Vanadium Oxide Cathode Active Material and Method of Making Same

This invention relates to electrochemical batteries, and more particularly to improved positive electrode active material mainly composed of an oxide of vanadium.

Lithium-based cells or batteries often comprise cathodes of transition metal oxides which are used as intercalation compounds. The intercalation reaction involves the interstitial introduction of a guest species, namely, lithium into the host lattice of the transition metal oxide, essentially without structural modification of the host lattice. Such intercalation reaction is essentially reversible because suitable transition states are achieved for both the forward and reverse of the intercalation reaction.

However, transition metal oxides when used as active cathode materials in rechargeable lithium batteries, show a declining capacity during cyclic operation of the battery. This may be attributable to volume changes of the host material which takes place when lithium is inserted and extracted. Because of the rigidity of the structural network into which lithium is inserted, such insertion can lead to large perturbations of the structure involving partial or complete breakage of certain bonds which can irreversibly destroy the oxide structure, resulting in poor electrical performance for the cathode. Such structural breakdown can occur whether the structure has two dimensional characteristics of a layered structure, or a more rigid three dimensional network oxide lattice.

Therefore, what is needed is a new cathode active material based on vanadium oxide in a form which maintains its capacity and has good charge/discharge cyclic characteristics over its useful operating life. What is also needed is a method to form such vanadium oxide based materials.

The present invention provides a lithium battery comprising a cathode active material having as its major component an oxide of vanadium, which is a compound of the general formula M.sub.x V.sub.3 O.sub.8. The vanadium oxide active material of the invention is prepared by a series of steps in which a precursor ZV.sub.3 O.sub.8 -based compound undergoes quantitative ionic substitution to provide M.sub.x V.sub.3 O.sub.8, where M is a mono-, di-, tri- or tetravalent metal or semi-metal (metallic) element, other than lithium. The value of x is greater than zero and less than two. Preferably x is one or close to one, and the nominal general formula is M.sub.1 V.sub.3 O.sub.8.

Preferably, the vanadium oxide based active material (M.sub.x V.sub.3 O.sub.8) is prepared for use in cells with an anode active material made of lithium or a compound which includes lithium. The cells also include an electrolyte which is electrochemically stable with respect to the cathode active material and lithium, and which allows lithium ions from the anode (negative electrode) to move therethrough to react electrochemically with the cathode active material of the invention.

Accordingly in one embodiment, a cathode active material of the general nominal formula M.sub.x V.sub.3 O.sub.8 (vanadium oxide compound) is prepared from the precursor material (ZV.sub.3 O.sub.8), preferably LiV.sub.3 O.sub.8, by substitution of the Z+ or Li+ ion for mono-, di-, tri- and tetravalent ions of other metals or semi-metals in a series of reactions. Although the starting material LiV.sub.3 O.sub.8 is preferred, it is also possible to achieve substitution of the Z+ ion using precursor compounds where Li+ is substituted by Na+ or K+. In addition, NaV.sub.3 O.sub.8 and KV.sub.3 O.sub.8 are suitable vanadium oxide compounds for use as the active material, and may be prepared from an LiV.sub.3 O.sub.8 precursor.

An active material of the formula M.sub.x V.sub.3 O.sub.8 may contain more than one type of element M. That is, an active material constituting a mixture of M ions may be used. For example, it is possible to use two transition metals (M', M") of similar or different valences in a single active material. In use, the active material of the nominal formula M.sub.x V.sub.3 O.sub.8 intercalates lithium, resulting in Li.sub.y M.sub.x V.sub.3 O.sub.8.

A preferred lithium cell comprises the positive electrode active material of the invention, a negative electrode which is metallic lithium, and an electrolyte which is a solid electrolyte or electrolyte separator in the form of a polymeric network containing an electrolyte solution comprising a metal salt of lithium.

Accordingly, it is an object of the invention to provide a new cathode (positive electrode) vanadium oxide based active material for a lithium battery. Another object is to provide a method of making the new cathode material and the battery containing such cathode material. It is also an object of the invention to provide a lithium battery having a cathode active material containing a vanadium oxide based active material of the general formula M.sub.x V.sub.3 O.sub.8, where M is selected to provide structural stability for maintaining structural integrity of the oxide based material during charge and discharge. Another object is to provide a lithium battery having good charge and discharge capacity over its useful operating life.

These and other objects, features and advantages will become apparent from the following description of the preferred embodiments, appended claims and accompanying drawings.

FIG. 1 is an illustration of a cross-section of a thin battery or cell embodying the invention.

