CA2175856C - A method for producing positive electrode material and lithium batteries incorporating this material - Google Patents
A method for producing positive electrode material and lithium batteries incorporating this material Download PDFInfo
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- CA2175856C CA2175856C CA002175856A CA2175856A CA2175856C CA 2175856 C CA2175856 C CA 2175856C CA 002175856 A CA002175856 A CA 002175856A CA 2175856 A CA2175856 A CA 2175856A CA 2175856 C CA2175856 C CA 2175856C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
Abstract
A positive electrode material for use in lithium batteries contains a compound represented by the chemical formula LixFe2(SO4)3 (0<x ? 2). This positive electrode material is made from low cost material which is available in abundant quantities. Moreover a lithium battery using this material has a large discharge energy and long cycle life.
Description
,.~. 217556 A Method For Producing Positive Electrode Material And Lithium Batteries Incorporating This Material This invention relates to lithium batteries, the manufacture of material used as the positive electrodes in those batteries, and in particular relates to rechargeable secondary lithium batteries.
Recently, with the increased awareness of environmental problems, the development of electric automobiles as replacements for internal combustion engine based vehicles using petrol, has been given considerable urgency. Furthermore, demand for batteries for use in the various portable electronic appliances such as portable telephones is also increasing. This situation has generated a need for improvements in the performance of secondary batteries, which can be reused following recharging. Of specific interest are batteries which can be miniaturized, have a high energy density, and which display a long cycle life.
Anhydrous electrolyte batteries containing negative electrodes composed of alkali metals such as lithium or their compounds, are an example of known batteries which meet these criteria. In these types of secondary batteries, metallic ions from the negative w 2175856 electrode react with the positive electrode via insertion or intercalation, thus the batteries are able to achieve a compatibility between high discharge capacity and charge/discharge reversibility.
In the past, the positive electrode material consisted of some type of sulfide compound, such as titanium disulfide.
However, the voltage of batteries employing sulfide compounds as the positive electrode material was, at approximately 2 volts, low, and so the batteries suffered from problems of low discharge energy. With such a low discharge voltage, use of these batteries in LSIs with drives rated at 3 or 3.3 volts required multiple batteries, which was inconvenient.
Subsequently, a high discharge voltage battery has been proposed and developed, containing LiCoOz as the positive electrode and with a discharge voltage in the 4 volt range.
Furthermore, batteries which employ an active material retainer which is capable of lithium insertion and extraction have also been proposed (lithium ion battery, rocking chair battery). The lithium ion battery is first constructed of an active material retainer with no lithium inserted, as the negative electrode, and a material such as LiCo02, which has been previously lithiated, as the positive electrode. Then by provision of a potential difference across the two electrodes, causing lithium to move from the positive electrode and be inserted in the negative electrode, high voltage battery is produced and functions. The negative electrode acts as a low potential negative electrode by being supplied with lithium from the positive electrode, and through the reaction. These lithium ion batteries are excellent batteries in that they have high energy densities, and display a particularly long cycle life.
However, as cobalt is expensive and exists in only small quantities in natural materials, and as there is no guarantee of a stable supply, positive electrode material employing LiCoOz is extremely expensive, and thus unsuitable for large scale use. In particular, in those instances where large batteries are needed in order to guarantee a large capacity, a significant amount of positive electrode material is required, making LiCoOz unsuitable.
Consequently, the future use of LiCoOz as the positive electrode of lithium batteries, the demand for which appears to set to increase, is hampered by problems of cost and resource. Furthermore, the synthesis of LiCoOz requires very high temperatures of 850-900°C, further increasing the cost of production.
In addition to LiCoOz, the compounds LiNiOz and LiMnzOa also allow production of high energy density rechargeable batteries with voltages in excess of 3 volts, but these compounds are also either expensive or difficult to resource in sufficient amount.
As a result of research into battery positive electrode materials which are cheap but still display high energy density, Fez(S04)3 was selected. As Fez(SOQ)3 is an iron based material, it is cheap and readily available in abundant quantities. Furthermore, its synthesis is also simple. A battery constructed with Fez(S04)3 as the positive electrode and lithium metal as the negative electrode has a high energy density and generates a discharge curve which is almost level at 3.6 volts.
However, batteries made using unlithiated Fez(S04)3 as the positive electrode material, differ from batteries which employ LiCoOz as the positive electrode, in that there is no supply of lithium from the positive electrode, and so the lithium used in the charging and discharging exists only in the negative electrode.
Consequently, the total amount of lithium in the battery is small, which creates the problem that the consumption of this lithium is relatively fast, resulting in a shortened cycle life.
Furthermore, as the use of Fe2(SOa)a as the positive electrode material results in no supply of lithium to the negative electrode, the use of an active material retainer, which is capable of lithium insertion and extraction and in which extraction capable lithium has not previously been retained, as the negative electrode is not suitable. Hence the use of such a negative electrode for a good performing lithium ion battery is impossible.
In order to solve these problems, the lithiation of the negative electrode active material retainer could be considered, but the lithiated active material retainer is then extremely unstable under normal atmospheric conditions and very difficult to handle, meaning that the actual production of a lithium ion battery employing a lithium inserted active material retainer for negative electrode is not practical.
The present invention has been developed in view of the abovementioned problems, with the object of providing;
a lithium battery which has a lithium positive electrode, displays excellent energy density and long cycle life properties, and yet is cheap and thus suitable for large scale use; the material for use in this positive electrode;
and a production method for that material.
The method of producing a positive electrode material for use in lithium batteries according to the present invention comprises chemically reacting a lithium compound, and Fe2 ( SOq ) 3, or a precursor which gives rise to Fe2 ( S04 ) 3.
to produce a compound represented by the chemical formula LiXFe2(S04)3 (0<xs2). The lithium compound has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts.
The lithium battery according to the present invention comprises a positive electrode, a negative electrode and an electrolyte. The material of the positive electrode comprises a compound represented by the chemical formula LixFe2(S04)3 (0<x52), obtained by chemically reacting a lithium compound which has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts, and Fe2 ( S04 ) 3, or a precursor which gives rise to Fe2 ( S04 ) s .
The present invention is able to provide a battery which is low cost, uses material which is available in abundant quantities, and in which the discharge voltage is s high and the cycle life long, and has the advantage of therefore being utilizable in a wide range of applications, including as a power source for electric cars and various portable electronic equipment.
Furthermore, as high temperatures are not required in the synthesis of the positive electrode material, not only is the cost of the starting materials low, but the cost of production can also be reduced.
Moreover, in the synthesis of the positive electrode material, if a lithium compound is used which has a redox potential relative to a lithium electrode of between I.5 and 3.6 volts, then even if an excess of the lithium compound is added to the reaction mixture, the value of x in LixFez(S04)3 will not exceed 2, meaning the synthesis is simple and the reaction time short.
Furthermore, since active material retaining bodies which are capable of lithium insertion and extraction, are suitable for use as the negative electrode in batteries of the present invention, batteries with a particularly long cycle life are obtainable.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a coin shaped battery according to the embodiments;
FIG. 2 is a graph showing the relationship between the x value in LiXFez(SOQ)a and the potential relative to a lithium electrode; and FIG. 3 is a graph showing voltage characteristics relative to specific capacity for a battery of a first embodiment.
Recently, with the increased awareness of environmental problems, the development of electric automobiles as replacements for internal combustion engine based vehicles using petrol, has been given considerable urgency. Furthermore, demand for batteries for use in the various portable electronic appliances such as portable telephones is also increasing. This situation has generated a need for improvements in the performance of secondary batteries, which can be reused following recharging. Of specific interest are batteries which can be miniaturized, have a high energy density, and which display a long cycle life.
