Compositions and methods for manufacturing a cathode for lithium secondary battery

Abstract

Disclosed are compositions and methods for producing a cathode for a secondary battery, where lithium manganese fluorophosphate such as Li.sub.2MnPO.sub.4F can be used as an electrode material. Li.sub.2MnPO.sub.4F is prepared by chemical intercalation of lithium, and can be used as an electrode material, and a non-lithium containing material can then be used as an anode material for manufacturing of a full cell. Furthermore, it is possible to provide a carbon coating for a cathode material for a lithium battery, which has improved electrical conductivity.

Claims

1. A method of producing a cathode composition for a secondary battery, comprising: (i) mixing sodium (Na) oxide, or a precursor thereof, manganese (Mn) oxide, or a precursor thereof, phosphate (P), or a precursor thereof, and fluoride (F), or a precursor thereof, for about 6 hours, by ball milling to produce a mixture; (ii) pretreating the mixture of step (i) under an air atmosphere at about 300° C. for about 2 hours; (iii) firing the pretreated mixture at about 500° C. to about 550° C. under argon gas to synthesize a compound of structure Na.sub.2MnPO.sub.4F; (iv) intercalating a source of lithium into the compound of structure Na.sub.2MnPO.sub.4F produced from step (iii) by ion exchange to produce the cathode composition for a lithium secondary battery of structure Li.sub.2MnPO.sub.4F; (v) mixing the cathode composition of structure Li2MnPO4F produced by step (iv) with a carbon conductive material at a ratio of about 60:40 to about 90:10 by ball milling to produce a coating mixture; and (vi) coating a cathode surface with the coating mixture to improve electric conductivity.

2. The method of claim 1, wherein step (iv) further comprises intercalating lithium ions into the compound of structure Na.sub.2MnPO.sub.4F produced from step (iii) by lithium intercalation/sodium deintercalation.

3. The method of claim 1, wherein step (iv) further comprises the step of chemically deintercalating sodium from the compound of structure Na.sub.2MnPO.sub.4F produced from step (iii), and chemically intercalating lithium into the compound of structure Na.sub.2MnPO.sub.4F.

4. The method of claim 1, wherein the carbon conductive material is selected from the group consisting of citric acid, sucrose, super-P, acetylene black, Ketchen Black, and carbon.

5. The method of claim 1, wherein the precursor of the sodium oxide is selected from the group consisting of sodium phosphate, sodium carbonate, sodium hydroxide, sodium acetate, sodium sulfate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide, and any mixture thereof.

6. The method of claim 1, wherein the precursor of the manganese oxide is selected from the group consisting of manganese metal, manganese oxide, manganese oxalate, manganese acetate, manganese nitrate, and any mixture thereof.

7. The method of claim 1, wherein the precursor of the phosphate is selected from the group consisting of ammonium phosphate, sodium phosphate, potassium phosphate, and any mixture thereof.

8. The method of claim 1, wherein the source of lithium is LiBr or LiI.

9. The method of claim 8, wherein the ion exchange is carried out with at least 0.5 M LiBr or at least 0.5 M LiI.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other features of the present invention will now be described in detail with reference to certain exemplary embodiments thereof illustrated in the accompanying drawings which are given hereinbelow by way of illustration only, and thus are not limitative of the present invention, and wherein:

(2) FIG. 1 shows electron microscopic images of a cathode material prepared by the method of Example 1 of the present invention;

(3) FIG. 2 shows charge/discharge curve graphs of a battery including the cathode material prepared according to the method of Example 1, at room temperature, at a discharge cut-off voltage of 2.0 V;

(4) FIG. 3 shows charge/discharge curve graphs of a battery including the cathode material prepared according to the method of Example 1, at room temperature, at a discharge cut-off voltage of 1.0 V; and

(5) FIG. 4 shows the discharge curve graphs of a battery including the cathode material prepared according to the method of Example 1, at a high temperature (60° C.).

(6) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.

DETAILED DESCRIPTION

(7) Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that the present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.

(8) Unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”

(9) Ranges provided herein are understood to be shorthand for all of the values within the range. For example, a range of 1 to 50 is understood to include any number, combination of numbers, or sub-range from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all intervening decimal values between the aforementioned integers such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9.

(10) The present invention provides a cathode material for a secondary battery, which includes a lithium manganese-based fluorophosphate compound represented by the following Formula:
Li.sub.2MnPO.sub.4F.