FIG. 2 contains charts (a,b) showing common oxidation states of representative elements (a) and transition elements (b).

FIG. 3 is a chart showing radii of various metallic elements.

As shown in FIG. 1, an electrochemical cell or battery 10 has a negative electrode side 12, a positive electrode side 14, and a separator 16 therebetween. In accordance with common usage, a battery may consist of one cell or multiple cells. The negative electrode is the anode during discharge, and the positive electrode is the cathode during discharge. The negative electrode side includes current collector 18, typically of nickel, iron, stainless steel, and/or copper foil, and a body of negative electrode active material 20. The negative electrode active material 20 is sometimes simply referred to as the negative electrode. The positive electrode side includes current collector 22, typically of aluminum, nickel, iron, stainless steel, and/or copper foil, or such foils having a protective conducting coating foil, and a body of positive electrode active material 24 which has as its main component one or more oxides of vanadium. The positive electrode active material 24 is sometimes simply referred to as the positive electrode. The separator 16 is typically a solid electrolyte, electrolyte separator. A suitable electrolyte separator (polymer electrolyte) is described in U.S. Pat. No. 4,830,939 incorporated herein by reference. The electrolyte separator is a solid organic polymer matrix containing an ionically conducting liquid with an alkali metal salt and the liquid is an aprotic polar solvent. The terms "solid electrolyte" and "electrolyte separator" are used interchangeably in industry. Sometimes, the term "separator" is used.

The composition of the positive electrode active material 24 has a significant influence on the performance of battery 10. This is because when transition metal oxides are used as cathode active materials in such batteries, a declining capacity occurs during cyclic operation of the battery. This is thought to be due to the volume changes of the material which take place when lithium is inserted and extracted from the transition metal intercalation material.

In the case of LiV.sub.3 O.sub.8, it is thought that the V.sub.3 O.sub.8 - layers are held together by Li+ ions. This produces rather weak bonding which is very likely to be responsible for structural instability of the material which manifests itself as a decline in capacity. It is thought that charge retention during cyclic operation can be improved by increasing the strength of the bonds which hold the V.sub.3 O.sub.8 - layers together and, therefore, maintain structural integrity of the vanadium oxide based (V.sub.3 O.sub.8 -) cathode active material.

Accordingly in one embodiment, a cathode active material of the general nominal formula M.sub.x V.sub.3 O.sub.8 (vanadium oxide compound) is prepared from the precursor material (ZV.sub.3 O.sub.8), preferably LiV.sub.3 O.sub.8, by substitution of the Z+ or Li+ ion for mono-, di-, tri- and tetravalent ions of other metals or semi-metals in a series of reactions. Although the starting material LiV.sub.3 O.sub.8 is preferred, it is also possible to achieve substitution of the Z+ ion using precursor compounds where Li+ is substituted by Na+ or K+. In addition, NaV.sub.3 O.sub.8 and KV.sub.3 O.sub.8 are suitable vanadium oxide compounds for use as the active material, and may be prepared from an LiV.sub.3 O.sub.8 precursor.

The ZV.sub.3 O.sub.8 precursor may readily be formed from a V.sub.2 O.sub.5 starting material which in turn is prepared from ammonium metavanadate. The process begins with heating the ammonium metavanadate (NH.sub.4 VO.sub.3) to a temperature of about 400.degree. C. to about 450.degree. C. to decompose it to crystalline V.sub.2 O.sub.5 in the presence of oxygen. Crystalline V.sub.2 O.sub.5 has been used to prepare cathodes for use with lithium-based anodes. The lithium vanadium oxide of the nominal general formula LiV.sub.3 O.sub.8 is prepared by forming an aqueous mixture of the V.sub.2 O.sub.5, prepared as described above, and including LiOH in the mixture. The amounts of V.sub.2 O.sub.5 and LiOH correspond to the stoichiometric amounts of the two compounds needed for formation of LiV.sub.3 O.sub.8. Preferably, excess LiOH is used. It is thought that part of the V.sub.2 O.sub.5 dissolves in solution, followed by reaction between the dissolved V.sub.2 O.sub.5, LiOH and water and then with the remaining solid V.sub.2 O.sub. 5, with the subsequent formation of LiV.sub.3 O.sub.8. The reaction is fairly slow at room temperature, but proceeds at a reasonable rate at 50.degree. C. to 60.degree. C. A process of adding progressively larger amounts of vanadium pentoxide to an LiOH solution is more fully described in U.S. Pat. No. 5,039,582 which is incorporated in its entirety by reference. The LiV.sub.3 O.sub.8 product typically forms a very fine precipitate. The lithium-vanadium oxide product of the nominal general formula LiV.sub.3 O.sub.8 is preferably in a completely amorphous state. The amorphous state is beneficial for rate capabilities and energy density.

