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 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 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.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.2, V.sub.2 O.sub.5, Cr.sub.2 O.sub.5, MnO.sub.2, TiS.sub.2, MoS.sub.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.sub.2 (Japanese Laid-Open Patent Publication Hei 7-122274 and Hei 7-235293) and amorphous oxides, such as SnSiO.sub.3, SnSi.sub.1-x P.sub.x O.sub.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 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 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 the oxo-acid is one of 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.

It is preferable that the metal or the 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 dendrite 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.sup.II are given as examples. Salts of nitrogen oxo-acids include nitrates M.sup.II (NO.sub.3).sub.2 and nitrites M.sup.II (NO.sub.2).sub.2.

Salts of sulfur oxo-acids include sulfates M.sup.II SO.sub.4, sulfites M.sup.II SO.sub.3, disulfates M.sup.II S.sub.2 O.sub.7, peroxomonosulfates M.sup.II SO.sub.5, peroxodisulfates M.sup.II S.sub.2 O.sub.8, thiosulfates M.sup.II S.sub.2 O.sub.3, disulfites M.sup.II S.sub.2 O.sub.5, thiosulfites M.sup.II S.sub.2 O.sub.2, hydrogensulfates such as M.sup.II (HSO.sub.4).sub.2, thionates such as dithionates M.sup.II S.sub.2 O.sub.6 and dithionites M.sup.II S.sub.2 O.sub.4, sulfoxylates such as M.sup.II SO.sub.2, and hydrogen-containing acid salts.

Preferable salts of phosphorus oxo-acids include hydrogenphosphates such as M.sup.II HPO.sub.4 and M.sup.II (H.sub.2 PO.sub.4).sub.2, phosphinates M.sup.II (PH.sub.2 O.sub.2).sub.2, and phosphonates M.sup.II PHO.sub.3.

Salts of carbon oxo-acids include carbonates M.sup.II CO.sub.3 and hydrogencarbonates M.sup.II (HCO.sub.3).sub.2.

Preferable salts of boron oxo-acids include hydrogenborates such as M.sup.II (H.sub.2 BO.sub.3).sub.2 and M.sup.II HBO.sub.3.

Salts of selenium oxo-acids include selenates M.sup.II SeO.sub.4, selenites M.sup.II SeO.sub.3, M.sup.II SeO.sub.5, hydrogenselenates M.sup.II (HSeO.sub.4).sub.2, and hydrogenselenites M.sup.II (HSeO.sub.3).sub.2.

Salts of tellurium oxo-acids include tellurates such as M.sup.II.sub.3 TeO.sub.6 and M.sub.II TeO.sub.4, and hydrogentellurates such as M.sup.II.sub.5 (H.sub.5 TeO.sub.6).sub.2, M.sup.II .sub.2 H.sub.2 TeO.sub.6, M.sup.II.sub.3 (H.sub.3 TeO.sub.6).sub.2, and M.sup.II H.sub.4 TeO.sub.6.

Available thiocyanates include M.sup.II (SCN).sub.2, while available cyanides and cyanates include M.sup.II (CN).sub.2 and M.sup.II (ONC).sub.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.sup.III represents a trivalent metal or semi-metal.

Available tungstates include M.sup.II WO.sub.4, M.sup.II WO.sub.3, M.sup.III WO.sub.6. Available molybdates include M.sup.II MoO.sub.4 and M.sup.III Mo.sub.4 O.sub.6. Available titanates include M.sup.II TiO.sub.3, M.sup.II TiO.sub.4, (M.sup.III).sub.2 TiO.sub.5, and M.sup.II Ti.sub.3 O.sub.7.

Available zirconates include M.sup.II ZrO.sub.3 and M.sup.II ZrO.sub.4. Available chromates include M.sup.III CrO.sub.3, M.sup.II CrO.sub.4, M.sup.II Cr.sub.2 O.sub.4, and (M.sup.III).sub.2 CrO.sub.6. Available niobates include M.sup.III NbO.sub.4, M.sup.II Nb.sub.2 O.sub.6, and (M.sup.III).sub.2 Nb.sub.2 O.sub.7.

Available tantalates include M.sup.III TaO.sub.4 and (M.sup.II).sub.2 Ta.sub.2 O.sub.7. Available manganates include M.sup.II MnO.sub.3, (M.sup.III).sub.2 MnO.sub.4, and (M.sup.III).sub.2 MnO.sub.6. Available vanadates include M.sup.III VO.sub.4, (M.sup.III).sub.2 VO.sub.5, and M.sup.II V.sub.2 O.sub.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) the salts including oxygen and any one of nitrogen, sulfur, phosphorus, carbon, boron, selenium, and tellurium, such as salts of oxo-acids of nitrogen, sulfur, phosphorus, carbon, boron, selenium and tellurium or by the salts further including hydrogen such as hydrogen-containing oxo-acids; b) cyanides containing nitrogen and carbon; c) cyanates containing nitrogen, carbon and oxygen; or d) thiocyanates containing nitrogen, carbon and sulfur and in which those salts 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 the salts of oxo-acid 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.sub.2 (SeO.sub.4).sub.m, M.sub.2 (SeO.sub.3).sub.m, M.sub.2 (SeO.sub.5).sub.m, M(HSeO.sub.4).sub.m, and M(HSeO.sub.3).sub.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, 3 g 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.sub.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 with 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.sub.2, Fe.sub.2 O.sub.3, SnO, and PbO, sulfides SnS and PbS, and amorphous metal oxides SnSiO.sub.3 and SnSi.sub.0.8 P.sub.0.2 O.sub.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.sub.1.8 Co.sub.0.2 O.sub.4 was prepared by mixing Li.sub.2 CO.sub.3, Mn.sub.3 O.sub.4, and CoCO.sub.3 at a predetermined molar ratio, heating the mixture at 900.degree. 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.degree. 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.degree. C. and a charge-discharge current of 1 mA/cm.sup.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.