(11) The cathode material for a secondary battery, which includes the Formula above, has a primary particle size of about 300 nm or less, is coated with carbon for improvement of conductivity, and shows a potential plateau by discharge at about 3.7 V to about 4.0V, and a discharge capacity of about 100 mAhg.sup.−1 or more at discharge of about 2.0 V, and a discharge capacity of about 200 mAhg.sup.−1 or more at discharge of about 1.0 V.

(12) The present invention provides a method for producing a cathode material for a secondary battery, the method including:

(13) (i) uniformly mixing sodium (Na) oxide or a precursor thereof, manganese (Mn) oxide or a precursor thereof, phosphate (P) or a precursor thereof, and fluoride (F) or a precursor thereof through ball milling, and carrying out pretreatment on the obtained mixture, followed by firing so as to synthesize a cathode material Na.sub.2MnPO.sub.4F; and

(14) (ii) intercalating lithium into the cathode material synthesized in step (i) through an ion exchange method so as to synthesize Li.sub.2MnPO.sub.4F.

(15) According to a preferred embodiment of the present invention, in step (i), the mixture is uniformly mixed for 6 hours by ball milling, and then subjected to pretreatment under an air atmosphere at 300° C. for 2 hours.

(16) According to a preferred embodiment of the present invention, step (ii) includes the step of intercalating lithium ions into the cathode material obtained from step (i) through lithium intercalation/sodium deintercalation by an ion exchange method.

(17) According to a preferred embodiment of the present invention, step (ii) includes the step of chemically deintercalating sodium from the cathode material obtained from step (i), and chemically intercalating lithium into the cathode material.

(18) According to a preferred embodiment of the present invention, the cathode material obtained from step (ii) is uniformly mixed with a carbon conductive material at a ratio of about 60:40 to about 90:10, followed by ball milling. It is contemplated within the scope of the invention that the aforementioned range includes all sub-ranges within the specified range. For example, the ratio of cathode material to carbon conductive material may range from about 60:40 to about 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 67:33, 68:32, 69:31, 70:30, 71:29, 72:28, 73:27, 74:26, 75:25, 76:24, 77:23, 78:22, 79:21, 80:20, 81:19, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11, or 90:10. Similarly, the ratio of cathode material to carbon conductive material may range from about 90:10 to about 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, or 60:40. It is further contemplated within the scope of the invention that the ratio of cathode material to carbon conductive material may include all intervening ratios, for example, about 60:40, about 61:39, about 62:38, about 63:37, about 64:36, about 65:35, about 66:34, about 67:33, about 68:32, about 69:31, about 70:30, about 71:29, about 72:28, about 73:27, about 74:26, about 75:25, about 76:24, about 77:23, about 78:22, about 79:21, about 80:20, about 81:19, about 82:18, about 83:17, about 84:16, about 85:15, about 86:14, about 87:13, about 88:12, about 89:11, and about 90:10, as well as all intervening decimal values. Then, the carbon conductive material is uniformly coated on a cathode surface so as to improve the electric conductivity.

(19) The precursor of the sodium oxide may be selected from sodium phosphate, sodium carbonate, sodium hydroxide, sodium acetate, sodium sulfate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide, and any mixture thereof.

(20) The precursor of the manganese oxide may be selected from manganese metal, manganese oxide, manganese oxalate, manganese acetate, manganese nitrate, and any mixture thereof.

(21) The precursor of phosphate may be selected from ammonium phosphate, sodium phosphate, potassium phosphate, and any mixture thereof.

(22) Furthermore, LiBr or LiI may be used to cause ion exchange between lithium and sodium during the intercalation of lithium by the ion exchange method.

(23) Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

(24) The present invention provides a cathode material for a secondary battery, which includes a compound represented by the Formula:
Li.sub.2MnPO.sub.4F.

(25) In the exemplary embodiment of the present invention, the cathode material shows a potential discharge plateau from about 3.7 V to about 4.0V, and is coated with carbon for conductivity improvement.

(26) Hereinafter, the method for producing a cathode material for a secondary battery, according to the present invention will be described. The specific production method will be more easily understood through the following Examples.

(27) For example, the cathode material Na.sub.2MnPO.sub.4F for a secondary battery is prepared by uniformly mixing sodium oxide or a precursor thereof, manganese oxide or a precursor thereof, phosphate or a precursor thereof, and fluoride or a precursor thereof through ball milling, carrying out pretreatment on the mixture, followed by firing so as to synthesize a cathode material Na.sub.2MnPO.sub.4F; and carrying out heat treatment by firing the mixture obtained from the pretreatment step. According to the invention, the prepared Na.sub.2MnPO.sub.4F has a particle size of about 1 μm or less, and an average particle size of about 300 nm Na.sub.2MnPO.sub.4F prepared according to the invention is introduced into an acetonitrile solution including, for example, LiBr dissolved therein. Then, Argon gas is flowed into the solution while the reaction temperature is raised so that ion exchange between lithium and sodium can be carried out. By washing and drying the resulting product of the ion exchange, a cathode material, lithium fluorophosphate Li.sub.2MnPO.sub.4F, is obtained.