Anhydrous electrolyte batteries containing negative electrodes composed of alkali metals such as lithium or their compounds, are an example of known batteries which meet these criteria. In these types of secondary batteries, metallic ions from the negative w 2175856 electrode react with the positive electrode via insertion or intercalation, thus the batteries are able to achieve a compatibility between high discharge capacity and charge/discharge reversibility.
In the past, the positive electrode material consisted of some type of sulfide compound, such as titanium disulfide.
However, the voltage of batteries employing sulfide compounds as the positive electrode material was, at approximately 2 volts, low, and so the batteries suffered from problems of low discharge energy. With such a low discharge voltage, use of these batteries in LSIs with drives rated at 3 or 3.3 volts required multiple batteries, which was inconvenient.
Subsequently, a high discharge voltage battery has been proposed and developed, containing LiCoOz as the positive electrode and with a discharge voltage in the 4 volt range.
Furthermore, batteries which employ an active material retainer which is capable of lithium insertion and extraction have also been proposed (lithium ion battery, rocking chair battery). The lithium ion battery is first constructed of an active material retainer with no lithium inserted, as the negative electrode, and a material such as LiCo02, which has been previously lithiated, as the positive electrode. Then by provision of a potential difference across the two electrodes, causing lithium to move from the positive electrode and be inserted in the negative electrode, high voltage battery is produced and functions. The negative electrode acts as a low potential negative electrode by being supplied with lithium from the positive electrode, and through the reaction. These lithium ion batteries are excellent batteries in that they have high energy densities, and display a particularly long cycle life.
However, as cobalt is expensive and exists in only small quantities in natural materials, and as there is no guarantee of a stable supply, positive electrode material employing LiCoOz is extremely expensive, and thus unsuitable for large scale use. In particular, in those instances where large batteries are needed in order to guarantee a large capacity, a significant amount of positive electrode material is required, making LiCoOz unsuitable.
Consequently, the future use of LiCoOz as the positive electrode of lithium batteries, the demand for which appears to set to increase, is hampered by problems of cost and resource. Furthermore, the synthesis of LiCoOz requires very high temperatures of 850-900°C, further increasing the cost of production.
In addition to LiCoOz, the compounds LiNiOz and LiMnzOa also allow production of high energy density rechargeable batteries with voltages in excess of 3 volts, but these compounds are also either expensive or difficult to resource in sufficient amount.
As a result of research into battery positive electrode materials which are cheap but still display high energy density, Fez(S04)3 was selected. As Fez(SOQ)3 is an iron based material, it is cheap and readily available in abundant quantities. Furthermore, its synthesis is also simple. A battery constructed with Fez(S04)3 as the positive electrode and lithium metal as the negative electrode has a high energy density and generates a discharge curve which is almost level at 3.6 volts.
However, batteries made using unlithiated Fez(S04)3 as the positive electrode material, differ from batteries which employ LiCoOz as the positive electrode, in that there is no supply of lithium from the positive electrode, and so the lithium used in the charging and discharging exists only in the negative electrode.
Consequently, the total amount of lithium in the battery is small, which creates the problem that the consumption of this lithium is relatively fast, resulting in a shortened cycle life.
Furthermore, as the use of Fe2(SOa)a as the positive electrode material results in no supply of lithium to the negative electrode, the use of an active material retainer, which is capable of lithium insertion and extraction and in which extraction capable lithium has not previously been retained, as the negative electrode is not suitable. Hence the use of such a negative electrode for a good performing lithium ion battery is impossible.
In order to solve these problems, the lithiation of the negative electrode active material retainer could be considered, but the lithiated active material retainer is then extremely unstable under normal atmospheric conditions and very difficult to handle, meaning that the actual production of a lithium ion battery employing a lithium inserted active material retainer for negative electrode is not practical.
The present invention has been developed in view of the abovementioned problems, with the object of providing;
a lithium battery which has a lithium positive electrode, displays excellent energy density and long cycle life properties, and yet is cheap and thus suitable for large scale use; the material for use in this positive electrode;
and a production method for that material.
The method of producing a positive electrode material for use in lithium batteries according to the present invention comprises chemically reacting a lithium compound, and Fe2 ( SOq ) 3, or a precursor which gives rise to Fe2 ( S04 ) 3.
to produce a compound represented by the chemical formula LiXFe2(S04)3 (0<xs2). The lithium compound has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts.
The lithium battery according to the present invention comprises a positive electrode, a negative electrode and an electrolyte. The material of the positive electrode comprises a compound represented by the chemical formula LixFe2(S04)3 (0<x52), obtained by chemically reacting a lithium compound which has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts, and Fe2 ( S04 ) 3, or a precursor which gives rise to Fe2 ( S04 ) s .
The present invention is able to provide a battery which is low cost, uses material which is available in abundant quantities, and in which the discharge voltage is s high and the cycle life long, and has the advantage of therefore being utilizable in a wide range of applications, including as a power source for electric cars and various portable electronic equipment.
Furthermore, as high temperatures are not required in the synthesis of the positive electrode material, not only is the cost of the starting materials low, but the cost of production can also be reduced.
Moreover, in the synthesis of the positive electrode material, if a lithium compound is used which has a redox potential relative to a lithium electrode of between I.5 and 3.6 volts, then even if an excess of the lithium compound is added to the reaction mixture, the value of x in LixFez(S04)3 will not exceed 2, meaning the synthesis is simple and the reaction time short.
Furthermore, since active material retaining bodies which are capable of lithium insertion and extraction, are suitable for use as the negative electrode in batteries of the present invention, batteries with a particularly long cycle life are obtainable.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a coin shaped battery according to the embodiments;
FIG. 2 is a graph showing the relationship between the x value in LiXFez(SOQ)a and the potential relative to a lithium electrode; and FIG. 3 is a graph showing voltage characteristics relative to specific capacity for a battery of a first embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The positive electrode material of lithium batteries of the present invention is characterized in containing the compound represented by the chemical formula LiXFe2(SOQ)3 (0<x s 2). Because this LiXFe2(SOQ)3 is an iron based material, it is cheap and abundant, unlike expensive metals such as cobalt. Consequently, positive electrode material containing LiXFe2(S04)3 can be produced very cheaply when compared with positive electrode material containing LiCo02. Furthermore, as the production method employs mainly low temperature operations, production costs can also be reduced.
Moreover, by using LiXFez(S04)3, batteries with high energy densities and a high voltage of approximately 3.6 volts are obtained.
Furthermore, because this material contains lithium, batteries incorporating positive electrodes containing this material are able to supply lithium from the positive to the negative electrode. Consequently, the total amount of lithium which exists in the battery is large, resulting in a longer cycle life. Moreover, as it is also suitable for use as the positive electrode in lithium ion batteries, where the negative electrode consists of a lithium insertion and extraction capable active material retainer, batteries with particularly long cycle life can be obtained.
It is necessary that the value of x in LixFe2(SO.a)s be kept to a value of 2 or less. This is because the inventors have found that, as shown in FIG. 2, if the x value in LiXFez(S04)3 exceeds 2 the potential decreases rapidly, and also that in this region of low potential the basic structure of LixFez(SOQ)3 breaks down and metallic iron separates out. This results in a marked lowering in discharge capacity even with recharging, and a subsequent loss in reversibility.
