Non-aqueous electrolyte secondary battery

Abstract: The present invention provides a non-aqueous electrolyte secondary battery having an anode active material with a high capacity and excellent cycle characteristics. The active material comprises a salt generated reacting a metal or a semi-metal and a compound selected from the group consisting of oxo-acids, thiocyanic acid, cyanogen, and cyanic acid, wherein each said oxo-acid comprises an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, tellurium, tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium, salts of said oxo-acids of phosphorus and boron being restricted to hydrogenphosphates and hydrogenborates.

Description: BACKGROUND OF THE INVENTION The present invention relates to an improvement in anodes of non-aqueous electrolyte secondary batteries. Non-aqueous electrolyte secondary batteries including lithium or a lithium compound for the anode are expected to have a high voltage and high energy density, and therefore, they are extensively studied. Known cathode active materials for the non-aqueous electrolyte secondary batteries are oxides and chalcogens of transition metals, such as LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , V 2 O 5 , Cr 2 O 5 , MnO 2 , TiS 2 , MoS 2 and the like. These compounds have a layered or tunneled crystal structure to allow lithium ions to freely intercalate and deintercalate. The use of metallic lithium for the anode active material has intensively been examined. Such use, however, has a drawback; lithium dendrite occurring on the surface of metallic lithium in the course of charging results in lowering the charge-discharge efficiency and may come into contact with the cathode to cause an inner short circuit. In order to solve this problem, the potentials for application of lithium alloys, such as lithium-aluminum, which can depress the growth of lithium dendrite and absorb and desorb lithium, for the anode have been studied. However, when lithium alloys are used for the anode, repeated charge and discharge causes pulverization of the alloys, posing a problem of poor cycle life characteristics. There are proposals for solving this problem by inhibiting pulverization of the alloys by including additional elements in the lithium-aluminum alloy (for example, Japanese Laid-Open Patent Publication Sho 62-119856 and Hei 4-109562), although the improvement is not sufficient. Lithium ion batteries recently developed have anodes composed of carbon material that reversibly intercalates and deintercalates lithium and has excellent cycle characteristics and safety though having a smaller capacity than those of the anode active materials mentioned above. With a view to enhancing the capacity, a number of studies have proposed application of oxides for the anode; for example, crystalline oxides, such as SnO and SnO 2 (Japanese Laid-Open Patent Publication Hei 7-122274 and Hei 7-235293) and amorphous oxides, such as SnSiO 3 , SnSi 1-x P x O 3 (Japanese Laid-Open Patent Publication Hei 7-288123). These oxides, however, do not sufficiently improve the characteristics. SUMMARY OF THE INVENTION The object of the present invention is thus to provide an anode for non-aqueous electrolyte secondary batteries having excellent charge-discharge cycle characteristics. The present invention provides an anode that absorbs lithium in the course of charging not to cause dendrite formation and has a large electric capacity and an excellent cycle life. The present invention is directed to a non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, the anode having an active material that comprises a salt which is formed of a metal or a semi-metal and a compound selected from the group consisting of an oxo-acid, thiocyanic acid, cyanogen, and cyanic acid, wherein each of said oxo-acids comprises an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, tellurium, tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium, and wherein said metal or semi-metal constituting the metal salt or the semi-metal salt is at least one selected from the group consisting of Al, Sn, Si, Pb, Cd, Bi, In, Zn, Mg, Ge, Ga, Ca, Ba, Ir, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, and Nb. Especially preferable are Sn, Pb, In, and Bi. The present invention gives a non-aqueous electrolyte secondary battery that is free from a short circuit due to dendrites and has a high energy density, an excellent cycle life, and a high reliability. While the novel features of the invention are set forth particularly in the appended claims, the invention, both as to organization and content, will be better understood and appreciated, along with other objects and features thereof, from the following detailed description taken in conjunction with the drawings. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING Fig. 1 is a vertical sectional view schematically illustrating a test cell used for evaluating the electrode characteristics of active materials in accordance with the present invention. Fig. 2 is a vertical sectional view schematically illustrating a cylindrical battery including an anode in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION As discussed above, the anode of the present invention comprises a metal salt or a semi-metal salt of a specific acid or cyanogen. In the following description, salts of a divalent metal M II are given as examples. Salts of nitrogen oxo-acids include nitrates M II (NO 3 ) 2 and nitrites M II (NO 2 ) 2 . Salts of sulfur oxo-acids include sulfates M II SO 4 , sulfites M II SO 3 , disulfates M II S 2 O 7 , peroxomonosulfates M II SO 5 , peroxodisulfates M II S 2 O 8 , thiosulfates M II S 2 O 3 , disulfites M II S 2 O 5 , thiosulfites M II S 2 O 2 , hydrogensulfates such as M II (HSO 4 ) 2 , thionates such as dithionates M II S 2 O 6 and dithionites M II S 2 O 4 , sulfoxylates such as M II SO 2 , and hydrogen-containing acid salts. Preferable salts of phosphorus oxo-acids include hydrogenphosphates such as M II HPO 4 and M II (H 2 PO 4 ) 2 , phosphinates M II (PH 2 O 2 ) 2 , and phosphonates M II PHO 3 . Salts of carbon oxo-acids include carbonates M II CO 3 and hydrogencarbonates M II (HCO 3 ) 2 . Preferable salts of boron oxo-acids include hydrogenborates such as M II (H 2 BO 3 ) 2 and M II HBO 3 . Salts of selenium oxo-acids include selenates M II SeO 4 , selenites M II SeO 3 , M II SeO 5 , hydrogenselenates M II (HSeO 4 ) 2 , and hydrogenselenites M II (HSeO 3 ) 2 . Salts of tellurium oxo-acids include tellurates such as M II 3 TeO 6 and M II TeO 4 , and hydrogentellurates such as M II 5 (H 5 TeO 6 ) 2 , M II 2 H 2 TeO 6 , M II 3 (H 3 TeO 6 ) 2 , and M II H 4 TeO 6 . Available thiocyanates include M II (SCN) 2 , while available cyanides and cyanates include M II (CN) 2 and M II (ONC) 2 . The metal salt and the semi-metal salt of the present invention are, however, not restricted to the above chemical compositions. Among the above salts, sulfates, hydrogensulfates, carbonates, hydrogenborates, and hydrogenphosphates are preferable for the improvement in cycle characteristics. The following gives salts of oxo-acids of transition elements W, Mo, Ti, Zr, Nb, Ta, Mn, and V as examples. In the following formulae, M III represents a trivalent metal or semi-metal. Available tungstates include M II WO 4 , M II WO 3 , M III WO 6 . Available molybdates include M II MoO 4 and M III Mo 4 O 6 . Available titanates include