Lithium secondary battery negative electrode active material and method for manufacturing same

Abstract

The teachings herein are directed at a lithium secondary battery negative electrode active material consisting of a Sn Sb based sulfide that delivers a high electrode capacity density, excellent output characteristics, and excellent cycle life characteristics and also provide a method for manufacturing the lithium secondary battery negative electrode active material, said method being capable of easily manufacturing the high performance lithium secondary battery negative electrode active material at low cost without requiring a high-temperature processing step and special facilities as required in a glass melting method. The negative electrode active material preferably is prepared using a method that includes a step of obtaining a Sn Sb based sulfide precipitate by adding an alkali metal sulfide to a mixed solution of a tin halide and an antimony halide.

Claims

1. A negative electrode for a lithium secondary battery comprising: a negative electrode active material containing a precipitate including an SnSb based sulfide obtained by adding alkali metal sulfide to a mixed solution of tin halide and antimony halide in a solvent, the solution further containing an organic acid, wherein the SnSb based sulfide has a disordered crystal structure which is in an intermediate state of a crystal and an amorphous; wherein the SnSb based sulfide includes 10 to 90 mole percent Sn based on the total moles of Sn and Sb; and wherein the organic acid includes tartaric acid, citric acid, malic acid, lactic acid, gluconic acid, succinic acid, fumaric acid, maleic acid, formic acid, valeric acid, acetic acid, ascorbic acid, or an amino acid.

2. The negative electrode according to claim 1, wherein the negative electrode active material includes a compound powder including a first component particle surface coated with a second component including the SnSb based sulfide, wherein the first component is an element or a compound comprising the element capable of occluding a lithium ion in early charge, and occluding and releasing the lithium ion in the subsequent charge and discharge.

3. The negative electrode according to claim 2, wherein a ratio of the first component to the SnSb based sulfide in the compound powder is the first component: 10 to 80 mass % and the SnSb based sulfide: 90 to 20 mass %, given the total of the both is 100 mass %.

4. The negative electrode according to claim 3, wherein a particle diameter D50 of the first component by a laser diffraction/a dispersion-type particle size distribution method is 0.1-20 micrometer.

5. The negative electrode according to claim 2, wherein a particle diameter D50 of the first component by a laser diffraction/a dispersion-type particle size distribution method is 0.1-20 micrometer.

6. The negative anode of claim 1, wherein the negative electrode active material has a conductive auxiliary agent, wherein the conductive auxiliary agent includes: i) a carbon based material selected from the group consisting of an acetylene black (AB), a ketjen black (KB), a carbon fiber (VGCF), a carbon nanotube (CNT), a graphene, and a soft carbon; or ii) an element selected from the group consisting of Li, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, W, Pb, and Bi.

7. The negative anode of claim 1, wherein the negative electrode active material is prepared without melting the precipitate.

8. The negative electrode of claim 1, wherein the solvent includes water, an alcohol, a ketone, an organic acid ester, or a hydrocarbon.

9. A method of manufacturing a negative electrode including a negative electrode active material for a lithium secondary battery including a precipitate containing SnSb based sulfide, comprising a step of obtaining a precipitate of SnSb based sulfide by adding alkali metal sulfide to a mixed solution of tin halide and antimony halide in a solvent, the solution further containing an organic acid, wherein the negative electrode includes the precipitate; the SnSb based sulfide includes 10 to 90 mole percent Sn based on the total moles of Sn and Sb; and the organic acid includes tartaric acid, citric acid, malic acid, lactic acid, gluconic acid, succinic acid, fumaric acid, maleic acid, formic acid, valeric acid, acetic acid, ascorbic acid, or an amino acid.

10. The method of manufacturing a negative electrode active material for lithium secondary battery according to claim 9, wherein the amount of alkali metal sulfide to be added is 1-4 mol with respect to 1 mol of the total amount of tin halide and antimony halide.

11. The method of manufacturing a negative electrode active material for lithium secondary battery according to claim 10, comprising: producing a compound powder with a first component particle surface being coated with a second component including the SnSb based sulfide by dispersing the first component powder in a mixed solution of tin halide and antimony halide, and subsequently adding an alkali metal sulfide solution into the mixed solution, or producing a compound powder with a first component particle surface being coated with a second component including the SnSb based sulfide by dispersing the first component powder in an alkali metal sulfide solution and subsequently adding the mixed solution of tin halide and antimony halide into the alkali metal sulfide solution, wherein the first component is an element or a compound comprising the element capable of occluding a lithium ion in early charge, and occluding and releasing the lithium ion in the subsequent charge and discharge.