Furthermore, the value of x is preferably large providing it is no greater than 2, with a value of 2 being the most favourable. The larger the value of x the greater the amount of lithium incorporated in the positive electrode, and consequently the greater the amount of lithium which can be supplied to the negative electrode, giving an improvement in capacity characteristics and a longer cycle life.
The LixFez(S04)3 can be obtained by chemical reaction between lithium metal or a lithium compound, and Fe2(S04)a or a precursor which gives rise to Fe2(S04)3. For example; it can be obtained by reaction of lithium metal or lithium compounds such as n-butyl lithium, or lithium napthylide, with iron sulfate in a solvent, and subsequent removal of the solvent and any unreacted materials.
In order to produce LixFez(S04)a using a lithium compound, a compound with stronger reducing properties than Fez(SOQ)a must be chosen. More specifically, incorporation of lithium into Fez(S04)3 requires reduction of the ferric ion, and in order to achieve that, the lithium compound must have a redox potential lower than that of Fez(S04)3.
Consequently, since the redox potential of Fez(SOQ)3 relative to a lithium electrode is 3.6 volts, lithium 2> lsgs6 compounds which display redox potentials of less than 3.6 volts relative to a lithium electrode can be used.
As metallic lithium has a redox potential of 0 volts relative to a lithium electrode, it meets the criterion of being less than 3.6 volts.
Furthermore, although LixFe2(SOQ)3 (0<x S 2) can be produced inside the battery by electrochemical reaction.
it is far simpler, and far more valuable from an industrial viewpoint, to synthesize LiXFez(S04)3 (0<x _s 2) directly by chemical reaction using a lithium compound which has a redox potential relative to a lithium electrode of less than 3.6 volts.
Furthermore, in the chemical synthesis of LixFea(SOa)3. in order to restrict the value of x to 2 or less, the quantities of metallic lithium or lithium compound, and of the Fea(SOa)a omits precursor are controlled so that the lithium/iron ratio is no greater than 1.
If the reaction rate is slow it is necessary to ensure an adequate reaction time. This is because if the reaction time is insufficient, the x value in LiXFe2(S04)a drops markedly, producing a decrease in the amount of lithium which can be subsequently supplied to the negative electrode.
It should be noted however that if reaction is carried out between different substances, then the individual reactions will not necessarily proceed at equal rates, meaning that even if reaction quantities are controlled, a possibility exists that for some portions of the mixture the lithium/iron ratio may exceed 1, and the x 2~~5~56 value in LixFe2(S04)3 may thus exceed 2, resulting in a loss of basic structure.
As a result of research by the inventors, it has been found that this problem can be resolved by using lithium compounds which display redox potentials relative to a lithium electrode of between 1.5 and 3.6 volts. The suggested reasons for this observation are outlined below.
As shown in FIG. 2, LiXFe2(SOQ)3 displays the property that when the x value exceeds 2, the potential relative to a lithium electrode drops to less than 1.5 volts.
Consequently, when Li2Fez(S04)3 is generated by reaction of a lithium compound having a potential relative to a lithium electrode of 1.5 volts or greater, with either Fe2(SOQ)3 or its precursor, then if the lithium content increases even slightly, the potential of Li2Fe2(SOQ)3 drops to less than 1.5 volts, and the lithium compound, which has a potential relative to a lithium electrode of greater than 1.5 volts, is no longer able to supply electrons to Li2Fe2(S04)3. As a result, the lithiation reaction stops, and LiaFez(SO<)3 is obtained with the x value not going above 2.
In this manner, by using above specified specific lithium compounds, even if more lithium than iron is used in the reaction system, the value of x in LiXFe2(S04)3 will not exceed 2. Consequently, the amount of lithium compounds used for reaction with a certain amount of Fe2(S04)a does not need to be measured to a high level of accuracy, making the synthesis of Li2Fe2(SOQ)3 simple. Moreover, adding excess lithium compound to increase the reactivity of the reaction system, still results in an x value of 2, thus offering a method for increasing the reaction rate.
Examples of lithium compounds which display potentials relative to a lithium electrode of between 1.5 and 3.6 volts include LiI(lithium iodide), Li2Cu02, and LiZMn20a. Of these compounds, lithium iodide is particularly suitable, as it offers the advantage of being comparatively more soluble in solvent, ~o that even if excess is added to the reaction system, its subsequent removal is straightforward. Furthermore, the iodine (IZ) produced after the insertion of lithium into either Fe2(SOa)3 or its precursor is also comparatively soluble in solvent, making its subsequent removal also straightforward.
The positive electrode material outlined above can be easily applied to use as the positive electrode in lithium batteries. Examples include, a method whereby a mixture of this type of positive electrode material and a powdered binder such as polytetrafluoroethylene is pressure bonded to a support body such as stainless steel; a method whereby in order to give conductivity to the mixture a further addition of a conductive powder such as acetylene black is made (further binder may be added as required), and this mixture then placed inside a metallic container or pressure bonded to a support body such as stainless steel;
and a method whereby a mixture of the positive electrode material and binder (with conductive agent added as required) is converted to a slurry by dispersion in a suitable solvent such as an organic solvent, and then applied to a metallic substrate.
There are no particular limitations on the z i ~SSS~
electrolyte liquid, providing it is a substance which allows the movement of lithium ions for electrochemical reaction at the positive and negative electrodes, and as such, solutions of a lithium salt with ion dissociation properties in an anhydrous solvent are appropriate.
Suitable examples include anhydrous electrolytic solutions or solid electrolytes formed from the dissolution of Lewis acids such as LiAsF6, LiBF4, LiPF6, LiA1C14, or LiC104 in an organic solvent such as dimethoxyethane, diethoxyethane, 2-methyltetrahydrofuran, ethylene carbonate, propylene carbonate, methyl formate, dimethyl sulfoxide, acetonitrile, butyrolactone, dimethyl formamide, dimethyl carbonate, diethyl carbonate, sulfolane, or ethyl methyl carbonate. Furthermore, if required, mixtures of these solutions can also be used.
For the negative electrode, metallic lithium or lithium compounds are used. An example of a suitable lithium compound is lithium aluminium metal alloy.
In order to use this type of material as the negative electrode, the material can be produced in sheet form, and this sheet then pressure bonded to a conductive mesh of nickel or stainless steel.
For lithium batteries containing a negative electrode formed in this way, from either metallic lithium or a lithium compound, and a positive electrode of the present invention, lithium is supplied by the positive electrode, and consequently, the total quantity of lithium in the battery is large, and the cycle life is long.
Furthermore, the use of an active material 21~5~56 retainer, which is capable of lithium insertion and extraction and in which extraction capable lithium has not previously been retained, as the negative electrode is also possible. This means that positive electrodes of the present invention, because they supply lithium to the negative electrode, can be used to produce particularly long life lithium ion batteries which have excellent properties, but because they do not contain expensive metals like cobalt, are still cheap.
Examples of active material retainers which are capable of lithium insertion and extraction include carbonaceous materials, LiaTi5012(Lia~3Ti5/3O4), and WOz.
Of these, the use of carbonaceous materials is most suitable as it produces a marked improvement in cycle properties.
Examples of carbonaceous material include graphite, hard carbon, and soft carbon.
Production of the negative electrode from these types of materials can be carried out using methods such as pressure bonding or application, in the same manner as described for the positive electrode.
Lithium batteries of the present invention are not limited to certain varieties of battery or specific battery shapes, and can be applied to a variety of battery types including coin shaped, cylindrically shaped, angular shaped, and button shaped batteries.
Furthermore, typical, existing materials can be used for the various other necessary components of the battery such as separators and battery cases, with there being no specific restrictions.
