CA2158242C - High voltage insertion compounds for lithium batteries - Google Patents
High voltage insertion compounds for lithium batteries Download PDFInfo
- Publication number
- CA2158242C CA2158242C CA002158242A CA2158242A CA2158242C CA 2158242 C CA2158242 C CA 2158242C CA 002158242 A CA002158242 A CA 002158242A CA 2158242 A CA2158242 A CA 2158242A CA 2158242 C CA2158242 C CA 2158242C
- Authority
- CA
- Canada
- Prior art keywords
- lithium
- insertion compound
- battery
- compound
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Insertion compounds having the formula Lix+yMzMn2-y-zO4 wherein the crystal structure is spinel-like, M is a transition metal, 0~x<1, 0~y < 0.33, and 0<z< about 1, can reversibly insert significant amounts of lithium at poten- tials greater than about 4.5 volts versus Li/Li+. In particular, M can be Ni or Cr. The reversible amount of lithium at such voltages can be greater for greater values of z. Such insertion compounds are suitable cathode materials for high voltage lithium batteries.
Description
2~~~242 HIGH VOLTAGE INSERTION COMPOUNDS FOR LITHIUM BATTERIES
FIELD OF THE INVENTION
This invention pertains to lithium insertion compounds and the use thereof in lithium batteries. Specifically, it pertains to the use of certain lithium transition metal oxides as high voltage cathode materials in lithium bat-teries.
BACKGROUND OF THE INVENTION
Insertion compounds are those that act as a host solid for the reversible insertion of guest atoms. Such com-pounds, particularly lithium insertion compounds, have been extensively studied in recent years for purposes that include use as electrode materials in advanced high energy density batteries. A new type of rechargeable lithium battery, known as a lithium-ion battery, is a product based on lithium insertion compounds that has just become avail-able commercially. These batteries have the greatest energy density (Wh/L) of presently available conventional rechargeable systems (ie. NiCd, NiMH, or lead acid bat-teries) and represent a preferred rechargeable power source for many consumer electronics applications. Additionally, lithium ion batteries operate around 3i~ volts which is often sufficiently high such that a single cell can suffice for many electronics applications.
Lithium ion batteries use two different insertion compounds for the active cathode and anode materials. The excellent reversibility of lithium insertion makes such compounds function extremely well in rechargeable battery applications wherein thousands of battery cycles can be obtained. In a lithium ion battery, lithium is extracted from the anode material while lithium is concurrently inserted into the cathode on discharge of the battery. The reverse processes occur on recharge of the battery.
Lithium atoms travel or "rock" from one electrode to the other as ions dissolved in a non-aqueous electrolyte with . ~ ~ ~1~~242 the associated electrons travelling in the circuit external to the battery.
The first commercial lithium ion batteries were 3.6 volt products based on LiCoOZ/pre-graphitic carbon electro chemistry from Sony Energy Tec. However, a wide range of carbonaceous compounds is suitable for use as the anode material, including coke (described in U.S. Patent No.
4,702,977) and pure graphite (described in U.S. Patent No.
4,423,125). Additionally, many other lithium transition metal oxide compounds are suitable for use as the cathode material, including LiNi02 (described in U.S. Patent No.
4,302,518) and LiMn204 (described in U.S. Patent No.
4,507,371). In the preceding, non-aqueous electrolytes are employed comprising LiBF4 or LiPF6 salts and solvent mixtures of ethylene carbonate, propylene carbonate, diethyl carbonate, and the like. Again, numerous options for the choice of salts and/or solvents in such batteries are known to exist in the art.
LiMnz04 is a particularly attractive cathode material candidate because manganese is significantly cheaper than cobalt and/or nickel. LiMnz04 refers to a stoichiometric lithium manganese oxide with a spinel crystal structure.
This stoichiometric compound however has been found to exhibit undesirably poor cycle life when used as the cathode in lithium ion batteries of conventional construc-tion. These cycle life problems have been overcome by varying the stoichiometry and methods of synthesis to some extent.
M.M. Thackeray et al. in U.S. Patent No. 5,316,877 show a capacity versus cycle life improvement that results from incorporating additional lithium into the conventional stoichiometric spinel LiMnz04. Therein, the compound was denoted as Li~DX~bMn2_X04+a. When D is Li, b is 0 and the improved compound can be denoted Li»XMnz_X04. wherein Osx<0.33. Although it was suggested that other metals D
could be incorporated with similar beneficial results, no mention was made therein regarding electrochemical behav-~1~8242 four of these compounds above 4.5 volts versus Li/Li+.
Actual electrochemical testing was restricted to voltages below 4.5V versus Li/Li+.
At the 11th International Seminar on Primary and Secondary Battery Technology and Application, Feb. 28-Mar.
3, 1994, Deerfield Beach, Florida, J.M. Tarascon confirmed the preceding result regarding capacity versus cycle life improvement by incorporating additional lithium into LiMn204. In this presentation, cyclic voltammograms also showed that both LiMnz04 and compounds comprising additional lithium exhibit small capacity peaks at around 4.5 volts and 4.9 volts versus Li/Li+. The small 4.5 V capacity decreased as the amount of additional lithium incorporated increased. On the other hand, the small 4.9 V capacity increased as the amount of additional lithium incorporated increased. It was noted that while some capacity was observed at voltages above 4.5 V and that this capacity increased with additional lithium content, this capacity was nonetheless extremely small. The useful capacity of the compound was obtained at voltages below 4.5 V and battery testing was confined to voltages below 4.5 V. In this presentation, no mention was made about nickel or chromium substituted compounds nor about the possibility of obtaining significant capacity at voltages above 4.5 V in such compounds.
In another article by the same author, J. M. Tarascon et al., J. Electrochem. Soc. Vol. 138, No. 10, (1991) 2859, the electrochemical properties of LiMnZ04 and various substituted compounds thereof were investigated. Included in the investigation were compounds LiXMnZ_~,04 (which can also be denoted as LiXNiZMn2_Z04) wherein y ranged up to values of 0.4. However, no electrochemical testing was performed above 4.5 volts versus Li/Li+. It was indicated therein that the lithium capacity of these nickel contain-ing compounds decreases with increasing nickel content.
Thus these nickel containing compounds appeared unattract-ive for battery applications.
w a ' ~1~82~2 Many substituted LiMn204 spinel insertion compounds have been reported in the art for application in lithium batteries. Much mention has been made of nickel and/or chromium substituted LiMn204 spinet insertion compounds.
For example, in laid-open Japanese Patent Application No.
04-141954, Matsushita report on Ni and Cr substituted compounds wherein up to 0.2 moles of transition metal was substituted per molecule of LiMnz04. Again, however, electrochemical testing was restricted to voltages below 4.5V. In the Journal of Power Sources, 43-44 (1993) 539-546 , W . Baochen et al . show that up to one chromium atom can be substituted for manganese in one mole of LiMn204.
Again, electrochemical testing was performed at voltages only up to 3.8 V versus Li/Li+. In U.S. Patent No.
FIELD OF THE INVENTION
This invention pertains to lithium insertion compounds and the use thereof in lithium batteries. Specifically, it pertains to the use of certain lithium transition metal oxides as high voltage cathode materials in lithium bat-teries.
BACKGROUND OF THE INVENTION
Insertion compounds are those that act as a host solid for the reversible insertion of guest atoms. Such com-pounds, particularly lithium insertion compounds, have been extensively studied in recent years for purposes that include use as electrode materials in advanced high energy density batteries. A new type of rechargeable lithium battery, known as a lithium-ion battery, is a product based on lithium insertion compounds that has just become avail-able commercially. These batteries have the greatest energy density (Wh/L) of presently available conventional rechargeable systems (ie. NiCd, NiMH, or lead acid bat-teries) and represent a preferred rechargeable power source for many consumer electronics applications. Additionally, lithium ion batteries operate around 3i~ volts which is often sufficiently high such that a single cell can suffice for many electronics applications.
Lithium ion batteries use two different insertion compounds for the active cathode and anode materials. The excellent reversibility of lithium insertion makes such compounds function extremely well in rechargeable battery applications wherein thousands of battery cycles can be obtained. In a lithium ion battery, lithium is extracted from the anode material while lithium is concurrently inserted into the cathode on discharge of the battery. The reverse processes occur on recharge of the battery.
Lithium atoms travel or "rock" from one electrode to the other as ions dissolved in a non-aqueous electrolyte with . ~ ~ ~1~~242 the associated electrons travelling in the circuit external to the battery.
The first commercial lithium ion batteries were 3.6 volt products based on LiCoOZ/pre-graphitic carbon electro chemistry from Sony Energy Tec. However, a wide range of carbonaceous compounds is suitable for use as the anode material, including coke (described in U.S. Patent No.
4,702,977) and pure graphite (described in U.S. Patent No.
4,423,125). Additionally, many other lithium transition metal oxide compounds are suitable for use as the cathode material, including LiNi02 (described in U.S. Patent No.
4,302,518) and LiMn204 (described in U.S. Patent No.
4,507,371). In the preceding, non-aqueous electrolytes are employed comprising LiBF4 or LiPF6 salts and solvent mixtures of ethylene carbonate, propylene carbonate, diethyl carbonate, and the like. Again, numerous options for the choice of salts and/or solvents in such batteries are known to exist in the art.
LiMnz04 is a particularly attractive cathode material candidate because manganese is significantly cheaper than cobalt and/or nickel. LiMnz04 refers to a stoichiometric lithium manganese oxide with a spinel crystal structure.
This stoichiometric compound however has been found to exhibit undesirably poor cycle life when used as the cathode in lithium ion batteries of conventional construc-tion. These cycle life problems have been overcome by varying the stoichiometry and methods of synthesis to some extent.
M.M. Thackeray et al. in U.S. Patent No. 5,316,877 show a capacity versus cycle life improvement that results from incorporating additional lithium into the conventional stoichiometric spinel LiMnz04. Therein, the compound was denoted as Li~DX~bMn2_X04+a. When D is Li, b is 0 and the improved compound can be denoted Li»XMnz_X04. wherein Osx<0.33. Although it was suggested that other metals D
could be incorporated with similar beneficial results, no mention was made therein regarding electrochemical behav-~1~8242 four of these compounds above 4.5 volts versus Li/Li+.