M II TiO 3 , M II TiO 4 , (M III ) 2 TiO 5 , and M II Ti 3 O 7 . Available zirconates include M II ZrO 3 and M II ZrO 4 . Available chromates include M III CrO 3 , M II CrO 4 , M II Cr 2 O 4 , and (M III ) 2 CrO 6 . Available niobates include M III NbO 4 , M II Nb 2 O 6 , and (M III ) 2 Nb 2 O 7 . Available tantalates include M III TaO 4 and (M II ) 2 Ta 2 O 7 . Available manganates include M II MnO 3 , (M III ) 2 MnO 4 , and (M III ) 2 MnO 6 . Available vanadates include M III VO 4 , (M III ) 2 VO 5 , and M II V 2 O 6 . Preferable are chromates,. tungstates, molybdates, vanadates, manganates, and tantalates, and especially preferable are chromates, tungstates, and molybdates for the improvement in cycle characteristics. The metal salt and the semi-metal salt of the present invention are, however, not restricted to the above chemical compositions. The present inventors have made an intensive study on the availability of various metal salts and semi-metal salts as the negative electrode material. It was found that such compounds can serve as the negative electrode materials with a high capacity and exceptional cycle life characteristics that have a crystal structure in which the metal or semi-metal is surrounded by a) anions including oxygen and any one of the elements nitrogen, sulfur, phosphorus, carbon, boron, selenium, and tellurium, such as anions of oxo-acids of nitrogen, sulfur, phosphorus, carbon, boron, selenium and tellurium or by anions further including hydrogen such as hydrogen-containing oxo-acids; b) cyanide anions containing nitrogen and carbon; c) cyanate anions containing nitrogen, carbon and oxygen; or d) thiocyanate anions containing nitrogen, carbon and sulfur and in which those anions are bonded to the metal or semi-metal by ionic force. The present inventors also discovered that such compounds can also serve as the negative electrode materials with a high capacity and superb cycle life characteristics that have a crystal structure in which the metal or semi-metal is surrounded by anions of oxo-acids of a transition element including oxygen and any one of tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese and vanadium, that is, tungstates, molybdates, titanates, zirconates, chromates, niobates, tantalates, manganates and vanadates. The prior art metal oxides have the greater tendency of covalent bonding and tougher skeletons than those of the metal salts and semi-metal salts in accordance with the present invention. While the prior art metal oxides are presumed to be relatively brittle under the conditions of expansion and contraction accompanied by intercalation and deintercalation of a large amount of lithium, however, the metal salts and semi-metal salts of the present invention are expected to be relatively tough under the conditions of expansion and contraction accompanied by intercalation and deintercalation of a large amount of lithium. It is also found that the existence of hydrogen in the salts of oxo-acids further improves the cycle characteristics, although the details have not yet been elucidated. The chemical compositions of the metal salts and the semi-metal salts discussed above represent only examples of divalent or trivalent metals and semi-metals. Chemical compositions of metal salts and semi-metal salts of different valences should be apparent to the skilled in the art. For example, selenates can be expressed by the following general formulae as the metal salts and semi-metal salts of the valence m: M 2 (SeO 4 ) m , M 2 (SeO 3 ) m , M 2 (SeO 5 ) m , M(HSeO 4 ) m , and M(HSeO 3 ) m . Some examples in accordance with the present invention are given below, although the anode material of the present invention is not restricted to the chemical compositions discussed in these examples. Example 1 Test cells shown in Fig. 1 were manufactured and tested for evaluation of the electrode characteristics of various metal and semi-metal nitrates and nitrites specified in Tables 1 and 2 and used as the anode active material. Referring to Fig. 1, numeral 1 designates a test electrode composed of a molded mixture containing an active material. The test electrode 1 is arranged on the substantial center of a battery casing 2. A separator 3 of a micro-porous polypropylene film was placed on the test electrode 1. After injection of an electrolyte solution, the opening of the battery casing 2 is sealed with a sealing plate 6 having a counter electrode 4 composed of a metallic lithium disc of 17.5 mm in diameter on the inner surface thereof and a polypropylene gasket 5 on the circumference thereof. This completes a test cell. The mixture included 6 g of an active material powder, 3g of graphite powder as a conductive agent, and 1 g of polyethylene powder as a binding agent. The test electrode 1 was obtained by press molding 0.1 g of the mixture to a disc of 17.5 mm in diameter. The electrolyte used was prepared by dissolving lithium perchlorate (LiClO 4 ) at a concentration of 1 mol/l in a 1:1 mixed solution (volume ratio) of ethylene carbonate and dimethoxyethane. At a constant electric current of 2 mA, the test cell was subjected to cathode polarization (which corresponds to charging in case that the active material-containing electrode is considered as the anode) until the electrode potential became 0 V with respect to the lithium counter electrode. The test cell was then subjected to anode polarization (which corresponds to discharging) until the electrode potential became 1.5 V woth respect to the counter electrode. After the repeated cathode polarization and anode polarization, and the electrode characteristics were evaluated. For the purpose of comparison, electrodes were manufactured in the above manner using the known compounds shown in Table 3, that is, crystalline oxides WO 2 , Fe 2 O 3 , SnO, and PbO, sulfides SnS and PbS, and amorphous metal oxides SnSiO 3 and SnSi 0.8 P 0.2 O 3.1 , and test cells were assembled and tested under the same conditions for evaluation of the electrode characteristics. Tables 1 through 3 show the discharge capacities per one gram of the active material in the first cycle. The measurement proved that all the test cells of Example 1 were capable of being charged and discharged. After the conclusion of cathode polarization of these test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 1. The above experiments show that cathode polarization makes lithium absorbed in the electrodes including the active materials of Example 1 and anode polarization makes the absorbed lithium released from the electrodes, thereby causing no deposit of metallic lithium. The electrodes of Example 1 have higher capacities than those of the comparative examples. Cylindrical batteries shown in Fig. 2 were manufactured and tested for evaluation of the cycle characteristics of the batteries using various metal and semi-metal nitrates and nitrites of Example 1. Each battery was manufactured in the following manner. A cathode active material LiMn 1.8 Co 0.2 O 4 was prepared by mixing Li 2 CO 3 , Mn 3 O 4 , and CoCO 3 at a predetermined molar ratio, heating the mixture at 900 C, and classifying the mixture to or below 100 meshes. A paste was prepared by mixing 100 g of the cathode active material, 10 g of carbon powder as a conductive agent, and 8 g (as the resin) of aqueous dispersion of polyethylene tetrafluoride as a binding agent, and pure water. The paste was