~. ~ 17 5~8 56 With lithium batteries of the present invention, charging can be carried out by application of a voltage of, for example, 3.9 volts to the negative electrode of the battery, causing lithium to be extracted from the LiXFez(S04)3 of the positive electrode, and then adhere to, or be inserted into, the negative electrode. The charged battery thus formed generates a potential of approximately 3.6 volts between the positive and negative electrodes, so that when some form of electrical load such as a resistor, is connected to the positive and negative electrodes, a current flows, causing the battery to discharge.
The present invention is explained in more specific terms below, in relation to actual embodiments, but it should be noted that the present invention is in no way limited to the embodiments presented. In all of the embodiments, battery production and measurements were carried out in a dry box, under an atmosphere of argon.
[Example 1]
FIG. 1 shows a coin shaped lithium battery being a first example of a battery according to the present invention. In brief, this lithium battery is constructed from a positive electrode case 3, in which is arranged a pellet of a positive electrode mixture 6 which contains LizFez(SOa)a. a negative electrode 4 which contains metallic lithium, an intervening micro-porous separator 5 made of polypropylene, and a stainless steel sealing cover 1 which sits on top of the negative electrode 4, and is sealed with a gasket 2 of polypropylene. The negative electrode 4, the 2~ ~ 585b separator 5, and the pellet of positive electrode mixture 6 are all impregnated with electrolyte solution. The electrolyte solution maintains the ion conductivity between the pellet of the positive electrode mixture 6 and the negative electrode 4, and is a number 1 normal solution of LiPF6 dissolved in an equal volume mixture of ethylene carbonate and dimethyl carbonate.
The lithium battery shown in the figure is a coin type battery of thickness 2mm and diameter 23mm, with a round disc shaped negative electrode 4 of thickness 0.07mm and diameter l8mm, and a pellet of positive electrode mixture 6 of thickness 0.5mm and diameter l5mm.
Assembly of lithium batteries of this construction is carried out by first pressure bonding the metallic lithium of the negative electrode 4 to the upturned sealer cover 1 and then fitting the cover 1 into the gasket 2. The separator 5 and the pellet of positive electrode mixture 6 are then placed on top of the negative electrode 4, and the whole assembly impregnated with electrolyte solution, and finally covered with the positive electrode case 3.
The pellet of positive electrode mixture 6 was produced as follows.
First, Fez(S04)3 was produced by heating (NHa)zFez(SO.a)z-6H20 under atmospheric conditions for 5 hours at 480°C: Next, this Fez(S04)3 was mixed with lithium iodide, to give a mixture with a lithium/iron ratio of 2, and the mixture heated for 5 hours at 82°C in acetonitrile. The powder thus obtained was washed with acetonitrile to remove the excess lithium iodide, to give LizFez(SOQ)3 (herein referred to as positive electrode material a).
The LizFez(SOQ)3 was then ground up to give a powder, mixed with a conductive agent (acetylene black) and a binder (polytetrafluoroethylene), and then roll formed to produce the pellets of positive electrode mixture 6.
(Example 2]
The battery of this embodiment (second example) is the same as that of the first example, with the exception of the positive electrode, which uses positive electrode material produced by the method described below.
First, Fez(S04)3 was produced by reacting FeS04~THz0 with hydrogen peroxide in concentrated sulfuric acid. Next, this Fez(SOQ)3 was mixed with lithium iodide LiI, to give a lithium/iron ratio of 2, and the mixture heated for 5 hours at 82°C in acetonitrile. The powder thus obtained was then washed with acetonitrile to remove the excess lithium iodide, to give Lil.9Fez(S04)3 (positive electrode material b).
[Example 3]
The battery of this embodiment (third example) is the same as that of the first example, with the exception of the positive electrode, which uses positive electrode material produced by the method described below.
First, FeS04~THz0 was placed in a flask fitted with a reflux condenser, concentrated sulfuric acid added, and the mixture refluxed under heat for 5 hours to give Fez(S04)3. Next, this Fez(SOa)3 was mixed with lithium iodide LiI, to give a lithium/iron ratio of 2, and the mixture heated for 5 hours at 82°C in acetonitrile. The powder thus obtained was then washed with acetonitrile to remove the excess lithium iodide, to give Lil.eFez(SOa)a (positive electrode material c).
[Example 4]
The battery of this embodiment (fourth example) is the same as that of the first example, with the exception of the positive electrode, which uses positive electrode material produced by the method described below.
First, Fez(SOa)3 was produced by heating (NHa)zFez(SOa)z~6Hz0 under atmospheric conditions for 5 hours at 480°C. Next, this Fez(SOa)3 was mixed with lithium iodide LiI, to give a lithium/iron ratio of 1, and the mixture heated for 5 hours at 82°C in acetonitrile.
The powder thus obtained was then washed with acetonitrile to remove the excess lithium iodide, to give Li,..6Fez(SOa)3 (positive electrode material d).
[Example 5]
The battery of this embodiment (fifth example) is the same as that of the first example, with the exception of the negative electrode, for which a carbonaceous material capable of lithium insertion and extraction was used. The negative electrode was produced by mixing the powdered carbonaceous material with a fluorocarbon resin binder, and suspending the mixture in Methylpyrrolidone to give a paste, which was then applied to copper foil, dried and then rolled.
[Test 1]
The batteries of the four examples above, were charged to a voltage of 4.5 volts at a current density of 0.5 mA/cmz, and then their discharge capacities measured by discharging the batteries until a voltage of 2.5 volts was reached.
In addition, the batteries were subjected to repeated charge-discharge cycles over this 2.5 - 4.5 volts range, at a charge-discharge current density of 0.5 mA/cmz, and their discharge capacities remeasured on the 10th discharge cycle. The measurements are shown in Table 1.
As a comparison, a lithium battery (control example 1) which, with the exception of the positive electrode which uses positive electrode material (positive electrode material e) produced by the method described below, was the same as the battery of the first example, was also charged to a voltage of 4.5 volts at a current density of 0.5 mA/cmz, and its discharge capacity measured by discharging until a voltage of 2.5 volts was reached.
Similarly, its discharge capacity following 10 charge-discharge cycles was also measured.
First, Fez(SOa)3 was produced by heating (NHa)zFez(SOa)z~6Hz0 under atmospheric conditions for 5 hours at 480°C. Next, this Fez(SOa)3 was combined with n-butyl lithium (which has a redox potential relative to a lithium electrode of less than 1.5 volts), to give a lithium/iron ratio of 2, and the mixture reacted in hexane 2 ~ 7 X856 for a period of one week. The powder thus obtained was then washed with hexane to remove the excess n-butyl lithium, to give a powdered product (positive electrode material e).
Analysis of this powder by X-ray diffraction resulted in the observation of peaks for metallic iron and lithium sulfate Li2S04, indicating that the basic structure of LixFe2(SOa)3 had broken down.
Table 1 Positive Initial discharge Discharge capacity electrode capacity following 10 charge-material discharge cycles Example a 13.4 (mAh) 13.2 (mAh) Example b 12.5 (mAh) 12.2 (mAh) Example c 12.2 (mAh) 12.1 (mAh) Example d 10.3 (mAh) 10.2 (mAh) Control a 2.1 (mAh) -example 1 As can be seen from Table 1, whereas the discharge capacity of the control example 1 is small, and furthermore disappears altogether following 10 charge-discharge cycles, the lithium batteries of examples 1-4 all display high discharge capacities, as well as only minimal lowering of these discharge capacities on repeated charging and discharging.