Actual electrochemical testing was restricted to voltages below 4.5V versus Li/Li+.
At the 11th International Seminar on Primary and Secondary Battery Technology and Application, Feb. 28-Mar.
3, 1994, Deerfield Beach, Florida, J.M. Tarascon confirmed the preceding result regarding capacity versus cycle life improvement by incorporating additional lithium into LiMn204. In this presentation, cyclic voltammograms also showed that both LiMnz04 and compounds comprising additional lithium exhibit small capacity peaks at around 4.5 volts and 4.9 volts versus Li/Li+. The small 4.5 V capacity decreased as the amount of additional lithium incorporated increased. On the other hand, the small 4.9 V capacity increased as the amount of additional lithium incorporated increased. It was noted that while some capacity was observed at voltages above 4.5 V and that this capacity increased with additional lithium content, this capacity was nonetheless extremely small. The useful capacity of the compound was obtained at voltages below 4.5 V and battery testing was confined to voltages below 4.5 V. In this presentation, no mention was made about nickel or chromium substituted compounds nor about the possibility of obtaining significant capacity at voltages above 4.5 V in such compounds.
In another article by the same author, J. M. Tarascon et al., J. Electrochem. Soc. Vol. 138, No. 10, (1991) 2859, the electrochemical properties of LiMnZ04 and various substituted compounds thereof were investigated. Included in the investigation were compounds LiXMnZ_~,04 (which can also be denoted as LiXNiZMn2_Z04) wherein y ranged up to values of 0.4. However, no electrochemical testing was performed above 4.5 volts versus Li/Li+. It was indicated therein that the lithium capacity of these nickel contain-ing compounds decreases with increasing nickel content.
Thus these nickel containing compounds appeared unattract-ive for battery applications.
w a ' ~1~82~2 Many substituted LiMn204 spinel insertion compounds have been reported in the art for application in lithium batteries. Much mention has been made of nickel and/or chromium substituted LiMn204 spinet insertion compounds.
For example, in laid-open Japanese Patent Application No.
04-141954, Matsushita report on Ni and Cr substituted compounds wherein up to 0.2 moles of transition metal was substituted per molecule of LiMnz04. Again, however, electrochemical testing was restricted to voltages below 4.5V. In the Journal of Power Sources, 43-44 (1993) 539-546 , W . Baochen et al . show that up to one chromium atom can be substituted for manganese in one mole of LiMn204.
Again, electrochemical testing was performed at voltages only up to 3.8 V versus Li/Li+. In U.S. Patent No.
5,084,366, Y. Toyoguchi demonstrated that a cycling benefit could be obtained by appropriate chromium substitution.
Again, electrochemical testing was performed only up to 4.5 V versus Li/Li+.
Historically, difficulties with electrolyte stability has hindered the electrochemical evaluation of insertion compounds at relatively high voltages with respect to lithium. However, progress has been made in this area.
U.S. Patent No. 5,192,629, for instance, reveals a non aqueous electrolyte suitable for use in a lithium ion battery comprising a Lip+XMn204 cathode that is oxidation resistant up to about 5 V.
With the availability of electrolytes that are stable at high voltage, lithium insertion compounds that deliver useable capacity at voltages above 4.5 V versus Li/Li+ can not only be studied more easily but can also be considered for use in commercial battery applications. For instance, it was shown in Canadian Patent Application Serial No.
2,102,738 that a related group of lithium insertion com-pounds having an inverse spinet structure can unexpectedly exhibit substantial high voltage capacity that can be accessed at reasonable rate. These inverse spinet com-pounds may have similar stoichiometry to the aforementioned ~1~~2~2 transition metal substituted LiMnz04 compounds, but the crystal structure differs significantly from that of spinel.
It appears that the electrochemical properties of most substituted LiMn204 spinel compounds (including nickel and chromium substituted compounds) have not been deter mined above 4.5 V with respect to lithium despite the extensive research performed thereon to date. Thus, such compounds apparently have not been considered for use in lithium batteries operating in this high voltage range.
Historical difficulties arising from a lack of stable high voltage electrolytes or previous negative capacity observa-tions at lower voltages have tended to indicate that voltages above 4.5 V are not feasible.
SUMMARY OF THE INVENTION
We have discovered unexpectedly that there can be substantial useable reversible lithium capacity in certain transition metal substituted LiMn204 spinel insertion compounds above 4.5 volts versus Li/Li+. For instance, we have found that the lithium capacity in LixNiZMnz_Z04 appar-ently does not decrease with increasing Ni content but instead is realized at higher voltages (above 4.5 volts versus Li/Li+) than in LiXMn204, a widely used material.
Thus, instead of being a less preferred battery material from an energy density viewpoint, LiXNiZMn2_Z04 can actually be preferred as it offers the possibility of higher voltage batteries.
The invention in one embodiment thus comprises transition metal substituted, LiMnz04 spinel, lithium insertion compounds that have useable reversible lithium capacity above 4.5 volts versus Li/Li+ . These lithium insertion compounds can be denoted as LiX+~IZMn2_y_Z04.
Therein, M represents the substituted transition metal and z is a number greater than zero and less than about 1. y is a number representing a relative 'shortage' of manganese and corresponding 'excess' amount of lithium and is greater than or equal to zero and less than 0.33. x is a number greater than or equal to zero and less than 1. The poten-tial of the lithium insertion compound is greater than about 4.5 volts versus Li/Li+. Lithium therefore can be reversibly inserted therein at potentials greater than about 4.5 volts versus Li/Li+. The lithium insertion compounds do not necessarily have an ideal spinel crystal structure as a result of transition metal substitution and/or low lithium content. However, the crystal structure of the lithium insertion compound is similar to spinet (ie. spinet-like or distorted spinet).
In particular, M can be nickel for values of z up to about 0.5. When M is nickel, quite substantial amounts of lithium can be reversibly inserted above 4.5 V when z is greater than about 0.3. Alternately, M can be chromium.
In this case, substantial amounts of lithium can be revers-ibly inserted when z is greater than about 0.5. ' For improved cycle life in battery applications, it can be advantageous to employ insertion compounds of the invention having 'excess' lithium. The amount of 'ex cess' lithium, y, can be about 0.1.
In another embodiment, the invention includes a process for making insertion compounds of the invention.
The process comprises extracting lithium from a precursor insertion compound having the formula Lip+~IZMn2_Y_Z04 and a spinet crystal structure. The extracting can be performed electrochemically.
The precursor insertion compound can be prepared by mixing reactant powders comprising electrolytic manganese dioxide, a transition metal source, and a lithium source in a stoichiometric manner; followed by heating the reac tant powder mixture in an oxygen containing atmosphere. As a transition metal source, either nickel nitrate or nickel oxide and chromium sesquioxide can be used for nickel and chromium respectively. Either lithium hydroxide or lithium carbonate can be used as the lithium source. The heating ~~.~~w42 _ 7 _ can be performed between about 750 and 900 degrees C, and more than one mixing and heating step may be desirable.
Lithium batteries also form another embodiment of the invention. Generally, the lithium batteries comprise a lithium compound anode; an electrolyte comprising a solvent and a lithium salt; and a cathode comprising an insertion compound of the invention. Thus, put another way, the invention involves the use of such insertion compounds as a cathode in a lithium battery wherein a portion of the capacity of the battery is obtained at a cathode voltage greater than about 4.5 volts versus Li/Li+. The batteries can be lithium ion types and can therefore have lithium compound anodes that are carbonaceous. The lithium salt can be LiBF4 and the solvent can comprise ethylene carbonate and diethyl carbonate. The solvent can additionally comprise ethyl methyl carbonate.
The cathode in the lithium battery can be easily formed by first constructing a battery with a precursor cathode comprising a precursor lithium insertion compound having the formula Lip+~IZMnz_y_Z04and a spinel crystal struc-ture. Thereafter, lithium is extracted electrochemically from the precursor cathode, thereby forming the high voltage insertion compound cathode.
BRIEF DESCRIPTION OF THE DRAWINGS
In drawings which illustrate specific embodiments of the invention, but which should not be construed as re-stricting the spirit or scope of the invention in any way:
Figure 1 depicts a cross-sectional view of a preferred embodiment of a cylindrical spiral-wound lithium ion battery.
Figure 2 shows the relationship between the lattice constant of the samples in the series of Inventive Example 1 versus nickel content.
23.~~~~
_8_ Figure 3 shows the voltage plotted against capacity per gram of precursor insertion compound for the batteries of the series of Inventive Example 1. The voltage curves have been offset for clarity. For the batteries comprising the z=0.5, 0.3, 0.2, 0.1, and 0.05 samples, the curves are offset by +0.5, 0, -0.5, -1, and -1.5 volts respectively.
Figure 4 shows the voltage plotted against capacity per gram of Li~Nio.4Mn~,604 cathode for the battery of Inven-tive Example 1 comprising 1.5M LiBF4/ethylene carbonate (EC)-diethyl carbonate (DEC)-ethyl methyl carbonate (EMC) electrolyte.
Figure 5 shows the capacity versus cycle number for the Li~Nio.4Mn~.604 battery that was cycled over 50 times in Inventive Example 1 Figures 6a and b compare the voltage versus capacity per gram of precursor insertion compound of the battery comprising the Li~.~Nio.SMn~_404 sample in Inventive Example 2 to that of another battery comprising the Li~Nio.SMn~.504 sample in Inventive Example 1 respectively.
Figure 7 shows the voltage versus capacity per gram of Li~Cro.SMn~.504 for the battery of Inventive Example 3.
Figure 8 shows the voltage plotted against capacity per gram of precursor insertion compound for the battery of Illustrative Example 2.
DETAILED DESCRIPTION OF SPECIFIC
EMBODIMENTS OF THE INVENTION
LiMn204 has an ideal spinel structure of space group Fd3m with Li atoms in 8a sites, Mn atoms in 16d sites, and oxygen atoms in 32e sites (see the International Tables for X-ray Crystallography, Volume 1, The Kynoch Press, Birming-ham, England, 1969) . The Lix+~IZMnz_y_Z04 compounds of the invention can be derived from LiMn204 without substantial change of the crystal structure. However, as a result of substitution of transition metal M and Li along with a varied amount, x, of inserted lithium, there can be a mild distortion of the structure from that of the ideal spinel.
