions of the present invention each include an oxide core of at least a first metal and a second metal in a first ratio, each formed by segregation of at least one of a first metal and a second metal from the core. A particulate metal oxide material comprising a plurality of multi-component metal oxide particles, comprising a surface coating of a metal oxide or hydroxide, not comprising a first metal and a second metal in a first ratio. Is included. The core is preferably Li_xM_yN_zO_TwoWherein M and N are metal atoms or main group elements, x, y and z are numbers from about 0 to about 1 and y and z are the M_yN_zThe formal charge for the portion is (4-x)] and can have a charging voltage of at least about 2.5V. The present invention also provides a lithium intercalation comprising a multiphase oxide core and a surface layer comprising a material that is a component of the multiphase oxide core and protecting the underlying intercalation material from chemical dissolution or reaction. It can be characterized as a multi-component oxide microstructure useful as a material. In a particularly preferred example, the multi-component oxide can be an aluminum-doped lithium manganese oxide composition. Such aluminum-doped lithium manganese oxide compositions having an orthorhombic structure also form part of the invention. Further, the present invention encompasses articles formed from the compositions of the present invention, especially electrodes for batteries, and batteries comprising such electrodes. The invention further comprises at least two compounds, of which at least one compound has an orthorhombic structure Li_xAl_yMn_1-yO_Two[Where y is not 0] or orthorhombic and monoclinic Li_xAl _yMn_1-yO_TwoA composite insert having a mixture of

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to an intercalation compound for use as a battery electrode.
More particularly, it relates to lithium ion manganese oxide compositions, articles made with such compositions, and batteries comprising electrodes formed from such compositions.

[0002]Background of the Invention The present inventor, or at least a part of them, has been responsible for lithium insertion into rechargeable batteries.
International application no. P
CT / US97 / 18839, filed Oct. 97 by Mayes et al.
Title "Polymer electrolytes, insertion compounds and electrodes for batteries", WO 98/1696
Published as 0, which is incorporated herein by reference. This patent specification has the formula: Li_xM_yN _z O_TwoWherein M and N are each a metal atom or a main group element.
Synthesis of such compositions demonstrated to have improved electrochemical properties
And a method. WO 98/16960 states that at least it relates to intercalating compounds.
To the extent it is incorporated herein.

[0003] The inventor has continued to study lithium insertion compounds and has identified new compounds with further improved properties for use in batteries. Accordingly, it is an object of the present invention to provide lithium insertion compounds having further improved properties for use in batteries and methods for their preparation. Other objects of the invention will become apparent from the following description, given by way of example only and with reference to certain examples.

[0004] According to one aspect of the Summary of the Invention invention, each includes an oxide core at least a first metal and a second metal in the first rate, the first metal and the second metal each from the core A plurality of multi-component metal oxide particles formed by at least one segregation, not including the first metal and the second metal in the first ratio, including a surface coating of a metal oxide or a hydroxide. A composition comprising a particulate metal oxide material is provided.

According to another aspect of the present invention, each includes an oxide core of at least a first metal and a second metal in a first ratio, each comprising an auxiliary metal oxide or hydroxide to the particles. formed by coating of an object does not include a first metal and a second metal and a first rate, include surface coating of a metal oxide or hydroxide, wherein the core is _{Li x M y N z O 2} [ Where M
Is a metal atom or main group element, N is a metal atom or main group element, x is a number from about 0 to about 1, y is a number from about 0 to about 1, and z is about is a number from 0 to about 1, and the y and z, formal charge relates M _y N _z portion of the compound (4-x
), The composition comprising a particulate metal oxide material having a charging voltage of at least about 2.5V.

[0006] According to another aspect of the present invention, comprising particles as described in the preceding two paragraphs, wherein the particles are ion insertion particles, at least a portion of which is in contact with a conductive material and an ion conductive material. Provide the goods you are doing.

According to another aspect of the present invention, the first component of the intercalation compound based on the multi-component oxide is disproportionately segregated from the plurality of compound particles to the surface of the plurality of compound particles, and the Forming a protective layer of the first component on the substrate; exposing the plurality of particles to chemical decomposition conditions; and causing the protective layer to shield the particles from the chemical decomposition conditions so that the particles form a protective layer. Making said particles more robust than said same particles without said conditions.

In accordance with another aspect of the present invention, there is provided a multiphase oxide core and one of the components of the multiphase oxide core that protects the intercalating material from chemical dissolution or reaction. A multi-component oxide useful as a lithium insertion material, including a surface layer.

According to another aspect of the present invention, lithium can be reversibly inserted, and some or all of one component of the multi-component oxide naturally forms a surface layer. The layer provides a multi-component oxide that protects the underlying insertion compound from chemical dissolution or reaction.

According to another aspect of the present invention, there is provided a composition of the formula Li _x Al _y Mn _1-y O _{2 wherein} y is not zero. According to another aspect of the present invention, the at least one component comprises at least one component.
An electrode for a primary lithium battery, wherein the components have a Li _x Al _y Mn _1-y O ₂ orthorhombic structure where _y is not zero.

According to another aspect of the invention, the composite intercalator comprises at least two compounds.
. At least one compound has an orthorhombic structure Li wherein y is not zero._xAl_yMn _1-y O_TwoHaving. According to another aspect of the present invention, a composite intercalator comprising at least two compounds is
During electrochemical cycling, from a single plateau at about 4 V to about 4
With a change in voltage vs. capacity curve up to two plateaus at V and 3V
Both have one type of compound.

According to another aspect of the present invention, the composite intercalating material comprising at least two compounds comprises a discharge capacity of at least about 100 mAh / g over a voltage range of 2.0-4.4 V; Having at least one compound having an energy density of at least about 400 Wh / kg after cycling.

[0013] According to another aspect of the present invention, comprising at least two separate insertion compounds,
Each compound has a different lithium chemical diffusion rate and provides a composite insertion compound having a continuously changing voltage-capacity profile than the voltage-capacity profile of any non-composite insertion compound.

According to another aspect of the present invention, it comprises at least two distinct insertion compounds,
Each compound has a different particle size and provides a composite insertion compound having a continuously changing voltage-capacity profile than the voltage-capacity profile of any non-composite insertion compound. Other aspects of the invention will become apparent from the following description, taken by way of example only and with reference to the accompanying drawings.

[0015] One embodiment of the Detailed Description of the Invention The present invention, wherein, y is a is less than about 0.5] composition _{Li x Al y Mn 1-y} O 2 to provide for the insertion compound family with. These compounds can be used as electrodes in lithium batteries and preferably have an x value of about 1 when synthesized by the methods described herein. These compounds are monoclinic LiM
It crystallizes as nO ₂ , orthorhombic LiMnO ₂ , or tetragonal spinel Li ₂ Mn ₂ O ₄ structural type, has other structural characteristics, and has performance characteristics related to the structural characteristics described herein. In one type of compound, the ion occupies primarily the site of octahedral coordination by oxygen. Upon periodic electrochemical insertion and de-intercalation in a lithium rechargeable battery, the compound is charged to a local cation order (charg
e), after which the Li ions occupy both octahedral and tetrahedral oxygen coordination sites,
The degree of change depends on the Li concentration in the compound. Compound structures obtained after electrochemical cycling include, but are not limited to, cubic spinel LiMn ₂ O ₄ or tetragonal spinel L
It can have an i ₂ Mn ₂ O ₄ structure. The compounds of the present invention have low material costs, high reversible charge capacity and energy density at room temperature, high reversible charge capacity and energy density at high temperatures (40-70 ° C), high temperature (40 (Eg, LiCoO ₂ , LiMn), including long life on storage at −70 ° C.) and safety as evidenced by the absence of a high exothermic reaction upon heating of a rechargeable lithium battery containing the compound. ₂ O ₄ (cubic spinel structure)
And LiNiO like _2, not found in typical insertion compounds used to date in the rechargeable lithium battery, having a combination of useful features.