applied onto a titanium core member, dried, and rolled out to a cathode plate. An anode plate was manufactured by mixing a metal or semi-metal nitrate or nitrite as an active material, graphite powder as a conductive agent, and Teflon powder as a binding agent at the weight ratio of 60 : 30 : 10, adding a petroleum solvent to the mixture to yield a paste, applying the paste onto a copper core member, and drying it at 100 C. A micro-porous polypropylene film was used as a separator. A cathode plate 11 with a cathode lead 14 which is composed of the same material as that of the core member and attached to the cathode plate 11 by spot welding, an anode plate 12 with an anode lead 15 welded thereto, and a separator 13 having a greater width than those of these electrode plates 11 and 12 were wound in spirals to constitute an electrode group. Polypropylene insulating plates 16 and 17 were placed on the top and bottom of the electrode group, and the assembly was inserted into a battery casing 18. After formation of a step on the upper portion of the battery casing 18 and injection of the same non-aqueous electrolyte as that of the above-mentioned test cell, the battery casing 18 was sealed with a sealing plate 19 having an anode terminal 20. This completes a battery. The batteries constructed as above were subjected to a charge-discharge cycle test at a temperature of 30 °C and a charge-discharge current of 1 mA/cm 2 in a charge-discharge voltage range of 4.3 V to 2.6 V. A rate of the discharge capacity at the 100-th cycle to the discharge capacity at the second cycle (hereinafter referred to as capacity maintenance rate) was measured. Anode plates were prepared and test batteries were assembled in the above manner for the comparative examples. The cycle characteristics of the comparative examples were also evaluated under the same conditions. Tables 1 through 3 show the results of evaluation. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al(NO 3 ) 3 284 75 Al(NO 2 ) 3 326 73 Sn(NO 3 ) 4 346 86 Sn(NO 2 ) 4 389 84 Sn(NO 3 ) 2 485 84 Sn(NO 2 ) 2 510 82 Si(NO 3 ) 4 390 83 Si(NO 2 ) 4 435 84 Pb(NO 3 ) 2 356 83 Pb(NO 2 ) 2 394 82 Cd(NO 3 ) 2 320 78 Cd(NO 2 ) 2 336 77 Bi(NO 3 ) 3 298 78 Bi(NO 2 ) 3 324 75 In(NO 3 ) 3 346 78 In(NO 2 ) 3 375 75 Zn(NO 3 ) 2 289 75 Zn(NO 2 ) 2 326 79 Ga(NO 3 ) 3 335 75 Ga(NO 2 ) 3 362 72 Ge(NO 3 ) 4 367 74 Ge(NO 2 ) 4 400 72 Mg(NO 3 ) 2 296 81 Mg(NO 2 ) 2 334 79 Sb(NO 3 ) 3 425 75 Sb(NO 2 ) 3 433 73 Ti(NO 3 ) 4 275 80 V(NO 3 ) 2 255 84 Cr(NO 2 ) 3 285 82 Mn(NO 3 ) 2 263 83 Fe(NO 3 ) 2 274 81 Co(NO 3 ) 2 269 80 Ni(NO 3 ) 2 271 80 Cu(NO 3 ) 2 265 78 Mo(NO 3 ) 2 222 77 W(NO 3 ) 4 215 80 Nb(NO 3 ) 3 220 79 Ca(NO 3 ) 2 286 79 Ba(NO 3 ) 2 275 80 Ir(NO 3 ) 3 266 81 Sr(NO 3 ) 2 286 79 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Ba 0.33 Sn 0.67 (NO 3 ) 2 425 86 Ca 0.33 Sn 0.67 (NO 3 ) 2 433 85 Sr 0.33 Sn 0.67 (NO 3 ) 2 443 85 Mg 0.33 Sn 0.67 (NO 3 ) 2 435 85 Mn 0.22 Sn 0.78 (NO 3 ) 2 410 86 Fe 0.12 Sn 0.88 (NO 3 ) 2 451 85 Co 0.18 Sn 0.82 (NO 3 ) 2 444 87 Cu 0.18 Sn 0.82 (NO 3 ) 2 435 86 Ti 0.12 Sn 0.82 (NO 3 ) 2 436 85 Zn 0.12 Sn 0.88 (NO 3 ) 2 442 87 Cr 0.12 Sn 0.82 (NO 3 ) 2 440 86 V 0.12 Sn 0.82 (NO 3 ) 2 421 87 Ba 0.33 Sn 0.67 (NO 3 ) 2 312 85 Ca 0.33 Pb 0.67 (NO 3 ) 2 319 87 Sr 0.33 Pb 0.67 (NO 3 ) 2 329 87 Mg 0.33 Pb 0.67 (NO 3 ) 2 326 85 Mn 0.22 Pb 0.78 (NO 3 ) 2 333 84 Fe 0.12 Pb 0.88 (NO 3 ) 2 329 86 Co 0.18 Pb 0.82 (NO 3 ) 2 326 85 Cu 0.18 Pb 0.82 (NO 3 ) 2 319 87 Ti 0.12 Pb 0.82 (NO 3 ) 2 314 81 Zn 0.12 Pb 0.88 (NO 3 ) 2 329 83 Cr 0.12 Pb 0.82 (NO 3 ) 2 320 84 W 0.09 Pb 0.82 (NO 3 ) 2 301 87 Fe 0.18 In 0.88 (NO 3 ) 3 324 82 Co 0.27 In 0.82 (NO 3 ) 3 315 83 Cu 0.27 In 0.82 (NO 3 ) 3 310 84 Ti 0.27 Bi 0.82 (NO 3 ) 3 275 80 Zn 0.27 Bi 0.88 (NO 3 ) 3 284 79 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) WO 2 190 9 Fe 2 O 3 185 10 SnO 522 5 SnSiO 3 453 20 PbO 453 2 SnS 498 6 PbS 436 3 SnSi 0.8 P 0.2 O 3.1 406 25 The batteries using the metal or semi-metal nitrate or nitrite of Example 1 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 2 Test cells discussed in Example 1 were manufactured and tested under the same conditions as those of Example 1 for evaluation of the electrode characteristics of various metal and semi-metal carbonates and hydrogencarbonates specified in Tables 4 and 5 and used as the anode active material. Tables 4 and 5 show the discharge capacities of the test cells in the first cycle. The measurement proved that all the test cells of Example 2 were capable of being charged and discharged. After the conclusion of cathode polarization of these test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 2. The above experiments show that cathode polarization makes lithium absorbed in the electrodes comprising the active materials of Example 2 and anode polarization makes the absorbed lithium released from the electrodes, thereby causing no deposit of metallic lithium. Cylindrical batteries discussed in Example 1 were manufactured and tested under the same conditions of those of Example 1 for evaluation of the cycle characteristics of the batteries using various metal and semi-metal carbonates and hydrogencarbonates of Example 2. Tables 4 and 5 show the capacity maintenance rates at the 100-th cycle. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (CO 3 ) 3 342 75 Al(HCO 3 ) 3 306 86 Sn(CO 3 ) 2 493 86 SnCO 3 534 82 Sn(HCO 3 ) 4 424 92 Sn(HCO 3 ) 2 490 90 Si(CO 3 ) 2 378 81 Si(HCO 3 ) 4 365 89 PbCO 3 441 82 Pb(HCO 3 ) 2 402 84 CdCO 3 397 75 Cd(HCO 3 ) 2 365 85 Bi 2 (CO 3 ) 3 369 73 Bi(HCO 3 ) 3 305 78 In 2 (CO 3 ) 3 461 76 In(HCO 3 ) 3 386 85 ZnCO 3 298 72 Zn(HCO 3 ) 2 268 82 Ga 2 (CO 3 ) 3 334 73 Sb(HCO 3 ) 3 315 75 Ga(HCO 3 ) 3 312 79 Ge(CO 3 ) 2 365 75 Ge(HCO 3 ) 4 335 83 MgCO 3 304 79 Mg(HCO 3 ) 2 292 85 Ti 2 (CO 3 ) 3 298 75 MnCO 3 263 86 VCO 3 198 86 Cr 2 (CO 3 ) 3 263 82 FeCO 3 246 84 CoCO 3 259 83 NiCO 3 264 81 CuCO 3 253 82 MoCO 3 221 82 BaCO 3 256 80 CaCO 3 263 75 W(CO 3 ) 2 215 75 Ir 2 (CO 3 ) 3 321 73 Sb 2 (CO 3 ) 3 365 78 Nb(CO 3 ) 5 187 80 SrCO 3 273 75 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Ba 0.2 Sn 0.8 CO 3 498 84 Ca 0.2 Sn 0.8 CO 3 485 85 Sr 0.2 Sn 0.8 CO 3 495 85 Mg 0.2 Sn 0.8 CO 3 500 86 Mn 0.2 Sn 0.8 CO 3 482 85 Fe 0.2 Sn 0.8 CO 3 479 87 Co 0.2 Sn 0.8 CO 3 486 86 Cu 0.2 Sn 0.8 CO 3 493 85 Ti 0.2 Sn 0.7 CO 3 475 84 Zn 0.2 Sn 0.8 CO 3 482 85 Cr 0.2 Sn 0.7 CO 3 473 85 Mo 0.2 Sn 0.8 CO 3 459 86 Ba 0.2 Pb 0.8 CO 3 421 83 Ca 0.2 Pb 0.8 CO 3 416 85 Sr 0.2 Pb 0.8 CO 3 416 85 Mg 0.2 Pb 0.8 CO 3 422 84 Mn 0.2 Pb 0.8 CO 3 418 87 Fe 0.2 Pb 0.8 CO 3 409 86 Co 0.2 Pb 0.8 CO 3 417 85 Cu 0.2 Pb 0.8 CO 3 415 84 Ti 0.2 Pb 0.7 CO 3 398 85 Zn 0.2 Pb 0.8 CO 3 405 86 Cr 0.2 Pb 0.7 CO 3 403 85 Mo 0.2 Pb 0.8 CO 3 398 87 (Fe 0.3 In 0.8 ) 2 (CO 3 ) 3 415 79 (Co 0.3 In 0.8 ) 2 (CO 3 ) 3 410 80 (Cu 0.3 In 0.8 ) 2 (CO 3 ) 3 416 81 (Ti 0.2 Bi 0.8 ) 2 (CO 3 ) 3 342 78 (Zn 0.3 Bi 0.8 ) 2 (CO 3 ) 3 331 77 Ba 0.2 Sn 0.8 (HCO 3 ) 2 452 92 Ca 0.2 Sn 0.8 (HCO 3 ) 2 441 94 Sr 0.2 Sn 0.8 (HCO 3 ) 2 443 94 Mg 0.2 Sn 0.8 (HCO 3 ) 2 451 93 Mn 0.2 Sn 0.8 (HCO 3 ) 2 443 91 Fe 0.2 Sn 0.8 (HCO 3 ) 2 439 92 Co 0.2 Sn 0.8 (HCO 3 ) 2 441 91 Cu 0.2 Sn 0.8 (HCO 3 ) 2 456 92 Ti 0.2 Sn 0.7 (HCO 3 ) 2 432 92 Zn 0.2 Sn 0.8 (HCO 3 ) 2 440 93 Cr 0.2 Sn 0.7 (HCO 3 ) 2 429 94 Mo 0.2 Sn 0.8 (HCO 3 ) 2 420 94 Ba 0.2 Pb 0.8 (HCO 3 ) 2 384 88 Ca 0.2 Pb 0.8 (HCO 3 ) 2 372 89 Sr 0.2 Pb 0.8 (HCO 3 ) 2 372 89 Mg 0.2 Pb 0.8 (HCO 3 ) 2 382 87 Mn 0.2 Pb 0.8 (HCO 3 ) 2 371 