Thus, the structure of the LiX+~IZMn2_Y_Z04 compounds might be described as spinel-like. (Note that both the ideal spinel and spinel-like structures differ significantly from that of an inverse spinel type such as LiNiV04 wherein the oxygen atoms still reside in 32e sites, but the Li atoms and the Ni atoms randomly fill half the 16d sites each with the V atoms filling the 8a sites.) In one respect, this invention comprises those inser-tion compounds that exhibit a useful amount of reversible lithium capacity at potentials greater than about 4.5 volts versus Li/Li+. Certain transition metal substitutions, for instance chromium or nickel, can result in suitable inser-tion compounds. The amount z of substituted transition metal that can be accommodated can vary with the choice of transition metal. For instance, z can range up to 1 when chromium is chosen. However, it appears that nickel can only be substituted up to a value of 0.5. Generally, the greater the value of z, the greater the amount of revers-ible lithium capacity above 4.5 volts. When M is nickel and z is greater than about 0.3, the amount of capacity realized above 4.5 V is substantial. Similarly, when M is chromium and z is greater than about 0..5, the amount of capacity realized above 4.5 V is substantial.
As in the teachings of the prior art, an additional amount, y, of lithium can be substituted in these insertion compounds in order to improve cyclability in battery applications. y can range up to a value of 0.33 based on valence arguments. In the examples to follow, a preferred value for y was about 1.
These insertion compounds can be derived from suitable precursor insertion compounds Lip+~IZMnz_y_Z04 having a spinel crystal structure. These precursor insertion compounds are known in the art to reversibly insert lithium at voltages below 4.5 V versus Li/Li+. Upon extracting Li from the precursor insertion compound, Lix+~IZMnz_y_Z04 compositions with x<1 are reached wherein lithium can be reversibly inserted above 4.5 V. The maximum value of x varies with the choice of transition metal M and the amount substituted therein, z.
The aforementioned precursor insertion compounds are conventional and can be prepared by appropriate heat treatment of suitable stoichiometric powder mixes in oxygen containing atmospheres. As shown in the examples to follow, suitable powder mixes can include electrolytic manganese dioxide (EMD) and lithium hydroxide or carbonate as sources of manganese and lithium respectively. As a source of the transition metal M, either nickel nitrate or oxide and chromium sesquioxide powder can be used for nickel and chromium respectively. Suitable heat treatment temperatures are typically in the range of about 750 to about 950 degrees C. The treatment atmosphere can be simply air or oxygen. Some effort (eg. multiple heating/mixing steps) is required to ensure uniform reac-tion in order to get a single phase product.
The extraction of lithium from the precursor insertion compound can be accomplished by chemical or electrochemical means. The latter method is preferred for conventional lithium ion battery applications and is performed in situ.
Generally, lithium batteries of the invention can be primary or secondary (rechargeable) and comprise the aforementioned insertion compounds as an electrode ma-terial. Various electrochemistries and battery configur-ations are possible. For instance, the batteries can have lithium metal, lithium alloy, and/or lithium insertion compound anodes. Various non-aqueous or aqueous electro-~1~~~~2 lytes can be used. Product configurations include pris-matic formats and miniature coin cells.
A preferred construction for a lithium ion type battery is depicted in the cross-sectional view of a conventional spiral-wound battery in Figure 1. A jelly roll 4 is created by spirally winding a cathode foil l, an anode foil 2, and two microporous polyolefin sheets 3 that act as separators.
Cathode foils are prepared by applying a mixture of a powdered (about 10 micron size typically) precursor inser tion compound, possibly other powdered cathode material if desired, a binder, and a conductive dilutant onto a thin aluminum foil. Typically, the application method first involves dissolving the binder in a suitable liquid car rier. Then, a slurry is prepared using this solution plus the other powdered solid components. The slurry is then coated uniformly onto the substrate foil. Afterwards, the carrier solvent is evaporated away. Often, both sides of the aluminum foil substrate are coated in this manner and subsequently the cathode foil is calendered.
Anode foils are prepared in a like manner except that a powdered (also typically about 10 micron size) carbon-aceous insertion compound is used instead of the cathode material and thin copper foil is usually used instead of aluminum. Anode foils are typically slightly wider than the cathode foils in order to ensure that anode foil is always opposite cathode foil.
The jelly roll 4 is inserted into a conventional battery can 10. A header 11 and gasket 12 are used to seal the battery 15. The header may include safety devices if desired. A combination safety vent and pressure operated disconnect device may be employed. Figure l shows one such combination that is described in detail in Canadian Patent Application No. 2,099,657. Additionally, a positive thermal coefficient device (PTC) maybe incorporated into the header to limit the short circuit current capability of the battery. The external surface of the header 11 is used ~1~~242 as the positive terminal, while the external surface of the can 10 serves as the negative terminal.
Appropriate cathode tab 6 and anode tab 7 connections are made to connect the internal electrodes to the external terminals. Appropriate insulating pieces 8 and 9 may be inserted to prevent the possibility of internal shorting.
Prior to crimping the header 11 to the can 10 in order to seal the battery, a suitable non-aqueous electrolyte 5 i~s added to fill the porous spaces in the jelly roll 4.
The battery as constructed is in a fully discharged state. Upon charging, lithium is extracted from the cathode and inserted into the anode. The initial charging thus serves to form the high voltage insertion compound in situ.
Those skilled in the art will understand that the types of and amounts of the component materials must be chosen based on component material properties and the desired performance and safety requirements. The use of a higher voltage cathode material poses additional require-ments over those of commercially available lithium ion batteries. Obviously, the electrolyte chosen must have a greater voltage stability window (in order to be stable at higher cathode potentials). Additionally, the hardware employed at cathode potential must also be stable at these higher voltages.
In the aforementioned J. Electrochem. Soc. article by J. M. Tarascon et al., it appeared that the reversible lithium capacity of LiXNiZMn2_Z04 decreased with increasing nickel content. However, as illustrated in the examples to follow, it appears that this lithium capacity is not 'lost' or made unavailable, with increasing nickel content.
Instead, it is unexpectedly realized at somewhat higher voltages. At this time, the physical reasons for the apparent voltage 'shift' of part of the lithium capacity are unclear. Additionally, it is unknown what the crystal structures are precisely and hence where the lithium atoms s- ~ ~1~~2~~
are exactly. However, similar behaviour is not unexpected for transition metals other than nickel and chromium.
The following Examples are provided to illustrate certain aspects of the invention but should not be con s strued as limiting in any way. Therein, laboratory coin cell batteries were used to determine electrochemical characteristics of the high voltage insertion compounds against a lithium metal anode. These coin cell batteries were assembled using conventional 2350 hardware in a dry room but otherwise as described in J.R. Dahn et al, Electrochimica Acta, 38, 1179 (1993). A stainless steel cap and special oxidation resistant case comprise the container and also serve as negative and positive terminals respectively. A gasket was used as a seal which also served to separate the two terminals. Mechanical pressure was applied to a stack comprising a lithium anode, separ-ator, and cathode by means of mild steel disc spring and stainless disc. The disc spring was selected such that a pressure of about 15 bar was applied following closure of the battery. 125 ~.m thick metal foil was used as a lithium anode. Celgard 2502 microporous polypropylene film was used as the separator. Except where indicated, the elec trolyte was a solution of 1.5M LiBF4 salt dissolved in a solvent mixture of EC and DEC in a volume ratio of 30/70 respectively.
Cathodes were made by uniformly coating a 20 ~,m thick aluminum foil substrate with a blend containing a mixture of insertion compound powder, Super S (product of Ensagri) carbon black conductive dilutant, and ethylene propylene dime monomer (EPDM) binder. This was accomplished by initially making a slurry containing cyclohexane solvent wherein the insertion compound powder and carbon black mixture (88 and 10 parts by weight respectively) were added to an appropriate amount of binder solution containing 4%
EPDM in cyclohexane, such that 2% of the final dried electrode mass would be EPDM. Excess cyclohexane was then added until the slurry viscosity was like that of a syrup, whereupon the :slurry was then coated onto the foil using a doctor blade spreader. Cyclohexane was then evaporated away at room temperature in air, leaving a deposited coating about 12 mg/cm2in weight. After drying, the electrode was compacted between flat plates at about 25 bar pressure. A disc cathode of diameter 16.2 mm was then cut from this larger electrode using a precision cutting jig.
The weight of the coating was typically about 12 mg/cm2.
The cathode was then weighed and the active insertion compound mass present was obtained by subtracting the weight of A1 foil, EPDM, and carbon black present.
Coin cell. batteries were thermostatted at 21~1°C
before testing and were then charged and discharged using constant current cyclers with t 1% current stability.
Current densit=ies were adjusted to be equivalent to C/40 rate unless indicated otherwise. Data was logged whenever the cell voltage changed by more than 0.001 V.
Inventive Example 1 A series of precursor insertion compounds LiINiZMn2_ZOa with z amounts of 0.05, 0.1, 0.2, 0.3, and 0.5 respectively was synthesized using mixtures of EMD (LiMn02 - TAD 1 grade from Mitsui), (NiN03).6H20, and LiOH powders in appropriate amounts. To get a homogeneous reaction product for samples with z amounts s 0.3, the mixtures were heat treated first at 750°C in air for 4 hours. The product was ground and mixed again followed by a second similar heat treatment for an additional 12 hours. For the sample with z=0.4, the synthesis was ~;imilar except that the second heat treatment lasted 24 hour:~ . For the sample with z=0 . 5 , the f first heat treatment laste=d 16 hours and the second heat treatment was performed at 850°C for 12 hours.
The precursor insertion compounds all had a spinel crystal structure with the Ni mainly occupying 16d posi tions. The lattice constant of the samples in the series ~1~~~
decreases with increasing nickel content as shown in Figure 2.
A series of laboratory coin cell batteries was con-structed as described in the preceding using these precur-sor insertion compounds as cathodes. Each battery was then charged to 4.9 volts, thereby extracting lithium from the cathode, and then cycled a few times. Figure 3 shows the battery voltage (insertion compound versus lithium) plotted against capacity per gram of precursor insertion compound for each battery of the series . The voltage curves have been offset for clarity. For the batteries comprising the z=0.5, 0.3, 0.2, 0.1, and 0.05 samples, the curves are offset by +0.5, 0, -0.5, -1, and -1.5 volts respectively.