Other embodiments of the present invention also include any primary or secondary (rechargeable) lithium battery, including the lithium batteries described herein, using the compounds of the present invention.

[0017] Another embodiment of the present invention is directed to a mixture of any of the above individual Li _x Al _y Mn _1-y O ₂ compounds and a compound having the composition Li _x Al _y Mn _1-y O ₂ , eg, LiCoO ₂ , Li
_{Al y Co 1-y O 2} , such as _{LiNiO 2, LiCo y Ni 1-} y O 2 or LiMn ₂ O _4, including any mixture with other known insertion compound. Such mixtures may have particular utility due to voltages that vary with charge capacity more smoothly than are obtained for certain individual compounds.

In the present specification, the following abbreviations are used: monoclinic Li _x Al _y Mn _1-y O ₂ (abbreviation: m-Li _x Al _y Mn _1-y O ₂ ) orthorhombic Li _x MnO ₂ (abbreviation: o-Li _x MnO ₂₎ orthorhombic _{Li x Al y Mn 1-y} O 2 ( _{abbreviation: o-Li x Al y Mn} 1-y O 2)

In each case, the insertion compound is prepared with an x value of about 1. As an insertion compound
In use, the value of x can approach 0 (eg, with active cathod material)
During the charging of the battery using the compound). In one embodiment, the monoclinic Li_xAl_yMn _1-y O_TwoHas a value from about 0.01 to about 0.5. In other embodiments, the oblique
Orthogonal Li_xAl_yMn_1-yO_TwoHas a value of about 0 to about 0.25. y =
In the case of 0, the compound is undoped orthorhombic Li_xMnO_TwoIt is.

In the present specification, “rhombic LiMnO 2_TwoOr "o-LiMnO"_TwoThe term "
, R.S. Hoppe, G .; Brachtel and M.C. Jansen (Z. Anor)
g. Allg. Chemie, 471, 1 (1975)).
Li of orthorhombic ordered rocksalt structure_xMnO _Two Means

Monoclinic Li _x Al _y Mn _1-y O ₂ One embodiment of the present invention provides an Al compound for forming the intercalation compound LiAl _y M _1-y O _2.
Addition of, reflects the discovery that readily allows the stabilization of alpha-NaFeO ₂ structure type not formed compound as a pure LiMnO ₂ in alpha-NaFeO ₂ structure. In this case, M can be, but is not limited to, Mn, Fe and Ti.
For example, LiMnO ₂ can be obtained as a pure compound or by tetragonal spinel Li ₂ by electrochemically or chemically inserting Li into spinel LiMn ₂ O _4.
Mn ₂ O ₄ can be crystallized in an orthorhombic symmetric phase.
O ₂ was formed only in α-NaFeO ₂ structure type (in this composition, having monoclinic symmetry, space group C2 / m) by ion exchange of Li ⁺ instead of Na ⁺ (A. R. Armstrong and PG Bruce, Nature, 381, 499, 1996). According to the method of the present invention as shown in Example 1, by heating a solid solution Li (Al, Mn) O ₂ in a reducing gas atmosphere, α-
It can be easily crystallized by a monoclinic deformation of the NaFeO ₂ structure type.

The insertion compound LiAl _y M _{1- y} O ₂ , which crystallizes in a monoclinic variant of the α-NaFeO ₂ structure type, has two characteristic voltages of insertion and a high energy density during electrochemical cycling. And an insertion compound having excellent cycling performance. In particular, this insertion compound is similar to the spinel based on Li-Mn-O, but without the loss of capacity during cycling, a characteristic of conventional spinels.
Cycling can be performed over a voltage and capacity range that includes a plateau at both about 4V and about 3V (relative to the Li metal anode). This allows practical use of both voltage regimes, resulting in a high practical energy density.

The compounds of the present invention are characterized by high energy densities and reversible capacities upon repeated cycling at elevated temperatures of 40-70 ° C., a markedly useful improvement in the art. In one embodiment, the energy density at elevated temperatures can be higher at room temperature than that exhibited by the same compound. The high temperature stability of the compound is clearly superior to the high temperature stability of typical lithium manganese oxide.

The present invention also includes a method for producing such a compound.

[0025]Example 1: Monoclinic by hydroxide precipitation and freeze drying and calcination in a reducing atmosphere Synthesis of LiAl _0.05 Mn _0.95 O ₂ and LiAl _0.25 Mn _0.75 O ₂ , Marking and their electrochemical testing at room and elevated temperatures Synthesis and structural analysis By the coprecipitation and lyophilization synthesis method, the total composition LiAl_0.05Mn_0.95O_Twoas well as
LiAl_0.25Mn_0.75O_TwoOf monoclinic Li_xAl_yMn_1-yO_TwoWas manufactured. LiO
H ・ H_TwoO (Alfa Aesar, 98%) and Mn (NO_Three)_Three・ 6H_TwoO (A
ldrich, 98%) and Al (NO_Three)_Three・ 9H_TwoO (Alfa Aesar
, 98%) and the aluminum levels y = 0.05 and y = 0.25.
A precursor having an overall Li: (Mn + Al) atomic ratio of 1.05: 1 was produced.
A slight excess of Li was included to compensate for possible loss of Li during firing. Mixed man
The gun-aluminum hydroxide is Mn (NO_Three)_Three・ 6H_TwoO and Al (NO_Three)_Three・ 9H _Two From a mixed aqueous solution with O, LiOH · in deionized water maintained at pH = 10.5
H_TwoO is dissolved in deionized water at a desired molar ratio (y / (1-y)) in a continuously stirred solution of O.
The coprecipitation was achieved by adding the dissolved 0.2M solution (including both metal nitrates).
I let you. The precipitate was digested for 12 hours and sedimented by centrifugation.
iOH ・ H_TwoDisperse in an aqueous O solution, settle the precipitate by centrifugation, and
The solution was decanted to remove residual nitrate ions. This
The rinsing process was performed 5 times. The rinsed precipitate is washed with 1.05 Li
: LiOH.H dissolved at a concentration that results in a total composition having the (Al + Mn) ratio_TwoO
Finally, the suspension is dispersed in an aqueous solution containing
The droplets were removed and placed in a commercial lyophilizer (VirTis Consol 12L).
L, Gardiner, NY).