12. The method of manufacturing a negative electrode active material for lithium secondary battery according to claim 9, comprising: producing a compound powder including a first component particle surface being coated with a second component including the SnSb based sulfide by dispersing the first component powder in a mixed solution of tin halide and antimony halide, and subsequently adding an alkali metal sulfide solution into the mixed solution, or producing a compound powder including a first component particle surface being coated with a second component including the by dispersing the first component powder in an alkali metal sulfide solution and subsequently adding the mixed solution of tin halide and antimony halide into the alkali metal sulfide solution, wherein said first component is an element or a compound comprising the element capable of occluding a lithium ion in early charge, and occluding and releasing the lithium ion in the subsequent charge and discharge.

13. The method of manufacturing a negative electrode active material for lithium secondary battery according to claim 12, wherein a ratio of the first component to the SnSb based sulfide in said compound powder is the first component: 10 to 80 mass % and the SnSb based sulfide: 90 to 20 mass %, given the total of the both is 100 mass %.

14. The method of manufacturing a negative electrode active material for lithium secondary battery according to claim 12, a particle diameter D50 of the first component by a laser diffraction/a dispersion-type particle size distribution method is 0.1-20 micrometer.

15. The method of manufacturing a negative electrode active material for lithium secondary battery according to claim 12, wherein the mixed solution of tin halide and antimony halide further contains an conductive auxiliary agent and/or a binding agent to produce a compound powder, wherein the first component particle surface is coated with SnSb based sulfide and the conductive auxiliary agent and/or the binding agent is contained in the SnSb based sulfide.

16. The method of claim 9, wherein the negative electrode active material has a conductive auxiliary agent, wherein the conductive auxiliary agent includes: i) a carbon based material selected from the group consisting of an acetylene black (AB), a ketjen black (KB), a carbon fiber (VGCF), a carbon nanotube (CNT), a graphene, and a soft carbon; or ii) an element selected from the group consisting of Li, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, W, Pb, and Bi.

17. The method of claim 9, wherein the negative electrode active material is prepared without melting the precipitate.

18. The method of claim 9, wherein the solvent includes water, an alcohol, a ketone, an organic acid ester, or a hydrocarbon.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a XRD pattern of variety kinds of precipitates.

(2) FIG. 2 is a XRD pattern of SnSb based sulfides of Examples 1-5.

(3) FIG. 3 is a cycle life characteristic of the negative electrode using the SnSb based sulfide of Examples 1-3, and 5 as an active material.

(4) FIG. 4 is a charge-and-discharge curve of the negative electrode using the SnSb based sulfide of Example 1 as an active material.

(5) FIG. 5 is a charge-and-discharge curve of the negative electrode using the SnSb based sulfide of Example 2 as an active material.

(6) FIG. 6 is a charge-and-discharge curve of the negative electrode using the SnSb based sulfide of Example 3 as an active material.

(7) FIG. 7 is a charge-and-discharge curve of the negative electrode using the SnSb based sulfide of Example 5 as an active material.

(8) FIG. 8 is a charge-and-discharge curve of the negative electrode using the SnSb based sulfide of Example 6 as an active material.

(9) FIG. 9 is a charge-and-discharge curve of the negative electrode using the SnSb based sulfide of a comparative example 1 as an active material.

DETAILED DESCRIPTION OF THE INVENTION

(10) Embodiments of the negative electrode active material for lithium secondary battery and its manufacturing method according to the present invention will be described below.

(11) The negative electrode active material for lithium secondary battery containing the SnSb based sulfide of the present invention is obtained by a step of obtaining a precipitate of SnSb based sulfide by adding alkali metal sulfide to a mixed solution of tin halide and antimony halide.

(12) Addition of alkali metal sulfide to the mixed solution of tin halide and antimony halide causes precipitation of the SnSb based sulfide. This precipitate can be filtered and dried to give a SnSb based sulfide. This SnSb based sulfide is used as a negative electrode active material of lithium secondary battery, so that it can have the same degree of battery performance as a SnSb based sulfide glass obtained by a glass melting method. The negative electrode using this SnSb based sulfide is less likely to rapidly generate heat in an internal short circuit test, such as nail penetration, resulting in improvement of battery safety.