90 Fe 0.2 Pb 0.8 (HCO 3 ) 2 367 91 Co 0.2 Pb 0.8 (HCO 3 ) 2 371 90 Cu 0.2 Pb 0.8 (HCO 3 ) 2 379 89 Ti 0.2 Pb 0.7 (HCO 3 ) 2 352 89 Zn 0.2 Pb 0.8 (HCO 3 ) 2 368 90 Cr 0.2 Pb 0.7 (HCO 3 ) 2 369 90 Mo 0.2 Pb 0.8 (HCO 3 ) 2 357 91 Fe 0.3 In 0.8 (HCO 3 ) 3 365 86 Co 0.3 In 0.8 (HCO 3 ) 3 359 88 Cu 0.3 In 0.8 (HCO 3 ) 3 358 87 Ti 0.2 Bi 0.8 (HCO 3 ) 3 301 86 Zn 0.3 Bi 0.8 (HCO 3 ) 3 286 87 The batteries using the metal or semi-metal carbonate or hydrogencarbonate of Example 2 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogencarbonates has remarkably improved the cycle characteristics. Example 3 The electrode characteristics of various metal and semi-metal hydrogenborates specified in Tables 6 through 8 and used as the anode active material were evaluated in Example 3. Test cells discussed in Example 1 were manufactured, and the discharge capacities were measured under the same conditions as those of Example 1. The results of measurement are shown in Tables 6 through 8. The measurement proved that all the test cells of Example 3 were capable of being charged and discharged. After the conclusion of cathode polarization of these test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 3. The above experiments show that cathode polarization makes lithium absorbed in the electrodes comprising the active materials of Example 3 and anode polarization makes the absorbed lithium released from the electrodes, thereby causing no deposit of metallic lithium. Cylindrical batteries discussed in Example 1 were manufactured, and the capacity maintence rates at the 100-th cycle were measured under the same conditions as those of Example 1. The results of measurement are shown in Tables 6 through 8. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (HBO 3 ) 3 305 78 Al(H 2 BO 3 ) 3 294 80 SnHBO 3 532 83 Sn(HBO 3 ) 2 453 85 Sn(H 2 BO 3 ) 4 405 86 Sn(H 2 BO 3 ) 2 493 85 Si(HBO 3 ) 2 326 82 Si(H 2 BO 3 ) 4 296 83 PbHBO 3 443 84 Pb(H 2 BO 3 ) 2 421 86 CdHBO 3 328 84 Bi 2 (HBO 3 ) 3 312 79 Bi(H 2 BO 3 ) 3 289 81 In 2 (HBO 3 ) 3 385 84 In(H 2 BO 3 ) 3 368 86 ZnHBO 3 268 79 Zn(H 2 BO 3 ) 2 268 81 Ga 2 (HBO 3 ) 3 338 79 Ga(H 2 BO 3 ) 3 312 82 Ge(HBO 3 ) 2 352 85 Ge(H 2 BO 3 ) 4 335 87 MgHBO 3 296 84 Mg(H 2 BO 3 ) 2 286 86 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Sb 2 (HBO 3 ) 3 310 80 Ba 0.1 Sn 0.9 HBO 3 486 84 Ca 0.1 Sn 0.9 HBO 3 482 85 Sr 0.1 Sn 0.9 HBO 3 482 85 Mg 0.1 Sn 0.9 HBO 3 479 84 Zn 0.1 Sn 0.9 HBO 3 481 86 Cu 0.1 Sn 0.9 HBO 3 469 87 Co 0.1 Sn 0.9 HBO 3 467 85 Fe 0.1 Sn 0.9 HBO 3 461 86 Ni 0.1 Sn 0.9 HBO 3 449 87 Ti 0.2 Sn 0.7 HBO 3 459 86 Cr 0.1 Sn 0.7 HBO 3 449 88 V 0.1 Sn 0.9 HBO 3 429 87 Mo 0.1 Sn 0.9 HBO 3 438 87 W 0.1 Sn 0.8 HBO 3 429 86 (Mn 0.3 In 0.9 ) 2 (HBO 3 ) 3 352 82 (Ni 0.3 In 0.8 ) 2 (HBO 3 ) 3 357 85 (Co 0.3 In 0.8 ) 3 (HBO 3 ) 3 349 85 (Mn 0.3 Bi 0.9 ) 2 (HBO 3 ) 3 291 82 (Ni 0.3 Bi 0.8 ) 2 (HBO 3 ) 3 281 82 (Co 0.3 Bi 0.8 ) 3 (HBO 3 ) 3 279 83 Salt Discharge capacity (mAg/g) Capacity maintenance rate(%) Ba 0.1 Pb 0.9 HBO 3 421 88 Ca 0.1 Pb 0.9 HBO 3 429 87 Sr 0.1 Pb 0.9 HBO 3 429 87 Mg 0.1 Pb 0.9 HBO 3 428 88 Zn 0.1 Pb 0.9 HBO 3 420 86 Cu 0.1 Pb 0.9 HBO 3 419 85 Co 0.1 Pb 0.9 HBO 3 425 84 Fe 0.1 Pb 0.9 HBO 3 422 85 Ni 0.1 Pb 0.9 HBO 3 428 86 Ti 0.2 Pb 0.7 HBO 3 419 89 Cr 0.1 Pb 0.7 HBO 3 401 85 V 0.1 Pb 0.9 HBO 3 398 87 Mo 0.1 Pb 0.9 HBO 3 392 86 W 0.1 Pb 0.8 HBO 3 382 87 The batteries using the metal or semi-metal hydrogenborates of Example 3 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 4 The electrode characteristics of various salts of oxo-acides of sulfur specified in Tables 9 through 16 and used as the anode active material were evaluated in Example 4. Tables 9 through 16 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (SO 4 ) 3 389 82 Al 2 (SO 3 ) 3 405 77 Al 2 (S 2 O 7 ) 3 342 83 Al 2 (SO 5 ) 3 370 81 Al 2 (S 2 O 8 ) 3 338 85 Al 2 (S 2 O 3 ) 3 375 81 Al 2 (S 2 O 6 ) 3 364 82 Al 2 (S 2 O 5 ) 3 372 8 3 Al 2 (S 2 O 2 ) 3 378 83 Al 2 (S 2 O 4 ) 3 364 84 Al 2 (SO 2 ) 3 415 80 Sn(SO 4 ) 2 482 85 Sn(SO 3 ) 2 521 80 Sn(S 2 O 7 ) 2 416 86 Sn(SO 5 ) 2 456 83 Sn(S 2 O 8 ) 2 403 84 Sn(S 2 O 3 ) 2 456 82 Sn(S 2 O 6 ) 2 423 88 Sn(S 2 O 5 ) 2 437 87 Sn(S 2 O 2 ) 2 464 84 Sn(S 2 O 4 ) 2 424 86 Sn(SO 2 ) 2 510 82 SnSO 4 532 82 SnSO 3 556 79 SnS 2 O 7 482 85 SnSO 5 502 83 Al(HSO 4 ) 3 356 91 Al(HSO 3 ) 3 375 87 Al(HS 2 O 7 ) 3 320 92 Al(HSO 5 ) 3 335 91 Al(HS 2 O 8 ) 3 314 89 Al(HS 2 O 3 ) 3 346 88 Al(HS 2 O 6 ) 3 352 89 Al(HS 2 O 5 ) 3 346 90 Al(HS 2 O 2 ) 3 348 91 Al(HS 2 O 4 ) 3 334 92 Al(HSO 2 ) 3 358 89 Sn(HSO 4 ) 4 446 95 Sn(HSO 3 ) 4 453 92 Sn(HS 2 O 7 ) 4 386 94 Sn(HSO 5 ) 4 423 93 Sn(HS 2 O 8 ) 4 379 94 Sn(HS 2 O 3 ) 4 433 93 Sn(HS 2 O 6 ) 4 402 97 Sn(HS 2 O 5 ) 4 410 96 Sn(HS 2 O 2 ) 4 439 94 Sn(HS 2 O 4 ) 4 403 95 Sn(HSO 2 ) 4 470 90 Sn(HSO 4 ) 2 486 93 Sn(HSO 3 ) 2 496 88 Sn(HS 2 O 7 ) 2 450 92 Sn(HSO 5 ) 2 457 91 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) SnS 2 O 8 460 86 SnS 2 O 3 505 79 SnS 2 O 6 476 85 SnS 2 O 5 483 85 SnS 2 O 2 536 80 SnS 2 O 4 497 81 SnSO 2 545 79 Si(SO 4 ) 2 395 85 Si(SO 3 ) 2 411 82 Si(S 2 O 7 ) 2 341 87 Si(SO 5 ) 2 362 85 Si(S 2 O 8 ) 2 322 87 Si(S 2 O 3 ) 2 375 84 Si(S 2 O 6 ) 2 332 85 Si(S 2 O 5 ) 2 343 84 Si(S 2 O 2 ) 2 378 82 Si(S 2 O 4 ) 2 350 85 Si(SO 2 ) 2 421 83 PbSO 4 452 84 PbSO 3 472 83 PbS 2 O 7 405 86 PbSO 5 432 85 PbS 2 O 8 400 86 PbS 2 O 3 441 84 PbS 2 O 6 411 85 PbS 2 O 5 419 85 PbS 2 O 2 445 82 PbS 2 O 4 412 84 Sn(HS 2 O 8 ) 2 426 93 Sn(HS 2 O 3 ) 2 472 91 Sn(HS 2 O 6 ) 2 436 94 Sn(HS 2 O 5 ) 2 440 94 Sn(HS 2 O 2 ) 2 471 91 Sn(HS 2 O 4 ) 2 446 93 Sn(HSO 2 ) 2 492 90 Si(HSO 4 ) 4 362 93 Si(HSO 3 ) 4 371 91 Si(HS 2 O 7 ) 4 312 94 Si(HSO 5 ) 4 335 95 Si(HS 2 O 8 ) 4 294 96 Si(HS 2 O 3 ) 4 341 93 Si(HS 2 O 6 ) 4 309 95 Si(HS 2 O 5 ) 4 312 94 Si(HS 2 O 2 ) 4 340 92 Si(HS 2 O 4 ) 4 318 93 Si(HSO 2 ) 4 390 90 Pb(HSO 4 ) 2 415 92 Pb(HSO 3 ) 2 426 91 Pb(HS 2 O 7 ) 2 386 95 Pb(HSO 5 ) 2 403 94 Pb(HS 2 O 8 ) 2 376 95 Pb(HS 2 O 3 ) 2 411 94 Pb(HS 2 O 6 ) 2 389 96 Pb(HS 2 O 5 ) 2 399 95 Pb(HS 2 O 2 ) 2 419 91 Pb(HS 2 O 4 ) 2 391 93 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) PbSO 2 475 81 CdSO 4 414 79 CdSO 3 426 78 CdS 2 O 7 378 81 CdSO 5 404 82 CdS 2 O 8 369 84 CdS 2 O 3 410 78 CdS 2 O 6 398 79 CdS 2 O 5 401 80 CdS 2 O 2 410 78 CdS 2 O 4 389 82 CdSO 2 420 76 Bi 2 (SO 4 ) 3 364 76 Bi 2 (SO 3 ) 3 381 75 Bi 2 (S 2 O 7 ) 3 324 79 Bi 2 (SO 5 ) 3 348 78 Bi 2 (S 2 O 8 ) 3 315 81 Bi 2 (S 2 O 3 ) 3 346 78 Bi 2 (S 2 O 6 ) 3 329 78 Bi 2 (S 2 O 5 ) 3 347 76 Bi 2 (S 2 O 2 ) 3 352 75 Bi 2 (S 2 O 4 ) 3 333 79 Bi 2 (SO 2 ) 3 379 75 In 2 (SO 4 ) 3 444 83 In 2 (SO 3 ) 3 459 81 In 2 (S 2 O 7 ) 3 398 86 In 2 (SO 5 ) 3 42 1 83 In 2 (S 2 O 8 ) 3 389 85 Pb(HSO 2 ) 2 435 91 Cd(HSO 4 ) 2 379 89 Cd(HSO 3 ) 2 398 88 Cd(HS 2 O 7 ) 2 346 92 Cd(HSO 5 ) 2 382 93 Cd(HS 2 O 8 ) 2 341 93 Cd(HS 2 O 3 ) 2 379 90 Cd(HS 2 O 6 ) 2 370 91 Cd(HS 2 O 5 ) 2 374 93 Cd(HS 2 O 2 ) 2 379 89 Cd(HS 2 O 4 ) 2 365 93 Cd(HSO 2 ) 2 391 89 Bi(HSO 4 ) 3 337 87 Bi(HSO 3 ) 3 349 86 Bi(HS 2 O 7 ) 3 298 87 Bi(HSO 5 ) 3 315 86 Bi(HS 2 O 8 ) 3 276 90 Bi(HS 2 O 3 ) 3 313 85 Bi(HS 2 O 6 ) 3 298 86 Bi(HS 2 O 5 ) 3 313 87 Bi(HS 2 O 2 ) 3 321 84 Bi(HS 2 O 4 ) 3 303 88 Bi(HSO 2 ) 3 336 86 In(HSO 4 ) 3 416 92 In(HSO 3 ) 3 420 91 In(HS 2 O 7 ) 3 367 95 In(HSO 5 ) 3 390 94 In(HS 2 O 8 ) 3 374 96 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) In 2 (S 2 O 3 ) 3 432 84 In 2 (S 2 O 6 ) 3 419 85 In 2 (S 2 O 5 ) 3 416 85 In 2 (S 2 O 2 ) 3 432 83 In 2 (S 2 O 4 ) 3 398 86 In 2 (SO 2 ) 3 456 81 ZnSO 4 362 75 ZnSO 3 379 73 ZnS 2 O 7 334 76 ZnSO 5 342 75 ZnS 2 O 8 320 76 ZnS 2 O 3 342 76 ZnS 2 O 6 320 76 ZnS 2 O 5 333 75 ZnS 2 O 2 354 74 ZnS 2 O 4 321 76 ZnSO 2 382 73 MgSO 4 333 81 MgSO 3 352 79 MgS 2 O 7 298 84 MgSO 5 320 82 MgS 2 O 8 302 83 MgS 2 O 3 325 81 MgS 2 O 6 300 83 MgS 2 O 5 311 82 MgS 2 O 2 328 82 MgS 2 O 4 305 83 MgSO 2 342 79 In(HS 2 O 3 ) 3 400 95 In(HS 2 O 6 ) 3 381 95 In(HS 2 O 5 ) 3 390 95 In(HS 2 O 2 ) 3 402 91 In(HS 2 O 4 ) 3 370 95 In(HSO 2 ) 3 420 92 Zn(HSO 4 ) 2 333 85 Zn(HSO 3 ) 2 342 84 Zn(HS 2 O 7 ) 2 300 87 Zn(HSO 5 ) 2 312 86 Zn(HS 2 O 8 ) 2 294 85 Zn(HS 2 O 3 ) 2 310 85 Zn(HS 2 O 6 ) 2 300 84 Zn(HS 2 O 5 ) 2 310 86 Zn(HS 2 O 2 ) 2 325 84 Zn(HS 2 O 4 ) 2 290 86 Zn(HSO 2 ) 2 341 84 Mg(HSO 4 ) 2 312 91 Mg(HSO 3 ) 2 330 89 Mg(HS 2 O 7 ) 2 271 93 Mg(HSO 5 ) 2 294 92 Mg(HS 2 O 8 ) 2 279 93 Mg(HS 2 O 3 ) 2 293 92 Mg(HS 2 O 6 ) 2 276 94 Mg(HS 2 O 5 ) 2 288 92 Mg(HS 2 O 2 ) 2 296 93 Mg(HS 2 O 4 ) 2 276 94 Mg(HSO 2 ) 2 302 90 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Ga 2 (SO 4 ) 3 364 76 Ga 2 (SO 3 ) 3 382 74 Ga 2 (S 2 O 7 ) 3 321 79 Ga 2 (SO 5 ) 3 352 75 Ga 2 (S 2 O 8 ) 3 312 77 Ga 2 (S 2 O 3 ) 3 352 75 Ga 2 (S 2 O 6 ) 3 333 76 Ga 2 (S 2 O 5 ) 3 342 75 Ga 2 (S 2 O 2 ) 3 354 74 Ga 2 (S 2 O 4 ) 3 326 76 Ga 2 (SO 2 ) 3 375 73 Ge(SO 4 ) 2 431 78 Ge(SO 3 ) 2 449 75 Ge(S 2 O 7 ) 2 395 81 Ge(SO 5 ) 2 423 78 Ge(S 2 O 8 ) 2 386 81 Ge(S 2 O 3 ) 2 425 77 Ge(S 2 O 6 ) 2 401 80 Ge(S 2 O 5 ) 2 408 79 Ge(S 2 O 2 ) 2 420 79 Ge(S 2 O 4 ) 2 390 82 Ge(SO 2 ) 2 435 77 Cr 2 (SO 4 ) 3 353 81 Cr 2 (SO 3 ) 3 369 80 W(SeO 4 ) 2 298 79 CoSO 4 352 82 CoSO 3 362 80 NiSO 4 349 81 Ca(HSO 4 ) 3 339 86 Ga(HSO 3 ) 3 352 85 Ga(HS 2 O 7 ) 3 301 88 Ga(HSO 5 ) 3 315 84 Ga(HS 2 O 8 ) 3 294 86 Ga(HS 2 O 3 ) 3 321 87 Ga(HS 2 O 6 ) 3 303 87 Ga(HS 2 O 5 ) 3 318 86 Ga(HS 2 O 2 ) 3 321 86 Ga(HS 2 O 4 ) 3 296 84 Ga(HSO 2 ) 3 348 84 Ge(HSO 4 ) 4 412 89 Ge(HSO 3 ) 4 421 86 Ge(HS 2 O 7 ) 4 370 92 Ge(HSO 5 ) 4 396 90 Ge(HS 2 O 8 ) 4 356 93 Ge(HS 2 O 3 ) 4 387 85 Ge(HS 2 O 6 ) 4 374 88 Ge(HS 2 O 5 ) 4 373 87 Ge(HS 2 O 2 ) 4 395 89 Ge(HS 2 O 4 ) 4 365 93 Ge(HSO 2 ) 4 402 89 Cr(HSO 4 ) 3 325 92 Cr(HSO 3 ) 3 341 90 W(HSO 4 ) 4 275 89 Co(HSO 4 ) 2 321 92 Co(HSO 3 ) 2 329 90 Ni(HSO 4 ) 2 319 90 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) NiSO 3 354 79 CuSO 4 326 82 CuSO 3 340 80 Ti 2 (SO 4 ) 3 315 83 Mo 2 (SO 4 ) 3 324 84 VSO 4 306 83 MnSO 4 345 82 MnSO 3 356 80 FeSO 4 354 81 FeSO 3 362 78 Nb 2 (SO 4 ) 5 257 82 CaSO 4 398 78 CaSO 3 405 76 SrSO 4 398 78 SrSO 3 405 76 BaSO 4 375 79 BaSO 3 386 78 Ni(HSO 3 ) 2 326 88 Cu(HSO 4 ) 2 301 93 Cu(HSO 3 ) 2 319 91 Ti(HSO 4 ) 3 284 90 Mo(HSO 4 ) 3 299 92 V(HSO 4 ) 2 274 92 Mn(HSO 4 ) 2 315 93 Mn(HSO 3 ) 2 320 90 Fe(HSO 4 ) 2 327 91 Fe(HSO 3 ) 2 333 89 Nb(HSO 4 ) 5 229 90 Ca(HSO 4 ) 2 375 87 Ca(HSO 3 ) 2 381 85 Sr(HSO 4 ) 2 375 87 Sr(HSO 3 ) 2 381 85 Ba(HSO 4 ) 2 352 87 Ba(HSO 3 ) 2 360 86 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Mg 0.1 Sn 0.9 SO 4 503 84 Sr 0.1 Sn 0.9 SO 4 503 84 Ca 0.1 Sn 0.9 SO 4 503 84 Zn 0.1 Sn 0.9 SO 4 500 85 Ni 0.1 Sn 0.9 SO 4 495 84 Fe 0.1 Sn 0.9 SO 4 492 86 Co 0.1 Sn 0.9 SO 4 489 87 Mn 0.1 Sn 0.9 SO 4 482 86 Cu 0.1 Sn 0.9 SO 4 485 85 Mo 0.1 Sn 0.9 SO 4 476 84 Vo 0.1 Sn 0.9 SO 4 473 86 W 0.1 Sn 0.8 SO 4 459 83 Cr 0.2 Sn 0.7 SO 4 476 84 Mo 0.2 Sn 0.7 SO 4 476 85 Mg 0.1 Pb 0.9 SO 4 420 86 Sr 0.1 Pb 0.9 SO 4 420 86 Ca 0.1 Pb 0.9 SO 4 420 86 Zn 0.1 Pb 0.9 SO 4 421 87 Ni 0.1 Pb 0.9 SO 4 415 86 Fe 0.1 Pb 0.9 SO 4 410 87 Co 0.1 Pb 0.9 SO 4 416 88 Mn 0.1 Pb 0.9 SO 4 408 86 Cu 0.1 Pb 0.9 SO 4 406 87 Mo 0.1 Pb 0.9 SO 4 398 85 V 0.1 Pb 0.9 SO 4 387 85 W 0.1 Pb 0.8 SO 4 376 85 Cr 0.2 Pb 0.7 SO 4 387 84 MO 0.2 Pb 0.7 SO 4 389 85 Mg 0.1 Sn 0.9 (HSO 4 ) 2 481 94 Sr 0.1 Sn 0.9 (HSO 4 ) 2 481 94 Ca 0.1 Sn 0.9 (HSO 4 ) 2 481 94 Zn 0.1 Sn 0.9 (HSO 4 ) 2 479 95 Ni 0.1 Sn 0.9 (HSO 4 ) 2 470 95 Fe 0.1 Sn 0.9 (HSO 4 ) 2 476 95 Co 0.1 Sn 0.9 (HSO 4 ) 2 469 94 Mn 0.1 Sn 0.9 (HSO 4 ) 2 465 96 Cu 0.1 Sn 0.9 (HSO 4 ) 2 462 94 Mo 0.1 Sn 0.9 (HSO 4 ) 2 459 95 V 0.1 Sn 0.9 (HSO 4 ) 2 451 95 W 0.1 Sn 0.8 (HSO 4 ) 2 432 94 Cr 0.2 Sn 0.7 (HSO 4 ) 2 455 94 Mo 0.2 Sn 0.7 (HSO 4 ) 2 452 95 Mg 0.1 Pb 0.9 (HSO 4 ) 2 394 95 Sr 0.1 Pb 0.9 (HSO 4 ) 2 394 95 Ca 0.1 Pb 0.9 (HSO 4 ) 2 394 95 Zn 0.1 Pb 0.9 (HSO 4 ) 2 394 94 Ni 0.1 Pb 0.9 (HSO 4 ) 2 384 97 Fe 0.1 Pb 0.9 (HSO 4 ) 2 381 95 Co 0.1 Pb 0.9 (HSO 4 ) 2 384 96 Mn 0.1 Pb 0.9 (HSO 4 ) 2 381 95 Cu 0.1 Pb 0.9 (HSO 4 ) 2 386 96 Mo 0.1 Pb 0.9 (HSO 4 ) 2 370 95 V 0.1 Pb 0.9 (HSO 4 ) 2 368 94 W 0.1 Pb 0.8 (HSO 4 ) 2 359 95 Cr 0.2 Pb 0.7 (HSO 4 ) 2 364 94 Mo 0.2 Pb 0.7 (HSO 4 ) 2 368 94 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) (Mg 0.3 In 0.8 ) 2 (SO 4 ) 3 410 85 (Zn 0.3 In 0.8 ) 2 (SO 4 ) 3 406 86 (Ni 0.3 In 0.5 ) 2 (SO 4 ) 3 398 86 (Co 0.3 Bi 0.8 ) 2 (SO 4 ) 3 333 80 (Fe 0.3 Bi 0.8 ) 2 (SO 4 ) 3 325 82 (Mn 0.3 Bi 0.8 ) 2 (SO 4 ) 3 330 80 Sn(SO 4 ) 0.5 (HSO 4 ) 498 90 Pb(SO 4 ) 0.5 (HSO 4 ) 425 90 In 2 (SO 4 ) 2.5 (HSO 4 ) 425 90 Bi 2 (SO 4 ) 2.5 (HSO 4 ) 343 84 Co 0.3 In 0.8 (HSO 4 ) 3 379 94 Fe 0.3 In 0.8 (HSO 4 ) 3 370 95 Mn 0.3 In 0.8 (HSO 4 ) 3 368 95 Mg 0.3 Bi 0.8 (HSO 4 ) 3 298 90 Zn 0.3 Bi 0.8 (HSO 4 ) 3 289 89 Ni 0.3 Bi 0.8 (HSO 4 ) 3 295 91 Sn(SO 4 ) 0.9 (HSO 4 ) 0.2 519 86 Pb(SO 4 ) 0.9 (HSO 4 ) 0.2 438 87 In 2 (SO 4 ) 2.9 (HSO 4 ) 0.2 438 86 Bi 2 (SO 4 ) 2.9 (HSO 4 ) 0.2 350 80 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 4. The batteries using the metal or semi-metal sulfate, sulfite, disulfate, peroxomonosulfate, peroxodisulfate, thiosulfate, disulfite, thiosulfite, hydrogensulfate, thionate, or sulfoxylate of Example 4 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogensulfates has remarkably improved the cycle characteristics. Example 5 The electrode characteristics of various salts of oxo-acids of selenium specified in Tables 17 through 20 and used as the anode active material were evaluated in Example 5. Tables 17 through 20 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (SeO 4 ) 3 362 83 Al 2 (SeO 3 ) 3 387 80 Sn(SeO 4 ) 2 462 84 Sn(SeO 3 ) 2 483 81 SnSeO 4 512 83 SnSeO 3 521 80 Sn 2 SeO 5 534 79 Si(SeO 4 ) 2 364 84 Si(SeO 3 ) 2 379 80 PbSeO 4 432 85 PbSeO 3 445 82 Pb 2 SeO 5 498 80 CdSeO 4 386 80 CdSeO 3 399 78 Bi 2 (SeO 4 ) 3 339 77 Bi 2 (SeO 3 ) 3 349 72 In 2 (SeO 4 ) 3 421 85 In 2 (SeO 3 ) 3 438 83 ZnSeO 4 339 74 ZnSeO 3 348 70 MgSeO 4 310 82 MgSeO 3 321 79 Ga 2 (SeO 4 ) 3 339 75 Ga 2 (SeO 3 ) 3 349 73 Ge(SeO 4 ) 2 405 77 Ge(SeO 3 ) 2 420 72 Al(HSeO 4 ) 3 341 92 Al(HSeO 3 ) 3 367 89 Sn(HSeO 4 ) 4 442 92 Sn(HSeO 3 ) 4 462 93 Sn(HSeO 4 ) 2 489 94 Sn(HSeO 3 ) 2 501 90 SnSeO 5 508 84 Si(HSeO 4 ) 4 342 92 Si(HSeO 3 ) 4 347 90 Pb(HSeO 4 ) 2 412 93 Pb(HSeO 3 ) 2 421 92 PbSeO 5 425 85 Cd(HSeO 4 ) 2 364 90 Cd(HSeO 3 ) 2 374 88 Bi (HS eO 4 ) 3 314 89 Bi(HSeO 3 ) 3 321 86 In(HSeO 4 ) 3 397 94 In(HSeO 3 ) 3 409 93 Zn(HSeO 4 ) 2 315 85 Zn(HSeO 3 ) 2 320 83 Mg(HSeO 4 ) 2 289 92 Mg(HSeO 3 ) 2 301 87 Ga(HSeO 4 ) 3 314 86 Ga(HSeO 3 ) 3 324 84 Ge(HSeO 4 ) 4 385 86 Ge(HSeO 3 ) 4 396 83 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Cr 2 (SeO 4 ) 3 321 75 Cr 2 (SeO 3 ) 3 331 76 W(SeO 4 ) 2 257 72 CoSeO 4 286 73 CoSeO 3 297 76 NiSeO 4 286 76 NiSeO 3 299 76 CuSeO 4 287 73 CuSeO 3 289 74 Ti 2 (SeO 4 ) 3 253 77 Mo 2 (Seo 4 ) 3 223 73 VSeO 4 282 79 MnSeO 4 265 73 MnSeO 3 276 75 FeSeO 4 282 74 FeSeO 3 293 75 Nb 2 (SeO 4 ) 5 215 75 CaSeO 4 321 74 CaSeO 3 334 76 SrSeO 3 334 76 BaSeO 4 345 73 BaSeO 3 353 74 Sb 2 (SeO 4 ) 3 364 72 Ir 2 (SeO 4 ) 3 345 73 Cr(HSeO 4 ) 3 305 84 Cr(HSeO 3 ) 3 314 86 W(HSeO 4 ) 4 234 83 Co(HSeO 4 ) 2 261 82 Co(HSeO 3 ) 2 271 85 Ni(HSeO 4 ) 2 264 84 Ni(HSeO 3 ) 2 274 85 Cu(HSeO 4 ) 2 264 84 Cu(HSeO 3 ) 2 259 84 Ti(HSeO 4 ) 3 230 86 Mo(HSeO 4 ) 3 201 84 V(HSeO 4 ) 2 261 89 Mn(HSeO 4 ) 2 241 82 Mn(HSeO 3 ) 2 251 84 Fe(HSeO 4 ) 2 260 86 Fe(HSeO 3 ) 2 271 85 Nb(HSeO 4 ) 5 195 84 Ca(HSeO 4 ) 2 301 82 Ca(HSeO 3 ) 2 309 85 Sr(HSeO 3 ) 2 309 85 Ba(HSeO 4 ) 2 314 84 Ba(HSeO 3 ) 2 321 83 Sb(HSeO 4 ) 3 335 86 Ir(HSeO 4 ) 3 315 85 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Mg 0.1 Sn 0.9 SeO 4 486 85 Zn 0.1 Sn 0.9 SeO 4 484 86 Ni 0.1 Sn 0.9 SeO 4 472 85 Fe 0.1 Sn 0.9 SeO 4 471 86 Co 0.1 Sn 0.9 SeO 4 476 87 Mn 0.1 Sn 0.9 SeO 4 483 84 Cu 0.1 Sn 0.9 SeO 4 475 85 Mo 0.1 Sn 0.9 SeO 4 465 86 V 0.1 Sn 0.9 SeO 4 459 88 W 0.1 Sn 0.8 SeO 4 443 88 Cr 0.2 Sn 0.7 SeO 4 433 86 Ca 0.1 Sn 0.9 SeO 4 492 85 Sr 0.1 Sn 0.9 SeO 4 492 85 Ba 0.1 Sn 0.9 SeO 4 475 86 Mg 0.1 Pb 0.9 SeO 4 415 85 Zn 0.1 Pb 0.9 SeO 4 409 86 Ni 0.1 Pb 0.9 SeO 4 414 87 Fe 0.1 Pb 0.9 SeO 4 401 88 Co 0.1 Pb 0.9 SeO 4 405 86 Mn 0.1 Pb 0.9 SeO 4 403 84 Cu 0.1 Pb 0.9 SeO 4 402 85 Mo 0.1 Pb 0.9 SeO 4 394 85 V 0.1 Pb 0.9 SeO 4 396 84 W 0.1 Pb 0.8 SeO 4 379 86 Cr 0.2 Pb 0.7 SeO 4 368 85 Ca 0.1 Pb 0.9 SeO 4 408 85 Sr 0.1 Pb 0.9 SeO 4 408 85 Ba 0.1 Pb 0.9 SeO 4 381 86 Mg 0.1 Sn 0.9 (HSeO 4 ) 2 453 94 Zn 0.1 Sn 0.9 (HSeO 4 ) 2 461 96 Ni 0.1 Sn 0.9 (HSeO 4 ) 2 453 95 Fe 0.1 Sn 0.9 (HSeO 4 ) 2 449 94 Co 0.1 Sn 0.9 (HSeO 4 ) 2 448 95 Mn 0.1 Sn 0.9 (HSeO 4 ) 2 457 92 Cu 0.1 Sn 0.9 (HSeO 4 ) 2 453 94 Mo 0.1 Sn 0.9 (HSeO 4 ) 2 441 95 V 0.1 Sn 0.9 (HSe O 4 ) 2 432 97 W 0.1 Sn 0.8 (HSeO 4 ) 2 420 96 Cr 0.2 Sn 0.7 (HSeO 4 ) 2 416 95 Ca 0.1 Sn 0.9 (HSeO 4 ) 2 470 95 Sr 0.1 Sn 0.9 (HSeO 4 ) 2 470 95 Ba 0.1 Sn 0.9 (HSeO 4 ) 2 448 94 Mg 0. Pb 0.9 (HSeO 4 ) 2 385 94 Zn 0.1 Pb 0.9 (HSeO 4 ) 2 389 95 Ni 0.1 Pb 0.9 (HSeO 4 ) 2 391 96 Fe 0.1 Pb 0.9 (HSeO 4 ) 2 371 98 Co 0.1 Pb 0.9 (HSeO 4 ) 2 379 95 Mn 0.1 Pb 0.9 (HSeO 4 ) 2 371 95 Cu 0.1 Pb 0.9 (HSeO 4 ) 2 376 96 Mo 0.1 Pb 0.9 (HSeO 4 ) 2 370 94 V 0.1 Pb 0.9 (HSeO 4 ) 2 369 95 W 0.1 Pb 0.8 (HSeO 4 ) 2 349 97 Cr 0.2 Pb 0.7 (HSeO 4 ) 2 333 96 Ca 0.1 Pb 0.9 (HSeO 4 ) 2 379 94 Sr 0.1 Pb 0.9 (HSeO 4 ) 2 379 94 Ba 0.1 Pb 0.9 (HSeO 4 ) 2 353 96 Salt Discharge capacity (mAh/g) Capacity maintenarate rate(%) (Mg 0.3 In 0.8 ) 2 (SeO 4 ) 3 398 86 (Zn 0.3 In 0.8 ) 2 (SeO 4 ) 3 387 87 (Ni 0.3 In 0.8 ) 2 (SeO 4 ) 3 379 86 (Co 0.3 Bi 0.8 ) 2 (SeO 4 ) 3 318 80 (Fe 0.3 Bi 0.8 ) 2 (SeO 4 ) 3 310 82 (Mn 0.3 Bi 0.8 ) 2 (SeO 4 ) 3 320 82 Co 0.3 In 0.8 (HSeO 4 ) 3 374 95 Fe 0.3 In 0.8 (HSeO 4 ) 3 361 98 Mn 0.3 In 0.8 (HSeO 4 ) 3 348 96 Mg 0.3 Bi 0.8 (HSeO 4 ) 3 279 91 Zn 0.3 Bi 0.8 (HSeO 4 ) 3 284 92 Ni 0.3 Bi 0.8 (HSeO 4 ) 3 298 93 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 5. The batteries using the metal or semi-metal selenate, selenite, hydrogenselenate, or hydrogenselenite of Example 5 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogenselenates and hydrogenselenites has remarkably improved the cycle characteristics. Example 6 The electrode characteristics of various salts of oxo-acids of tellurium specified in Tables 21 through 23 and used as the anode active material were evaluated in Example 6. Tables 21 through 23 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (TeO 4 ) 3 346 82 SnTeO 4 426 84 SnTe 3 O 8 385 87 Sn 3 TeO 6 489 85 Si(TeO 4 ) 2 337 83 PbTeO 4 405 84 PbTe 3 O 8 352 85 Pb 3 TeO 6 453 82 CdTeO 4 354 79 Bi 2 (TeO 4 ) 3 314 79 Bi 2 TeO 6 345 77 In 2 (TeO 4 ) 3 384 82 In 2 TeO 6 405 80 Sb 2 TeO 6 384 78 Ir 2 TeO 6 351 78 ZnTeO 4 302 75 MgTeO 4 289 81 Ga 2 TeO 6 314 74 Ge(TeO 4 ) 2 370 75 Ti 2 TeO 6 221 78 Cr 2 TeO 6 287 74 NiTeO 4 253 76 FeTeO 4 254 75 MnTeO 4 247 74 CoTeO 4 253 75 VTeO 4 241 76 CuTeO 4 251 75 Al(HTeO 4 ) 3 319 89 Sn(HTeO 4 ) 2 397 90 SnH 4 TeO 6 359 95 Sn 2 H 2 TeO 6 459 94 Si(HTeO 4 ) 4 307 93 Pb(HTeO 4 ) 2 372 92 PbH 4 TeO 6 321 94 Pb 2 H 2 TeO 6 426 93 Cd(HTeO 4 ) 2 320 90 Bi(HTeO 4 ) 3 284 87 BiH 3 T eO 6 314 87 In(HTeO 4 ) 3 359 89 InH 3 TeO 6 374 90 SbH 3 TeO 6 352 89 IrrH 3 TeO 6 321 88 Zn(HTeO 4 ) 2 275 86 Mg(HSeO 4 ) 2 264 89 GaH 3 TeO 6 275 86 Ge(HTeO 4 ) 4 342 86 TiH 3 TeO 6 198 87 CrH 3 TeO 6 255 86 Ni(HTeO 4 ) 2 234 87 Fe(HSeO 4 ) 2 229 86 Mn(HT eO 4 ) 2 219 85 Co(HSeO 4 ) 2 218 85 V(HTeO 4 ) 2 214 87 Cu(HTeO 4 ) 2 216 85 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) MoTeO 4 234 73 W(TeO 4 ) 2 215 73 CaTeO 4 315 74 SrTeO 4 315 74 BaTeO 4 305 75 Mg 0.1 Sn 0.9 TeO 4 402 86 Cag 0.1 Sn 0.9 TeO 4 402 86 Srg 0.1 Sn 0.9 TeO 4 4 402 86 Zn 0.1 Sn 0.9 TeO 4 405 85 Ni 0.1 Sn 0.9 TeO 4 400 86 Fe 0.1 Sn 0.9 TeO 4 398 87 Co 0.1 Sn 0.9 TeO 4 396 86 Mn 0.1 Sn 0.9 TeO 4 389 85 Cu 0.1 Sn 0.9 TeO 4 390 85 Mo 0.1 Sn 0.9 TeO 4 379 87 V 0.1 Sn 0.9 TeO 4 378 88 W 0.1 Sn 0.8 TeO 4 369 85 Cr 0.2 Sn 0.7 TeO 4 374 86 Mg 0.1 Pb 0.9 TeO 4 375 86 Ca 0.1 Pb 0.9 TeO 4 375 86 Sr 0.1 Pb 0.9 TeO 4 375 86 Zn 0.1 Pb 0.9 TeO 4 379 85 Ni 0.1 Pb 0.9 TeO 4 370 87 Fe 0.1 Pb 0.9 TeO 4 367 88 Co 0.1 Pb 0.9 TeO 4 368 87 Mn 0.1 Pb 0.9 TeO 4 364 86 Cu 0.1 Pb 0.9 TeO 4 362 87 Mo 0.1 Pb 0.9 TeO 4 354 87 V 0.1 Pb 0.9 TeO 4 352 86 W 0.1 Pb 0.8 TeO 4 341 85 Mo(HTeO 4 ) 2 215 81 W(HTeO 4 ) 4 185 82 Ca(HTeO 4 ) 2 289 84 Sr(HTeO 4 ) 2 289 84 Ba(HTeO 4 ) 2 279 83 Mg 0.1 Sn 0.9 (HTeO 4 ) 2 375 95 Ca 0.1 Sn 0.9 (HTeO 4 ) 2 375 95 Sr 0.1 Sn 0.9 (HTeO 4 ) 2 375 95 Zn 0.1 Sn 0.9 (HTeO 4 ) 2 379 94 Ni 0.1 Sn 0.9 (HTeO 4 ) 2 374 95 Fe 0.1 Sn 0.9 (HTeO 4 ) 2 370 96 Co 0.1 Sn 0.9 (HTeO 4 ) 2 375 95 Mn 0.1 Sn 0.9 (HTeO 4 ) 2 369 94 Cu 0.1 Sn 0.9 (HTeO 4 ) 2 371 94 Mo 0.1 Sn 0.9 (HTeO 4 ) 2 352 95 V 0.1 Sn 0.9 (HTeO 4 ) 2 349 97 W 0.1 Sn 0.8 (HTeO 4 ) 2 342 95 Cr 0.2 Sn 0.7 (HTeO 4 ) 2 344 94 Mg 0.1 Pb 0.9 (HTeO 4 ) 2 335 95 Ca 0.1 Pb 0.9 (HTeO 4 ) 2 335 95 Sr 0.1 Pb 0.9 (HTeO 4 ) 2 335 95 Zn 0.1 Pb 0.9 (HTeO 4 ) 2 339 94 Ni 0.1 Pb 0.9 (HTeO 4 ) 2 348 95 Fe 0.1 Pb 0.9 (HTeO 4 ) 2 332 96 Co 0.1 Pb 0.9 (HTeO 4 ) 2 321 95 Mn 0.1 Pb 0.9 (HTeO 4 ) 2 322 94 CuPb 0.9 (HTeO 4 ) 2 337 95 Mo 0.1 Pb 0.9 (HTeO 4 ) 2 326 94 V 0.1 Pb 0.9 (HTeO 4 ) 2 322 95 W 0.1 Pb 0.8 (HTeO 4 ) 2 320 96 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Cr 0.2 Pb 0.7 TeO 4 361 84 (Mg 0.3 In 0.8 ) 2 TeO 6 374 82 (Zn 0.3 In 0.8 ) 2 TeO 6 370 83 (Fe 0.3 In 0.8 ) 2 TeO 6 364 84 (Mg 0.3 Bi 0.8 ) 2 TeO 6 315 79 (Zn 0.3 Bi 0.8 ) 2 TeO 6 318 80 (Fe 0.3 Bi 0.8 ) 2 TeO 6 308 81 Cr 0.2 Pb 0.7 (HTeO 4 ) 2 337 93 Co 0.3 In 0.8 H 3 TeO 6 351 93 Ni 0.3 In 0.8 H 3 TeO 6 341 92 Mn 0.3 In 0.8 H 3 TeO 6 338 92 Co 0.3 Bi 0.8 H 3 TeO 6 287 88 Ni 0.3 Bi 0.8 H 3 TeO 6 286 90 Mn 0.3 Bi 0.8 H 3 TeO 6 279 90 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 6. The batteries using the metal or semi-metal tellurate or hydrogentellurate of Example 6 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Especially the use of hydrogentellurates has remarkably improved the cycle characteristics. Example 7 The electrode characteristics of various metal and semi-metal hydrogenphosphates, phosphinates, and phosphonates specified in Tables 24 through 27 and used as the anode active material were evaluated in Example 7. Tables 24 through 27 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al(PH 2 O 2 ) 3 366 83 Al 2 (PHO 3 ) 3 353 84 Al 2 (HPO 4 ) 3 348 85 Al(H 2 PO 4 ) 3 315 87 Sn(PH 2 O 2 ) 4 412 88 Sn(PHO 3 ) 2 455 89 Sn(HPO 4 ) 2 452 88 Sn(H 2 PO 4 ) 4 384 89 Sn(PH 2 O 2 ) 2 452 82 SnPHO 3 486 92 SnHPO 4 485 95 Sn(H 2 PO 4 ) 2 402 86 Si(PH 2 O 2 ) 4 304 85 Si(PHO 3 ) 2 332 86 Bi(PH 2 O 2 ) 3 333 82 Bi 2 (PHO 3 ) 3 345 83 Bi 2 (HPO 4 ) 3 340 83 