The precursor powder was calcined at 945 ° C. for 2 hours under various oxygen partial pressures and furnace cooled to room temperature. The effect of oxygen partial pressure on phase stability was measured by calcining in the range of PO ₂ = 10 ⁻² to 10 ⁻⁷ atm, controlled by flowing a premixed argon / oxygen or CO / CO ₂ mixture. . Calcination in argon, argon / oxygen or a buffered CO / CO ₂ mixture yields a high Mn ³⁺ fraction with a monoclinic LiMnO ₂ isomorphous crystal structure of Li _x Al _y Mn _1-y O ₂ was obtained.

The structure of m-Li _x Al _y Mn _1-y O ₂ was confirmed by X-ray powder diffraction and structural simulation using commercial software. An X-ray diffraction scan of the oxide powder obtained by calcining the aluminum-doped precursor at 945 ° C. under various oxygen partial pressures is shown in FIG. First considering the composition LiAl _0.25 Mn _0.75 O ₂ at high oxygen partial pressures of 10 ^-2 and 10 ^-3 atm, the resulting phase is LiM
n ₂ O ₄ , Li ₂ MnO ₃ and γ-LiAlO ₂ (tetragonal phase). When the oxygen partial pressure is reduced to 10 ^-4 atm, a new phase having the same structure as m-LiMnO ₂ and o-LiMnO ₂ appears. M-LiMnO _2, characterized by its strongest peak at 2θ = 18.3 °, becomes the dominant phase at oxygen partial pressures less than 10 ⁻⁵ atm. The identification of this phase is discussed in more detail below. As the oxygen partial pressure falls to the range of 10 ^-4 to 10 ^-6 atm, the amount of o-LiMnO ₂ slightly increases, but about 94%.
Remains in the minor phase through a 5 ° C. firing temperature. Composition LiAl _{0.0 5} Mn _0.95 O _2, when firing in a reducing atmosphere in the temperature (PO ₂ = 1
0 ^-7 atm, FIG. 1), exclusively showing the m-LiMnO ₂ phase. These phases show that the predominant manganese valence state is 3+ at oxygen partial pressures of less than 10 ^-4 atm and that under these conditions the solid solution between the LiAlO ₂ endmember and the LiMnO ₂ end element Is obtained. However, unlike with any of the pure final element in these firing conditions, the structure is a structure of the m-LiMnO _2.

The XRD pattern of m-LiMnO _{2 is} the XRD pattern of tetragonal Li ₂ Mn ₂ O ₄ spinel.
Because it is very similar to the pattern, meticulous phase identification is required in this system. The latter spinel phase has been obtained by lithiation of LiMn ₂ O ₄ spinel (JM Tarascon and D. Guyomard, J. Electroch).
em. Soc. , 138, 2864 (1991)). Capitaine et al. (F
. Capitaine, P .; Gravereau and C.I. Delmas, Sol
id State Ionics, 89, 197 (1996)) claims that monoclinic and tetragonal phases can be distinguished from one another by diffraction lines in the 64-68 ° 2θ range. The present inventor has described the XRD patterns of m-LiMnO ₂ , Li ₂ Mn ₂ O ₄ and the hypothetical solid solution m-LiAl _0.25 Mn _0.75 O ₂ by commercial software Cerius (v.3.5, Molecular Simulati).
ons Inc. , San Diego, CA). m
The structure of LiMnO ₂ is Armstrong and Bruce (AR Armst).
long and P.L. G. FIG. Bruce, Nature, 381, 499 (1996))
Was simulated using crystallographic data from Li, and the structure of Li ₂ Mn ₂ O ₄ was Mos
bah et al. (A. Mosbah, A. Verbaere and M. Tournoux).
, Mat. Res. Bull. , 18, 1375 (1983)), the structure of m-LiAl _0.25 Mn _0.75 O ₂ was determined using the lattice parameters measured in this study (see below) and the Armstrong and Bruce oxygen parameters. Perfectly ordered α-N except that 25% of Mn was replaced by Al
The aFeO ₂ structure was estimated and simulated.

The simulated result is expressed as LiAl_0.25Mn_0.75O_TwoExperimental XRD pattern
2 is shown in FIG. The difference between these three simulated patterns is
Peak positions in the 60-68 ° range, enlarged in the inset for each pattern
And relative intensity. Monoclinic phase, m-LiMnO_TwoAnd m-Li
Al_0.25Mn_0.75O_TwoMeans (202) and 65.1 ° and 66.6 °, respectively.
(020) peak, the latter peak having a higher intensity. Li_TwoMn_TwoO _Four Shows (400) and (323) peaks at 66.1 ° and 67.0 °, respectively.
However, the former peak has a higher intensity. Experimental pattern in FIG. 2 (d)
Are the peak positions (65.1 ° and 66.6 °) corresponding to the monoclinic phase and the relative intensity.
Indicates the degree.

[0030] Other distinguishing features between the different phases are found in the range 61-62 °. m-
LiMnO ₂ has two peaks (311) and (113), which are more closely spaced in m-LiAl _0.25 Mn _0.75 O ₂ . Li ₂ Mn ₂ O ₄ has only one peak (224) in this 2θ range. Experimental pattern (Fig. 2 (
d)) is consistent with the simulation for m-LiAl _0.25 Mn _0.75 O ₂ but not the simulation for m-LiMnO ₂ . Therefore, these results not only confirm that the m-Li _x Al _y Mn _1-y O ₂ compound of the present invention has a monoclinic structure, but also that they have Al actually substituted with Mn. Also make sure.

As a further basis for the effect of Al doping, FIG.
FIG. 4 shows the XRD pattern of an undoped LiMnO ₂ sample obtained by calcining a precursor without additives at 945 ° C. under 10 ⁻⁶ atm oxygen partial pressure. It can be seen that o-LiMnO ₂ is the predominant phase.

The lattice parameters of the m-LiAl _0.25 Mn _0.75 O ₂ sample were calculated from the XRD data using the Cohen least-squares method, and were converted to pure m-LiMnO ₂ obtained by the ion exchange method in Table 1. With the lattice parameter of. There is no significant difference between the values of b and β, and a and c slightly decrease.

Table 1

[Table 1]

The stabilization of the m-LiAl _y Mn _1-y O ₂ phase is most possible with the addition of aluminum, not just because of the firing conditions. The present inventor has proposed LiAlO ₂ (α-LiA)
Since it has previously been shown that the α-NaFeO ₂ polymorph of ＯO ₂ ) changes irreversibly to γ-LiAlO ₂ above 600 ° C., it may not be a stable phase under these conditions. Admit. _{Therefore, Li x Al y Mn 1-} y O 2 solid solution of the present invention, end element LiAlO ₂ and LiMnO in not stable conditions in both alpha-NaFeO ₂ structure _2, alpha-NaFeO _crystallize in structures Can be seen.
This finding is surprising given the prior art.