(13) A solvent of the mixed solution of tin halide and antimony halide can be, but not particularly limited to, water, alcohols, ketones, organic acids, organic acid esters, and hydrocarbons. When, for example, tin halide is tin chloride (SnCl.sub.2), antimony halide is antimony chloride (SbCl.sub.3), and alkali metal sulfide is sodium sulfide (Na.sub.2S), SnS and Sb.sub.2S.sub.3 can precipitate simultaneously to compound a SnSb co-precipitate by a reaction of the following formula 1.
2SnCl.sub.2+2SbCl.sub.3+4Na.sub.2S.fwdarw.SnS+Sb.sub.2S.sub.3+8NaCl(formula 1)

(14) A ratio of Sn and Sb in the above-mentioned mixed solution is preferably, but not limited to, Sn: 10 to 90 mol %, and more preferably 10 to 70 mol %, with respect to the total amount 100 mol % of Sn and Sb. If the ratio of Sn exceeds 90 mol %, its capacity decreases as the cycle proceeds, which is not preferable.

(15) In the manufacturing method of the present invention, it is preferable that the mixed solution of the tin halide and antimony halide further contains an organic acid.

(16) The organic acid is a substance of acidic property (acidity) among substances combined with an organic in which a carbon is a principal component.

(17) The organic acid includes, but not specifically limited to, for example a tartaric acid, citric acid, malic acid, lactic acid, gluconic acid, succinic acid, fumaric acid, maleic acid, formic acid, valeric acid, stearic acid, acetic acid, ascorbic acid, amino acid, etc.

(18) It is not easy to dissolve tin halides, especially SbCl.sub.3, into water just by adding water and stirring it, thus requiring long-term dissolving time. For example, if SnCl.sub.2 and SbCl.sub.3 are dissolved simultaneously, precipitates of Sb.sub.2S.sub.3 with a large particle diameter are generated since SbCl.sub.3 is hard to dissolve, often resulting in ununiform powders.

(19) In order to address this issue, the solubility of various halides can be improved by an addition of the organic acid. This allows for shortening of the time required for the dissolution and obtaining of uniform SnSb based sulfide powders.

(20) Also, efficient disordered crystallization of the SnSb based sulfide can be achieved by the addition of the organic acid. The disordered crystal refers to a substance in the intermediate state between a crystal and an amorphous. Taking antimony sulfide as an example, it has a structure wherein an antimony array is regular but a location and an array of a sulfur element around the antimony are random, and the antimony element exhibiting crystal structure and the sulfur element exhibiting amorphous structure are mixed in one substance. The disordered crystal provides a broad or weak diffraction peak in X-ray diffraction analysis.

(21) In order to examine what kinds of effects the addition of the organic acid has on the obtained SnSb based sulfide, an organic acid with a tartaric acid added and an organic acid without the tartaric acid were prepared, and then a XRD measurement was performed. XRD patterns of various precipitates are shown in FIG. 1.

(22) A tin sulfide-derived peak was observed for the precipitates obtained by mixing SnCl.sub.2 aqueous solution and Na.sub.2S aqueous solution. An antimony sulfide peak was observed for the precipitates obtained by mixing SbCl.sub.3 aqueous solution and Na.sub.2S aqueous solution.

(23) On the other hand, it was found out that a XRD pattern became broad in precipitates obtained by mixing SbCl.sub.3 aqueous solution and Na.sub.2S aqueous solution with the tartaric acid added, and that the precipitates have a specific effect, the disordered crystallization of the precipitates.

(24) Precipitates obtained by mixing the mixed aqueous solution of SnCl.sub.2 and SbCl.sub.3 added with the tartaric acid and Na.sub.2S aqueous solution had a XRD pattern substantially consistent with that of the SnSb based sulfide produced by a glass melting method. Accordingly, the manufacturing method by the precipitation of the present invention proved to be capable of preparing the sulfides.

(25) In the manufacturing method of the present invention, it is preferable that the amount of alkali metal sulfide to be added is 1-4 mol with respect to 1 mol of the total amount of tin halide and antimony halide.