A significant reversible lithium capacity between about 4.5 and 4.9 volts (on a rough plateau at an average 4.7 volts) is observed even for z values as low as 0.05.
With increasing z, the reversible lithium capacity at high voltage increases. For z values of 0.3 and up, this capacity becomes quite substantial and exceeds the revers ible capacity below 4.5 volts. In each case however, the total reversible capacity between the starting composition and that at 4.9 volts is roughly the same, around 125 mAh/g. (This is also roughly the same as the reversible extractable lithium capacity for LiMn204 spinel . ) Thus, the presence of the substituted nickel seems to 'shift' a portion of the voltage curve above 4.5 volts.
Another coin cell battery was made with cathode comprising Li~Nio.4Mn~.604 from the above series but with an electrolyte comprising 1.5M LiBF4 salt in a solvent mixture of EC, DEC, and EMC in a volume ratio of 20/30/50 respectively. Figure 4 shows the voltage plotted against capacity per gram of precursor insertion compound for this battery. The results are similar to that of the corresponding battery in Figure 1.
Another coin cell battery was made with cathode comprising Li~Nio.4Mn~.604 similar to the above series and cycled between 3.0 and 4.9 volts at ?1°C at a C/10 rate ~1~~24~
charge and C rate discharge. Figure 5 shows the capacity versus cycle number for this battery. Little capacity loss is seen over 50 cycles.
Inventive Example 2 A precursor insertion compound Li~.~Nio.SMn~.404 was synthesized in the following manner. First, LiMn204 was prepared by heat treating an appropriate mixture of EMD
(LiMnOz - TAD 1 grade from Mitsui) and LiZC03 powders at 900°C in air for 20 hours. Additional Li2C03 and Ni0 powders were then mixed in with the LiMnz04 product followed by heat treatment in air at 900°C for 20 hours. Finally, this product was ground, remixed, and heat treated for an additional 12 hours at 850°C in oxygen.
A laboratory coin cell battery was constructed as described in the preceding using this precursor insertion compound as the cathode. The battery was then charged to 4.8 volts, thereby extracting lithium from the cathode, and then cycled a few times. Figures 6a and b compare the voltage versus capacity per gram of precursor insertion compound of this battery to that of another similarly cycled battery comprising the Li~Nio_SMn~.504 sample in Inventive Example 1 respectively.
The voltage curves are similar except that the Li~Nio.SMn~_504 sample (wherein y=0) has a larger recharge capacity than discharge capacity. Consequently, the curve shifts to the right in this plot with each cycle. The larger recharge capacity is indicative of an irreversible decomposition or degradation process, possibly of the electrolyte or cathode material. The voltage curve of the Li~.~Nio.SMn~.404 sample shows significantly better results.
Inventive Example 3 A precursor insertion compound Li~Cro.SMn~_504 was synthesized using an appropriate mixture of EMD, CrZ03, and LiOH powders. The mixture was heat treated in air at 800°C
for 4 hours, ground, remixed, and heat treated again at 900°C for 11 hours.
A laboratory coin cell battery was constructed as described in the preceding using this precursor insertion compound as the cathode. The battery was then charged, thereby extracting lithium from the cathode, and then cycled a few times. Figure 7 shows the voltage versus capacity per gram of precursor insertion compound for this battery. There is substantial reversible lithium capacity between about 4.8 and 5.2 volts. However, there is also significant shifting of the voltage curve with each cycle, perhaps indicative of more severe electrolyte decomposition at these higher voltages.
The preceding Examples show that LiX+~IZMnZ_y_Z04 compounds can exhibit substantial useful reversible lithium capacity above 4.5 volts versus lithium when M is nickel or chro mium. Additionally, cycling characteristics can be im proved when y>0.
Illustrative Example 1 An attempt was made to synthesize precursor insertion compound Li~.~Nio.SMn~.404 directly from an appropriate mixture of EMD, NiO, and Li2C03 powders but otherwise as in Inventive Example 2. The mixture was first heat treated in air at 900°C for 20 hours. Then, the product was ground, remixed, and heat treated for an additional 12 hours at 850°C in oxygen. The result was a mixture of the phases NiO, Li2Mn03 and a Lip+~,l~TiZMnz_y_Z04 compound. The preparation of relatively pure precursor insertion compounds is not always straightforward.
~1~~242 Illustrative Example 2 A laboratory coin cell battery was constructed as described in the preceding with cathode comprising Li~Nio.SMn~,504 precursor insertion compound from the series of Inventive Example 1 and an electrolyte comprising 1.2M LiPF6 salt in a solvent mixture of EC, DEC, and EMC in a volume ratio of 20/30/50 respectively. The battery was then charged to 4.9 volts, thereby extracting lithium from the cathode, and then cycled once. Figure 8 shows the voltage plotted against capacity per gram of precursor insertion compound for this battery. An enormous recharge capacity is observed suggesting that this electrolyte is unsuitable for use in this situation. With the exception of the salt employed, this battery is similar to that of Figure 4.
LiPF6 salt thus appears unsuitable for use in this situ-ation.
As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this inven tion without departing from the spirit or scope thereof.
For example, it may be possible to synthesize precursor insertion compounds comprising hydrogen instead of lithium.
If the hydrogen is removed thereafter by heating or the like, a high voltage insertion compound of the invention might be synthesized, ready for use in a primary battery application, all in the absence of lithium. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
Again, electrochemical testing was performed only up to 4.5 V versus Li/Li+.
Historically, difficulties with electrolyte stability has hindered the electrochemical evaluation of insertion compounds at relatively high voltages with respect to lithium. However, progress has been made in this area.
U.S. Patent No. 5,192,629, for instance, reveals a non aqueous electrolyte suitable for use in a lithium ion battery comprising a Lip+XMn204 cathode that is oxidation resistant up to about 5 V.
With the availability of electrolytes that are stable at high voltage, lithium insertion compounds that deliver useable capacity at voltages above 4.5 V versus Li/Li+ can not only be studied more easily but can also be considered for use in commercial battery applications. For instance, it was shown in Canadian Patent Application Serial No.
2,102,738 that a related group of lithium insertion com-pounds having an inverse spinet structure can unexpectedly exhibit substantial high voltage capacity that can be accessed at reasonable rate. These inverse spinet com-pounds may have similar stoichiometry to the aforementioned ~1~~2~2 transition metal substituted LiMnz04 compounds, but the crystal structure differs significantly from that of spinel.
It appears that the electrochemical properties of most substituted LiMn204 spinel compounds (including nickel and chromium substituted compounds) have not been deter mined above 4.5 V with respect to lithium despite the extensive research performed thereon to date. Thus, such compounds apparently have not been considered for use in lithium batteries operating in this high voltage range.
Historical difficulties arising from a lack of stable high voltage electrolytes or previous negative capacity observa-tions at lower voltages have tended to indicate that voltages above 4.5 V are not feasible.
SUMMARY OF THE INVENTION
We have discovered unexpectedly that there can be substantial useable reversible lithium capacity in certain transition metal substituted LiMn204 spinel insertion compounds above 4.5 volts versus Li/Li+. For instance, we have found that the lithium capacity in LixNiZMnz_Z04 appar-ently does not decrease with increasing Ni content but instead is realized at higher voltages (above 4.5 volts versus Li/Li+) than in LiXMn204, a widely used material.
Thus, instead of being a less preferred battery material from an energy density viewpoint, LiXNiZMn2_Z04 can actually be preferred as it offers the possibility of higher voltage batteries.
The invention in one embodiment thus comprises transition metal substituted, LiMnz04 spinel, lithium insertion compounds that have useable reversible lithium capacity above 4.5 volts versus Li/Li+ . These lithium insertion compounds can be denoted as LiX+~IZMn2_y_Z04.
Therein, M represents the substituted transition metal and z is a number greater than zero and less than about 1. y is a number representing a relative 'shortage' of manganese and corresponding 'excess' amount of lithium and is greater than or equal to zero and less than 0.33. x is a number greater than or equal to zero and less than 1. The poten-tial of the lithium insertion compound is greater than about 4.5 volts versus Li/Li+. Lithium therefore can be reversibly inserted therein at potentials greater than about 4.5 volts versus Li/Li+. The lithium insertion compounds do not necessarily have an ideal spinel crystal structure as a result of transition metal substitution and/or low lithium content. However, the crystal structure of the lithium insertion compound is similar to spinet (ie. spinet-like or distorted spinet).
In particular, M can be nickel for values of z up to about 0.5. When M is nickel, quite substantial amounts of lithium can be reversibly inserted above 4.5 V when z is greater than about 0.3. Alternately, M can be chromium.
In this case, substantial amounts of lithium can be revers-ibly inserted when z is greater than about 0.5. ' For improved cycle life in battery applications, it can be advantageous to employ insertion compounds of the invention having 'excess' lithium. The amount of 'ex cess' lithium, y, can be about 0.1.
In another embodiment, the invention includes a process for making insertion compounds of the invention.
The process comprises extracting lithium from a precursor insertion compound having the formula Lip+~IZMn2_Y_Z04 and a spinet crystal structure. The extracting can be performed electrochemically.
The precursor insertion compound can be prepared by mixing reactant powders comprising electrolytic manganese dioxide, a transition metal source, and a lithium source in a stoichiometric manner; followed by heating the reac tant powder mixture in an oxygen containing atmosphere. As a transition metal source, either nickel nitrate or nickel oxide and chromium sesquioxide can be used for nickel and chromium respectively. Either lithium hydroxide or lithium carbonate can be used as the lithium source. The heating ~~.~~w42 _ 7 _ can be performed between about 750 and 900 degrees C, and more than one mixing and heating step may be desirable.