The formation of Al and Mn solid solutions in the compounds of the present invention can be determined by transmission electron microscopy (T
EM) and composition mapping by scanning transmission electron microscopy (STEM) (composi
nation mapping). M-Li as manufactured
The Al _0.05 Mn _0.95 O ₂ powder was analyzed on a Vacuum Generator HB603 STEM. Bright field and annular dark field (annular-d
ark field) imaging and energy dispersive X-ray mapping were performed. FIG. 4 shows a bright field image of the powder particles together with an X-ray map showing the distribution of Al and Mn. With a constant Al / Mn X-ray relative intensity ratio throughout the powder particles, the presence of Mn is always A
It seems to be accompanied by the presence of l. This indicates that the initial composition appears to be the most uniform. The surface composition of this powder was analyzed using X-ray photoelectron spectroscopy (XPS) before and after ion sputtering to remove the surface layer. The XPS results showed no significant difference in Al / Mn ratio before and after sputtering, demonstrating that surface atomic layers of different composition were not initially present. Therefore, the excellent intercalation propeties of the compounds of the present invention, discussed below.
Rties) is believed to be that the actual formation of a solid solution _{m-LiAl y Mn 1-y} O 2 is produced.

The maximum amount of Al that dissolves in the structure of m-LiAl _y Mn _1-y O ₂ can be limited.
5 and 6 show STEM images and X-ray composition maps of LiAl _0.25 Mn _0.75 O ₂ after storage in a closed container at room temperature for 6 months. A completely different separation of the powder into Al- and Mn-rich regions can be seen. Analysis of energy dispersive X-ray spectrum showed that about 5 atomic% of Al remains in the mixed solid solution _{m-LiAl y Mn 1-y} O 2. FIG. 7 shows the results of X-ray diffraction from this powder before and after storage. A broad background has emerged after storage that can demonstrate the presence of an amorphous phase.
The peak intensity and peak position of the monoclinic α-NaFeO ₂ phase also changed. These results indicate that the m-Li _x Al _y Mn _1-y O ₂ solid solution has a tendency to phase separate into an Al-enriched oxide and a Mn-enriched oxide even at room temperature.

[0037] Such separation also occurs during electrochemical cycling, where the Al-enriched oxide protects the Mn-enriched oxide in a rechargeable lithium battery from exposure to the surrounding medium containing the electrolyte. Tend to bring about. Second, the natural separation of the aluminum component as a surface layer protects and stabilizes the underlying intercalation compound from dissolution and chemical attack in a lithium ion battery environment, thereby increasing the charge capacity,
It can contribute to low volume decay during cycling and high stability against volume loss at high temperatures.

Other components of the multicomponent oxide intercalating compound, which are naturally separated, can also play a protective role in this case played by the aluminum oxide / hydroxide. Other such components include boron oxide, phosphorus oxide, silicon oxide and oxides of 3d metals.

Room temperature electrochemical properties The insertion compounds were tested in an electrochemical test cell containing two stainless steel electrodes with a Teflon holder. Oxide powder, carbon black (Cabot), graphite (TIMCAL America) and poly (vinylidene fluoride) (PV
The cathode was prepared by mixing together DF) (Aldrich) in a weight ratio of 78: 6: 6: 10. PVDF was pre-dissolved in gamma-butyrolactone (Aldrich) before mixing with the other components. After evaporating γ-butyrolactone in air at 150 ° C., the components were compressed at about 4 t / cm ² pressure to form pellets weighing 10-25 mg and having a cross-sectional area of 0.5 cm ² . Next, the pellet was dried under primary vacuum at 140 ° C for 24 hours and transferred to an argon-filled glove box. 0.75mm thick lithium ribbon (
Aldrich) was used as the anode. The separator is a film of Celgard 2400 ^™ (Hoechst-Celanese, Charlotte, NC) and the electrolyte is ethylene carbonate (EC) and diethylene carbonate (D
Consisted of a 1 M solution of LiPF _{6 in} EC). The ratio of EC to DEC was 1: 1 by volume. All cell handling was performed in an argon-filled glove box. Charged by MACCOR automated test equipment (Series 4000)
A discharge test was performed. The cell was charged and discharged between the voltage limits of 2.0V and 4.4V.

FIG. 8 shows m-LiAl as a cathode._0.25Mn_0.75O_Two(945 ° C, PO_Two= 10^-6 atm), the first of the cells manufactured using lithium metal as the anode.
2 shows a charge-discharge curve (C / 5 rate). Single cell at ~ 4.1V
FIG. 4 shows a charging voltage plateau, having a first charging capacity of about 203 mAh / g. (Honmei
In all cases, the volume is calculated on the basis of oxide weight). First discharge curve
Indicates a capacity of about 119 mAh / g and the appearance of two voltage steps. More cycling
After ringing, the voltage steps become more pronounced. FIG. 8 further shows in the 20th cycle
FIG. 4 shows a charge-discharge curve in FIG.
A toe is seen, demonstrating insertion at two different lithium sites. m-Li
Al_0.05Mn_0.95O_TwoThe composition exhibits similar room temperature characteristics. Therefore, these trials
The experiment showed that the monoclinic compound of the present invention occupies a layer of octahedral site in Li and (Al, Mn).
) Is synthesized by both cations. During electrochemical cycling
Alternatively, lithium can be inserted into both tetrahedral and octahedral sites. FIG. 9 shows C /
M-LiAl during cycling in the range of 2.0 V to 4.4 V at 5 rates _0.25 Mn_0.75O_Two1 shows the development of the charge capacity and the discharge capacity. First 5 cycles
An initial drop in capacity to only about 100 mAh / g is seen,
The ring gradually increases the discharge capacity, and after about 15 cycles, ~ 148 mAh
/ G is saturated. Cycling on both 4V and 3V plateaus
The fact that it can be done without capacity attenuation
LiMn whose capacity decreases rapidly_TwoO_FourThe behavior is clearly different from spinel.
m-LiAl_0.25Mn_0.75O_TwoThe material was also tested at lower C / 15 rates
Was. To facilitate any cycling decay, first sample at C / 5 rate
Cycled 12 times. The 13th cycle at C / 15 rate is C
FIG. 10 shows a comparison with the result at the / 5 rate. At low reversible capacity rates
With an energy density of 545 Wh / kg, it can be increased to 182 mAh / g.
Can be seen. At the C / 5 rate, the energy density is 450 Wh / kg.

[0041]High temperature electrochemical properties Compound m-LiAl_0.05Mn_0.95O_TwoAnd m-LiAl_0.25Mn_0.75O_Two55
Tests were carried out in the same cell structure as above at elevated temperatures of from 70C to 70C. Typical prior art
LiMn_TwoO_FourSpinel is useful for cycling at these high temperatures
Rapidly loses capacity when stored at elevated temperatures. For example, laptop computer
For use in applications that generate heat, such as heat sinks or high discharge rate applications.
Is conventional LiMn_TwoO_FourA major limitation on spinel applications. Of the present invention
To facilitate testing of compounds, the C / 2 rate (C is volume and C / 2 is 2 hours
1.6 mA / cm, which substantially corresponds to fully charging or discharging between ^Two Charging current of 0.4 mA / cm, which is approximately equivalent to the C / 8 rate^TwoDischarge current density
And were used. FIG. 11 shows m-LiAl_0.25Mn_0.75O_Two60 ° C and 7 for cell
3 shows a cycling test at 0 ° C. The first three cycles are performed at 60 ° C
Thereafter, the temperature was increased to 70 ° C. After a total of 7 cycles, the energy density is 48
2 Wh / kg. FIG. 12 shows m-LiAl_0.25Mn_0.75O_TwoRoom temperature for cell
The test results at (23 ° C.) and 55 ° C. are shown. Obviously, the capacity at room temperature
It is higher at 55 ° C than at 55 ° C. This result is surprising based on the prior art.
is there. 13 to 16 show m-LiAl at 55 ° C._0.05Mn_0.95O_TwoIn
The charge-discharge curves of the first, sixth, seventeenth, and thirty-fourth cycles, respectively, are shown. this
Et al., As in the room temperature test, provide a quick access to a voltage profile that includes two voltage plateaus.
Indicates deployment. FIG. 17 shows m-LiAl at 55 ° C._0.05Mn_0.95O_TwoAnd ML
iAl_0.25Mn_0.75O_TwoExtended cycling results (2.0-4.4 V
). m-LiAl_0.05Mn_0.95O_TwoAs for the capacity after 42 cycles
Stays above 150 mAh / g. m-LiAl_0.25Mn_0.75O_Twoabout
, Capacity to plateau over 200 mAh / g over the first 10 cycles
To rise. From the STEM results, the solid solution phases of these two compositions were similar.
Having the composition m-LiAl_0.05Mn_0.95O_TwoHigh capacity is electrochemically inert
It is understood that this is due to the small amount of the aluminum oxide phase. At 55 ° C
After 65 cycles, m-LiAl_0.05Mn_0.95O_TwoAfter cooling to room temperature,
It showed a capacity of 120 mAh / g.