Furthermore, the x value in LiXFez(SOQ)3 was closest to 2 in the examples 1 through 3, wherein excess 2 l 75g~~
lithium iodide was added during the synthesis of the positive electrode material, and these examples display particularly high discharge capacities and small reductions in discharge capacity upon continued charging and discharging.
FIG. 3 shows the voltage characteristics of the lithium battery of example 1 in terms of the specific capacity per gram of positive electrode material. As is shown in FIG. 3, the lithium battery of example 1 displays recharge cycle characteristics which are as good as those of batteries employing LiCo02.
[Test 2]
Using the lithium batteries from examples 1 and 5, the charge-discharge cycles were continued, at the same 2.5 -4.5 volts range and charge-discharge current density of 0.5 mA/cmz, to test the change in discharge capacity.
Furthermore, for the purposes of comparison, a lithium battery (control example 2) which, with the exception of the positive electrode, which uses Fez(S04)3 synthesized by heating (NHQ)zFez(S04)2~6Hz0 under atmospheric conditions for 5 hours at 480°C, was the same as the battery of the first example, was also tested for change in discharge capacity, by employing the same charge-discharge cycles, with a 2.5 - 4.5 volts range and a charge-discharge current density of 0.5 mA/cm2.
In the case of the battery of the control example 2, the initial discharge capacity was 12.0 mAh, and the capacity was maintained at approximately this level for 35 ,.~ 2115 5~6 charge-discharge cycles, but beyond that the capacity dropped rapidly, and by the 39th cycle the discharge capacity had fallen to half the initial value.
Disassembly of the battery of the control example 2 revealed that the lithium of the negative electrode had lost its luster, and that the drop in discharge capacity was due to a depletion in the amount of lithium available for charging and discharging.
In contrast, the discharge capacity of the lithium battery of example 1 was maintained at approximately the initial discharge capacity level for 50 charge-discharge cycles, but beyond that the capacity dropped rapidly, and by the 55th cycle the discharge capacity had fallen to half the initial value. As such, the battery of example 1 displays a long cycle life. This is because, unlike the battery of the control example 2, the battery of example 1 is able to utilize the lithium from the positive electrode, meaning there is a greater total amount of lithium available for charging and discharging.
Disassembly of the battery of example 1 revealed that the lithium of the negative electrode had lost its luster, and that the drop in discharge capacity was due to a depletion in the amount of lithium available for charging and discharging.
Furthermore, in the case of the battery of example 5, the discharge capacity was maintained at approximately the initial discharge capacity level, even after 100 charge-discharge cycles. As such, the lithium battery of example 5 displays good rechargeability and an extremely long cycle life.
In the above examples, examples are given of the production of lithium batteries, where the compound represented by the formula LiXFeZ(SOQ)3 (0<x s 2) is synthesized by particular synthetic methods, and then used as the positive electrode. However needless to say, lithium batteries where the positive electrode utilizes the same compound LixFe2(S04)3 (0<x s 2) which has been synthesized by alternative methods, will yield the same results.
The positive electrode material of lithium batteries of the present invention is characterized in containing the compound represented by the chemical formula LiXFe2(SOQ)3 (0<x s 2). Because this LiXFe2(SOQ)3 is an iron based material, it is cheap and abundant, unlike expensive metals such as cobalt. Consequently, positive electrode material containing LiXFe2(S04)3 can be produced very cheaply when compared with positive electrode material containing LiCo02. Furthermore, as the production method employs mainly low temperature operations, production costs can also be reduced.
Moreover, by using LiXFez(S04)3, batteries with high energy densities and a high voltage of approximately 3.6 volts are obtained.
Furthermore, because this material contains lithium, batteries incorporating positive electrodes containing this material are able to supply lithium from the positive to the negative electrode. Consequently, the total amount of lithium which exists in the battery is large, resulting in a longer cycle life. Moreover, as it is also suitable for use as the positive electrode in lithium ion batteries, where the negative electrode consists of a lithium insertion and extraction capable active material retainer, batteries with particularly long cycle life can be obtained.
It is necessary that the value of x in LixFe2(SO.a)s be kept to a value of 2 or less. This is because the inventors have found that, as shown in FIG. 2, if the x value in LiXFez(S04)3 exceeds 2 the potential decreases rapidly, and also that in this region of low potential the basic structure of LixFez(SOQ)3 breaks down and metallic iron separates out. This results in a marked lowering in discharge capacity even with recharging, and a subsequent loss in reversibility.
Furthermore, the value of x is preferably large providing it is no greater than 2, with a value of 2 being the most favourable. The larger the value of x the greater the amount of lithium incorporated in the positive electrode, and consequently the greater the amount of lithium which can be supplied to the negative electrode, giving an improvement in capacity characteristics and a longer cycle life.
The LixFez(S04)3 can be obtained by chemical reaction between lithium metal or a lithium compound, and Fe2(S04)a or a precursor which gives rise to Fe2(S04)3. For example; it can be obtained by reaction of lithium metal or lithium compounds such as n-butyl lithium, or lithium napthylide, with iron sulfate in a solvent, and subsequent removal of the solvent and any unreacted materials.
In order to produce LixFez(S04)a using a lithium compound, a compound with stronger reducing properties than Fez(SOQ)a must be chosen. More specifically, incorporation of lithium into Fez(S04)3 requires reduction of the ferric ion, and in order to achieve that, the lithium compound must have a redox potential lower than that of Fez(S04)3.
Consequently, since the redox potential of Fez(SOQ)3 relative to a lithium electrode is 3.6 volts, lithium 2> lsgs6 compounds which display redox potentials of less than 3.6 volts relative to a lithium electrode can be used.
As metallic lithium has a redox potential of 0 volts relative to a lithium electrode, it meets the criterion of being less than 3.6 volts.
Furthermore, although LixFe2(SOQ)3 (0<x S 2) can be produced inside the battery by electrochemical reaction.
it is far simpler, and far more valuable from an industrial viewpoint, to synthesize LiXFez(S04)3 (0<x _s 2) directly by chemical reaction using a lithium compound which has a redox potential relative to a lithium electrode of less than 3.6 volts.
Furthermore, in the chemical synthesis of LixFea(SOa)3. in order to restrict the value of x to 2 or less, the quantities of metallic lithium or lithium compound, and of the Fea(SOa)a omits precursor are controlled so that the lithium/iron ratio is no greater than 1.
If the reaction rate is slow it is necessary to ensure an adequate reaction time. This is because if the reaction time is insufficient, the x value in LiXFe2(S04)a drops markedly, producing a decrease in the amount of lithium which can be subsequently supplied to the negative electrode.
It should be noted however that if reaction is carried out between different substances, then the individual reactions will not necessarily proceed at equal rates, meaning that even if reaction quantities are controlled, a possibility exists that for some portions of the mixture the lithium/iron ratio may exceed 1, and the x 2~~5~56 value in LixFe2(S04)3 may thus exceed 2, resulting in a loss of basic structure.
As a result of research by the inventors, it has been found that this problem can be resolved by using lithium compounds which display redox potentials relative to a lithium electrode of between 1.5 and 3.6 volts. The suggested reasons for this observation are outlined below.
As shown in FIG. 2, LiXFe2(SOQ)3 displays the property that when the x value exceeds 2, the potential relative to a lithium electrode drops to less than 1.5 volts.