TABLE 1______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al(NO.sub.3).sub.3 284 75Al(NO.sub.2).sub.3 326 73Sn(NO.sub.3).sub.4 346 86Sn(NO.sub.2).sub.4 389 84Sn(NO.sub.3).sub.2 485 84Sn(NO.sub.2).sub.2 510 82Si(NO.sub.3).sub.4 390 83Si(NO.sub.2).sub.4 435 84Pb(NO.sub.3).sub.2 356 83Pb(NO.sub.2).sub.2 394 82Cd(NO.sub.3).sub.2 320 78Cd(NO.sub.2).sub.2 336 77Bi(NO.sub.3).sub.3 298 78Bi(NO.sub.2).sub.3 324 75In(NO.sub.3).sub.3 346 78In(NO.sub.2).sub.3 375 75Zn(NO.sub.3).sub.2 289 75Zn(NO.sub.2).sub.2 326 79Ga(NO.sub.3).sub.3 335 75Ga(NO.sub.2).sub.3 362 72Ge(NO.sub.3).sub.4 367 74Ge(NO.sub.2).sub.4 400 72Mg(NO.sub.3).sub.2 296 81Mg(NO.sub.2).sub.2 334 79Sb(NO.sub.3).sub.3 425 75Sb(NO.sub.2).sub.3 433 73Ti(NO.sub.3).sub.4 275 80V(NO.sub.3).sub.2 255 84Cr(NO.sub.2).sub.3 285 82Mn(NO.sub.3).sub.2 263 83Fe(NO.sub.3).sub.2 274 81Co(NO.sub.3).sub.2 269 80Ni(NO.sub.3).sub.2 271 80Cu(NO.sub.3).sub.2 265 78Mo(NO.sub.3).sub.2 222 77W(NO.sub.3).sub.4 215 80Nb(NO.sub.3).sub.3 220 79Ca(NO.sub.3).sub.2 286 79Ba(NO.sub.3).sub.2 275 80Ir(NO.sub.3).sub.3 266 81Sr(NO.sub.3).sub.2 286 79______________________________________ TABLE 2______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Ba.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2 425 86Ca.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2 433 85Sr.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2 443 85Mg.sub.0.33 Sn.sub.0.67 (NO.sub.3).sub.2 435 85Mn.sub.0.22 Sn.sub.0.78 (NO.sub.3).sub.2 410 86Fe.sub.0.12 Sn.sub.0.88 (NO.sub.3).sub.2 451 85Co.sub.0.18 Sn.sub.0.82 (NO.sub.3).sub.2 444 87Cu.sub.0.18 Sn.sub.0.82 (NO.sub.3).sub.2 435 86Ti.sub.0.12 Sn.sub.0.82 (NO.sub.3).sub.2 436 85Zn.sub.0.12 Sn.sub.0.88 (NO.sub.3).sub.2 442 87Cr.sub.0.12 Sn.sub.0.82 (NO.sub.3).sub.2 440 86Vo.sub.0.12 Sn.sub.0.82 (NO.sub.3).sub.2 421 87Ba.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2 312 85Ca.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2 319 87Sr.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2 329 87Mg.sub.0.33 Pb.sub.0.67 (NO.sub.3).sub.2 326 85Mn.sub.0.22 Pb.sub.0.78 (NO.sub.3).sub.2 333 84Fe.sub.0.12 Pb.sub.0.88 (NO.sub.3).sub.2 329 86Co.sub.0.18 Pb.sub.0.82 (NO.sub.3).sub.2 326 85Cu.sub.0.18 Pb.sub.0.82 (NO.sub.3).sub.2 319 87Ti.sub.0.12 Pb.sub.0.82 (NO.sub.3).sub.2 314 81Zn.sub.0.12 Pb.sub.0.88 (NO.sub.3).sub.2 329 83Cr.sub.0.12 Pb.sub.0.82 (NO.sub.3).sub.2 320 84W.sub.0.09 Pb.sub.0.82 (NO.sub.3).sub.2 301 87Fe.sub.0.18 In.sub.0.88 (NO.sub.3).sub.3 324 82Co.sub.0.27 In.sub.0.82 (NO.sub.3).sub.3 315 83Cu.sub.0.27 In.sub.0.82 (NO.sub.3).sub.3 310 84Ti.sub.0.27 Bi.sub.0.82 (NO.sub.3).sub.3 275 80Zn.sub.0.27 Bi.sub.0.88 (NO.sub.3).sub.3 284 79______________________________________ TABLE 3______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________WO.sub.2 190 9Fe.sub.2 O.sub.3 185 10SnO 522 5SnSiO.sub.3 453 20PbO 453 2SnS 498 6PbS 436 3SnSi.sub.0.8 P.sub.0.2 O.sub.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.