(28) In order to increase electrical conductivity, the obtained cathode material, Li.sub.2MnPO.sub.4F, was subjected to carbon coating.

(29) The precursor of the sodium oxide may be any suitable sodium containing compound including, but not particularly limited to, sodium phosphate, sodium carbonate, sodium hydroxide, sodium acetate, sodium sulfate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide, and any mixture thereof.

(30) The precursor of the manganese oxide may be any suitable manganese containing compound including, but not particularly limited to, manganese metal, manganese oxide, manganese oxalate, manganese acetate, manganese nitrate, and any mixture thereof.

(31) The precursor of phosphate may be any suitable phosphate containing compound including, but not particularly limited to, lithium phosphate, sodium phosphate, potassium phosphate and any mixture thereof.

(32) The precursor of fluorine may be any suitable fluorine containing compound including, but not particularly limited to, metal fluoride, fluoride, and a mixture thereof. The lithium source used for the ion exchange may be any suitable lithium containing compound including, but not particularly limited to, LiBr, LiI, or any lithium compound mixture suitable for causing ion exchange.

(33) The solvent used for the ion exchange may be any solvent suitable for including, but not limited to, acetonitrile. The carbon conductive material may be, but is not particularly limited to, citric acid, sucrose, super-P, acetylene black, Ketchen Black, or any suitable carbon material.

(34) The cathode material of the exemplary embodiment of the present invention prepared as described above may be used for manufacturing a lithium secondary battery. Herein, the manufacturing method is the same as that of a conventional lithium secondary battery manufacturing method except for the application of the cathode material. Hereinafter, the configuration and the manufacturing method of the secondary battery will be briefly described.

(35) First, in a manufacturing process for a cathode plate using the inventive cathode material, the cathode material is added with one, two, or more kinds of conventionally used additives, such as, for example, a conductive material, a binding agent, a filler, a dispersing agent, an ion conductive material, and a pressure enhancer, as required, and the mixture is formed into a slurry or paste with an appropriate solvent (such as, e.g., an organic solvent). Then, the obtained slurry or paste is applied to an electrode supporting substrate by an appropriate technique such as, for example, the “doctor blade” method, etc., and then dried. Then, through pressing by rolling a roll, a final cathode plate is manufactured.

(36) According to an exemplary embodiment of the invention, examples of the conductive material include graphite, carbon black, acetylene black, Ketchen Black, carbon fiber, metal powder, and the like. The binding agent may include, but is not limited to, PVdF, polyethylene, and the like. The electrode supporting substrate (collector) may include, but is not limited to, a foil or a sheet of copper, nickel, stainless steel, aluminum, carbon fiber, and the like.

(37) By using the cathode plate prepared as described above, a lithium secondary battery is manufactured. The lithium secondary battery may be manufactured into a variety of different shapes including, but not limited to, a coin shape, a button shape, a sheet shape, a cylindrical shape, or a square shape. Also, an anode, an electrolyte, and a separator for the lithium secondary battery are the same as those used in a conventional lithium secondary battery.

(38) The anode material may be a graphite-based material that does not include lithium. Additionally, the anode material may also include one, two, or more kinds of transition metal composite oxides including lithium. The anode material may also include silicon, tin, etc.

(39) The electrolyte may be, but is not limited to, a non-aqueous electrolyte including lithium salt dissolved in an organic solvent, an inorganic solid electrolyte, or a composite of an inorganic solid electrolyte. The solvent for the non-aqueous electrolyte may be, but is not limited to, one, two, or more solvents selected from the group of esters (such as, e.g., ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate), lactones (such as, e.g., butyl lactone), ethers (such as, e.g., 1,2-dimethoxy ethane, ethoxy methoxy ethane), or nitriles (such as, e.g., acetonitrile). Examples of lithium salt of the non-aqueous electrolyte may include, but is not limited to, LiAsF.sub.6, LiBF.sub.4, LiPF.sub.6, or the like.

(40) Also, as the separator, a porous film prepared from a polyolefin such as, for example, PP and/or PE, or a porous material such as non-woven fabric may be used.

EXAMPLES

(41) Hereinafter, the following examples are provided to further illustrate the invention, but they should not be considered as the limit of the invention. The following examples illustrate the invention and are not intended to limit the same.