Lithium batteries also form another embodiment of the invention. Generally, the lithium batteries comprise a lithium compound anode; an electrolyte comprising a solvent and a lithium salt; and a cathode comprising an insertion compound of the invention. Thus, put another way, the invention involves the use of such insertion compounds as a cathode in a lithium battery wherein a portion of the capacity of the battery is obtained at a cathode voltage greater than about 4.5 volts versus Li/Li+. The batteries can be lithium ion types and can therefore have lithium compound anodes that are carbonaceous. The lithium salt can be LiBF4 and the solvent can comprise ethylene carbonate and diethyl carbonate. The solvent can additionally comprise ethyl methyl carbonate.
The cathode in the lithium battery can be easily formed by first constructing a battery with a precursor cathode comprising a precursor lithium insertion compound having the formula Lip+~IZMnz_y_Z04and a spinel crystal struc-ture. Thereafter, lithium is extracted electrochemically from the precursor cathode, thereby forming the high voltage insertion compound cathode.
BRIEF DESCRIPTION OF THE DRAWINGS
In drawings which illustrate specific embodiments of the invention, but which should not be construed as re-stricting the spirit or scope of the invention in any way:
Figure 1 depicts a cross-sectional view of a preferred embodiment of a cylindrical spiral-wound lithium ion battery.
Figure 2 shows the relationship between the lattice constant of the samples in the series of Inventive Example 1 versus nickel content.
23.~~~~
_8_ Figure 3 shows the voltage plotted against capacity per gram of precursor insertion compound for the batteries of the series of Inventive Example 1. The voltage curves have been offset for clarity. For the batteries comprising the z=0.5, 0.3, 0.2, 0.1, and 0.05 samples, the curves are offset by +0.5, 0, -0.5, -1, and -1.5 volts respectively.
Figure 4 shows the voltage plotted against capacity per gram of Li~Nio.4Mn~,604 cathode for the battery of Inven-tive Example 1 comprising 1.5M LiBF4/ethylene carbonate (EC)-diethyl carbonate (DEC)-ethyl methyl carbonate (EMC) electrolyte.
Figure 5 shows the capacity versus cycle number for the Li~Nio.4Mn~.604 battery that was cycled over 50 times in Inventive Example 1 Figures 6a and b compare the voltage versus capacity per gram of precursor insertion compound of the battery comprising the Li~.~Nio.SMn~_404 sample in Inventive Example 2 to that of another battery comprising the Li~Nio.SMn~.504 sample in Inventive Example 1 respectively.
Figure 7 shows the voltage versus capacity per gram of Li~Cro.SMn~.504 for the battery of Inventive Example 3.
Figure 8 shows the voltage plotted against capacity per gram of precursor insertion compound for the battery of Illustrative Example 2.
DETAILED DESCRIPTION OF SPECIFIC
EMBODIMENTS OF THE INVENTION
LiMn204 has an ideal spinel structure of space group Fd3m with Li atoms in 8a sites, Mn atoms in 16d sites, and oxygen atoms in 32e sites (see the International Tables for X-ray Crystallography, Volume 1, The Kynoch Press, Birming-ham, England, 1969) . The Lix+~IZMnz_y_Z04 compounds of the invention can be derived from LiMn204 without substantial change of the crystal structure. However, as a result of substitution of transition metal M and Li along with a varied amount, x, of inserted lithium, there can be a mild distortion of the structure from that of the ideal spinel.
Thus, the structure of the LiX+~IZMn2_Y_Z04 compounds might be described as spinel-like. (Note that both the ideal spinel and spinel-like structures differ significantly from that of an inverse spinel type such as LiNiV04 wherein the oxygen atoms still reside in 32e sites, but the Li atoms and the Ni atoms randomly fill half the 16d sites each with the V atoms filling the 8a sites.) In one respect, this invention comprises those inser-tion compounds that exhibit a useful amount of reversible lithium capacity at potentials greater than about 4.5 volts versus Li/Li+. Certain transition metal substitutions, for instance chromium or nickel, can result in suitable inser-tion compounds. The amount z of substituted transition metal that can be accommodated can vary with the choice of transition metal. For instance, z can range up to 1 when chromium is chosen. However, it appears that nickel can only be substituted up to a value of 0.5. Generally, the greater the value of z, the greater the amount of revers-ible lithium capacity above 4.5 volts. When M is nickel and z is greater than about 0.3, the amount of capacity realized above 4.5 V is substantial. Similarly, when M is chromium and z is greater than about 0..5, the amount of capacity realized above 4.5 V is substantial.
As in the teachings of the prior art, an additional amount, y, of lithium can be substituted in these insertion compounds in order to improve cyclability in battery applications. y can range up to a value of 0.33 based on valence arguments. In the examples to follow, a preferred value for y was about 1.
These insertion compounds can be derived from suitable precursor insertion compounds Lip+~IZMnz_y_Z04 having a spinel crystal structure. These precursor insertion compounds are known in the art to reversibly insert lithium at voltages below 4.5 V versus Li/Li+. Upon extracting Li from the precursor insertion compound, Lix+~IZMnz_y_Z04 compositions with x<1 are reached wherein lithium can be reversibly inserted above 4.5 V. The maximum value of x varies with the choice of transition metal M and the amount substituted therein, z.
The aforementioned precursor insertion compounds are conventional and can be prepared by appropriate heat treatment of suitable stoichiometric powder mixes in oxygen containing atmospheres. As shown in the examples to follow, suitable powder mixes can include electrolytic manganese dioxide (EMD) and lithium hydroxide or carbonate as sources of manganese and lithium respectively. As a source of the transition metal M, either nickel nitrate or oxide and chromium sesquioxide powder can be used for nickel and chromium respectively. Suitable heat treatment temperatures are typically in the range of about 750 to about 950 degrees C. The treatment atmosphere can be simply air or oxygen. Some effort (eg. multiple heating/mixing steps) is required to ensure uniform reac-tion in order to get a single phase product.
The extraction of lithium from the precursor insertion compound can be accomplished by chemical or electrochemical means. The latter method is preferred for conventional lithium ion battery applications and is performed in situ.
Generally, lithium batteries of the invention can be primary or secondary (rechargeable) and comprise the aforementioned insertion compounds as an electrode ma-terial. Various electrochemistries and battery configur-ations are possible. For instance, the batteries can have lithium metal, lithium alloy, and/or lithium insertion compound anodes. Various non-aqueous or aqueous electro-~1~~~~2 lytes can be used. Product configurations include pris-matic formats and miniature coin cells.
A preferred construction for a lithium ion type battery is depicted in the cross-sectional view of a conventional spiral-wound battery in Figure 1. A jelly roll 4 is created by spirally winding a cathode foil l, an anode foil 2, and two microporous polyolefin sheets 3 that act as separators.
Cathode foils are prepared by applying a mixture of a powdered (about 10 micron size typically) precursor inser tion compound, possibly other powdered cathode material if desired, a binder, and a conductive dilutant onto a thin aluminum foil. Typically, the application method first involves dissolving the binder in a suitable liquid car rier. Then, a slurry is prepared using this solution plus the other powdered solid components. The slurry is then coated uniformly onto the substrate foil. Afterwards, the carrier solvent is evaporated away. Often, both sides of the aluminum foil substrate are coated in this manner and subsequently the cathode foil is calendered.
Anode foils are prepared in a like manner except that a powdered (also typically about 10 micron size) carbon-aceous insertion compound is used instead of the cathode material and thin copper foil is usually used instead of aluminum. Anode foils are typically slightly wider than the cathode foils in order to ensure that anode foil is always opposite cathode foil.
The jelly roll 4 is inserted into a conventional battery can 10. A header 11 and gasket 12 are used to seal the battery 15. The header may include safety devices if desired. A combination safety vent and pressure operated disconnect device may be employed. Figure l shows one such combination that is described in detail in Canadian Patent Application No. 2,099,657. Additionally, a positive thermal coefficient device (PTC) maybe incorporated into the header to limit the short circuit current capability of the battery. The external surface of the header 11 is used ~1~~242 as the positive terminal, while the external surface of the can 10 serves as the negative terminal.
Appropriate cathode tab 6 and anode tab 7 connections are made to connect the internal electrodes to the external terminals. Appropriate insulating pieces 8 and 9 may be inserted to prevent the possibility of internal shorting.
Prior to crimping the header 11 to the can 10 in order to seal the battery, a suitable non-aqueous electrolyte 5 i~s added to fill the porous spaces in the jelly roll 4.
The battery as constructed is in a fully discharged state. Upon charging, lithium is extracted from the cathode and inserted into the anode. The initial charging thus serves to form the high voltage insertion compound in situ.
Those skilled in the art will understand that the types of and amounts of the component materials must be chosen based on component material properties and the desired performance and safety requirements. The use of a higher voltage cathode material poses additional require-ments over those of commercially available lithium ion batteries. Obviously, the electrolyte chosen must have a greater voltage stability window (in order to be stable at higher cathode potentials). Additionally, the hardware employed at cathode potential must also be stable at these higher voltages.
In the aforementioned J. Electrochem. Soc. article by J. M. Tarascon et al., it appeared that the reversible lithium capacity of LiXNiZMn2_Z04 decreased with increasing nickel content. However, as illustrated in the examples to follow, it appears that this lithium capacity is not 'lost' or made unavailable, with increasing nickel content.
Instead, it is unexpectedly realized at somewhat higher voltages. At this time, the physical reasons for the apparent voltage 'shift' of part of the lithium capacity are unclear. Additionally, it is unknown what the crystal structures are precisely and hence where the lithium atoms s- ~ ~1~~2~~
are exactly. However, similar behaviour is not unexpected for transition metals other than nickel and chromium.
The following Examples are provided to illustrate certain aspects of the invention but should not be con s strued as limiting in any way. Therein, laboratory coin cell batteries were used to determine electrochemical characteristics of the high voltage insertion compounds against a lithium metal anode. These coin cell batteries were assembled using conventional 2350 hardware in a dry room but otherwise as described in J.R. Dahn et al, Electrochimica Acta, 38, 1179 (1993). A stainless steel cap and special oxidation resistant case comprise the container and also serve as negative and positive terminals respectively. A gasket was used as a seal which also served to separate the two terminals. Mechanical pressure was applied to a stack comprising a lithium anode, separ-ator, and cathode by means of mild steel disc spring and stainless disc. The disc spring was selected such that a pressure of about 15 bar was applied following closure of the battery. 125 ~.m thick metal foil was used as a lithium anode. Celgard 2502 microporous polypropylene film was used as the separator. Except where indicated, the elec trolyte was a solution of 1.5M LiBF4 salt dissolved in a solvent mixture of EC and DEC in a volume ratio of 30/70 respectively.