TABLE 4______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (CO.sub.3).sub.3 342 75Al(HCO.sub.3).sub.3 306 86Sn(CO.sub.3).sub.2 493 86SnCO.sub.3 534 82Sn(HCO.sub.3).sub.4 424 92Sn(HCO.sub.3).sub.2 490 90Si(CO.sub.3).sub.2 378 81Si(HCO.sub.3).sub.4 365 89PbCO.sub.3 441 82Pb(HCO.sub.3).sub.2 402 84CdCO.sub.3 397 75Cd(HCO.sub.3).sub.2 365 85Bi.sub.2 (CO.sub.3).sub.3 369 73Bi(HCO.sub.3).sub.3 305 78In.sub.2 (CO.sub.3).sub.3 461 76In(HCO.sub.3).sub.3 386 85ZnCO.sub.3 298 72Zn(HCO.sub.3).sub.2 268 82Ga.sub.2 (CO.sub.3).sub.3 334 73Sb(HCO.sub.3).sub.3 315 75Ga(HCO.sub.3).sub.3 312 79Ge(CO.sub.3).sub.2 365 75Ge(HCO.sub.3).sub.4 335 83MgCO.sub.3 304 79Mg(HCO.sub.3).sub.2 292 85Ti.sub.2 (CO.sub.3).sub.3 298 75MnCO.sub.3 263 86VCO.sub.3 198 86Cr.sub.2 (CO.sub.3).sub.3 263 82FeCO.sub.3 246 84CoCO.sub.3 259 83NiCO.sub.3 264 81CuCO.sub.3 253 82MoCO.sub.3 221 82BaCO.sub.3 256 80CaCO.sub.3 263 75W(CO.sub.3).sub.2 215 75Ir.sub.2 (CO.sub.3).sub.3 321 73Sb.sub.2 (CO.sub.3).sub.3 365 78Nb(CO.sub.3).sub.5 187 80SrCO.sub.3 273 75______________________________________ TABLE 5______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Ba.sub.0.2 Sn.sub.0.8 CO.sub.3 498 84Ca.sub.0.2 Sn.sub.0.8 CO.sub.3 485 85Sr.sub.0.2 Sn.sub.0.8 CO.sub.3 495 85Mg.sub.0.2 Sn.sub.0.8 CO.sub.3 500 86Mn.sub.0.2 Sn.sub.0.8 CO.sub.3 482 85Fe.sub.0.2 Sn.sub.0.8 CO.sub.3 479 87Co.sub.0.2 Sn.sub.0.8 CO.sub.3 486 86Cu.sub.0.2 Sn.sub.0.8 CO.sub.3 493 85Ti.sub.0.2 Sn.sub.0.7 CO.sub.3 475 84Zn.sub.0.2 Sn.sub.0.8 CO.sub.3 482 85Cr.sub.0.2 Sn.sub.0.7 CO.sub.3 473 85Mo.sub.0.2 Sn.sub.0.8 CO.sub.3 459 86Ba.sub.0.2 Pb.sub.0.8 CO.sub.3 421 83Ca.sub.0.2 Pb.sub.0.8 CO.sub.3 416 85Sr.sub.0.2 Pb.sub.0.8 CO.sub.3 416 85Mg.sub.0.2 Pb.sub.0.8 CO.sub.3 422 84Mn.sub.0.2 Pb.sub.0.8 CO.sub.3 418 87Fe.sub.0.2 Pb.sub.0.8 CO.sub.3 409 86Co.sub.0.2 Pb.sub.0.8 CO.sub.3 417 85Cu.sub.0.2 Pb.sub.0.8 CO.sub.3 415 84Ti.sub.0.2 Pb.sub.0.7 CO.sub.3 398 85Zn.sub.0.2 Pb.sub.0.8 CO.sub.3 405 86Cr.sub.0.2 Pb.sub.0.7 CO.sub.3 403 85Mo.sub.0.2 Pb.sub.0.8 CO.sub.3 398 87(Fe.sub.0.3 In.sub.0.8).sub.2 (CO.sub.3).sub.3 415 79(Co.sub.0.3 In.sub.0.8).sub.2 (CO.sub.3).sub.3 410 80(Cu.sub.0.3 In.sub.0.8).sub.2 (CO.sub.3).sub.3 416 81(Ti.sub.0.2 Bi.sub.0.8).sub.2 (CO.sub.3).sub.3 342 78(Zn.sub.0.3 Bi.sub.0.8).sub.2 (CO.sub.3).sub.3 331 77Ba.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 452 92Ca.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 441 94Sr.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 443 94Mg.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 451 93Mn.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 443 91Fe.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 439 92Co.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 441 91Cu.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 456 92Ti.sub.0.2 Sn.sub.0.7 (HCO.sub.3).sub.2 432 92Zn.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 440 93Cr.sub.0.2 Sn.sub.0.7 (HCO.sub.3).sub.2 429 94Mo.sub.0.2 Sn.sub.0.8 (HCO.sub.3).sub.2 420 94Ba.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 384 88Ca.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 372 89Sr.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 372 89Mg.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 382 87Mn.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 371 90Fe.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 367 91Co.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 371 90Cu.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 379 89Ti.sub.0.2 Pb.sub.0.7 (HCO.sub.3).sub.2 352 89Zn.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 368 90Cr.sub.0.2 Pb.sub.0.7 (HCO.sub.3).sub.2 369 90Mo.sub.0.2 Pb.sub.0.8 (HCO.sub.3).sub.2 357 91Fe.sub.0.3 In.sub.0.8 (HCO.sub.3).sub.3 365 86Co.sub.0.3 In.sub.0.8 (HCO.sub.3).sub.3 359 88Cu.sub.0.3 In.sub.0.8 (HCO.sub.3).sub.3 358 87Ti.sub.0.2 Bi.sub.0.8 (HCO.sub.3).sub.3 301 86Zn.sub.0.3 Bi.sub.0.8 (HCO.sub.3).sub.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.

TABLE 6______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (HBO.sub.3).sub.3 305 78Al(H.sub.2 BO.sub.3).sub.3 294 80SnHBO.sub.3 532 83Sn(HBO.sub.3).sub.2 453 85Sn(H.sub.2 BO.sub.3).sub.4 405 86Sn(H.sub.2 BO.sub.3).sub.2 493 85Si(HBO.sub.3).sub.2 326 82Si(H.sub.2 BO.sub.3).sub.4 296 83PbHBO.sub.3 443 84Pb(H.sub.2 BO.sub.3).sub.2 421 86CdHBO.sub.3 328 84Bi.sub.2 (HBO.sub.3).sub.3 312 79Bi(H.sub.2 BO.sub.3).sub.3 289 81In.sub.2 (HBO.sub.3).sub.3 385 84In(H.sub.2 BO.sub.3).sub.3 368 86ZnHBO.sub.3 268 79Zn(H.sub.2 BO.sub.3).sub.2 268 81Ga.sub.2 (HBO.sub.3).sub.3 338 79Ga(H.sub.2 BO.sub.3).sub.3 312 82Ge(HBO.sub.3).sub.2 352 85Ge(H.sub.2 BO.sub.3).sub.4 335 87MgHBO.sub.3 296 84Mg(H.sub.2 BO.sub.3).sub.2 286 86______________________________________ TABLE 7______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Sb.sub.2 (HBO.sub.3).sub.3 310 80Ba.sub.0.1 Sn.sub.0.9 HBO.sub.3 486 84Ca.sub.0.1 Sn.sub.0.9 HBO.sub.3 482 85Sr.sub.0.1 Sn.sub.0.9 HBO.sub.3 482 85Mg.sub.0.1 Sn.sub.0.9 HBO.sub.3 479 84Zn.sub.0.1 Sn.sub.0.9 HBO.sub.3 481 86Cu.sub.0.1 Sn.sub.0.9 HBO.sub.3 469 87Co.sub.0.1 Sn.sub.0.9 HBO.sub.3 467 85Fe.sub.0.1 Sn.sub.0.9 HBO.sub.3 461 86Ni.sub.0.1 Sn.sub.0.9 HBO.sub.3 449 87Ti.sub.0.2 Sn.sub.0.7 HBO.sub.3 459 86Cr.sub.0.1 Sn.sub.0.7 HBO.sub.3 449 88V.sub.0.1 Sn.sub.0.9 HBO.sub.3 429 87Mo.sub.0.1 Sn.sub.0.9 HBO.sub.3 438 87W.sub.0.1 Sn.sub.0.8 HBO.sub.3 429 86(Mn.sub.0.3 In.sub.0.9).sub.2 (HBO.sub.3).sub.3 352 82(Ni.sub.0.3 In.sub.0.8).sub.2 (HBO.sub.3).sub.3 357 85(Co.sub.0.3 In.sub.0.8).sub.3 (HBO.sub.3).sub.3 349 85(Mn.sub.0.3 Bi.sub.0.9).sub.2 (HBO.sub.3).sub.3 291 82(Ni.sub.0.3 Bi.sub.0.8).sub.2 (HBO.sub.3).sub.3 281 82(Co.sub.0.3 Bi.sub.0.8).sub.3 (HBO.sub.3).sub.3 279 83______________________________________ TABLE 8______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Ba.sub.0.1 Pb.sub.0.9 HBO.sub.3 421 88Ca.sub.0.1 Pb.sub.0.9 HBO.sub.3 429 87Sr.sub.0.1 Pb.sub.0.9 HBO.sub.3 429 87Mg.sub.0.1 Pb.sub.0.9 HBO.sub.3 428 88Zn.sub.0.1 Pb.sub.0.9 HBO.sub.3 420 86Cu.sub.0.1 Pb.sub.0.9 HBO.sub.3 419 85Co.sub.0.1 Pb.sub.0.9 HBO.sub.3 425 84Fe.sub.0.1 Pb.sub.0.9 HBO.sub.3 422 85Ni.sub.0.1 Pb.sub.0.9 HBO.sub.3 428 86Ti.sub.0.2 Pb.sub.0.7 HBO.sub.3 419 89Cr.sub.0.1 Pb.sub.0.7 HBO.sub.3 401 85V.sub.0.1 Pb.sub.0.9 HBO.sub.3 398 87Mo.sub.0.1 Pb.sub.0.9 HBO.sub.3 392 86W.sub.0.1 Pb.sub.0.8 HBO.sub.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-acids 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.