Consequently, when Li2Fez(S04)3 is generated by reaction of a lithium compound having a potential relative to a lithium electrode of 1.5 volts or greater, with either Fe2(SOQ)3 or its precursor, then if the lithium content increases even slightly, the potential of Li2Fe2(SOQ)3 drops to less than 1.5 volts, and the lithium compound, which has a potential relative to a lithium electrode of greater than 1.5 volts, is no longer able to supply electrons to Li2Fe2(S04)3. As a result, the lithiation reaction stops, and LiaFez(SO<)3 is obtained with the x value not going above 2.
In this manner, by using above specified specific lithium compounds, even if more lithium than iron is used in the reaction system, the value of x in LiXFe2(S04)3 will not exceed 2. Consequently, the amount of lithium compounds used for reaction with a certain amount of Fe2(S04)a does not need to be measured to a high level of accuracy, making the synthesis of Li2Fe2(SOQ)3 simple. Moreover, adding excess lithium compound to increase the reactivity of the reaction system, still results in an x value of 2, thus offering a method for increasing the reaction rate.
Examples of lithium compounds which display potentials relative to a lithium electrode of between 1.5 and 3.6 volts include LiI(lithium iodide), Li2Cu02, and LiZMn20a. Of these compounds, lithium iodide is particularly suitable, as it offers the advantage of being comparatively more soluble in solvent, ~o that even if excess is added to the reaction system, its subsequent removal is straightforward. Furthermore, the iodine (IZ) produced after the insertion of lithium into either Fe2(SOa)3 or its precursor is also comparatively soluble in solvent, making its subsequent removal also straightforward.
The positive electrode material outlined above can be easily applied to use as the positive electrode in lithium batteries. Examples include, a method whereby a mixture of this type of positive electrode material and a powdered binder such as polytetrafluoroethylene is pressure bonded to a support body such as stainless steel; a method whereby in order to give conductivity to the mixture a further addition of a conductive powder such as acetylene black is made (further binder may be added as required), and this mixture then placed inside a metallic container or pressure bonded to a support body such as stainless steel;
and a method whereby a mixture of the positive electrode material and binder (with conductive agent added as required) is converted to a slurry by dispersion in a suitable solvent such as an organic solvent, and then applied to a metallic substrate.
There are no particular limitations on the z i ~SSS~
electrolyte liquid, providing it is a substance which allows the movement of lithium ions for electrochemical reaction at the positive and negative electrodes, and as such, solutions of a lithium salt with ion dissociation properties in an anhydrous solvent are appropriate.
Suitable examples include anhydrous electrolytic solutions or solid electrolytes formed from the dissolution of Lewis acids such as LiAsF6, LiBF4, LiPF6, LiA1C14, or LiC104 in an organic solvent such as dimethoxyethane, diethoxyethane, 2-methyltetrahydrofuran, ethylene carbonate, propylene carbonate, methyl formate, dimethyl sulfoxide, acetonitrile, butyrolactone, dimethyl formamide, dimethyl carbonate, diethyl carbonate, sulfolane, or ethyl methyl carbonate. Furthermore, if required, mixtures of these solutions can also be used.
For the negative electrode, metallic lithium or lithium compounds are used. An example of a suitable lithium compound is lithium aluminium metal alloy.
In order to use this type of material as the negative electrode, the material can be produced in sheet form, and this sheet then pressure bonded to a conductive mesh of nickel or stainless steel.
For lithium batteries containing a negative electrode formed in this way, from either metallic lithium or a lithium compound, and a positive electrode of the present invention, lithium is supplied by the positive electrode, and consequently, the total quantity of lithium in the battery is large, and the cycle life is long.
Furthermore, the use of an active material 21~5~56 retainer, which is capable of lithium insertion and extraction and in which extraction capable lithium has not previously been retained, as the negative electrode is also possible. This means that positive electrodes of the present invention, because they supply lithium to the negative electrode, can be used to produce particularly long life lithium ion batteries which have excellent properties, but because they do not contain expensive metals like cobalt, are still cheap.
Examples of active material retainers which are capable of lithium insertion and extraction include carbonaceous materials, LiaTi5012(Lia~3Ti5/3O4), and WOz.
Of these, the use of carbonaceous materials is most suitable as it produces a marked improvement in cycle properties.
Examples of carbonaceous material include graphite, hard carbon, and soft carbon.
Production of the negative electrode from these types of materials can be carried out using methods such as pressure bonding or application, in the same manner as described for the positive electrode.
Lithium batteries of the present invention are not limited to certain varieties of battery or specific battery shapes, and can be applied to a variety of battery types including coin shaped, cylindrically shaped, angular shaped, and button shaped batteries.
Furthermore, typical, existing materials can be used for the various other necessary components of the battery such as separators and battery cases, with there being no specific restrictions.
~. ~ 17 5~8 56 With lithium batteries of the present invention, charging can be carried out by application of a voltage of, for example, 3.9 volts to the negative electrode of the battery, causing lithium to be extracted from the LiXFez(S04)3 of the positive electrode, and then adhere to, or be inserted into, the negative electrode. The charged battery thus formed generates a potential of approximately 3.6 volts between the positive and negative electrodes, so that when some form of electrical load such as a resistor, is connected to the positive and negative electrodes, a current flows, causing the battery to discharge.
The present invention is explained in more specific terms below, in relation to actual embodiments, but it should be noted that the present invention is in no way limited to the embodiments presented. In all of the embodiments, battery production and measurements were carried out in a dry box, under an atmosphere of argon.
[Example 1]
FIG. 1 shows a coin shaped lithium battery being a first example of a battery according to the present invention. In brief, this lithium battery is constructed from a positive electrode case 3, in which is arranged a pellet of a positive electrode mixture 6 which contains LizFez(SOa)a. a negative electrode 4 which contains metallic lithium, an intervening micro-porous separator 5 made of polypropylene, and a stainless steel sealing cover 1 which sits on top of the negative electrode 4, and is sealed with a gasket 2 of polypropylene. The negative electrode 4, the 2~ ~ 585b separator 5, and the pellet of positive electrode mixture 6 are all impregnated with electrolyte solution. The electrolyte solution maintains the ion conductivity between the pellet of the positive electrode mixture 6 and the negative electrode 4, and is a number 1 normal solution of LiPF6 dissolved in an equal volume mixture of ethylene carbonate and dimethyl carbonate.
The lithium battery shown in the figure is a coin type battery of thickness 2mm and diameter 23mm, with a round disc shaped negative electrode 4 of thickness 0.07mm and diameter l8mm, and a pellet of positive electrode mixture 6 of thickness 0.5mm and diameter l5mm.
Assembly of lithium batteries of this construction is carried out by first pressure bonding the metallic lithium of the negative electrode 4 to the upturned sealer cover 1 and then fitting the cover 1 into the gasket 2. The separator 5 and the pellet of positive electrode mixture 6 are then placed on top of the negative electrode 4, and the whole assembly impregnated with electrolyte solution, and finally covered with the positive electrode case 3.
The pellet of positive electrode mixture 6 was produced as follows.
First, Fez(S04)3 was produced by heating (NHa)zFez(SO.a)z-6H20 under atmospheric conditions for 5 hours at 480°C: Next, this Fez(S04)3 was mixed with lithium iodide, to give a mixture with a lithium/iron ratio of 2, and the mixture heated for 5 hours at 82°C in acetonitrile. The powder thus obtained was washed with acetonitrile to remove the excess lithium iodide, to give LizFez(SOQ)3 (herein referred to as positive electrode material a).
The LizFez(SOQ)3 was then ground up to give a powder, mixed with a conductive agent (acetylene black) and a binder (polytetrafluoroethylene), and then roll formed to produce the pellets of positive electrode mixture 6.