Cathodes were made by uniformly coating a 20 ~,m thick aluminum foil substrate with a blend containing a mixture of insertion compound powder, Super S (product of Ensagri) carbon black conductive dilutant, and ethylene propylene dime monomer (EPDM) binder. This was accomplished by initially making a slurry containing cyclohexane solvent wherein the insertion compound powder and carbon black mixture (88 and 10 parts by weight respectively) were added to an appropriate amount of binder solution containing 4%
EPDM in cyclohexane, such that 2% of the final dried electrode mass would be EPDM. Excess cyclohexane was then added until the slurry viscosity was like that of a syrup, whereupon the :slurry was then coated onto the foil using a doctor blade spreader. Cyclohexane was then evaporated away at room temperature in air, leaving a deposited coating about 12 mg/cm2in weight. After drying, the electrode was compacted between flat plates at about 25 bar pressure. A disc cathode of diameter 16.2 mm was then cut from this larger electrode using a precision cutting jig.
The weight of the coating was typically about 12 mg/cm2.
The cathode was then weighed and the active insertion compound mass present was obtained by subtracting the weight of A1 foil, EPDM, and carbon black present.
Coin cell. batteries were thermostatted at 21~1°C
before testing and were then charged and discharged using constant current cyclers with t 1% current stability.
Current densit=ies were adjusted to be equivalent to C/40 rate unless indicated otherwise. Data was logged whenever the cell voltage changed by more than 0.001 V.
Inventive Example 1 A series of precursor insertion compounds LiINiZMn2_ZOa with z amounts of 0.05, 0.1, 0.2, 0.3, and 0.5 respectively was synthesized using mixtures of EMD (LiMn02 - TAD 1 grade from Mitsui), (NiN03).6H20, and LiOH powders in appropriate amounts. To get a homogeneous reaction product for samples with z amounts s 0.3, the mixtures were heat treated first at 750°C in air for 4 hours. The product was ground and mixed again followed by a second similar heat treatment for an additional 12 hours. For the sample with z=0.4, the synthesis was ~;imilar except that the second heat treatment lasted 24 hour:~ . For the sample with z=0 . 5 , the f first heat treatment laste=d 16 hours and the second heat treatment was performed at 850°C for 12 hours.
The precursor insertion compounds all had a spinel crystal structure with the Ni mainly occupying 16d posi tions. The lattice constant of the samples in the series ~1~~~
decreases with increasing nickel content as shown in Figure 2.
A series of laboratory coin cell batteries was con-structed as described in the preceding using these precur-sor insertion compounds as cathodes. Each battery was then charged to 4.9 volts, thereby extracting lithium from the cathode, and then cycled a few times. Figure 3 shows the battery voltage (insertion compound versus lithium) plotted against capacity per gram of precursor insertion compound for each battery of the series . The voltage curves have been offset for clarity. For the batteries comprising the z=0.5, 0.3, 0.2, 0.1, and 0.05 samples, the curves are offset by +0.5, 0, -0.5, -1, and -1.5 volts respectively.
A significant reversible lithium capacity between about 4.5 and 4.9 volts (on a rough plateau at an average 4.7 volts) is observed even for z values as low as 0.05.
With increasing z, the reversible lithium capacity at high voltage increases. For z values of 0.3 and up, this capacity becomes quite substantial and exceeds the revers ible capacity below 4.5 volts. In each case however, the total reversible capacity between the starting composition and that at 4.9 volts is roughly the same, around 125 mAh/g. (This is also roughly the same as the reversible extractable lithium capacity for LiMn204 spinel . ) Thus, the presence of the substituted nickel seems to 'shift' a portion of the voltage curve above 4.5 volts.
Another coin cell battery was made with cathode comprising Li~Nio.4Mn~.604 from the above series but with an electrolyte comprising 1.5M LiBF4 salt in a solvent mixture of EC, DEC, and EMC in a volume ratio of 20/30/50 respectively. Figure 4 shows the voltage plotted against capacity per gram of precursor insertion compound for this battery. The results are similar to that of the corresponding battery in Figure 1.
Another coin cell battery was made with cathode comprising Li~Nio.4Mn~.604 similar to the above series and cycled between 3.0 and 4.9 volts at ?1°C at a C/10 rate ~1~~24~
charge and C rate discharge. Figure 5 shows the capacity versus cycle number for this battery. Little capacity loss is seen over 50 cycles.
Inventive Example 2 A precursor insertion compound Li~.~Nio.SMn~.404 was synthesized in the following manner. First, LiMn204 was prepared by heat treating an appropriate mixture of EMD
(LiMnOz - TAD 1 grade from Mitsui) and LiZC03 powders at 900°C in air for 20 hours. Additional Li2C03 and Ni0 powders were then mixed in with the LiMnz04 product followed by heat treatment in air at 900°C for 20 hours. Finally, this product was ground, remixed, and heat treated for an additional 12 hours at 850°C in oxygen.
A laboratory coin cell battery was constructed as described in the preceding using this precursor insertion compound as the cathode. The battery was then charged to 4.8 volts, thereby extracting lithium from the cathode, and then cycled a few times. Figures 6a and b compare the voltage versus capacity per gram of precursor insertion compound of this battery to that of another similarly cycled battery comprising the Li~Nio_SMn~.504 sample in Inventive Example 1 respectively.
The voltage curves are similar except that the Li~Nio.SMn~_504 sample (wherein y=0) has a larger recharge capacity than discharge capacity. Consequently, the curve shifts to the right in this plot with each cycle. The larger recharge capacity is indicative of an irreversible decomposition or degradation process, possibly of the electrolyte or cathode material. The voltage curve of the Li~.~Nio.SMn~.404 sample shows significantly better results.
Inventive Example 3 A precursor insertion compound Li~Cro.SMn~_504 was synthesized using an appropriate mixture of EMD, CrZ03, and LiOH powders. The mixture was heat treated in air at 800°C
for 4 hours, ground, remixed, and heat treated again at 900°C for 11 hours.
A laboratory coin cell battery was constructed as described in the preceding using this precursor insertion compound as the cathode. The battery was then charged, thereby extracting lithium from the cathode, and then cycled a few times. Figure 7 shows the voltage versus capacity per gram of precursor insertion compound for this battery. There is substantial reversible lithium capacity between about 4.8 and 5.2 volts. However, there is also significant shifting of the voltage curve with each cycle, perhaps indicative of more severe electrolyte decomposition at these higher voltages.
The preceding Examples show that LiX+~IZMnZ_y_Z04 compounds can exhibit substantial useful reversible lithium capacity above 4.5 volts versus lithium when M is nickel or chro mium. Additionally, cycling characteristics can be im proved when y>0.
Illustrative Example 1 An attempt was made to synthesize precursor insertion compound Li~.~Nio.SMn~.404 directly from an appropriate mixture of EMD, NiO, and Li2C03 powders but otherwise as in Inventive Example 2. The mixture was first heat treated in air at 900°C for 20 hours. Then, the product was ground, remixed, and heat treated for an additional 12 hours at 850°C in oxygen. The result was a mixture of the phases NiO, Li2Mn03 and a Lip+~,l~TiZMnz_y_Z04 compound. The preparation of relatively pure precursor insertion compounds is not always straightforward.
~1~~242 Illustrative Example 2 A laboratory coin cell battery was constructed as described in the preceding with cathode comprising Li~Nio.SMn~,504 precursor insertion compound from the series of Inventive Example 1 and an electrolyte comprising 1.2M LiPF6 salt in a solvent mixture of EC, DEC, and EMC in a volume ratio of 20/30/50 respectively. The battery was then charged to 4.9 volts, thereby extracting lithium from the cathode, and then cycled once. Figure 8 shows the voltage plotted against capacity per gram of precursor insertion compound for this battery. An enormous recharge capacity is observed suggesting that this electrolyte is unsuitable for use in this situation. With the exception of the salt employed, this battery is similar to that of Figure 4.
LiPF6 salt thus appears unsuitable for use in this situ-ation.
As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this inven tion without departing from the spirit or scope thereof.
For example, it may be possible to synthesize precursor insertion compounds comprising hydrogen instead of lithium.
If the hydrogen is removed thereafter by heating or the like, a high voltage insertion compound of the invention might be synthesized, ready for use in a primary battery application, all in the absence of lithium. Accordingly, the scope of the invention is to be construed in accordance with the substance defined by the following claims.
Claims (28)
1. A lithium insertion compound having the formula Li x+y M z Mn2-y-z O4 wherein the insertion compound has a spinel-like crystal structure, M is a transition metal, x is a number greater than or equal to zero and less than 1, y is a number greater than or equal to zero and less than 0.33, z is a number greater than zero and less than about 1, and the potential of the lithium insertion compound is greater than about 4.5 volts versus Li/Li+.
2. An insertion compound as claimed in claim 1 wherein M
is nickel.
is nickel.
3. An insertion compound as claimed in claim 2 wherein z is less than about 0.5.
4. An insertion compound as claimed in claim 3 wherein z is greater than about 0.3.
5. An insertion compound as claimed in claim 1 wherein M
is chromium.
is chromium.
6. An insertion compound as claimed in claim 5 wherein z is greater than about 0.5.
7. An insertion compound as claimed in claim 1 wherein y is about 0.1.
8. A process for making the insertion compound as claimed in claim 1 comprising extracting lithium, by chemical or electrochemical means, from a precursor insertion compound having the formula Li1+y M z Mn2-y-z O4 and a spinel crystal structure, said precursor insertion compound prepared by heat treatment of stoichiometric powder mixes in an oxygen containing atmosphere.
9. A process as claimed in claim 8 wherein the extracting is performed electrochemically.
10. A process as claimed in claim 8 wherein the precursor insertion compound is prepared by mixing reactant powders comprising electrolytic manganese dioxide, a transition metal source, and a lithium source in a stoichiometric manner; and heating the reactant powder mixture in an oxygen containing atmosphere.
11. A process as claimed in claim 10 wherein M is nickel and the transition metal source is nickel nitrate or nickel oxide.