TABLE 9______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (SO.sub.4).sub.3 389 82Al.sub.2 (SO.sub.3).sub.3 405 77Al.sub.2 (S.sub.2 O.sub.7).sub.3 342 83Al.sub.2 (SO.sub.5).sub.3 370 81Al.sub.2 (S.sub.2 O.sub.8).sub.3 338 85Al.sub.2 (S.sub.2 O.sub.3).sub.3 375 81Al.sub.2 (S.sub.2 O.sub.6).sub.3 364 82Al.sub.2 (S.sub.2 O.sub.5).sub.3 372 83Al.sub.2 (S.sub.2 O.sub.2).sub.3 378 83Al.sub.2 (S.sub.2 O.sub.4).sub.3 364 84Al.sub.2 (SO.sub.2).sub.3 415 80Sn(SO.sub.4).sub.2 482 85Sn(SO.sub.3).sub.2 521 80Sn(S.sub.2 O.sub.7).sub.2 416 86Sn(SO.sub.5).sub.2 456 83Sn(S.sub.2 O.sub.8).sub.2 403 84Sn(S.sub.2 O.sub.3).sub.2 456 82Sn(S.sub.2 O.sub.6).sub.2 423 88Sn(S.sub.2 O.sub.5).sub.2 437 87Sn(S.sub.2 O.sub.2).sub.2 464 84Sn(S.sub.2 O.sub.4).sub.2 424 86Sn(SO.sub.2).sub.2 510 82SnSO.sub.4 532 82SnSO.sub.3 556 79SnS.sub.2 O.sub.7 482 85SnSO.sub.5 502 83Al(HSO.sub.4).sub.3 356 91Al(HSO.sub.3).sub.3 375 87Al(HS.sub.2 O.sub.7).sub.3 320 92Al(HSO.sub.5).sub.3 335 91Al(HS.sub.2 O.sub.8).sub.3 314 89Al(HS.sub.2 O.sub.3).sub.3 346 88Al(HS.sub.2 O.sub.6).sub.3 352 89Al(HS.sub.2 O.sub.5).sub.3 346 90Al(HS.sub.2 O.sub.2).sub.3 348 91Al(HS.sub.2 O.sub.4).sub.3 334 92Al(HSO.sub.2).sub.3 358 89Sn(HSO.sub.4).sub.4 446 95Sn(HSO.sub.3).sub.4 453 92Sn(HS.sub.2 O.sub.7).sub.4 386 94Sn(HSO.sub.5).sub.4 423 93Sn(HS.sub.2 O.sub.8).sub.4 379 94Sn(HS.sub.2 O.sub.3).sub.4 433 93Sn(HS.sub.2 O.sub.6).sub.4 402 97Sn(HS.sub.2 O.sub.5).sub.4 410 96Sn(HS.sub.2 O.sub.2).sub.4 439 94Sn(HS.sub.2 O.sub.4).sub.4 403 95Sn(HSO.sub.2).sub.4 470 90Sn(HSO.sub.4).sub.2 486 93Sn(HSO.sub.3).sub.2 496 88Sn(HS.sub.2 O.sub.7).sub.2 450 92Sn(HSO.sub.5).sub.2 457 91______________________________________ TABLE 10______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________SnS.sub.2 O.sub.8 460 86SnS.sub.2 O.sub.3 505 79SnS.sub.2 O.sub.6 476 85SnS.sub.2 O.sub.5 483 85SnS.sub.2 O.sub.2 536 80SnS.sub.2 O.sub.4 497 81SnSO.sub.2 545 79Si(SO.sub.4).sub.2 395 85Si(SO.sub.3).sub.2 411 82Si(S.sub.2 O.sub.7).sub.2 341 87Si(SO.sub.5).sub.2 362 85Si(S.sub.2 O.sub.8).sub.2 322 87Si(S.sub.2 O.sub.3).sub.2 375 84Si(S.sub.2 O.sub.6).sub.2 332 85Si(S.sub.2 O.sub.5).sub.2 343 84Si(S.sub.2 O.sub.2).sub.2 378 82Si(S.sub.2 O.sub.4).sub.2 350 85Si(SO.sub.2).sub.2 421 83PbSO.sub.4 452 84PbSO.sub.3 472 83PbS.sub.2 O.sub.7 405 86PbSO.sub.5 432 85PbS.sub.2 O.sub.8 400 86PbS.sub.2 O.sub.3 441 84PbS.sub.2 O.sub.6 411 85PbS.sub.2 O.sub.5 419 85PbS.sub.2 O.sub.2 445 82PbS.sub.2 O.sub.4 412 84Sn(HS.sub.2 O.sub.8).sub.2 426 93Sn(HS.sub.2 O.sub.3).sub.2 472 91Sn(HS.sub.2 O.sub.6).sub.2 436 94Sn(HS.sub.2 O.sub.5).sub.2 440 94Sn(HS.sub.2 O.sub.2).sub.2 471 91Sn(HS.sub.2 O.sub.4).sub.2 446 93Sn(HSO.sub.2).sub.2 492 90Si(HSO.sub.4).sub.4 362 93Si(HSO.sub.3).sub.4 371 91Si(HS.sub.2 O.sub.7).sub.4 312 94Si(HSO.sub.5).sub.4 335 95Si(HS.sub.2 O.sub.8).sub.4 294 96Si(HS.sub.2 O.sub.3).sub.4 341 93Si(HS.sub.2 O.sub.6).sub.4 309 95Si(HS.sub.2 O.sub.5).sub.4 312 94Si(HS.sub.2 O.sub.2).sub.4 340 92Si(HS.sub.2 O.sub.4).sub.4 318 93Si(HSO.sub.2).sub.4 390 90Pb(HSO.sub.4).sub.2 415 92Pb(HSO.sub.3).sub.2 426 91Pb(HS.sub.2 O.sub.7).sub.2 386 95Pb(HSO.sub.5).sub.2 403 94Pb(HS.sub.2 O.sub.8).sub.2 376 95Pb(HS.sub.2 O.sub.3).sub.2 411 94Pb(HS.sub.2 O.sub.6).sub.2 389 96Pb(HS.sub.2 O.sub.5).sub.2 399 95Pb(HS.sub.2 O.sub.2).sub.2 419 91Pb(HS.sub.2 O.sub.4).sub.2 391 