Bi(H 2 PO 4 ) 3 324 85 In(PH 2 O 2 ) 3 365 82 In 2 (PHO 3 ) 3 380 81 In 2 (HPO 4 ) 3 377 83 In(H 2 PO 4 ) 3 333 86 Zn(PH 2 O 2 ) 2 298 83 ZnPHO 3 298 83 ZnHPO 4 295 83 Zn(H 2 PO 4 ) 2 264 84 Mg(PH 2 O 2 ) 2 281 84 MgPHO 3 288 83 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Si(HPO 4 ) 2 322 87 Si(H 2 PO 4 ) 2 285 88 Pb(PH 2 O 2 ) 2 420 85 PbPHO 3 425 85 PbHPO 4 418 89 Pb(H 2 PO 4 ) 2 405 90 Cd(PH 2 O 2 ) 2 380 82 CdPHO 3 385 83 CdHPO 4 384 83 Cd(H 2 PO 4 ) 2 375 86 Sb 2 (HPO 4 ) 3 321 82 Ti 2 (HPO 4 ) 3 275 84 V 2 (HPO 4 ) 3 250 85 Cr 2 (HPO 4 ) 3 284 84 Mn 2 (HPO 4 ) 3 275 85 MgHPO 4 286 84 Mg(H 2 PO 4 ) 2 267 87 Ga(PH 2 O 2 ) 3 321 82 Ga 2 (PHO 3 ) 3 335 83 Ga 2 (HPO 4 ) 3 325 84 Ga(H 2 PO 4 ) 3 305 86 Ge(PH 2 O 2 ) 4 367 83 Ge(PHO 3 ) 2 382 84 Ge(HPO 4 ) 2 375 87 Ge(H 2 PO 4 ) 4 342 89 Fe 2 (HPO 4 ) 3 264 85 CoHPO 4 264 84 NiHPO 4 261 84 CuHPO 4 275 85 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) SrHPO 4 332 85 Ca 0.2 Sn 0.8 HPO 4 451 88 Sr 0.2 Sn 0.8 HPO 4 451 88 Ba 0.2 Sn 0.8 HPO 4 432 89 Zn 0.2 Sn 0.8 HPO 4 437 92 Fe 0.2 Sn 0.8 HPO 4 441 91 Ni 0.2 Sn 0.8 HPO 4 438 92 Co 0.2 Sn 0.8 HPO 4 442 92 Mn 0.2 Sn 0.8 HPO 4 429 90 Ti 0.2 Sn 0.7 HPO 4 415 91 Cu 0.2 Sn 0.8 HPO 4 429 92 Cr 0.2 Sn 0.7 HPO 4 418 93 V 0.2 Sn 0.8 HPO 4 404 91 W 0.1 Sn 0.8 HPO 4 406 90 BaHPO 4 312 86 Ca 0.2 Pb 0.8 HPO 4 372 90 Sr 0.2 Pb 0.8 HPO 4 372 90 Ba 0.2 Pb 0.8 HPO 4 359 91 Zn 0.2 Pb 0.8 HPO 4 382 93 Fe 0.2 Pb 0.8 HPO 4 374 94 Ni 0.2 Pb 0.8 HPO 4 368 93 Co 0.2 Pb 0.8 HPO 4 376 92 Mn 0.2 Pb 0.8 HPO 4 374 93 Ti 0.2 Pb 0.7 HPO 4 369 94 Cu 0.2 Pb 0.8 HPO 4 371 93 Cr 0.2 Pb 0.7 HPO 4 368 95 V 0.2 Pb 0.8 HPO 4 365 93 W 0.1 Pb 0.8 HPO 4 345 93 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Sn 2 (P 2 O 7 ) 0.9 (HPO 4 ) 0.2 495 82 Sn 2 (P 2 O 7 ) 0.8 (HPO 4 ) 0.4 490 88 Pb 2 (P 2 O 7 ) 0.9 (HPO 4 ) 0.2 425 80 Pb 2 (P 2 O 7 ) 0.8 (HPO 4 ) 0.4 422 82 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 7. The batteries using the metal or semi-metal hydrogenphosphate, phosphinate, or phosphonate of Example 7 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 8 The electrode characteristics of various metal and semi-metal cyanides, cyanates, and thiocyanates specified in Tables 28 through 30 and used as the anode active material were evaluated in Example 8. Tables 28 through 30 show the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al(CN) 3 382 76 Al(SCN) 3 286 82 Al(ONC) 3 364 80 Sn(CN) 4 529 85 Sn(SCN) 4 326 92 Sn(ONC) 4 436 90 Sn(CN) 2 537 82 Sn(SCN) 2 487 95 Sn(ONC) 2 506 93 Si(CN) 4 315 76 Si(SCN) 4 292 82 Si(ONC) 4 310 79 Pb(CN) 2 454 82 Pb(SCN) 2 346 88 Pb(ONC) 2 386 87 Cd(CN) 2 372 75 Cd(SCN) 2 315 79 Cd(ONC) 2 340 79 Bi(CN) 3 324 75 Bi(SCN) 3 286 86 Bi(ONC) 3 316 80 In(CN) 3 412 82 In(SCN) 3 375 89 In(ONC) 3 369 86 Zn(CN) 2 315 76 Zn(SCN) 2 285 83 Zn(ONC) 2 310 79 Ga(CN) 3 348 74 Ga(SCN) 3 302 79 Ga(ONC) 3 326 76 Ge(CN) 4 390 78 Ge(SCN) 4 352 86 Ge(ONC) 4 389 82 Mg(CN) 2 320 79 Mg(SCN) 2 289 89 Mg(ONC) 2 341 85 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Ti(CN) 3 265 75 Ti(SCN) 3 251 77 Ti(ONC) 3 263 75 V(CN) 2 275 81 V(SCN) 2 245 82 V(ONC) 2 263 80 Mn(CN) 2 278 82 Mn(SCN) 2 261 87 Mn(ONC) 2 275 85 Sb(CN) 3 315 76 Sb(SCN) 3 281 80 Sb(ONC) 3 298 78 Cr(CN) 3 301 82 Cr(SCN) 3 275 84 Cr(ONC) 3 280 83 Fe(CN) 2 269 75 Fe(SCN) 2 245 79 Fe(ONC) 2 257 79 W(CN) 4 215 81 W(SCN) 4 201 82 W(ONC) 4 210 81 Co(CN) 2 269 78 Co(SCN) 2 245 84 Co(ONC) 2 253 80 Ni(CN) 2 275 82 Ni(SCN) 2 257 86 Ni(ONC) 2 261 81 Cu(CN) 2 251 77 Cu(SCN) 2 235 80 Cu(ONC) 2 246 78 Mo(CN) 3 235 77 Mo(SCN) 3 211 79 Mo(ONC) 3 225 77 Ca(CN) 2 325 78 Ca(SCN) 2 314 84 Ca(ONC) 2 322 80 Ba(CN) 2 333 79 Ba(SCN) 2 301 87 Ba(ONC) 2 311 81 Nb(CN) 2 222 82 Nb(SCN) 2 201 83 Nb(ONC) 2 216 81 Sr(SCN) 2 314 84 Sr(ONC) 2 322 80 Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) ZnSn(CN) 4 402 87 MgSn(SCN) 4 382 92 CaSn(SCN) 4 382 92 Sr(SCN) 4 382 92 FeSn(ONC) 4 376 91 NiSn(CN) 4 398 88 CoSn(SCN) 4 375 93 MnSn(ONC) 4 390 92 TiSn(CN) 5 385 87 CuSn(SCN) 4 360 93 NiPb(CN) 4 382 83 CoPb(SCN) 4 362 85 MnPb(ONC) 4 375 84 ZnPb(CN) 4 395 84 MgPb(SCN) 4 376 89 CaPb(SCN) 4 376 89 SrPb(SCN) 4 376 89 FePb(ONC) 4 375 89 TiPb(CN) 5 376 84 CuPb(SCN) 4 326 89 CuIn(CN) 5 355 84 FeIn(SCN) 5 335 91 CoIn(ONC) 5 345 88 MgIn(CN) 5 365 85 CuBi(CN) 5 324 78 FeBi(SCN) 5 315 87 BaBi(ONC) 5 320 83 CaBi(CN) 3 321 77 MgBi(CN) 3 315 78 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 8. The batteries using the metal or semi-metal cyanide, cyanate, or thiocyanate of Example 8 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 9 The electrode characteristics of various metal and semi-metal tungstates specified in Table 31 and used as the anode active material were evaluated in Example 9. Table 31 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 3 (WO 4 ) 3 292 86 AlWO 4 301 83 SnWO 4 477 94 Sn 2 W 3 O 8 436 95 Sn(WO 4 ) 2 402 96 Si(WO 4 ) 2 282 95 PbWO 4 405 95 PbWO 3 419 94 CdWO 4 326 91 CdWO 3 345 90 Bi 2 WO 6 382 90 Bi 2 (WO 4 ) 3 368 92 In 2 (WO 4 ) 3 426 90 In(WO 3 ) 3 398 94 Sb 2 (WO 4 ) 3 350 90 ZnWO 4 208 86 ZnWO 3 226 89 Ga 2 (WO 4 ) 3 321 89 Ga 2 (WO 3 ) 3 333 88 Ge(WO 4 ) 2 341 89 Ge(WO 3 ) 2 353 86 MgWO 4 301 87 MgWO 3 313 86 CaWO 4 301 87 CaWO 3 313 86 SrWO 4 301 87 SrWO 3 313 86 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 9. The batteries using the metal or semi-metal tungstate of Example 9 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 10 The electrode characteristics of various metal and semi-metal molybdates specified in Table 32 and used as the anode active material were evaluated in Example 10. Table 32 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (MoO 4 ) 3 302 87 SnMo 2 O 8 426 94 SnMoO 4 472 92 SiMo 2 O 8 340 90 PbMoO 4 456 94 CdMoO 4 346 91 Bi 2 (MoO 4 ) 3 402 93 In 2 (MoO 4 ) 3 436 94 InMo 4 O 6 398 96 Sb 2 (MoO 4 ) 3 348 90 ZnMoO 4 268 87 Ga 2 (MoO 4 ) 3 359 89 GeMoO 4 371 90 MgMoO 4 324 88 CaMoO 4 324 88 SrMoO 4 324 88 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 10. The batteries using the metal or semi-metal molybdate of Example 10 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 11 The electrode characteristics of various metal and semi-metal titanates specified in Table 33 and used as the anode active material were evaluated in Example 11. Table 33 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) AlTiO 5 326 73 SnTiO 4 443 82 SiTiO 8 321 75 PbTiO 3 476 80 PbTi 3 O 7 402 81 CdTiO 3 354 76 Bi 2 TiO 5 498 81 Bi 2 Ti 2 O 7 424 82 In 2 TiO 5 478 83 Sb 3 Ti 2 O 10 369 80 ZnTiO 3 324 76 GaTiO 5 371 75 GeTiO 3 380 74 MgTiO 4 334 71 CaTiO 4 334 71 SrTiO 4 334 71 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 11. The batteries using the metal or semi-metal titanate of Example 11 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 12 The electrode characteristics of various metal and semi-metal zirconates specified in Table 34 and used as the anode active material were evaluated in Example 12. Table 34 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 (ZrO 3 ) 3 304 71 SnZrO 3 484 78 SiZrO 4 342 76 PbZrO 3 466 77 CdZrO 3 357 71 Bi 2 (ZrO 3 ) 3 419 77 In 2 (ZrO 3 ) 3 443 78 Sb 2 (ZrO 3 ) 3 354 75 ZnZrO 3 294 73 Ga 2 (ZrO 3 ) 3 372 74 GeZrO 3 379 72 MgZrO 3 339 73 CaZrO 3 339 73 SrZrO 3 339 73 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 12. The batteries using the metal or semi-metal zirconate of Example 12 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 13 The electrode