An alternative method of forming the precursor LiV.sub.3 O.sub.8 is by melting of V.sub.2 O.sub.5 with Li.sub.2 CO.sub.3 at a temperature of at least about 600.degree. C. The melt, once cooled, gives rise to solid material which may then be crushed for further processing. In a variation of the process, the melt is cooled from a temperature of about 800.degree. C. to about 900.degree. C., and rapidly quenched to obtain a high degree of an amorphous character and a less crystalline character. In contrast, the amorphous form of LiV.sub.3 O.sub.8, described above, is readily obtained by synthesis in a water solution by reaction between lithium hydroxide (LiOH) and vanadium pentoxide (V.sub.2 O.sub.5) in suitable proportions. The amorphous form of the LiV.sub.3 O.sub.8, when heated to very high temperatures of about 350.degree. C., begins to acquire a crystalline structure. As stated, it is thought that the amorphous form of LiV.sub.3 O.sub.8 is preferred. Similar methods may also be used to form the ZV.sub.3 O.sub.8 precursor where lithium is replaced by sodium or potassium. For example, Na.sub.2 CO.sub.3 is used in the process described above in place of Li.sub.2 CO.sub.3.

The starting precursor material, ZV.sub.3 O.sub.8 is used in a series of steps where ion exchange occurs. In the first step, the ZV.sub.3 O.sub.8 (namely, LiV.sub.3 O.sub.8, NaV.sub.3 O.sub.8, KV.sub.3 O.sub.8) is dispersed in a first solution which contains about 1 molar aqueous (sulfuric acid) H.sub.2 SO.sub.4. Other acids and equivalent concentrations may be used, however, sulfuric acid is preferred because of the relative inertness of the sulphate ion. The dispersed mixture is stirred for 2 to 10 hours, whereby the Z+ ion (i.e. Li+, Na+ or K+) is exchanged almost quantitatively by H+. This occurs at a temperature in a range of about 10.degree. C. to about 85.degree. C. It is preferred to stir the solution. The product of this step is represented by the general formula HV.sub.3 O.sub.8. The H+ ion is in turn readily ion exchanged with other mono-, di-, tri- and tetravalent metal and semi-metal (metallic) ions in the next step of the process. This second step replaces the hydrogen ion with M ions, where M+ is the monovalent, divalent, trivalent or tetravalent ion of the final compound desired M.sub.x V.sub.3 O.sub.8. This stage consists of forming a solution comprising the HV.sub.3 O.sub.8 product and a salt of the metal or semi-metal (M). The ion exchange of the H+ ion for the M+ ion occurs at a temperature in a range of about 10.degree. C. to about 85.degree. C. The product of this reaction quantitatively forms in about 2 to about 10 hours. It is preferred to stir the solution.

In the first step, to ensure that the reaction is as complete as possible, the powder may be filtered and dispersed in new, fresh 1 M H.sub.2 SO.sub.4, several times. Since H+ is consumed, the pH of the solution decreases during the reaction. The start conditions are defined by the concentration of the acid and the end conditions are dependent on the solid's affinity for protons, the exchange degree and temperature. When HV.sub.3 O.sub.8 is formed, it is filtered and washed with water to remove the traces of acid. When the washing water is neutral, filtrate drying is not essential. In the second step, the washing water is dispersed in a salt solution of the M ion which is to be ion exchanged into the structure. The reaction rate is proportional to the concentration, and in general, concentrations close to the solubility limit are used. This will of course depend on the compound. The reaction rate may also be increased by the use of alkaline metal salts because the OH-- will facilitate extraction of the H+ from the structure. However, this only occurs if the ion exchange reaction on the particle surface is the rate determining reaction. The process provides quantitative ion exchange, that is, 90 to 100% of the H+ is replaced by M+. It is preferred that close to 100% exchange is achieved. It is possible to use more than one metal salt so that H+ is replaced by more than one type of M ion.