93______________________________________ TABLE 11______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________PbSO.sub.2 475 81CdSO.sub.4 414 79CdSO.sub.3 426 78CdS.sub.2 O.sub.7 378 81CdSO.sub.5 404 82CdS.sub.2 O.sub.8 369 84CdS.sub.2 O.sub.3 410 78CdS.sub.2 O.sub.6 398 79CdS.sub.2 O.sub.5 401 80CdS.sub.2 O.sub.2 410 78CdS.sub.2 O.sub.4 389 82CdSO.sub.2 420 76Bi.sub.2 (SO.sub.4).sub.3 364 76Bi.sub.2 (SO.sub.3).sub.3 381 75Bi.sub.2 (S.sub.2 O.sub.7).sub.3 324 79Bi.sub.2 (SO.sub.5).sub.3 348 78Bi.sub.2 (S.sub.2 O.sub.8).sub.3 315 81Bi.sub.2 (S.sub.2 O.sub.3).sub.3 346 78Bi.sub.2 (S.sub.2 O.sub.6).sub.3 329 78Bi.sub.2 (S.sub.2 O.sub.5).sub.3 347 76Bi.sub.2 (S.sub.2 O.sub.2).sub.3 352 75Bi.sub.2 (S.sub.2 O.sub.4).sub.3 333 79Bi.sub.2 (SO.sub.2).sub.3 379 75In.sub.2 (SO.sub.4).sub.3 444 83In.sub.2 (SO.sub.3).sub.3 459 81In.sub.2 (S.sub.2 O.sub.7).sub.3 398 86In.sub.2 (SO.sub.5).sub.3 421 83In.sub.2 (S.sub.2 O.sub.8).sub.3 389 85Pb(HSO.sub.2).sub.2 435 91Cd(HSO.sub.4).sub.2 379 89Cd(HSO.sub.3).sub.2 398 88Cd(HS.sub.2 O.sub.7).sub.2 346 92Cd(HSO.sub.5).sub.2 382 93Cd(HS.sub.2 O.sub.8).sub.2 341 93Cd(HS.sub.2 O.sub.3).sub.2 379 90Cd(HS.sub.2 O.sub.6).sub.2 370 91Cd(HS.sub.2 O.sub.5).sub.2 374 93Cd(HS.sub.2 O.sub.2).sub.2 379 89Cd(HS.sub.2 O.sub.4).sub.2 365 93Cd(HSO.sub.2).sub.2 391 89Bi(HSO.sub.4).sub.3 337 87Bi(HSO.sub.3).sub.3 349 86Bi(HS.sub.2 O.sub.7).sub.3 298 87Bi(HSO.sub.5).sub.3 315 86Bi(HS.sub.2 O.sub.8).sub.3 276 90Bi(HS.sub.2 O.sub.3).sub.3 313 85Bi(HS.sub.2 O.sub.6).sub.3 298 86Bi(HS.sub.2 O.sub.5).sub.3 313 87Bi(HS.sub.2 O.sub.2).sub.3 321 84Bi(HS.sub.2 O.sub.4).sub.3 303 88Bi(HSO.sub.2).sub.3 336 86In(HSO.sub.4).sub.3 416 92In(HSO.sub.3).sub.3 420 91In(HS.sub.2 O.sub.7).sub.3 367 95In(HSO.sub.5).sub.3 390 94In(HS.sub.2 O.sub.8).sub.3 374 96______________________________________ TABLE 12______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________In.sub.2 (S.sub.2 O.sub.3).sub.3 432 84In.sub.2 (S.sub.2 O.sub.6).sub.3 419 85In.sub.2 (S.sub.2 O.sub.5).sub.3 416 85In.sub.2 (S.sub.2 O.sub.2).sub.3 432 83In.sub.2 (S.sub.2 O.sub.4).sub.3 398 86In.sub.2 (SO.sub.2).sub.3 456 81ZnSO.sub.4 362 75ZnSO.sub.3 379 73ZnS.sub.2 O.sub.7 334 76ZnSO.sub.5 342 75ZnS.sub.2 O.sub.8 320 76ZnS.sub.2 O.sub.3 342 76ZnS.sub.2 O.sub.6 320 76ZnS.sub.2 O.sub.5 333 75ZnS.sub.2 O.sub.2 354 74ZnS.sub.2 O.sub.4 321 76ZnSO.sub.2 382 73MgSO.sub.4 333 81MgSO.sub.3 352 79MgS.sub.2 O.sub.7 298 84MgSO.sub.5 320 82MgS.sub.2 O.sub.8 302 83MgS.sub.2 O.sub.3 325 81MgS.sub.2 O.sub.6 300 83MgS.sub.2 O.sub.5 311 82MgS.sub.2 O.sub.2 328 82MgS.sub.2 O.sub.4 305 83MgSO.sub.2 342 79In(HS.sub.2 O.sub.3).sub.3 400 95In(HS.sub.2 O.sub.6).sub.3 381 95In(HS.sub.2 O.sub.5).sub.3 390 95In(HS.sub.2 O.sub.2).sub.3 402 91In(HS.sub.2 O.sub.4).sub.3 370 95In(HSO.sub.2).sub.3 420 92Zn(HSO.sub.4).sub.2 333 85Zn(HSO.sub.3).sub.2 342 84Zn(HS.sub.2 O.sub.7).sub.2 300 87Zn(HSO.sub.5).sub.2 312 86Zn(HS.sub.2 O.sub.8).sub.2 294 85Zn(HS.sub.2 O.sub.3).sub.2 310 85Zn(HS.sub.2 O.sub.6).sub.2 300 84Zn(HS.sub.2 O.sub.5).sub.2 310 86Zn(HS.sub.2 O.sub.2).sub.2 325 84Zn(HS.sub.2 O.sub.4).sub.2 290 86Zn(HSO.sub.2).sub.2 341 84Mg(HSO.sub.4).sub.2 312 91Mg(HSO.sub.3).sub.2 330 89Mg(HS.sub.2 O.sub.7).sub.2 271 93Mg(HSO.sub.5).sub.2 294 92Mg(HS.sub.2 O.sub.8).sub.2 279 93Mg(HS.sub.2 O.sub.3).sub.2 293 92Mg(HS.sub.2 O.sub.6).sub.2 276 94Mg(HS.sub.2 O.sub.5).sub.2 