These results indicate that the compounds of the present invention have electrochemical properties superior to those of conventional lithium manganese oxide spinel. These properties are superior to those of the monoclinic LiMnO ₂ produced by ion exchange of Li with NaMnO ₂ , which rapidly loses capacity when cycled across both voltage plateaus (G. Vitins). And K. West, J. Electr
ochem. Soc. 144, 8, No. 2587-2592, 1997).
The stability of the insertion compounds of the present invention when cycling over both voltage plateaus reduces the actual capacity and energy density of the compound, and can only be cycled repeatedly over one voltage plateau without significant loss of capacity. Other Li
-Increased compared to Mn-O compounds. The fact that the addition of Al to lithium manganese oxide results in such an improvement is surprising, based on the prior art.
In fact, F. Le Cras et al. (Solid State Ionics, 89
, Pp. 203-213, 1996), that the spinel composition LiAlMnO ₄ shows cycling rapid volume reduction upon over similar voltage range, without the teachings of the present invention, are reported.

Orthorhombic Li _x Al _y Mn _1-y O ₂ A further embodiment of the present invention relates to an orthorhombic Lithium battery using an organic liquid electrolyte, which has high temperature stability and very high capacity and energy density. Crystalline Li _x A
l also includes the synthesis of _y Mn _1-y O _2. Example 2 shows that such compounds can be synthesized.

Example 2 An orthorhombic Li _x Al _y Mn _1-y O ₂ compound starting composition Li _1.05 Al _0.05 Mn _0.95 O ₂ was prepared by the method of Example 1,
Calcination at 900 ° C. for 2 hours in a CO / CO ₂ mixture producing an oxygen partial pressure of 10 ⁻⁶ atm. FIG. 19 shows that the composition contains three phases: monoclinic Li _x Al _y Mn _1-y O ₂ , orthorhombic Li _x Al _y Mn _1-y O ₂ and Li ₂ MnO _3. . This result indicates that an orthorhombic Li _x Al _y Mn _1-y O ₂ compound is obtained.

In a second experiment, a precursor with a total composition of Li _1.05 Al _0.05 Mn _0.95 O ₂ was produced by the method of Example 1. This composition previously produced m-Li _x Al _y Mn _1-y O ₂ when fired at 945 ° C. under a reducing atmosphere, as described in the preceding examples. CO / CO ₂ which produces an oxygen partial pressure PO ₂ = 10 ⁻¹⁰ atm
The firing was performed at 900 ° C. for 2 hours in a gas atmosphere. An X-ray diffraction pattern of the obtained substance is shown in FIG. This figure shows that the major phase as the orthorhombic phase is detectable with only a small amount of monoclinic phase and very little Mn ₃ O ₄ .

The evidence that the orthorhombic phase is Al-doped includes: The sample contains a total of about 5% Al on a cationic scale. The intensity of the X-ray diffraction peak shows that at most 15 mol% of the monoclinic phase and 5 mol% of Mn ₃ O ₄ are present. Previous experiments by the inventor have shown that the solid solubility of Al in the monoclinic phase at 945 ° C. is about 5%. At the firing temperature of the present invention of 900 ° C., this is even lower. Al in monoclinic phase which makes 5% solubility 15% of the whole
Considering the upper limit of the amount, it is very likely that 4.25% of Al will be distributed between the orthorhombic phase and Mn ₃ O ₄ . Since the total amount of Mn ₃ O ₄ is at most about 5%, the orthorhombic phase can be doped with Al, and there is a possibility that o-Li _x Al _y Mn _1-y O ₂ is synthesized. Very large.

Preferred embodiments of this compound have an aluminum content of y less than about 0.25. This o-Li _x Al _y Mn _1-y O ₂ material was made into an electrochemical cell as described in Example 1. FIG. 20 shows that the charging current is 183 mA / g and the discharging current is 91 mA.
The discharge capacity of this cell is shown as a function of the number of cycles at a test temperature of 55 ° C. in a cycling test of / g. This is because C in the 10th cycle
A high current density corresponding approximately to a /0.8 charge rate and a C / 1.6 discharge rate. The discharge capacity increased rapidly over the first few cycles, reaching a value of about 150 mAh / g in the tenth cycle. The corresponding energy density is about 450 Wh
/ Kg. 21 to 23 show charge-discharge curves of the first, sixth and eighth cycles, respectively. As with the undoped o-LiAlMnO ₂ material, the material was subjected to a conditioning step during which two voltage plateaus occurred during cycling and after repeated cycling at high charge-discharge rates,
It produces a capacity and energy density that is significantly better than conventional LiMn ₂ O ₄ spinel. In addition, like the m-Li _x Al _y Mn _1-y O ₂ compound, this material exhibits these excellent properties at elevated temperatures. Therefore, it is possible to demonstrate the utility of _{o-Li x Al y Mn 1} -y O 2 as insertion electrode for rechargeable lithium batteries.

Multicomponent Metal Oxides Another embodiment of the present invention is a lithium-intercalated particle Li _x , for example as described herein.
It includes forming a shielding layer on the outside of the M _y N _z particulate metal oxide materials which may be ion intercalation particles such as O _2. These particles are multi-component metal oxide particles, each of which is a primary metal oxide.
Includes an oxide core of at least a first metal and a second metal in a ratio, and a metal oxide or hydroxide surface coating that does not contain the first metal and the second metal in the first ratio.
The surface coating may be formed by segregation of at least one of the first metal and the second metal from the core. These particles can be used in battery configurations as described herein. The particles shielded by the surface layer, according to one embodiment, disproportionately segregate the first component of the intercalation compound based on the multi-component oxide from the plurality of compound particles to the surface of the plurality of particles, It can be manufactured by forming a protective layer of the first component on the particles. The particles can be exposed to chemical degradation conditions and the layer can shield the particles from the chemical degradation conditions so that the particles exhibit greater robustness under these conditions than the same particles without a surface layer .