Example 1

(42) Sodium carbonate (Na.sub.2CO.sub.3), manganese oxalate.hydrate (MnC.sub.2O.sub.4.2H.sub.2O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO.sub.3), and ammonium phosphate (NH.sub.4H.sub.2PO.sub.4) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours so as to uniformly the materials.

(43) The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 500° C. for 6 hours under an argon gas atmosphere. Then, the resulting Na.sub.2MnPO.sub.4F was precipitated in acetonitrile including 3 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a reaction temperature of 80° C.

(44) The test sample, in which ion exchange was completed, was washed with anhydrous ethanol so as to remove the remaining NaBr, and subsequently dried. Then, the resulting test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling and then, prepared as a cathode material composite.

Comparative Example 1

(45) Sodium carbonate (Na.sub.2CO.sub.3), manganese oxalate.hydrate (MnC.sub.2O.sub.4.2H.sub.2O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO.sub.3), and ammonium phosphate (NH.sub.4H.sub.2PO.sub.4) were introduced in predetermined amounts with respect to the total amount of 5 g, and uniformly mixed by hand mixing for 30 minutes.

(46) The resulting mixture was subjected to pretreatment at 300° C. for about 2 hours under an air atmosphere, and fired at 500° C. for 6 hours under an argon gas atmosphere. Then, the resulting Na.sub.2MnPO.sub.4F was precipitated in acetonitrile including 3 M of LiBr dissolved therein, and reacted together with the flow of argon gas at A reaction temperature of 80° C. After the completion of the reaction, the resulting test sample was collected, washed with anhydrous ethanol, and subsequently dried, so as to remove the remaining impurities. Then, only a pure test sample was collected.

Comparative Example 2

(47) Sodium carbonate (Na.sub.2CO.sub.3), manganese oxalate.hydrate (MnC.sub.2O.sub.4.2H.sub.2O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO.sub.3), and ammonium phosphate (NH.sub.4H.sub.2PO.sub.4) were introduced in predetermined amounts with respect to the total amount of 10 g, and uniformly mixed by ball milling for 6 hours.

(48) The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 600° C. for 6 hours under an argon gas atmosphere. Then, the resulting Na.sub.2MnPO.sub.4F was precipitated in acetonitrile including 3 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a reaction temperature of 80° C. After the completion of the reaction, the resulting test sample was collected, washed with anhydrous ethanol, and subsequently dried, so as to remove the remaining impurities. Then, only a pure test sample was collected.

Comparative Example 3

(49) Sodium carbonate (Na.sub.2CO.sub.3), manganese oxalate.hydrate (MnC.sub.2O.sub.4.2H.sub.2O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO.sub.3), and ammonium phosphate (NH.sub.4H.sub.2PO.sub.4) were introduced in predetermined amounts with respect to the total amount of 10 g, and uniformly mixed by ball milling for 6 hours.

(50) The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 600° C. for 3 hours under an argon gas atmosphere. Then, the resulting Na.sub.2MnPO.sub.4F was precipitated in acetonitrile including 3 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a reaction temperature of 80° C. After the completion of the reaction, the resultant test sample was collected, washed with anhydrous ethanol, and subsequently dried so as to remove the remaining impurities. Then, only a pure test sample was collected.

Comparative Example 4

(51) Sodium carbonate (Na.sub.2CO.sub.3), manganese oxalate.hydrate (MnC.sub.2O.sub.4.2H.sub.2O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO.sub.3), and ammonium phosphate (NH.sub.4H.sub.2PO.sub.4) were introduced in predetermined amounts with respect to the total amount of 10 g, and uniformly mixed by ball milling for 6 hours.

(52) The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 550° C. for 6 hours under an argon gas atmosphere. Then, the resulting Na.sub.2MnPO.sub.4F was precipitated in acetonitrile including 3 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a reaction temperature of 80° C. After the completion of the reaction, the resulting test sample was collected, washed with anhydrous ethanol, and subsequently dried so as to remove the remaining impurities. Then, only a pure test sample was collected.

Comparative Example 5

(53) Sodium carbonate (Na.sub.2CO.sub.3), manganese oxalate.hydrate (MnC.sub.2O.sub.4.2H.sub.2O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO.sub.3), and ammonium phosphate (NH.sub.4H.sub.2PO.sub.4) were introduced in predetermined amounts with respect to the total amount of 10 g, and uniformly mixed by ball milling for 6 hours.

(54) The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 550° C. for 3 hours under an argon gas atmosphere. Then, the resulting Na.sub.2MnPO.sub.4F was precipitated in acetonitrile including 3 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a reaction temperature of 80° C. After the completion of the reaction, the resulting test sample was collected, washed with anhydrous ethanol, and subsequently dried so as to remove the remaining impurities. Then, only a pure test sample was collected.