288 92Mg(HS.sub.2 O.sub.2).sub.2 296 93Mg(HS.sub.2 O.sub.4).sub.2 276 94Mg(HSO.sub.2).sub.2 302 90______________________________________ TABLE 13______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Ga.sub.2 (SO.sub.4).sub.3 364 76Ga.sub.2 (SO.sub.3).sub.3 382 74Ga.sub.2 (S.sub.2 O.sub.7).sub.3 321 79Ga.sub.2 (SO.sub.5).sub.3 352 75Ga.sub.2 (S.sub.2 O.sub.8).sub.3 312 77Ga.sub.2 (S.sub.2 O.sub.3).sub.3 352 75Ga.sub.2 (S.sub.2 O.sub.6).sub.3 333 76Ga.sub.2 (S.sub.2 O.sub.5).sub.3 342 75Ga.sub.2 (S.sub.2 O.sub.2).sub.3 354 74Ga.sub.2 (S.sub.2 O.sub.4).sub.3 326 76Ga.sub.2 (SO.sub.2).sub.3 375 73Ge(SO.sub.4).sub.2 431 78Ge(SO.sub.3).sub.2 449 75Ge(S.sub.2 O.sub.7).sub.2 395 81Ge(SO.sub.5).sub.2 423 78Ge(S.sub.2 O.sub.8).sub.2 386 81Ge(S.sub.2 O.sub.3).sub.2 425 77Ge(S.sub.2 O.sub.6).sub.2 401 80Ge(S.sub.2 O.sub.5).sub.2 408 79Ge(S.sub.2 O.sub.2).sub.2 420 79Ge(S.sub.2 O.sub.4).sub.2 390 82Ge(SO.sub.2).sub.2 435 77Cr.sub.2 (SO.sub.4).sub.3 353 81Cr.sub.2 (SO.sub.3).sub.3 369 80W(SeO.sub.4).sub.2 298 79CoSO.sub.4 352 82CoSO.sub.3 362 80NiSO.sub.4 349 81Ga(HSO.sub.4).sub.3 339 86Ga(HSO.sub.3).sub.3 352 85Ga(HS.sub.2 O.sub.7).sub.3 301 88Ga(HSO.sub.5).sub.3 315 84Ga(HS.sub.2 O.sub.8).sub.3 294 86Ga(HS.sub.2 O.sub.3).sub.3 321 87Ga(HS.sub.2 O.sub.6).sub.3 303 87Ga(HS.sub.2 O.sub.5).sub.3 318 86Ga(HS.sub.2 O.sub.2).sub.3 321 86Ga(HS.sub.2 O.sub.4).sub.3 296 84Ga(HSO.sub.2).sub.3 348 84Ge(HSO.sub.4).sub.4 412 89Ge(HSO.sub.3).sub.4 421 86Ge(HS.sub.2 O.sub.7).sub.4 370 92Ge(HSO.sub.5).sub.4 396 90Ge(HS.sub.2 O.sub.8).sub.4 356 93Ge(HS.sub.2 O.sub.3).sub.4 387 85Ge(HS.sub.2 O.sub.6).sub.4 374 88Ge(HS.sub.2 O.sub.5).sub.4 373 87Ge(HS.sub.2 O.sub.2).sub.4 395 89Ge(HS.sub.2 O.sub.4).sub.4 365 93Ge(HSO.sub.2).sub.4 402 89Cr(HSO.sub.4).sub.3 325 92Cr(HSO.sub.3).sub.3 341 90W(HSO.sub.4).sub.4 275 89Co(HSO.sub.4).sub.2 321 92Co(HSO.sub.3).sub.2 329 90Ni(HSO.sub.4).sub.2 319 90______________________________________ TABLE 14______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________NiSO.sub.3 354 79CuSO.sub.4 326 82CuSO.sub.3 340 80Ti.sub.2 (SO.sub.4).sub.3 315 83Mo.sub.2 (SO.sub.4).sub.3 324 84VSO.sub.4 306 83MnSO.sub.4 345 82MnSO.sub.3 356 80FeSO.sub.4 354 81FeSO.sub.3 362 78Nb.sub.2 (SO.sub.4).sub.5 257 82CaSO.sub.4 398 78CaSO.sub.3 405 76SrSO.sub.4 398 78SrSO.sub.3 405 76BaSO.sub.4 375 79BaSO.sub.3 386 78Ni(HSO.sub.3).sub.2 326 88Cu(HSO.sub.4).sub.2 301 93Cu(HSO.sub.3).sub.2 319 91Ti(HSO.sub.4).sub.3 284 90Mo(HSO.sub.4).sub.3 299 92V(HSO.sub.4).sub.2 274 92Mn(HSO.sub.4).sub.2 315 93Mn(HSO.sub.3).sub.2 320 90Fe(HSO.sub.4).sub.2 327 91Fe(HSO.sub.3).sub.2 333 89Nb(HSO.sub.4).sub.5 229 90Ca(HSO.sub.4).sub.2 375 87Ca(HSO.sub.3).sub.2 381 85Sr(HSO.sub.4).sub.2 375 87Sr(HSO.sub.3).sub.2 381 85Ba(HSO.sub.4).sub.2 352 87Ba(HSO.sub.3).sub.2 360 86______________________________________ TABLE 15______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Mg.sub.0.1 Sn.sub.0.9 SO.sub.4 503 84Sr.sub.0.1 Sn.sub.0.9 SO.sub.4 503 84Ca.sub.0.1 Sn.sub.0.9 SO.sub.4 503 84Zn.sub.0.1 Sn.sub.0.9 SO.sub.4 500 85Ni.sub.0.1 Sn.sub.0.9 SO.sub.4 495 84Fe.sub.0.1 Sn.sub.0.9 SO.sub.4 492 86Co.sub.0.1 Sn.sub.0.9 SO.sub.4 489 87Mn.sub.0.1 Sn.sub.0.9 SO.sub.4 482 86Cu.sub.0.1 Sn.sub.0.9 SO.sub.4 485 85Mo.sub.0.1 Sn.sub.0.9 SO.sub.4 476 84V.sub.0.1 Sn.sub.0.9 SO.sub.4 473 86W.sub.0.1 Sn.sub.0.8 SO.sub.4 459 