In a preferred embodiment, the insertion compound is an Al / Mn compound and the aluminum component is segregated from the manganese-enriched oxide so that the amorphous aluminum oxide or hydroxide is formed as a layer on the crystalline insertion compound. Produces a naturally formed microstructure. This surface layer protects and stabilizes the underlying intercalation compound from dissolution and chemical attack in the environment of the lithium-ion battery, thereby providing high charge capacity, low capacity decay when cycling and high stability against capacity loss at high temperatures. To contribute.

This aspect of the invention includes an optional component of a multi-component oxide intercalating compound that tends to separate spontaneously and tends to do so as a surface layer, wherein the surface layer is in this example It can play a protective role as does aluminum oxide / hydroxide. Other such components are boron oxide, phosphorus oxide, silicon oxide and 3
d Includes metal oxides.

Example 3 A powder of the composition LiAl _0.25 Mn _0.75 O ₂ prepared according to Example 1 is stored in air at room temperature for 4 months and then transmitted electron microscopy (TEM) and scanning transmission. Inspected by electron microscopy (STEM). This powder shows, by powder X-ray diffraction, an α-NaFeO ₂ structure type monoclinic derivative as a main crystal phase, and the Mn-enriched crystalline oxide particles have an Al-enriched amorphous or nano-crystalline phase. A microstructure surrounded by a crystalline layer is shown. This layer is probably a partially hydrated aluminum oxide. This tends to form spontaneously from the overall composition of the substance Li _x Al _y Mn _1-y O ₂ .

The stabilizing effect of adding aluminum to Li _x Al _y Mn _1-y O ₂ is based on α-NaFe
Testing with LiAl _0.05 Mn _0.95 O ₂ stabilized with the O ₂ structural type demonstrated a range of compositions. Composition LiAl _0.05 M
n _0.95 O ₂ was prepared using the method described in Example 1. The sample was fired at 945 ° C. under a reducing atmosphere. X-ray diffraction (FIG. 24) shows that the resulting powder was α-NaFe as previously found in the composition LiAl _0.25 Mn _0.75 O _2.
It was shown to have monoclinic derivatives of the O ₂ structure type. LiAl as produced _{0 .05} Mn _0.95 O ₂ powder Vacuum Generator HB603 STE
Inspection in M, bright field imaging and energy dispersibility X for Al and Mn
Line mapping was performed. FIG. 4 shows a bright field image of the powder particles together with an X-ray map showing Al and Mn distributions. The presence of Mn indicates a constant Al / M throughout the powder particles.
It appears to be accompanied by the presence of Al in nX-ray relative intensity ratios. This composition seems most likely to be homogeneous, with no initial separation of Al and Mn into discernable surface layers or discrete regions.

[0053] Figure 5 and 6 shows the STEM results for LiAl _{0. 25} Mn _0.75 O ₂ powder after storage at six months at room temperature in a sealed container. Separation of the powder into separate Al- and Mn-rich regions is observed. FIG. 7 shows the results of X-ray diffraction from this powder before and after storage. A broad background appears after storage, typically indicating the presence of an amorphous phase. The peak intensity and peak position of the monoclinic α-NaFeO ₂ phase also changed. These results show that the Li _x Al _y Mn _1-y O ₂ solid solution produced according to the present invention has a strong tendency of phase separation into Al-rich oxide and Mn-rich oxide even at room temperature. It is thought to show. Such separation can occur during electrochemical cycling, resulting in a structure where the Al-enriched oxide protects the Mn-enriched oxide from exposure to ambient media, including electrolytes, in rechargeable lithium batteries. .

Composition-Containing Cathode Using Mixture of Insertion Compounds The advantages afforded by any one of the above compounds can be realized in any mixture of two or more. That is, it is not necessary to obtain a single phase compound to achieve the advantages of high energy density, long cycle life and high temperature stability discussed above. By physically mixing the separately manufactured powders,
Alternatively, as exemplified by Example 2, such a mixture can be obtained by producing a single substance to produce more than one phase. Therefore, according to the present invention,
In embodiments, the mixture is a composite insert comprising at least two mixtures.

In one embodiment, the complex defined by the mixture comprises at least two different compounds, each of the at least two different compounds having at least about 1%
, Preferably at least about 5%, more preferably at least about 10%. Each of the at least two different compounds can be present in large amounts, in some embodiments, for example, at least about 25% or 35%.

In one embodiment, the composite intercalant comprising at least two compounds comprises at least one compound having an orthorhombic structure Li _x Al _y Mn _1-y O ₂ [y is not zero]. . In another embodiment, the composite intercalant comprises a mixture of orthorhombic and monoclinic Li _x Al _y Mn _1-y O ₂ . In other embodiments, the complex comprises _{Li x Al y Mn 1-y} O 2 and orthorhombic Li _x MnO ₂ or _{Li x Al y Mn 1-y} O 2 monoclinic.

Such a mixture can provide additional improvements in properties that are not obtained with a single compound or phase. Certain embodiments result in advantageous voltage versus capacity curves (hereinafter referred to as "voltage profiles"). The above result is
Monoclinic Li _x Al _y Mn _1-y O ₂ and orthorhombic Li _x MnO ₂ or Li _x Al _y Mn _1-y
O ₂ has different rates of lithium insertion and deinsertion, indicating that the latter two compounds are typically slow. However, both compounds show a two-step voltage profile with a plateau at about 4V and about 3V. If both compounds are present in one electrode, they insert and deinsert lithium at different rates. This has the effect of "voltage averaging", such that the voltage profile of the resulting compound has a poorly defined plateau. For many battery applications, a gradually changing voltage profile is advantageous.

A composite electrode that produces a smooth voltage profile as described above can be obtained by mixing compounds with different compounds with completely different lithium chemical diffusion rates or with similar or the same lithium chemical diffusion rates, but with different particle sizes. Obtained by a mixture of In order to obtain such voltage smoothing, the rate-limiting transport step at the electrode most likely appears to be diffusion in one or more intercalating compounds. Such a composite cathode can be obtained not only by the compounds of Examples 1 to 3, but also by any combination of the individual insertion compounds, so that the lithium diffusion in the compound is rate-limiting. It meets the requirements of completely different lithium chemical diffusion rates or widely varying particle sizes in the structure.

One embodiment of the present invention contains at least two individual insertion compounds, each compound having a different lithium chemical diffusion rate and a more continuous change than the voltage versus capacity profile of any non-complex insertion compound. A composite insertion compound having a voltage versus capacity profile is provided.

Another aspect of the invention is that the compound contains at least two individual insertion compounds, each compound having a different particle size and a voltage versus voltage profile that varies more continuously than the voltage versus capacity profile of any non-composite insertion compound. A composite insertion compound having a volume profile is provided.

In one embodiment, the lithium battery electrode contains a compound having a different particle size and a voltage versus capacity profile, as described above, wherein the compound causes the slowest lithium transport step in the electrode to occur. It has a sufficient particle size to be the diffusion of lithium in the compound.

[0062] In one embodiment of the present invention, the composite intercalator comprises about 4 times during electrochemical cycling.
At least two compounds having at least one compound having a change in voltage versus capacity curve from a single plateau at V to two plateaus at about 4V and 3V, respectively.