12. A process as claimed in claim 10 wherein M is chromium and the transition metal source is chromium sesquioxide.
13. A process as claimed in claim 10 wherein the lithium source is lithium hydroxide or lithium carbonate.
14. A process as claimed in claim 10 wherein the heating is performed between about 750 and 900 degrees C.
15. A process as claimed in claim 10 wherein the precursor insertion compound is prepared by mixing and heating the reactant powder mixture more than once.
16. A lithium battery comprising a lithium compound anode;
an electrolyte comprising a solvent and a lithium salt; and a cathode comprising a lithium insertion compound having the formula Li x+y M z Mn2-y-z O4 wherein the lithium insertion compound has a spinel-like crystal structure, M is a transition metal, x is a number greater than or equal to zero and less than 1, y is a number greater than or equal to zero and less than 0.33, z is a number greater than zero and less than about 1, and the potential of the lithium insertion compound is greater than about 4.5 volts versus Li/Li+.
an electrolyte comprising a solvent and a lithium salt; and a cathode comprising a lithium insertion compound having the formula Li x+y M z Mn2-y-z O4 wherein the lithium insertion compound has a spinel-like crystal structure, M is a transition metal, x is a number greater than or equal to zero and less than 1, y is a number greater than or equal to zero and less than 0.33, z is a number greater than zero and less than about 1, and the potential of the lithium insertion compound is greater than about 4.5 volts versus Li/Li+.
17. A lithium battery as claimed in claim 16 wherein the lithium compound anode is carbonaceous.
18. A lithium battery as claimed in claim 16 wherein the lithium salt is LiBF4.
19. A lithium battery as claimed in claim 16 wherein the solvent comprises ethylene carbonate and diethyl carbonate.
20. A lithium battery as claimed in claim 19 wherein the solvent additionally comprises ethyl methyl carbonate.
21. A lithium battery as claimed in claim 16 wherein M is nickel.
22. A lithium battery as claimed in claim 21 wherein z is less than about 0.5.
23. A lithium battery as claimed in claim 21 wherein z is greater than about 0.3.
24. A lithium battery as claimed in claim 16 wherein M is chromium.
25. A lithium battery as claimed in claim 24 wherein z is greater than about 0.5.
26. A lithium battery as claimed in claim 16 wherein y is about 0.1.
27. A lithium battery as claimed in claim 16 wherein the cathode is formed in the battery by extracting lithium electrochemically from a precursor cathode comprising a precursor insertion compound, the precursor insertion compound having the formula Li1+y M z Mn2-y-z O4 and a spinel crystal structure.
28. Use of the insertion compound as claimed in claim 1 as a cathode in a lithium battery wherein a portion of the capacity of the battery is obtained at a cathode voltage greater than about 4.5 volts versus Li/Li+.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002158242A CA2158242C (en) | 1995-09-13 | 1995-09-13 | High voltage insertion compounds for lithium batteries |
| US08/583,974 US5631104A (en) | 1995-09-13 | 1996-01-11 | High voltage insertion compounds for lithium batteries |
| GB9615799A GB2305168B (en) | 1995-09-13 | 1996-07-26 | High voltage insertion compounds for lithium batteries |
| JP8232991A JPH09147867A (en) | 1995-09-13 | 1996-09-03 | High-voltage insertion compound for lithium battery |
| FR9611162A FR2738673B1 (en) | 1995-09-13 | 1996-09-09 | HIGH VOLTAGE INSERTION COMPOUNDS FOR LITHIUM BATTERIES |
| DE19636861A DE19636861A1 (en) | 1995-09-13 | 1996-09-11 | High-voltage storage connections for lithium batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002158242A CA2158242C (en) | 1995-09-13 | 1995-09-13 | High voltage insertion compounds for lithium batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2158242A1 CA2158242A1 (en) | 1997-03-14 |
| CA2158242C true CA2158242C (en) | 2000-08-15 |
Family
ID=4156595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002158242A Expired - Lifetime CA2158242C (en) | 1995-09-13 | 1995-09-13 | High voltage insertion compounds for lithium batteries |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5631104A (en) |
| JP (1) | JPH09147867A (en) |
| CA (1) | CA2158242C (en) |
| DE (1) | DE19636861A1 (en) |
| FR (1) | FR2738673B1 (en) |
| GB (1) | GB2305168B (en) |
Families Citing this family (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09245836A (en) * | 1996-03-08 | 1997-09-19 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
| US6132902A (en) * | 1996-06-14 | 2000-10-17 | Fuji Photo Film Co., Ltd. | Electric automobile and electric power drive therefor |
| US5763120A (en) * | 1996-06-25 | 1998-06-09 | Valence Technology, Inc. | Lithium manganese oxide cathodes with high capacity and stability |
| DE69701063T2 (en) * | 1996-06-27 | 2000-07-13 | The Honjo Chemical Corp., Osaka | Process for the production of lithium manganese oxide with spinel structure |
| JP2002511179A (en) | 1996-10-11 | 2002-04-09 | マサチューセッツ・インスティテュート・オブ・テクノロジー | Solid electrolytes, intercalation compounds and electrodes for batteries |
| US5858324A (en) * | 1997-04-17 | 1999-01-12 | Minnesota Mining And Manufacturing Company | Lithium based compounds useful as electrodes and method for preparing same |
| TW434187B (en) * | 1997-05-07 | 2001-05-16 | Fuji Chem Ind Co Ltd | A process for preparing a spinel type of lithium manganese complex oxide |
| EP0989622B1 (en) * | 1997-06-12 | 2001-10-31 | Sanyo Electric Co., Ltd. | Non-aqueous electrolytic secondary cell |
| CA2240805C (en) * | 1997-06-19 | 2005-07-26 | Tosoh Corporation | Spinel-type lithium-manganese oxide containing heteroelements, preparation process and use thereof |
| JPH11219722A (en) | 1998-02-03 | 1999-08-10 | Matsushita Electric Ind Co Ltd | Lithium secondary battery |
| US6045950A (en) * | 1998-06-26 | 2000-04-04 | Duracell Inc. | Solvent for electrolytic solutions |
| JP3142522B2 (en) * | 1998-07-13 | 2001-03-07 | 日本碍子株式会社 | Lithium secondary battery |
| JP4274630B2 (en) * | 1999-05-21 | 2009-06-10 | 三井金属鉱業株式会社 | Method for producing spinel type lithium manganate |
| US6322928B1 (en) | 1999-09-23 | 2001-11-27 | 3M Innovative Properties Company | Modified lithium vanadium oxide electrode materials and products |
| US6248477B1 (en) | 1999-09-29 | 2001-06-19 | Kerr-Mcgee Chemical Llc | Cathode intercalation compositions, production methods and rechargeable lithium batteries containing the same |
| AU2789500A (en) * | 1999-10-08 | 2001-04-23 | Isobel Davidson | Cathode active material for lithium electrochemical cells |
| US6350543B2 (en) | 1999-12-29 | 2002-02-26 | Kimberly-Clark Worldwide, Inc. | Manganese-rich quaternary metal oxide materials as cathodes for lithium-ion and lithium-ion polymer batteries |
| CN1307376A (en) | 2000-01-27 | 2001-08-08 | 钟馨稼 | Rechargeable solid Cr-F-Li accumulator |
| JP4910228B2 (en) | 2000-07-11 | 2012-04-04 | ソニー株式会社 | Nonaqueous electrolyte secondary battery |
| JP5013386B2 (en) * | 2000-11-17 | 2012-08-29 | 日立マクセルエナジー株式会社 | Positive electrode active material for non-aqueous secondary battery and non-aqueous secondary battery using the same |
| DE10104988A1 (en) * | 2001-02-03 | 2002-08-08 | Varta Geraetebatterie Gmbh | Process for the production of electrode foils |
| JP4836371B2 (en) * | 2001-09-13 | 2011-12-14 | パナソニック株式会社 | Positive electrode active material and non-aqueous electrolyte secondary battery including the same |
| DE60235944D1 (en) | 2001-10-18 | 2010-05-27 | Nec Corp | Positive electrode active material, positive electrode and non-aqueous secondary electrolyte battery using these |
| FR2831993A1 (en) * | 2001-11-08 | 2003-05-09 | Cit Alcatel | HIGH VOLTAGE LITHIUM INSERTION COMPOUND FOR USE AS A CATHODIC ACTIVE SUBSTANCE OF RECHARGEABLE LITHIUM ELECTROCHEMICAL GENERATOR |
| CN100373670C (en) * | 2002-03-01 | 2008-03-05 | 松下电器产业株式会社 | Positive electrode active material, method for producing same, and nonaqueous electrolyte secondary battery |
| US9391325B2 (en) * | 2002-03-01 | 2016-07-12 | Panasonic Corporation | Positive electrode active material, production method thereof and non-aqueous electrolyte secondary battery |
| JP4197237B2 (en) * | 2002-03-01 | 2008-12-17 | パナソニック株式会社 | Method for producing positive electrode active material |
| CN100417595C (en) * | 2002-11-19 | 2008-09-10 | 比亚迪股份有限公司 | Method for preparing lithium transition metal composite oxides from carbonate precursors |
| JP4581333B2 (en) * | 2003-04-01 | 2010-11-17 | 住友金属鉱山株式会社 | Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same |
| JP4924860B2 (en) * | 2003-11-18 | 2012-04-25 | 株式会社Ｇｓユアサ | Method for producing non-aqueous electrolyte secondary battery |
| JP4770113B2 (en) * | 2003-12-04 | 2011-09-14 | 日本電気株式会社 | Positive electrode active material for secondary battery, positive electrode for secondary battery, and secondary battery |
| FR2890241B1 (en) * | 2005-08-25 | 2009-05-22 | Commissariat Energie Atomique | HIGH SPEED SPINELLE STRUCTURE POSITIVE ELECTRODE MATERIAL BASED ON NICKEL AND MANGANESE FOR LITHIUM ACCUMULATORS |
| WO2010089152A1 (en) | 2009-02-09 | 2010-08-12 | Varta Microbattery Gmbh | Button cells and method for producing same |
| DE102009060800A1 (en) | 2009-06-18 | 2011-06-09 | Varta Microbattery Gmbh | Button cell with winding electrode and method for its production |