(26) If the amount of the alkali metal sulfides to be added is less than 1 mol with respect to a total amount of 1 mol of the tin halide and antimony halide, a precipitation reaction is less likely to progress, causing the obtained SnSb based sulfide to contain a lot of unreacted substances. On the other hand, if the amount of the alkali metal sulfides to be added is more than 4 mol with respect to a total amount of 1 mol of the tin halide and antimony halide, the deposited sulfide disappears and the desired SnSb based sulfide cannot be obtained.

(27) The precipitates of the SnSb based sulfide may be obtained by any one of the following steps of:

(28) (1) producing a compound powder with A component particle surface being coated with SnSb based sulfide by dispersing A component powder in a mixed solution of tin halide and antimony halide, and subsequently adding an alkali metal sulfide solution into the mixed solution to produce, or

(29) (2) producing a compound powder with A component particle surface being coated with SnSb based sulfide by dispersing A component powder in an alkali metal sulfide solution and subsequently adding the mixed solution of tin halide and antimony halide into the alkali metal sulfide solution,

(30) Wherein the A component is an element or a compound comprising the element which can occlude a lithium ion in early charge and occlude and release the lithium ion in the subsequent charge and discharge.

(31) The A component may be a primary particle itself or also be an aggregated secondary particle etc. The SnSb based sulfide may be completely coated on the entire surface of the A component, or may be coated on only a part of the A component. If it is coated on only a part of the A component, 25% or more of the surface area of the A component should only be coated with the SnSb based sulfide. In the present invention, the ratio of the A component coated with the SnSb based sulfide can be measured from the ratio of the surface of the A component particle covered with the SnSb based sulfide using, for example, s SEM photograph.

(32) The A component contained in the compound powder may be at least one or more kinds of an element selected from the group consisting of, but not specifically limited to, for example, Li, Na, C, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, W, Pb, and Bi, or an alloy, oxide, chalcogenide, or halide using these elements, as long as the A component can occlude lithium ions in the early charge and occlude and release the lithium ions in the subsequent charge and discharge. From a perspective that the region of discharge plateau can be observed within the range of 0-1V (with respect to electric potential for lithium), at least one or more kinds of an element selected from the group consisting of Li, C, Mg, Al, Si, Ti, Zn, Ge, Ag, In, Sn, and Pb, or an alloy, oxide, chalcogenide, or halide using these elements are preferable among them. Furthermore, from a perspective of energy density, Al, Si, Zn, Ge, Ag, and Sn, etc. are preferable as an element, each combination such as SiAl, AlZn, SiMg, AlGe, SiGe, SiAg, SiSn, ZnSn, GeAg, GeSn, GeSb, AgSn, AgGe, and SnSb, etc are preferable as an alloy, SiO, SnO, SnO.sub.2, SnC.sub.2O.sub.4, and Li.sub.4Ti.sub.5O.sub.12, etc. are preferable as an oxide, SnS, and SnS.sub.2, etc. are preferable as a chalcogenide, and SnF.sub.2, SnCl.sub.2, SnI.sub.2, and SnI.sub.4, etc. are preferable as a halide. Also, two or more kinds of these A components may be used.

(33) In the manufacturing method of the present invention, a ratio of A component to SnSb based sulfide in the compound powder is preferably A component: 10 to 80 mass % and SnSb based sulfide: 90 to 20 mass %, given the total of the both is 100 mass %.

(34) Furthermore, it is more preferable that the A component is 20 to 70 mass % and the SnSb based sulfide is 80 to 30 mass %.

(35) For example, in the case where the A component is Si, when the A component (Si) is 10-35 mass % and the SnSb based sulfide is 90-65 mass %, the capacity per active material weight is 400-1,600 mAh/g and the cycle life characteristics is highly improved. Thus, the active material is promising as a long life type of negative electrode. On the other hand, when the A component (Si) is 35-80 mass % and the SnSb based sulfide is 65-20 mass %, the capacity per active material weight is as very high as 1300-3500 mAh/g. Thus, the active material is promising as a high capacity type of negative electrode.

(36) In the manufacturing method of the present invention, the particle diameter D50 by the laser diffraction/dispersion type particle size distribution method of the A component is preferably 0.1-20 micrometer.

(37) If it is less than 0.1 micrometer, the A component is easy to aggregate, often resulting in ununiform compound powders. If it is more than 20 micrometer, a crack is generated in the A component in charging and discharging, thereby decreasing the cycle life.