Experimental Example 1: Test on Performance of an Electrode

(55) The primary particle size of cathode materials prepared from Experimental Example 1, and Comparative Examples 1 and 2 was measured, and metal composition within the cathode materials was analyzed by ICP emission spectrochemical analysis. The results are noted in Table 1.

(56) TABLE-US-00001 TABLE 1 Composition analysis LiBr result (molar ratio) molarity Primary particle size Li Na Mn PO.sub.4 Exp. 1 3.0M 300 nm 2.0 0 1.0 1.0 Comp. Exp. 1 3.0M 2 μm 0 2.0 1.0 1.0 Comp. Exp. 2 3.0M 1 μm 0 2.0 1.0 1.0 Comp. Exp. 3 3.0M 800 nm 0.2 1.8 1.0 1.0 Comp. Exp. 4 3.0M 700 nm 0.35 1.65 1.0 1.0 Comp. Exp. 5 3.0M 500 nm 0.4 1.6 1.0 1.0

(57) The cathode material from Example 1, which had a primary particle size of 300 nm, was prepared into Li.sub.2MnPO.sub.4F by ion exchange between lithium and sodium. It was found that ion exchange did not occur in cathode materials having a primary particle size of 1 μm or more (i.e., from Comparative Examples 1 to 3). In cathode materials having a primary particle size of 500 nm to 800 nm (i.e., from Comparative Examples 3 to 5), it was found that when ion exchange was carried out using the same lithium source (i.e., 3 M LiBr), only a small amount of lithium was reacted and exchanged.

(58) Accordingly, it was found that in order to intercalate lithium into Na.sub.2MnPO.sub.4F through a chemical method, such as ion exchange, it is important to control the particle size. According to the invention, the particle size was controlled by carrying out by controlling the ball milling and heat treatment conditions; however, one of ordinary skill in the art will understand that these conditions may vary according to the types of devices and procedures used for the aforementioned methods. The important aspect is that the ability to obtain Li.sub.2MnPO.sub.4F through complete substitution of two lithiums is efficient only when the primary particle size is controlled to a predetermined size or less.

(59) By using powder of the cathode material composite from Example 1, 95 wt % of cathode material composite was mixed with 5 wt % of binding agent PVdF, and then a slurry was prepared by using N-methyl pyrrolidone (NMP) as a solvent.

(60) The slurry was applied to aluminum (Al) foil with a thickness of 20 μm, and then dried and consolidated by press. The resulting product was dried under a vacuum at 120° C. for 16 hours, so as to provide a circular electrode with a diameter of 16 mm.

(61) As a counter electrode, a lithium metal foil punched with a diameter of 16 mm was used, and a polypropylene (PP) film was used as a separator. Also, as an electrolyte, a solution containing 1 M LiPF.sub.6 in ethylene carbonate (EC) and dimethoxy ethane (DME) mixed in a ratio of 1:1 (v/v) was used. The electrolyte was impregnated in the separator, and the separator was positioned between the operating electrode and the counter electrode. Then, the electrode performance of a battery was tested by using a case (SUS) as an electrode test cell. The measurement results including discharge capacity are noted in Table 2 below.

(62) TABLE-US-00002 TABLE 2 Discharge capacity at room temperature Discharge voltage (mAhg.sup.−1) (V) Example 1 120 2.0 222 1.0

(63) As shown in FIG. 1, when the surface of a test sample was observed by an electron microscope before and after ion exchange treatment, it was observed that the surface of the test sample became rough after ion exchange due to deintercalation of sodium and intercalation of lithium.

(64) The results of the test of electrochemical characteristics revealed a capacity of 120 mAhg.sup.−1 at a discharge cut-off voltage of 2.0 V, and a capacity of 222 mAhg.sup.−1 at a discharge cut-off voltage of 1.0 V.

(65) Charge/discharge curve graphs of a battery including the cathode material from Example 1, at room temperature, are shown in FIGS. 2 and 3. Also, as shown in FIG. 4, charge/discharge curve graphs of a battery including the cathode material from Example 1, at a high temperature (60° C.), show that the potential plateau is 3.9 V. Accordingly, the cathode material of the invention, lithium manganese fluorophosphate Li.sub.2MnPO.sub.4F, synthesized through an ion exchange method, can be subjected to charge/discharge by electrochemical intercalation/deintercalation of lithium; consequently, the cathode material displays a sufficient discharge capacity.

(66) The invention has been described in detail with reference to exemplary thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.