In one aspect of the invention, at least about 1 over a voltage range of 2.0 to 4.4V.
00 mAh / g discharge capacity and at least about 400 Wh / kg after 50 cycles
At least one compound having at least one compound having an energy density of
Class of compounds.

It is understood by those skilled in the art that all parameters listed herein are meant to be exemplary, and that the actual parameters will depend on the particular application to which the method and apparatus of the present invention will be applied. It will be easily understood. Therefore, it is understood that the above embodiments are provided by way of example only, and, within the scope of the appended claims and their equivalents, the invention may be practiced otherwise than as described herein. Should.

[Brief description of the drawings]

FIG. 1 shows the powder X-ray diffraction pattern of LiAl _y Mn _1-y O ₂ produced according to Example 1 and calcined at 945 ° C. for 2 hours under various oxygen partial pressures (middle circle: m with hkl designation) _{-LiMnO 2; *: o-LiMnO} 2; +: LiMn 2 O 4; the hollowed circle:
Li ₂ MnO ₃ ; hollow square: LiAlO ₂ ). The upper pattern of LiAl _0.05 Mn _0.95 O ₂ corresponds to the firing condition of PO ₂ = 10 ⁻⁷ atm.

FIG. 2 (a) m-LiMnO_Two(B) m-LiAl_0.25Mn_0.75O_TwoAnd (c) Li _Two Mn_TwoO_FourSimulated X-ray diffraction pattern of (d) produced according to Example 1
LiAl_0.25Mn_0.75O_TwoThis is shown in comparison with the experimental pattern shown in FIG.

FIG. 3 shows the undoped precursor prepared according to Example 1 at 945 ° C. and P
The powder X-ray diffraction pattern after calcination at O ₂ = 10 ⁻⁶ atm for 2 hours is shown (
*: O-LiMnO ₂ ; Δ: Mn ₃ O ₄ ).

FIG. 4 shows a photocopy of a bright-field scanning transmission electron microscope image of m-LiAl _0.05 Mn _0.95 O ₂ powder particles produced according to Example 1, together with an energy dispersive X-ray map showing the Al and Mn distribution. .

FIG. 5: m-LiA manufactured according to Example 1 and stored at room temperature for 6 months.
Shown is a photocopy of a bright field scanning transmission electron microscope image of l _0.25 Mn _0.75 O ₂ powder particles, along with an energy dispersive X-ray map showing Al and Mn distributions.

FIG. 6: m-LiA prepared according to Example 1 and stored at room temperature for 6 months.
Shown is a photocopy of a bright field scanning transmission electron microscope image of l _0.25 Mn _0.75 O ₂ powder particles, along with an energy dispersive X-ray map showing Al and Mn distribution.

FIG. 7 compares the powder X-ray diffraction patterns of m-LiAl _0.25 Mn _0.75 O ₂ prepared according to Example 1 before and after storage at room temperature for 6 months.

8: 0.4 of the electrochemical test cell containing m-LiAl _0.25 Mn _0.75 O ₂ according to Example 1 between 2.0 V and 4.4 V in (a) cycle 1 and (b) cycle 20. FIG.
3 shows a charge-discharge curve at an electron density of mA / cm ² (C / 5 rate).

FIG. 9 shows an electrochemical test cell containing m-LiAl _0.25 Mn _0.75 O ₂ according to Example 1 at 0.4 mA / cm ² electron density (C / 5 rate) between 2.0 V and 4.4 V. Shows specific capacity versus cycle number.

FIG. 10 shows discharge curves at C / 5 and C / 15 rates for an electrochemical test cell containing m-LiAl _0.25 Mn _0.75 O ₂ cycled as described in Example 1.

FIG. 11: mL cycled at 60 ° C. and 70 ° C. as described in Example 1.
Figure 4 shows voltage versus time results for an electrochemical test cell containing iAl _0.25 Mn _0.75 O ₂ .

FIG. 12 shows the specific capacity versus the number of cycles at room temperature (23 ° C.) and 55 ° C. for an electrochemical test cell containing m-LiAl _0.25 Mn _0.75 O ₂ according to Example 1.

FIG. 13 shows a first charge-discharge curve at 55 ° C. of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 1.

14 shows a charge-discharge curve of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 1 at 55 ° C. in cycle 6. FIG.

FIG. 15 shows a charge-discharge curve at 55 ° C., cycle 17, of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 1.

FIG. 16 shows a charge-discharge curve of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 1 at 55 ° C., cycle 34.

FIG. 17: m-LiAl cycled at 55 ° C. according to Example 1._0.25Mn _0.75 O_TwoAnd m-LiAl_0.05Mn_0.95O_TwoCapacity of electrochemical test cell containing
Indicates the number of cycles.

FIG. 18 shows a powder X-ray diffraction pattern of the composition m-LiAl _0.05 Mn _0.95 O ₂ calcined at 900 ° C. and PO ₂ = 10 ⁻⁶ atm for 2 hours according to Example 2.

FIG. 19 shows a powder X-ray diffraction pattern of a composition m-LiAl _0.05 Mn _0.95 O ₂ calcined at 900 ° C. and PO ₂ = 10 ⁻¹⁰ atm for 2 hours according to Example 2.

FIG. 20: m-LiAl cycled at 55 ° C. according to Example 2._0.05Mn _0.95 O_Two5 shows the specific capacity versus number of cycles for an electrochemical test cell containing.

FIG. 21 shows a first charge-discharge curve at 55 ° C. of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 2.

FIG. 22 shows a charge-discharge curve at 55 ° C., cycle 6 of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 2.

FIG. 23 shows a charge-discharge curve at 55 ° C., cycle 8 of an electrochemical test cell containing m-LiAl _0.05 Mn _0.95 O ₂ according to Example 2.

FIG. 24 shows a powder X-ray diffraction pattern of m-LiAl _0.05 Mn _0.95 O ₂ produced according to Example 1.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] November 22, 1999 (1999.11.22)

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──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Sadway, Donald Earl Massachusetts, United States of America State 02154, Waltham, Trapero Road 75 (72) Inventor Jean, Jan-Ill Massachusetts, United States 02171, North Quincy, Marina Drive 100, Apartment 406 (72) Inventor Hwan, Byne, United States 02140, Massachusetts, Cambridge, Alberta Terrace 6, Apartment 3F Term (Reference) 4G048 AA04 AB01 AC06 AD03 AD06 AE05 AE07 5H029 AJ03 AJ05 AK 03 AL03 AM03 AM05 AM07 HJ04 HJ05 HJ19 5H050 AA07 AA08 BA06 BA17 CA08 CA09 CB03 FA18 HA02 HA04 HA05 HA19

Claims (39)