(38) In the manufacturing method of the present invention, the step of generating compound powders is preferably a step of generating compound powders with the mixed solution of the tin halide and antimony halide further containing a conductive auxiliary agent and/or binding agent, wherein the A component particle surface is coated with SnSb based sulfide and the conductive auxiliary agent and/or the binding agent is contained in the SnSb based sulfide.

(39) It is preferable to use, but not specifically limited to, a carbon black as a conductive auxiliary agent, since a metal or conductive polymer possibly reacts with the SnSb based sulfide. The carbon black includes an acetylene black (AB), ketjen black (KB), carbon fiber (VGCF), carbon nanotube (CNT), graphite, graphene, soft carbon, hard carbon, etc.

(40) When the SnSb based sulfide is 100 mass %, the content of the conductive auxiliary agent is preferably 0.1-10 mass %, and more preferably 0.5-5 mass % for 100 mass %. If the content is 0.1 to 10 mass %, a sufficient conductive improvement effect is achieved, allowing for an improvement of high rate discharging characteristic and holding capacity lowering to a minimum due to falling of the SnSb based sulfide from the A component. If a conducting agent with high cohesiveness, for example, the carbon black is used among the above-mentioned conductive auxiliary agents, it is preferable to disperse the conductive auxiliary agent by an agitator or supersonic wave, etc.

EXAMPLE

(41) Hereinafter, the present invention will be explained more specifically by Examples but is not limited to these Examples.

(42) (1) Preparation of SnSb Based Sulfide

(43) In order to make a predetermined ratio of Sn and Sb showing in Table 1 below, a tin chloride (SnCl.sub.2) aqueous solution was mixed with an antimony chloride (SbCl.sub.3) aqueous solution to produce a tin-antimony chloride aqueous solution. The amount of tartaric acid as shown in Table 1 was added to this tin-antimony chloride aqueous solution, and then a sodium sulfide aqueous solution containing the amount of sodium sulfide (Na.sub.2S) as shown in Table 1 was mixed with the solution to prepare precipitates of the SnSb based sulfide.

(44) TABLE-US-00001 TABLE 1 Sn:Sb Tartaric (Molar Ratio) SnCl.sub.22H.sub.2O SbCl.sub.3 NA.sub.2S Acid Example 1 90:10 8.148 g 0.494 g 3.5 g 4.160 g Example 2 70:30 6.370 g 1.448 g 4.2 g 4.104 g Example 3 50:50 4.982 g 2.341 g 5.08 g 4.069 g Example 4 30:70 1.384 g 1.584 g 5.38 g 4.201 g Example 5 10:90 0.500 g 2.185 g 6.48 g 4.000 g

(45) XRD patterns of the obtained precipitates of the SnSb based sulfide in Examples 1-5 are shown in FIG. 2. In the SnSb based sulfides of Examples 1-5, no sharp peak derived from Sb.sub.2S.sub.3 or SnS.sub.2 is observed and the disordered crystallization can be found.

(46) (2) Preparation of SnSb Based Sulfide with A Component Added

(47) In order to make a predetermined ratio of Sn and Sb showing in Table 2 below, a tin chloride (SnCl.sub.2) aqueous solution was mixed with an antimony chloride (SbCl.sub.3) aqueous solution to produce a tin-antimony chloride aqueous solution. The amount of tartaric acid as shown in Table 2 was added to this tin-antimony chloride aqueous solution, and then a sodium sulfide aqueous solution containing the amount of sodium sulfide (Na.sub.2S) and the A component as shown in Table 2 was mixed with the solution and dispersed to prepare precipitates of the SnSb based sulfide with the A component added.