(Example 2]
The battery of this embodiment (second example) is the same as that of the first example, with the exception of the positive electrode, which uses positive electrode material produced by the method described below.
First, Fez(S04)3 was produced by reacting FeS04~THz0 with hydrogen peroxide in concentrated sulfuric acid. Next, this Fez(SOQ)3 was mixed with lithium iodide LiI, to give a lithium/iron ratio of 2, and the mixture heated for 5 hours at 82°C in acetonitrile. The powder thus obtained was then washed with acetonitrile to remove the excess lithium iodide, to give Lil.9Fez(S04)3 (positive electrode material b).
[Example 3]
The battery of this embodiment (third example) is the same as that of the first example, with the exception of the positive electrode, which uses positive electrode material produced by the method described below.
First, FeS04~THz0 was placed in a flask fitted with a reflux condenser, concentrated sulfuric acid added, and the mixture refluxed under heat for 5 hours to give Fez(S04)3. Next, this Fez(SOa)3 was mixed with lithium iodide LiI, to give a lithium/iron ratio of 2, and the mixture heated for 5 hours at 82°C in acetonitrile. The powder thus obtained was then washed with acetonitrile to remove the excess lithium iodide, to give Lil.eFez(SOa)a (positive electrode material c).
[Example 4]
The battery of this embodiment (fourth example) is the same as that of the first example, with the exception of the positive electrode, which uses positive electrode material produced by the method described below.
First, Fez(SOa)3 was produced by heating (NHa)zFez(SOa)z~6Hz0 under atmospheric conditions for 5 hours at 480°C. Next, this Fez(SOa)3 was mixed with lithium iodide LiI, to give a lithium/iron ratio of 1, and the mixture heated for 5 hours at 82°C in acetonitrile.
The powder thus obtained was then washed with acetonitrile to remove the excess lithium iodide, to give Li,..6Fez(SOa)3 (positive electrode material d).
[Example 5]
The battery of this embodiment (fifth example) is the same as that of the first example, with the exception of the negative electrode, for which a carbonaceous material capable of lithium insertion and extraction was used. The negative electrode was produced by mixing the powdered carbonaceous material with a fluorocarbon resin binder, and suspending the mixture in Methylpyrrolidone to give a paste, which was then applied to copper foil, dried and then rolled.
[Test 1]
The batteries of the four examples above, were charged to a voltage of 4.5 volts at a current density of 0.5 mA/cmz, and then their discharge capacities measured by discharging the batteries until a voltage of 2.5 volts was reached.
In addition, the batteries were subjected to repeated charge-discharge cycles over this 2.5 - 4.5 volts range, at a charge-discharge current density of 0.5 mA/cmz, and their discharge capacities remeasured on the 10th discharge cycle. The measurements are shown in Table 1.
As a comparison, a lithium battery (control example 1) which, with the exception of the positive electrode which uses positive electrode material (positive electrode material e) produced by the method described below, was the same as the battery of the first example, was also charged to a voltage of 4.5 volts at a current density of 0.5 mA/cmz, and its discharge capacity measured by discharging until a voltage of 2.5 volts was reached.
Similarly, its discharge capacity following 10 charge-discharge cycles was also measured.
First, Fez(SOa)3 was produced by heating (NHa)zFez(SOa)z~6Hz0 under atmospheric conditions for 5 hours at 480°C. Next, this Fez(SOa)3 was combined with n-butyl lithium (which has a redox potential relative to a lithium electrode of less than 1.5 volts), to give a lithium/iron ratio of 2, and the mixture reacted in hexane 2 ~ 7 X856 for a period of one week. The powder thus obtained was then washed with hexane to remove the excess n-butyl lithium, to give a powdered product (positive electrode material e).
Analysis of this powder by X-ray diffraction resulted in the observation of peaks for metallic iron and lithium sulfate Li2S04, indicating that the basic structure of LixFe2(SOa)3 had broken down.
Table 1 Positive Initial discharge Discharge capacity electrode capacity following 10 charge-material discharge cycles Example a 13.4 (mAh) 13.2 (mAh) Example b 12.5 (mAh) 12.2 (mAh) Example c 12.2 (mAh) 12.1 (mAh) Example d 10.3 (mAh) 10.2 (mAh) Control a 2.1 (mAh) -example 1 As can be seen from Table 1, whereas the discharge capacity of the control example 1 is small, and furthermore disappears altogether following 10 charge-discharge cycles, the lithium batteries of examples 1-4 all display high discharge capacities, as well as only minimal lowering of these discharge capacities on repeated charging and discharging.
Furthermore, the x value in LiXFez(SOQ)3 was closest to 2 in the examples 1 through 3, wherein excess 2 l 75g~~
lithium iodide was added during the synthesis of the positive electrode material, and these examples display particularly high discharge capacities and small reductions in discharge capacity upon continued charging and discharging.
FIG. 3 shows the voltage characteristics of the lithium battery of example 1 in terms of the specific capacity per gram of positive electrode material. As is shown in FIG. 3, the lithium battery of example 1 displays recharge cycle characteristics which are as good as those of batteries employing LiCo02.
[Test 2]
Using the lithium batteries from examples 1 and 5, the charge-discharge cycles were continued, at the same 2.5 -4.5 volts range and charge-discharge current density of 0.5 mA/cmz, to test the change in discharge capacity.
Furthermore, for the purposes of comparison, a lithium battery (control example 2) which, with the exception of the positive electrode, which uses Fez(S04)3 synthesized by heating (NHQ)zFez(S04)2~6Hz0 under atmospheric conditions for 5 hours at 480°C, was the same as the battery of the first example, was also tested for change in discharge capacity, by employing the same charge-discharge cycles, with a 2.5 - 4.5 volts range and a charge-discharge current density of 0.5 mA/cm2.
In the case of the battery of the control example 2, the initial discharge capacity was 12.0 mAh, and the capacity was maintained at approximately this level for 35 ,.~ 2115 5~6 charge-discharge cycles, but beyond that the capacity dropped rapidly, and by the 39th cycle the discharge capacity had fallen to half the initial value.
Disassembly of the battery of the control example 2 revealed that the lithium of the negative electrode had lost its luster, and that the drop in discharge capacity was due to a depletion in the amount of lithium available for charging and discharging.
In contrast, the discharge capacity of the lithium battery of example 1 was maintained at approximately the initial discharge capacity level for 50 charge-discharge cycles, but beyond that the capacity dropped rapidly, and by the 55th cycle the discharge capacity had fallen to half the initial value. As such, the battery of example 1 displays a long cycle life. This is because, unlike the battery of the control example 2, the battery of example 1 is able to utilize the lithium from the positive electrode, meaning there is a greater total amount of lithium available for charging and discharging.
Disassembly of the battery of example 1 revealed that the lithium of the negative electrode had lost its luster, and that the drop in discharge capacity was due to a depletion in the amount of lithium available for charging and discharging.
Furthermore, in the case of the battery of example 5, the discharge capacity was maintained at approximately the initial discharge capacity level, even after 100 charge-discharge cycles. As such, the lithium battery of example 5 displays good rechargeability and an extremely long cycle life.
In the above examples, examples are given of the production of lithium batteries, where the compound represented by the formula LiXFeZ(SOQ)3 (0<x s 2) is synthesized by particular synthetic methods, and then used as the positive electrode. However needless to say, lithium batteries where the positive electrode utilizes the same compound LixFe2(S04)3 (0<x s 2) which has been synthesized by alternative methods, will yield the same results.