83Cr.sub.0.2 Sn.sub.0.7 SO.sub.4 476 84Mo.sub.0.2 Sn.sub.0.7 SO.sub.4 476 85Mg.sub.0.1 Pb.sub.0.9 SO.sub.4 420 86Sr.sub.0.1 Pb.sub.0.9 SO.sub.4 420 86Ca.sub.0.1 Pb.sub.0.9 SO.sub.4 420 86Zn.sub.0.1 Pb.sub.0.9 SO.sub.4 421 87Ni.sub.0.1 Pb.sub.0.9 SO.sub.4 415 86Fe.sub.0.1 Pb.sub.0.9 SO.sub.4 410 87Co.sub.0.1 Pb.sub.0.9 SO.sub.4 416 88Mn.sub.0.1 Pb.sub.0.9 SO.sub.4 408 86Cu.sub.0.1 Pb.sub.0.9 SO.sub.4 406 87Mo.sub.0.1 Pb.sub.0.9 SO.sub.4 398 85V.sub.0.1 Pb.sub.0.9 SO.sub.4 387 85W.sub.0.1 Pb.sub.0.8 SO.sub.4 376 85Cr.sub.0.2 Pb.sub.0.7 SO.sub.4 387 84Mo.sub.0.2 Pb.sub.0.7 SO.sub.4 389 85Mg.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 481 94Sr.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 481 94Ca.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 481 94Zn.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 479 95Ni.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 470 95Fe.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 476 95Co.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 469 94Mn.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 465 96Cu.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 462 94Mo.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 459 95V.sub.0.1 Sn.sub.0.9 (HSO.sub.4).sub.2 451 95W.sub.0.1 Sn.sub.0.8 (HSO.sub.4).sub.2 432 94Cr.sub.0.2 Sn.sub.0.7 (HSO.sub.4).sub.2 455 94Mo.sub.0.2 Sn.sub.0.7 (HSO.sub.4).sub.2 452 95Mg.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 394 95Sr.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 394 95Ca.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 394 95Zn.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 394 94Ni.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 384 97Fe.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 381 95Co.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 384 96Mn.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 381 95Cu.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 386 96Mo.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 370 95V.sub.0.1 Pb.sub.0.9 (HSO.sub.4).sub.2 368 94W.sub.0.1 Pb.sub.0.5 (HSO.sub.4).sub.2 359 95Cr.sub.0.2 Pb.sub.0.7 (HSO.sub.4).sub.2 364 94Mo.sub.0.2 Pb.sub.0.7 (HSO.sub.4).sub.2 368 94______________________________________ TABLE 16______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________(Mg.sub.0.3 In.sub.0.8).sub.2 (SO.sub.4).sub.3 410 85(Zn.sub.0.3 In.sub.0.8).sub.2 (SO.sub.4).sub.3 406 86(Ni.sub.0.3 In.sub.0.8).sub.2 (SO.sub.4).sub.3 398 86(Co.sub.0.3 Bi.sub.0.8).sub.2 (SO.sub.4).sub.3 333 80(Fe.sub.0.3 Bi.sub.0.8).sub.2 (SO.sub.4).sub.3 325 82(Mn.sub.0.3 Bi.sub.0.8).sub.2 (SO.sub.4).sub.3 330 80Sn(SO.sub.4).sub.0.5 (HSO.sub.4) 498 90Pb(SO.sub.4).sub.0.5 (HSO.sub.4) 425 90In.sub.2 (SO.sub.4).sub.2.5 (HSO.sub.4) 425 90Bi.sub.2 (SO.sub.4).sub.2.5 (HSO.sub.4) 343 84Co.sub.0.3 In.sub.0.8 (HSO.sub.4).sub.3 379 94Fe.sub.0.3 In.sub.0.8 (HSO.sub.4).sub.3 370 95Mn.sub.0.3 In.sub.0.8 (HSO.sub.4).sub.3 368 95Mg.sub.0.3 Bi.sub.0.8 (HSO.sub.4).sub.3 298 90Zn.sub.0.3 Bi.sub.0.8 (HSO.sub.4).sub.3 289 89Ni.sub.0.3 Bi.sub.0.8 (HSO.sub.4).sub.3 295 91Sn(SO.sub.4).sub.0.9 (HSO.sub.4).sub.0.2 519 86Pb(SO.sub.4).sub.0.9 (HSO.sub.4).sub.0.2 438 87In.sub.2 (SO.sub.4).sub.2.9 (HSO.sub.4).sub.0.2 438 86Bi.sub.2 (SO.sub.4).sub.2.9 (HSO.sub.4).sub.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.