| US8496855B2 (en) * | 2009-07-27 | 2013-07-30 | Samsung Electronics Co., Ltd. | Cathode active material, cathode including cathode active material, and lithium battery including cathode |
| US20120305835A1 (en) * | 2010-02-12 | 2012-12-06 | Hiroyuki Yamaguchi | Positive electrode active material for lithium secondary battery |
| US20130032753A1 (en) | 2010-02-23 | 2013-02-07 | Manabu Yamamoto | Positive electrode active substance precursor particles, positive electrode active substance particles and non-aqueous electrolyte secondary battery |
| US9299475B2 (en) | 2010-11-05 | 2016-03-29 | Nec Corporation | Positive electrode active material for secondary battery and secondary battery using the same |
| WO2012077472A1 (en) | 2010-12-09 | 2012-06-14 | 日本電気株式会社 | Positive electrode active material for secondary battery and secondary battery using same |
| JP5316567B2 (en) * | 2011-02-25 | 2013-10-16 | 日本電気株式会社 | The manufacturing method of the positive electrode active material for secondary batteries, and the manufacturing method of a secondary battery. |
| CA2831756A1 (en) | 2011-03-31 | 2012-10-04 | Toda Kogyo Corporation | Positive electrode active substance particles for non-aqueous electrolyte secondary batteries and process of production thereof |
| JP5647069B2 (en) | 2011-05-18 | 2014-12-24 | 日立マクセル株式会社 | Non-aqueous secondary battery |
| CN103548185B (en) | 2011-05-30 | 2016-10-12 | 日本电气株式会社 | Secondary cell active substance and use its secondary cell |
| WO2013008581A1 (en) | 2011-07-13 | 2013-01-17 | 日本電気株式会社 | Active material for secondary batteries |
| JP5632350B2 (en) * | 2011-11-02 | 2014-11-26 | 日揮触媒化成株式会社 | Spinel-type lithium-manganese composite oxide and method for producing the same |
| WO2013153690A1 (en) | 2012-04-13 | 2013-10-17 | 日本電気株式会社 | Positive electrode active material for secondary cell, and secondary cell using same |
| US9887421B2 (en) | 2014-01-27 | 2018-02-06 | Ada Technologies Inc. | LiwNixMnyOz spinels and method of making and using the same |
| US9755235B2 (en) | 2014-07-17 | 2017-09-05 | Ada Technologies, Inc. | Extreme long life, high energy density batteries and method of making and using the same |
| WO2016140352A1 (en) | 2015-03-04 | 2016-09-09 | 日揮触媒化成株式会社 | Positive electrode active substance for non-aqueous electrolyte secondary battery, positive electrode and non-aqueous electrolyte secondary battery |
| TW201704155A (en) * | 2015-03-06 | 2017-02-01 | 公立大學法人兵庫縣立大學 | Lithium-nickel-manganese composite oxide, method for producing the same, and positive electrode, electricity storage device eachusing the same |
| WO2016209460A2 (en) | 2015-05-21 | 2016-12-29 | Ada Technologies, Inc. | High energy density hybrid pseudocapacitors and method of making and using the same |
| WO2017023797A1 (en) | 2015-07-31 | 2017-02-09 | Ada Technologies, Inc. | High energy and power electrochemical device and method of making and using same |
| US20180241072A1 (en) | 2015-08-24 | 2018-08-23 | Sumitomo Metal Mining Co., Ltd. | Nonaqueous electrolyte secondary battery positive electrode active material and method for manufacturing same, and nonaqueous electrolyte secondary battery |
| WO2018015208A1 (en) | 2016-07-20 | 2018-01-25 | Haldor Topsøe A/S | A METHOD FOR THE PRECIPITATION OF CARBONATE PRECURSORS WITH A LOW Na, K AND S CONTENT FOR LITHIUM ION BATTERIES |
| KR20190042572A (en) | 2016-08-25 | 2019-04-24 | 할도르 토프쉐 에이/에스 | Cathode active materials for high-voltage secondary batteries |
| US11024846B2 (en) | 2017-03-23 | 2021-06-01 | Ada Technologies, Inc. | High energy/power density, long cycle life, safe lithium-ion battery capable of long-term deep discharge/storage near zero volt and method of making and using the same |
| MX2024002799A (en) * | 2021-09-15 | 2024-04-16 | Emd Acquisition Llc | Method for preparing electrolytic manganese dioxide. |
| US12515966B2 (en) | 2022-04-25 | 2026-01-06 | GM Global Technology Operations LLC | Method to create a lithium manganese nickel oxide cathode using ultra-pure electrolytic manganese dioxide for improved electrochemical cell performance |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3068002D1 (en) * | 1979-04-05 | 1984-07-05 | Atomic Energy Authority Uk | Electrochemical cell and method of making ion conductors for said cell |
| US4507371A (en) * | 1982-06-02 | 1985-03-26 | South African Inventions Development Corporation | Solid state cell wherein an anode, solid electrolyte and cathode each comprise a cubic-close-packed framework structure |
| US4423125A (en) * | 1982-09-13 | 1983-12-27 | Bell Telephone Laboratories, Incorporated | Ambient temperature rechargeable battery |
| US4702977A (en) * | 1985-04-30 | 1987-10-27 | Toshiba Battery Co., Ltd. | Secondary battery using non-aqueous solvent |
| EP0390185B1 (en) * | 1989-03-30 | 1994-06-22 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| DE4025208A1 (en) * | 1990-08-09 | 1992-02-13 | Varta Batterie | ELECTROCHEMICAL SECONDARY ELEMENT |
| JP2584123B2 (en) * | 1990-10-02 | 1997-02-19 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
| JPH05299092A (en) * | 1992-01-17 | 1993-11-12 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte lithium secondary battery and manufacturing method thereof |
| US5192629A (en) * | 1992-04-21 | 1993-03-09 | Bell Communications Research, Inc. | High-voltage-stable electrolytes for Li1+x Mn2 O4 /carbon secondary batteries |
| ZA936168B (en) * | 1992-08-28 | 1994-03-22 | Technology Finance Corp | Electrochemical cell |
| FR2704216A1 (en) * | 1993-04-23 | 1994-10-28 | Centre Nat Rech Scient | Electrode materials for rechargeable lithium batteries and their method of synthesis |
| US5425932A (en) * | 1993-05-19 | 1995-06-20 | Bell Communications Research, Inc. | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
| CA2102738C (en) * | 1993-11-09 | 1999-01-12 | George T. Fey | Inverse spinel compounds as cathodes for lithium batteries |
| EP0720247B1 (en) * | 1994-12-16 | 1998-05-27 | Matsushita Electric Industrial Co., Ltd. | Manufacturing processes of positive active materials for lithium secondary batteries and lithium secondary batteries comprising the same |
-
1995
- 1995-09-13 CA CA002158242A patent/CA2158242C/en not_active Expired - Lifetime
-
1996
- 1996-01-11 US US08/583,974 patent/US5631104A/en not_active Expired - Lifetime
- 1996-07-26 GB GB9615799A patent/GB2305168B/en not_active Expired - Lifetime
- 1996-09-03 JP JP8232991A patent/JPH09147867A/en active Pending
- 1996-09-09 FR FR9611162A patent/FR2738673B1/en not_active Expired - Lifetime
- 1996-09-11 DE DE19636861A patent/DE19636861A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| GB2305168A (en) | 1997-04-02 |
| FR2738673B1 (en) | 2000-01-21 |
| GB9615799D0 (en) | 1996-09-04 |
| DE19636861A1 (en) | 1997-03-27 |
| CA2158242A1 (en) | 1997-03-14 |
| FR2738673A1 (en) | 1997-03-14 |
| US5631104A (en) | 1997-05-20 |
| JPH09147867A (en) | 1997-06-06 |
| GB2305168B (en) | 1999-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2158242C (en) | High voltage insertion compounds for lithium batteries | |
| US5882218A (en) | Lithium manganese oxide insertion compounds and use in rechargeable batteries | |
| US5518842A (en) | Inverse spinel compounds as cathodes for lithium batteries | |
| US5196279A (en) | Rechargeable battery including a Li1+x Mn2 O4 cathode and a carbon anode | |
| EP0903798B1 (en) | Boron trifluoride as an electrolyte additive for improving cycle life of non-aqueous rechargeable lithium batteries | |
| US5948569A (en) | Lithium ion electrochemical cell | |
| KR100458099B1 (en) | Lithium-containing, lithium-intercalating phosphates and their use as the positive or negative electrode material in a lithium secondary battery | |
| EP1909345B1 (en) | Cathode active material for a lithium battery | |
| US5449577A (en) | Method for increasing the reversible capacity of lithium transition metal oxide cathodes | |
| US5700597A (en) | Method for preparing Li1+x Mn2-x-y My O4 for use in lithium batteries | |
| US5789112A (en) | Lithium manganese oxide compound and method of preparation | |
| US20080070122A1 (en) | Cathode active material and lithium battery employing the same | |
| US20050069768A1 (en) | Lithium electrochemical generator comprising at least a bipolar electrode with conductive aluminium or aluminium alloy substrates | |
| KR20040040439A (en) | Improved lithium-ion batteries | |
| KR20130108620A (en) | Lithium ion batteries with supplemental lithium | |
| KR20010086991A (en) | Organic electrolytic solution and lithium secondary battery adopting the same | |
| EP0669667B1 (en) | Aqueous electrochemical preparation of insertion compounds and use in non-aqueous rechargeable batteries | |
| US5641465A (en) | Lithium maganese oxide compound and method of preparation | |
| US8530093B2 (en) | Electrode active material, method of preparing the same, electrode for lithium secondary battery which includes the same, and lithium secondary battery using the electrode | |
| JPH0982360A (en) | Non-aqueous electrolyte secondary battery | |
| JPH09245830A (en) | Non-aqueous electrolyte secondary battery | |
| JPH08339824A (en) | Non-aqueous electrolyte secondary battery | |
| EP4564502A1 (en) | Lithium secondary battery and method for producing same | |
| JPH10233231A (en) | Non-aqueous electrolyte secondary battery | |
| JP2002056849A (en) | Lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20150914 |