It is preferred that the M ion of the final product be a monovalent ion, such as Na+, K+, Rb+, Cs+, Ag+, Cu+; a divalent ion such as Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Sc.sup.2+, Fe.sup.2+, Ni.sup.2+, Co.sup.2+, Cu.sup.2+ and Zn.sup.2+, a trivalent ion (L.sup.3+, L=lanthanide, Cr.sup.3+, Fe.sup.3+) or a tetravalent ion such as Ce.sup.4+. Such M ions selected are from the group of metal and semi-metal elements which constitute about three-quarters of the Periodic Table. Such metal and semi-metal elements are also commonly referred to as metallic elements. The value of x in M.sub.x V.sub.3 O.sub.8 is greater than zero and less than two. Preferably, x is one or close to one, and the nominal general formula is M.sub.1 V.sub.3 O.sub.8.

Metallic elements are distinguished from non-metallic elements by their luster, malleability, conductivity and usual ability to form a positive ion. Semi-metals are also considered in the group as having metallic characteristics, as distinguished from non-metals. Metals and semi-metals are capable of forming positive ions and are conductors of electricity. Conductivity of semi-metals is small, on the order of 10 to 10.sup.-5 ohm.sup.-1 cm.sup.-1. Metals have higher conductivities generally greater than 10.sup.4 ohm.sup.-1 cm.sup.-1. Such metals and semi-metals appear in the left hand part of the Periodic Table and are separated from the non-metals by a diagonal band of semi-metals that run from boron to tellurium. The classification of elements close to this group of semi-metals is not always understood. However, metallic behavior is found among the transition elements, the members of groups I and II, and the heavier elements of groups IIIB, IVB and VB. Transition elements occur between groups IIA and IIIB in the long form of the Periodic Table.

As stated earlier, the MV.sub.3 O.sub.8 compounds include M which is a monovalent, divalent, trivalent or tetravalent ion. Common oxidation states of representative elements, and the transition elements which are particularly preferred as the ion M, are given in FIG. 2.

In order to obtain quantitative substitution of the H+ ion (in the HV.sub.3 O.sub.8) for the M+ ion defined above, suitable sulfates, nitrates and other organic or inorganic salts of the appropriate metal or semi-metal ion (M+) are used. A second solution is formed containing the HV.sub.3 O.sub.8. It is preferred that the anion of the salt is large in order to prevent inclusion of the anion in the final product lattice. The product of the ionic substitution reaction is preferably filtered and dried before use. It is thought that some of the formed vanadium oxide compounds (M.sub.x V.sub.3 O.sub.8) will be structurally similar to or perhaps identical to the structure of the precursor ZV.sub.3 O.sub.8 starting materials, whereas others will convert to one or more structurally different phases during drying.

Preferred salts for use in the substitution of the H+ ion are sulfates and nitrates. Other salts which may be used are carbonates and other inorganic salts. Organic salts may also be used. Examples of salts are as follows: magnesium nitrate, cobaltous nitrate, manganese nitrate, nickel nitrate, ferric nitrate, zinc nitrate, magnesium carbonates, cobaltous carbonates, manganese carbonates, nickel carbonates, zinc carbonates, ferrous carbonate, magnetic iron oxide, cobaltic oxide, manganese dioxide, nickelic oxide, cupric oxide, cupric nitrate, cuptic carbonates, magnesium sulfate, cobaltons sulfate, manganese sulfate, nickel sulfate, ferrous sulfate, ferric sulfate, cuptic sulfate, zinc sulfate, magnesium oxalate, cobaltous oxalate, manganese oxalate, nickel oxalate, ferrous oxalate, zinc oxalate, cuptic oxalate, magnesium acetate, cobaltous acetate, manganese acetate, nickel acetate, ferrous acetate, ferric acetate, cuptic acetate, zinc acetate, magnesium formate, cobaltous formate, manganese formate, nickel formate, ferrous formate, cuprous formate, zinc formate. There is also, magnesium chlorate, cobaltous chlorate, nickel chlorate, cupric chlorate, magnesium perchlorate, cobaltous erchlorate, nickel perchlorate, ferric perchlorate, cupric perchlorate, manganese perchlorate and zinc perchlorate; and magnesium oxide, cobaltous oxide, manganese oxide, nickel oxide, ferric oxide, cuprous oxide, zinc oxide, magnesium hydroxide, cobaltous hydroxide, manganese hydroxide, nickel hydroxide, ferric hydroxide, cuprous hydroxide and zinc hydroxide.

Although many examples of the ion, sulfates, nitrates and other salts thereof are presented above, these examples are not limiting and others may be used in the invention.

As stated, it is preferred that the anion of the salt is large enough to prevent its inclusion into the product. Therefore, it is preferred that such anions are larger than the proton of the M ion in the M.sub.x V.sub.3 O.sub.8 composition. The atomic radii of various metallic elements are given in FIG. 3. This figure and similar tables having atomic radii serve as a guide to selecting the salt to be used with the M ion. Such charts are typically developed by determining the internuclear distance in a metallic crystal using x-ray diffraction. The apparent radius of an atom depends, to a certain degree, on the crystal structure.