Claims (10)
1. A method of producing a positive electrode material for use in lithium batteries comprising the step:
chemically reacting a lithium compound and Fe2(SO4)3, or a precursor which gives rise to Fe2(SO4)3, to produce a compound represented by the chemical formula LiXFe2(SO4)3 (0 < x ~ 2);
wherein the lithium compound has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts.
chemically reacting a lithium compound and Fe2(SO4)3, or a precursor which gives rise to Fe2(SO4)3, to produce a compound represented by the chemical formula LiXFe2(SO4)3 (0 < x ~ 2);
wherein the lithium compound has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts.
2. The method according to claim 1, wherein a sufficient amount of the lithium compound is added to make the proportion of Li with respect to Fe greater than 1.
3. The method according to claim 1 or 2, wherein the lithium compound comprises lithium iodide.
4. The method according to claim 1, 2 or 3, wherein the precursor comprises (NH4)2Fe2(SO4)2.6H2O or FeSO4.7H2O.
5. A lithium battery comprising:
a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises LiXFe2(SO4)3 (0 < x ~ 2) obtained by chemically reacting a lithium compound which has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts, and Fe2(SO4)3, or a precursor which gives rise to Fe2(SO4)3.
a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises LiXFe2(SO4)3 (0 < x ~ 2) obtained by chemically reacting a lithium compound which has a redox potential relative to a lithium electrode of between 1.5 and 3.6 volts, and Fe2(SO4)3, or a precursor which gives rise to Fe2(SO4)3.
6. The lithium battery according to claim 5, wherein the lithium compound comprises lithium iodide.
7. The lithium battery according to claim 5 or 6, wherein the negative electrode comprises a lithium insertion and extraction capable active material retainer, and the electrolyte comprises a substance that allows movement of lithium ions for electrochemical reactions at the positive and negative electrodes.
8. The lithium battery according to claim 7, wherein the active material retainer comprises a carbonaceous material.
9. The lithium battery according to claim 5 or 6, wherein the negative electrode comprises lithium or a lithium compound, and the electrolyte comprises a substance which allows movement of lithium ions for electromechanical reactions at the positive and negative electrodes.
10. The lithium battery according to any one of claims 5 to 9, wherein the precursor comprises (NH4) 2Fe2 (SO4) 2. 6H2O or FeSO4. 7H2O.
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|---|---|---|---|
| JP14390595 | 1995-05-18 | ||
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| US6514640B1 (en) | 1996-04-23 | 2003-02-04 | Board Of Regents, The University Of Texas System | Cathode materials for secondary (rechargeable) lithium batteries |
| US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
| US5908716A (en) * | 1997-04-15 | 1999-06-01 | Valence Technology, Inc. | Lithium--containing sulfates, method of preparation and uses thereof |
| US6436577B1 (en) * | 1997-06-12 | 2002-08-20 | Sanyo Electric Co., Ltd. | Non-aqueous electrolytic secondary cell |
| US6536547B1 (en) | 1999-05-05 | 2003-03-25 | Daniel J. Meaney, Jr. | Hybrid electric vehicle having alternate power sources |
| US6892840B2 (en) | 1999-05-05 | 2005-05-17 | Daniel J. Meaney, Jr. | Hybrid electric vehicle having alternate power sources |
| US7524584B2 (en) | 2000-04-27 | 2009-04-28 | Valence Technology, Inc. | Electrode active material for a secondary electrochemical cell |
| US6387568B1 (en) * | 2000-04-27 | 2002-05-14 | Valence Technology, Inc. | Lithium metal fluorophosphate materials and preparation thereof |
| US8057769B2 (en) * | 2000-04-27 | 2011-11-15 | Valence Technology, Inc. | Method for making phosphate-based electrode active materials |
| US6777132B2 (en) * | 2000-04-27 | 2004-08-17 | Valence Technology, Inc. | Alkali/transition metal halo—and hydroxy-phosphates and related electrode active materials |
| US6964827B2 (en) * | 2000-04-27 | 2005-11-15 | Valence Technology, Inc. | Alkali/transition metal halo- and hydroxy-phosphates and related electrode active materials |
| KR101209358B1 (en) | 2001-12-21 | 2012-12-07 | 메사추세츠 인스티튜트 오브 테크놀로지 | Conductive lithium storage electrode |
| US6815122B2 (en) | 2002-03-06 | 2004-11-09 | Valence Technology, Inc. | Alkali transition metal phosphates and related electrode active materials |
| US7482097B2 (en) * | 2002-04-03 | 2009-01-27 | Valence Technology, Inc. | Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials |
| US20030190527A1 (en) * | 2002-04-03 | 2003-10-09 | James Pugh | Batteries comprising alkali-transition metal phosphates and preferred electrolytes |
| US7422823B2 (en) * | 2002-04-03 | 2008-09-09 | Valence Technology, Inc. | Alkali-iron-cobalt phosphates and related electrode active materials |
| US7041239B2 (en) * | 2003-04-03 | 2006-05-09 | Valence Technology, Inc. | Electrodes comprising mixed active particles |
| US20070141468A1 (en) * | 2003-04-03 | 2007-06-21 | Jeremy Barker | Electrodes Comprising Mixed Active Particles |
| US20050163699A1 (en) * | 2004-01-23 | 2005-07-28 | Jeremy Barker | Fluorosulfate-based electrode active materials and method of making the same |
| US7842420B2 (en) | 2005-02-03 | 2010-11-30 | A123 Systems, Inc. | Electrode material with enhanced ionic transport properties |
| TWI365562B (en) * | 2008-10-03 | 2012-06-01 | Ind Tech Res Inst | Positive electrode and method for manufacturing the same and lithium battery utilizing the same |
| GB201201717D0 (en) | 2012-02-01 | 2012-03-14 | Faradion Ltd | Sulfate electrodes |
| FR2987498B1 (en) | 2012-02-29 | 2017-08-11 | Univ Picardie | SULFATES USEFUL AS ELECTRODE MATERIALS |
| JP6423794B2 (en) * | 2013-09-11 | 2018-11-14 | 国立大学法人 東京大学 | Positive electrode material for sodium ion secondary battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4132547A (en) * | 1977-05-27 | 1979-01-02 | Westinghouse Electric Corp. | Method of producing self-supporting fully activated iron electrodes by thermal reduction-sintering |
| JP2847663B2 (en) * | 1992-10-06 | 1999-01-20 | 日本電信電話株式会社 | Non-aqueous electrolyte battery |
| JP3395370B2 (en) * | 1994-03-22 | 2003-04-14 | ソニー株式会社 | Lithium secondary battery |
| JPH07302618A (en) * | 1994-05-09 | 1995-11-14 | Nippon Telegr & Teleph Corp <Ntt> | Secondary battery with nonaqueous solvent electrolyte |
-
1996
- 1996-05-06 US US08/642,857 patent/US5695893A/en not_active Expired - Lifetime
- 1996-05-06 CA CA002175856A patent/CA2175856C/en not_active Expired - Lifetime
- 1996-05-14 EP EP96401050A patent/EP0743692B1/en not_active Expired - Lifetime
- 1996-05-14 DE DE69609766T patent/DE69609766T2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5695893A (en) | 1997-12-09 |
| EP0743692A1 (en) | 1996-11-20 |
| DE69609766D1 (en) | 2000-09-21 |
| EP0743692B1 (en) | 2000-08-16 |
| DE69609766T2 (en) | 2001-04-12 |
| CA2175856A1 (en) | 1996-11-19 |
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