[Claims] 2. The method of claim 1, wherein each of the first and second metal oxide cores comprises a first ratio of at least a first metal and a second metal oxide core, each formed by segregation of at least one of the first metal and the second metal from the core. A particulate metal oxide material including a plurality of multi-component metal oxide particles, including a surface coating of a metal oxide or hydroxide, not including a first metal and a second metal in a first ratio. Composition. 2. An article comprising a plurality of particles according to claim 1, wherein the particles are ion insertion particles that are at least partially in contact with the conductive material and are present on the ion conductive material. 3. The article of claim 2, wherein the article is configured and arranged as an electrode usable in an ion-conducting battery. 4. The composition of claim 1, wherein each particle comprises a surface layer having a thickness of at least about 2% of the diameter of the particle. 5. The composition of claim 1, wherein each particle comprises a surface layer having a thickness of at least about 5% of the diameter of the particle. 6. The composition of claim 1, wherein each particle comprises a surface layer at least 5 nm thick. 7. The composition according to claim 1, wherein the surface coating is amorphous or vitreous. 8. The composition according to claim 1, wherein the surface coating of the plurality of particles and each particle have the same crystal structure. 9. The composition of claim 1, wherein the surface coating is an epitaxy crystal layer that extends the crystal lattice of each of the plurality of particles. 10. Each comprising an oxide core of at least a first metal and a second metal in a first ratio, each formed by application of an auxiliary metal oxide or hydroxide to the particles. does not include a first metal and a second metal first rate, include surface coating of a metal oxide or hydroxide, wherein the core is _{Li x M y N z O 2} [ wherein, M is a metal atom Or a main group element, N is a metal atom or main group element, x is a number from about 0 to about 1, y is a number from about 0 to about 1, and z is about 0 to about 1 a number in the range 1, and the y and z, formal charge relates M _y N _z portion of the compound containing a number such that (4-x)], a plurality of multi-component metal oxide particles And a particulate metal oxide material having a charging voltage of at least about 2.5V. 11. A protective layer of the first component, wherein the first component of the intercalation compound based on the multicomponent oxide is disproportionately segregated from the plurality of compound particles to the surface of the plurality of compound particles. Exposing the plurality of particles to chemical decomposition conditions; and shielding the particles from the chemical decomposition conditions so that the particles are larger than the same particles without the protective layer. Making robust under the conditions. During 12. multicomponent oxide insertion compound based on compound is _{Li x M y N z O 2} [ wherein, M is a metal atom or a main group element, N is a metal atom or a main group element, x is is a number from about 0 to about 1, y is a number from about 0 to about 1, z is a number from about 0 to about 1, and the y and z, of the compound M _y N _z The formal charge on the part is (4
-X), and having a charging voltage of at least about 2.5V. 13. A multiphase oxide microstructure core and a surface layer of one material that is a component of the multiphase oxide microstructure core that protects the underlying intercalation material from chemical dissolution or reaction. A multi-component oxide microstructure useful as a lithium insertion material, comprising: 14. The intercalating compound in which lithium can be reversibly inserted and some or all of one component of the multicomponent oxide forms a surface layer spontaneously, with this surface layer underlying Multi-component oxide that protects against chemical dissolution or reaction. 15. The multicomponent oxide according to claim 13, wherein the oxide is an aluminum-containing insertion oxide and has a naturally formed aluminum surface protective layer. 16. The multi-component oxide according to claim 13, wherein the oxide is a manganese oxide-lithium-aluminum oxide mixture and has a naturally formed aluminum-enriched oxide surface protective layer. 17. The composition of claim 17, wherein the oxide has a composition selected from the group consisting of Li _x Al _y Mn _1-y O ₂ and Li _x Al _y Mn _2-y O ₄ , wherein each composition is a naturally formed aluminum rich material. The multi-component oxide according to claim 13, which has a functionalized oxide surface protective layer. 18. The composition of claim 1, wherein the oxide has a composition selected from the group consisting of Li _x Al _y Mn _1-y O ₂ and Li _x Al _y Mn _2-y O ₄ , wherein each composition is initially a single phase 14. The multi-component oxide of claim 13, having a crystalline solid solution, but having a naturally formed aluminum-enriched surface protective layer over time. 19. The composition according to claim 19, wherein the oxide comprises a composition selected from the group consisting of Li _x Al _y Mn _1-y O ₂ and Li _x Al _y Mn _2-y O ₄ , wherein each composition is initially a single phase 14. The multicomponent oxide of claim 13, having a crystalline solid solution, but having a naturally formed aluminum-enriched surface protective layer upon electrochemical insertion and removal of lithium. 20. A Li _x Al _y Mn _1-y O ₂ orthorhombic structure in which _y is not 0. 21. The method of claim 20, wherein x is about 1 and y is less than about 0.25.
The described structure. 22. The method of claim 20, wherein x is about 1 and y is less than about 0.10.
The described structure. 23. The structure of claim 21, wherein y is less than about 0.05. 24. For a primary lithium battery having at least one component, wherein the at least one component has a Li _x Al _y Mn _1-y O ₂ orthorhombic structure in which _y is not 0. electrode. 25. The electrode according to claim 24, wherein the battery is a rechargeable lithium battery. 26. A composition substantially as described herein in connection with the accompanying examples. 27. A method of making an insertion composition substantially as described herein in connection with the accompanying examples. 28. A multi-component oxide substantially as described herein in connection with the accompanying examples. 29. A non-aqueous electrolyte comprising a lithium ion conductive non-aqueous electrolyte comprising an anode, a cathode capable of adsorbing and desorbing lithium in a reversible manner, wherein the anode comprises the composition of claim 1. Aqueous electrolyte lithium secondary battery. 30. A multi-component as claimed in claim 13 or claim 14, comprising an anode, a cathode capable of adsorbing and desorbing lithium in a reversible manner, and a lithium ion conductive non-aqueous electrolyte. A non-aqueous electrolyte lithium secondary battery including an oxide microstructure. 31. Use of the composition according to claim 1 or the multicomponent oxide microstructure according to claim 13 or 14 for the manufacture of a non-aqueous electrolyte lithium secondary battery. 32. A voltage-to-capacity containing at least two individual insertion compounds, each compound having a different lithium chemical diffusion rate, and varying more continuously than the voltage-to-capacity profile of any non-composite insertion compound. Compound insertion compound with profile. 33. A composition comprising at least two individual insertion compounds, each compound having a different particle size and having a voltage-capacity profile that varies more continuously than the voltage-capacity profile of any non-composite insertion compound. Complex insertion compound. 34. An electrode for a lithium battery containing the compound of claim 33, wherein the compound is sufficient to cause the slowest lithium transport step in the electrode to be diffusion of lithium in the compound. The electrode having a suitable particle size. 35. A composite intercalating material having at least two compounds, wherein at least one compound has an orthorhombic structure Li _x Al _y Mn _1-y O ₂ , wherein y is not zero. . 36. The method of claim 35, further comprising monoclinic Li _x Al _y Mn _1-y O _2.
The composite insert as described. 37. A method comprising: at least one compound, wherein at least one compound undergoes a change in voltage versus capacity curve upon electrochemical cycling from a single plateau at about 4V to two plateaus at about 4V and 3V, respectively. A composite insert having the formula: 38. At least two compounds, wherein at least one compound has a discharge capacity of at least about 100 mAh / g over a voltage range of 2.0 to 4.4 V and an energy of at least about 400 Wh / kg after 50 cycles. A composite insert having a density. 39. A composition comprising at least two compounds, wherein at least one compound is monoclinic Li _x Al _y Mn _1-y O ₂ and the second compound is orthorhombic Li _x Mn
O ₂ or wherein, y is not _{0] Li x Al y Mn 1} -y O 2 composite insert material is.