The vanadium oxide compound of the invention (M.sub.x V.sub.3 O.sub.8) may be used to prepare electrodes by mixing the M.sub.x V.sub.3 O.sub.8, carbon (typical Shawinigan Black) and an electrolyte/binder. A typical composition is as given in Table 1. Carbon particles for use in electrodes may be obtained from a variety of sources such as Union Carbide, Noury Chemical Corporation, and other major chemical companies. In an as-received condition, such carbon particles have a BET surface area on the order of hundreds of square meters per gram. The particles have an average or median particle size or equivalent average diameter in the range of about 10 to about 100 nanometers (0.01 to 0.1 microns), and typically in the order of 30 nanometers. Thus, the carbon particles are very fine and of submicron size.

The cathode is coated onto nickel foil followed by electron beam curing (cross-linking/polymerization) of the acrylate component. Then the electrolyte is coated on top of the cathode and cured with ultraviolet light. The lithium electrode is applied on top of the electrolyte separator and the battery is finally placed in a flexible pouch which is heat sealed under vacuum.

The charge distribution in the LiV.sub.3 O.sub.8 is thought to correspond to Li.sup.+1 (V.sup.+5).sub.3 and (O.sup.-2).sub.8 which is +1, +15, -16. In the case of a tetravalent ion such as Ce.sup.+4, the charge distribution is Ce.sup.+4 (V.sup.+4).sub.3 (O.sup.-2).sub.8 which is +4, +12, -16. Thus, the tetravalent ion has a positive charge (Ce.sup.+4) not greater than the positive charge of the vanadium (V.sup.+4) in the oxide in an initial condition before any lithium is intercalated. In some cases, during use of the battery, the average positive charge of the vanadium (V) may be less than the positive charge of M in the MV.sub.3 O.sub.8, as Li+ is taken up. For example, assuming M is tetravalent (e.g. Ce+.sup.4), vanadium may be reduced first. In mixed valence compounds, one ion tends to be reduced before the other one(s). To achieve a usable potential difference, the positive electrode is electrochemically oxidized, while the anode is reduced. Thus, during charging, a quantity y (y of lithium ion Li+) are accepted or intercalated into the positive electrode active material of the invention. It is thought that when this occurs, the oxidation states of M and V (in Li.sub.y M.sub.x V.sub.3 O.sub.8) change. It is expected that during typical operation, the positive electrode can intercalate up to about 3 to about 4 moles Li+ per mole of M.sub.x V.sub.3 O.sub.8 where M is monovalent (+1); up to about 3 to about 5 moles Li+ per mole MV.sub.3 O.sub.8 where M is bivalent (+2); up to about 3 to about 6 moles where M is trivalent (+3); and up to about 3 to about 7 moles where M is tetravalent (+4). In all such cases, it is assumed that each mole of MV.sub.3 O.sub.8 has one M ion (i.e. M.sub.x, where x=1 ). Accordingly, upon operation of the battery, the nominal general formula is Li.sub.y M.sub.x V.sub.3 O.sub.8 where y begins with y equal to about zero and then y increases up to y equal to about seven, depending on the M ion present or combination of M ions present. Of course, as the cell cycles, the value of y continuously changes A trivalent ion, such as Fe.sup.+3 is able to exist in a Fe.sup.+2 state and is expected to contribute to the capacity by changing to a lower oxidation state upon Li+ intercalation. The M ion Cu.sup.+2 is capable of a +1 oxidation state and would provide a similar advantage. Refer to FIG. 2 for oxidation states.

The cathode properties of MV.sub.3 O.sub.8 are expected to be similar to or better than those of LiV.sub.3 O.sub.8. The cathode properties of the metal substituted LiV.sub.3 O.sub.8, that is, MV.sub.3 O.sub.8 where M is a metal, and preferably a transition metal are expected to be better than the cathode properties of the alkalized V.sub.3 O.sub.8, namely, NaV.sub.3 O.sub.8 and KV.sub.3 O.sub.8. Accordingly, in the case of ions with higher charge, and metals which can exist in several oxidation states (FIG. 2), it is likely that the second metal ion will participate in the insertion reaction, whereby the capacity of the cathode is increased compared to the precursor material.

While this invention has been described in terms of certain embodiments thereof, it is not intended that it be limited to the above description, but rather only to the extent set forth in the following claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined in the appended claims.