(48) TABLE-US-00002 TABLE 2 Sn:Sb (Molar Tartaric Ratio) SnCl.sub.22H.sub.2O SbCl.sub.3 NA.sub.2S AComponent Acid Exam- 70:30 6.210 g 1.461 g 4.1 g 1.8 g 4.100 g ple 6 (A Compo- nent:Si) Exam- 70:30 6.217 g 1.442 g 4.1 g 3.0 g 4.100 g ple 7 (A Compo- nent:Si) Exam- 70:30 6.199 g 1.450 g 4.1 g 4.9 g 4.099 g ple 8 (A Compo- nent:Si) Exam- 70:30 6.215 g 1.447 g 4.1 g 1.9 g 4.080 g ple 9 (A Compo- nent:Sn) Exam- 70:30 6.200 g 1.444 g 4.1 g 1.8 g 4.011 g ple 10 (A Compo- nent:SiO)
(3) Preparation of SnSb Based Sulfide Glass

(49) A sulfur, antimony, tin, and germanium were blended so as to become 60:9:16:15 mol % and the contents were melted by heat treatment to produce a sulfide glass. As a heat treatment condition, after the sulfide glass was increasingly heated to a prescribed temperature with the heating rate of 20 C./hour, and then was kept at the same temperature for 12 hours. Then, it was naturally cooled down to the room temperature to be completed. The obtained sulfide was found to be vitrified according to the XRD measurement using a X-ray diffractometer (FIG. 1).

(50) Production of Test Negative Electrode

(51) The obtained precipitates of the SnSb based sulfide in Examples 1-10 were filtered, dried, and used as negative electrode active materials. Also, for a comparison, the above-mentioned SnSb based sulfide glass was used as a negative electrode active material in Comparative Example 1 and Si (made by Fukuda Metal: D50=1 micrometer) was used as a negative electrode active material in Comparative Example 2, respectively.

(52) These negative electrode active materials, a carbon powder agent (made from Lion Corporation: ECP300), and a polyimide binder were blended so as to become 80:5:15 mass %, and the slurried material was coated on a 10 micrometer thick of stainless foil and dried under reduced pressure at 250 C. to obtain a test negative electrode.

(53) Cell Testing

(54) A CR2032 coin cell equipped with a test negative electrode, a glass filter (GA-100), a metal lithium counter electrode, and a 1M LiPF.sub.6 (EC:DEC=50:50 vol %) electrolytic solution was used for a cell testing.

(55) The cycle life characteristics of the negative electrodes in Examples 1-10 and Comparative Examples 1-2 are summarized in Table 3. A charging and discharging test condition was set as environmental temperature: 30 C., cutoff potential: 0-1 (V, vs. Li.sup.+/Li), and charging and discharging current rate: 0.2 C. As an example, the cycle life characteristics of the negative electrodes in Examples 1-3, and 5 are shown in FIG. 3. Also, the charge and discharge curves in Examples 1-3, 5, and 6 and Comparative Example 1 are shown in FIGS. 4-9.

(56) In Example 1, high capacity was seen because of the relatively high ratio of Sn, while capacity lowering was gradually found as the cycle proceeds. On the other hand, in each sample of Examples 2, 3, and 5, relatively stable capacity was seen, and high capacity was seen in Example 2 among them.

(57) In Examples 6-10, further higher capacity could be achieved as compared with Example 3, since the A component was added to the component of Example 3.

(58) TABLE-US-00003 TABLE 3 Discharging Capacity 1 cycle 10 cycle 100 cycle Example 1 439 mAh/g 396 mAh/g 378 mAh/g Example 2 362 mAh/g 322 mAh/g 314 mAh/g Example 3 347 mAh/g 283 mAh/g 271 mAh/g Example 4 230 mAh/g 196 mAh/g 189 mAh/g Example 5 116 mAh/g 78 mAh/g 77 mAh/g Example 6 1070 mAh/g 858 mAh/g 705 mAh/g Example 7 1280 mAh/g 1005 mAh/g 761 mAh/g Example 8 1510 mAh/g 1104 mAh/g 785 mAh/g Example 9 590 mAh/g 466 mAh/g 371 mAh/g Example 10 850 mAh/g 680 mAh/g 612 mAh/g Comparative 583 mAh/g 570 mAh/g 553 mAh/g Example 1 Comparative 3263 mAh/g 2530 mAh/g 245 mAh/g Example 2

INDUSTRIAL APPLICABILITY

(59) The negative electrode active material obtained by the manufacturing method of the present invention has the equivalent performance to the negative electrode active material obtained by the glass melting method, and the manufacturing method of the present invention requires no high temperature processing steps or special facilities as needed in the conventional glass melting method and allows for easy production at low cost, such that it can be conveniently utilized for use in main power supplies, etc., of, for example, a mobile communication device, a portable electronic device, a battery-assisted bicycle, a battery-assisted two-wheeled vehicle, and an electric vehicle.