characteristics of various metal and semi-metal vanadates specified in Table 35 and used as the anode active material were evaluated in Example 13. Table 35 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) AlVO 4 319 82 SnV 2 O 6 452 89 Sn 2 V 2 O 6 489 87 SiV 2 O 7 324 84 Pb 2 V 2 O 6 477 86 PbV 2 O 6 427 88 CdV 2 O 6 326 83 BiVO 4 436 86 Bi 2 VO 5 496 85 InVO 4 498 85 In 2 VO 5 504 83 SbVO 4 354 83 ZnV 2 O 6 311 81 GaVO 4 368 83 GeV 2 O 6 341 84 MgV 2 O 6 312 79 CaV 2 O 6 312 79 SrV 2 O 6 312 79 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 13. The batteries using the metal or semi-metal vanadate of Example 13 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 14 The electrode characteristics of various metal and semi-metal chromates specified in Table 36 and used as the anode active material were evaluated in Example 14. Table 36 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) AlCrO 3 342 87 SnCrO 4 463 94 Sn 2 CrO 6 504 92 Si(CrO 4 ) 2 341 89 Pb 3 CrO 6 511 91 PbCrO 4 484 93 CdCr 2 O 4 324 87 BiCrO 3 432 91 Bi 2 CrO 6 426 93 InCrO 3 445 92 In 2 CrO 6 486 90 Sb 2 (CrO 4 ) 3 352 88 ZnCrO 4 336 87 Ga 3 (CrO 4 ) 2 381 86 GeCrO 4 382 85 MgCr 2 O 7 304 87 CaCr 2 O 7 304 87 SrCr 2 O 7 304 87 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 14. The batteries using the metal or semi-metal chromate of Example 14 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 15 The electrode characteristics of various metal and semi-metal niobates specified in Table 37 and used as the anode active material were evaluated in Example 15. Table 37 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) AlNbO 4 324 71 SnNb 2 O 6 424 75 Sn 2 Nb 2 O 7 468 74 SiNbO 4 342 71 PbNb 2 O 6 403 74 Pb 2 Nb 2 O 7 426 72 Cd 2 Nb 2 O 7 314 71 BiNbO 4 415 73 InNbO 4 445 74 SbNbO 4 370 73 ZnNb 2 O 6 204 71 GaNbO 4 364 72 GeNb 2 O 6 368 73 MgNb 2 O 6 301 72 CaNb 2 O 6 301 72 SrNb 2 O 6 301 72 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 15. The batteries using the metal or semi-metal niobate of Example 15 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 16 The electrode characteristics of various metal and semi-metal tantalates specified in Table 38 and used as the anode active material were evaluated in Example 16. Table 38 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) AlTaO 4 302 81 Sn 2 Ta 2 O 7 476 88 SiTa 2 O 7 272 82 Pb 2 Ta 2 O 7 406 87 Cd 2 Ta 2 O 7 314 84 BiTaO 4 404 86 InTaO 4 446 85 SbTaO 4 364 85 Zn 2 Ta 2 O 7 246 83 GaTaO 4 356 81 Ge 2 Ta 2 O 7 346 81 Mg 2 Ta 2 O 7 304 79 Ca 2 Ta 2 O 7 304 79 Sr 2 Ta 2 O 7 304 79 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 16. The batteries using the metal or semi-metal tantalate of Example 16 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Example 17 The electrode characteristics of various metal and semi-metal manganates specified in Table 39 and used as the anode active material were evaluated in Example 17. Table 39 shows the discharge capacities of the test cells and the capacity maintenance rates of the cylindrical batteries at the 100-th cycle measured under the same conditions as those of Example 1. Salt Discharge capacity (mAh/g) Capacity maintenance rate(%) Al 2 MnO 6 326 80 SnMnO 3 486 89 SnMn 2 O 4 424 90 SiMnO 3 314 81 PbMnO 3 443 87 CdMnO 3 369 82 Bi 2 MnO 4 424 84 Bi 2 MnO 6 412 86 In 2 MnO 4 461 84 In 2 MnO 6 452 84 Sb 2 MnO 4 392 83 Sb 2 MnO 6 376 84 ZnMnO 3 314 81 Ga 2 MnO 4 386 81 GeMnO 3 349 82 MgMnO 3 326 78 CaMnO 3 326 78 SrMnO 3 326 78 After the conclusion of cathode polarization of the test cells in the tenth cycle, the test cells were decomposed. No deposit of metallic lithium was observed in any of the test cells of Example 17. The batteries using the metal or semi-metal manganate of Example 17 as the anode active material have the improved cycle characteristics, compared with the prior art metal oxides. Although all the above examples refer to the cylindrical batteries, the principle of the present invention is not restricted to this structure but may be applicable to secondary batteries of various types, such asd coin-type, rectangular-type, and cylinder-type. In the above examples, LiMn 1.8 Co 0.2 O 4 was used as the cathode active material. The similar effects can be exerted for a variety of other cathode active materials allowing reversible charge and discharge operations, such as LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , and the like. As discussed above, the present invention uses an anode of high capacity and excellent cycle life and thereby provides a non-aqueous electrolyte secondary battery that is free of a short circuit due to dendrite formation and has a higher energy density and a high reliability.

Claims: A non-aqueous electrolyte secondary battery comprising a cathode capable of being charged and discharged, a non-aqueous electrolyte, and an anode capable of being charged and discharged, said anode having an active material that comprises a salt which is formed of a metal or a semi-metal and a compound selected from the group consisting of oxo-acids, thiocyanic acid, cyanogen, and cyanic acid, wherein each of said oxo-acids comprises an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, tellurium, tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium, salts of said oxo-acids of phosphorus and boron being restricted to hydrogenphosphates and hydrogenborates; wherein said metal or semi-metal is at least one selected from the group consisting of Al, Sn, Si, Pb, Cd, Bi, In, Zn, Mg, Ge, Ga, Ca, Ba, Sr, B, Ir, Sb, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W, and Nb. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said anode comprises a mixture of said active material, carbon material, and a binding agent. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of nitrogen is at least one selected from the group consisting of nitrates and nitrites. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of sulfur is at least one selected from the group consisting of sulfates, sulfites, disulfates, peroxomonosulfates, peroxodisulfates, thiosulfates, dithionates, disulfites, thiosulfites, dithionites, and sulfoxylates. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of phosphorus is at least one selected from the group consisting of monohydrogenphosphates, dihydrogenphosphates, phosphinates, and phosphonates. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of boron is at least one selected from the group consisting of monohydrogenborates and dihydrogenborates. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of selenium is at least one selected from the group consisting of selenates M 2 (SeO 4 ) m , selenites M 2 (SeO 3 ) m , M 2 (SeO 5 ) m , M(HSeO 4 ) m , and M(HSeO 3 ) m , where M denotes a metal or semi-metal having a valence m. The non-aqueous electrolyte secondary battery in accordance with claim 1, wherein said metal salt or semi-metal salt of said oxo-acid of tellurium is at least one selected from the group consisting of M 6 (TeO 6 ) m , M 2 (TeO 4 ) m , M 5 (H 5 TeO 6 ) m , M 4 (H 2 TeO 6 ) m , M 2 (H 3 TeO 6 ) m , and M 2 (H 4 TeO 6 ) m , where M denotes a metal or semi-metal having a valence m.2

Inventors: BITO YASUHIKO, ITO SHUJI, MURATA TOSHIHIDE, TOYOGUCHI YOSHINORI, BITO, YASUHIKO, ITO, SHUJI, MURATA, TOSHIHIDE, TOYOGUCHI, YOSHINORI
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1997
Main classification: H01M4
IPC codes: H01M4, H01M10