TABLE 17______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (SeO.sub.4).sub.3 362 83Al.sub.2 (SeO.sub.3).sub.3 387 80Sn(SeO.sub.4).sub.2 462 84Sn(SeO.sub.3).sub.2 483 81SnSeO.sub.4 512 83SnSeO.sub.3 521 80Sn.sub.2 SeO.sub.5 534 79Si(SeO.sub.4).sub.2 364 84Si(SeO.sub.3).sub.2 379 80PbSeO.sub.4 432 85PbSeO.sub.3 445 82Pb.sub.2 SeO.sub.5 498 80CdSeO.sub.4 386 80CdSeO.sub.3 399 78Bi.sub.2 (SeO.sub.4).sub.3 339 77Bi.sub.2 (SeO.sub.3).sub.3 349 72In.sub.2 (SeO.sub.4).sub.3 421 85In.sub.2 (SeO.sub.3).sub.3 438 83ZnSeO.sub.4 339 74ZnSeO.sub.3 348 70MgSeO.sub.4 310 82MgSeO.sub.3 321 79Ga.sub.2 (SeO.sub.4).sub.3 339 75Ga.sub.2 (SeO.sub.3).sub.3 349 73Ge(SeO.sub.4).sub.2 405 77Ge(SeO.sub.3).sub.2 420 72Al(HSeO.sub.4).sub.3 341 92Al(HSeO.sub.3).sub.3 367 89Sn(HSeO.sub.4).sub.4 442 92Sn(HSeO.sub.3).sub.4 462 93Sn(HSeO.sub.4).sub.2 489 94Sn(HSeO.sub.3).sub.2 501 90SnSeO.sub.5 508 84Si(HSeO.sub.4).sub.4 342 92Si(HSeO.sub.3).sub.4 347 90Pb(HSeO.sub.4).sub.2 412 93Pb(HSeO.sub.3).sub.2 421 92PbSeO.sub.5 425 85Cd(HSeO.sub.4).sub.2 364 90Cd(HSeO.sub.3).sub.2 374 88Bi(HSeO.sub.4).sub.3 314 89Bi(HSeO.sub.3).sub.3 321 86In(HSeO.sub.4).sub.3 397 94In(HSeO.sub.3).sub.3 409 93Zn(HSeO.sub.4).sub.2 315 85Zn(HSeO.sub.3).sub.2 320 83Mg(HSeO.sub.4).sub.2 289 92Mg(HSeO.sub.3).sub.2 301 87Ga(HSeO.sub.4).sub.3 314 86Ga(HSeO.sub.3).sub.3 324 84Ge(HSeO.sub.4).sub.4 385 86Ge(HSeO.sub.3).sub.4 396 83______________________________________ TABLE 18______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Cr.sub.2 (SeO.sub.4).sub.3 321 75Cr.sub.2 (SeO.sub.3).sub.3 331 76W(SeO.sub.4).sub.2 257 72CoSeO.sub.4 286 73CoSeO.sub.3 297 76NiSeO.sub.4 286 76NiSeO.sub.3 299 76CuSeO.sub.4 287 73CuSeO.sub.3 289 74Ti.sub.2 (SeO.sub.4).sub.3 253 77Mo.sub.2 (SeO.sub.4).sub.3 223 73VSeO.sub.4 282 79MnSeO.sub.4 265 73MnSeO.sub.3 276 75FeSeO.sub.4 282 74FeSeO.sub.3 293 75Nb.sub.2 (SeO.sub.4).sub.5 215 75CaSeO.sub.4 321 74CaSeO.sub.3 334 76SrSeO.sub.3 334 76BaSeO.sub.4 345 73BaSeO.sub.3 353 74Sb.sub.2 (SeO.sub.4).sub.3 364 72Ir.sub.2 (SeO.sub.4).sub.3 345 73Cr(HSeO.sub.4).sub.3 305 84Cr(HSeO.sub.3).sub.3 314 86W(HSeO.sub.4).sub.4 234 83Co(HSeO.sub.4).sub.2 261 82Co(HSeO.sub.3).sub.2 271 85Ni(HSeO.sub.4).sub.2 264 84Ni(HSeO.sub.3).sub.2 274 85Cu(HSeO.sub.4).sub.2 264 84Cu(HSeO.sub.3).sub.2 259 84Ti(HSeO.sub.4).sub.3 230 86Mo(HSeO.sub.4).sub.3 201 84V(HSeO.sub.4).sub.2 261 89Mn(HSeO.sub.4).sub.2 241 82Mn(HSeO.sub.3).sub.2 251 84Fe(HSeO.sub.4).sub.2 260 86Fe(HSeO.sub.3).sub.2 271 85Nb(HSeO.sub.4).sub.5 195 84Ca(HSeO.sub.4).sub.2 301 82Ca(HSeO.sub.3).sub.2 309 85Sr(HSeO.sub.3).sub.2 309 85Ba(HSeO.sub.4).sub.2 314 84Ba(HSeO.sub.3).sub.2 321 83Sb(HSeO.sub.4).sub.3 335 86Ir(HSeO.sub.4).sub.3 315 85______________________________________ TABLE 19______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Mg.sub.0.1 Sn.sub.0.9 SeO.sub.4 486 85Zn.sub.0.1 Sn.sub.0.9 SeO.sub.4 484 86Ni.sub.0.1 Sn.sub.0.9 SeO.sub.4 472 85Fe.sub.0.1 Sn.sub.0.9 SeO.sub.4 471 86Co.sub.0.1 Sn.sub.0.9 SeO.sub.4 476 87Mn.sub.0.1 Sn.sub.0.9 SeO.sub.4 483 84Cu.sub.0.1 Sn.sub.0.9 SeO.sub.4 475 85Mo.sub.0.1 Sn.sub.0.9 SeO.sub.4 465 86V.sub.0.1 Sn.sub.0.9 SeO.sub.4 459 88W.sub.0.1 Sn.sub.0.8 SeO.sub.4 443 88Cr.sub.0.2 Sn.sub.0.7 SeO.sub.4 433 86Ca.sub.0.1 Sn.sub.0.9 SeO.sub.4 492 85Sr.sub.0.1 Sn.sub.0.9 SeO.sub.4 492 85Ba.sub.0.1 Sn.sub.0.9 SeO.sub.4 475 86Mg.sub.0.1 Pb.sub.0.9 SeO.sub.4 415 85Zn.sub.0.1 Pb.sub.0.9 SeO.sub.4 409 86Ni.sub.0.1 Pb.sub.0.9 SeO.sub.4 414 87Fe.sub.0.1 Pb.sub.0.9 SeO.sub.4 401 88Co.sub.0.1 Pb.sub.0.9 SeO.sub.4 405 86Mn.sub.0.1 Pb.sub.0.9 SeO.sub.4 403 84Cu.sub.0.1 Pb.sub.0.9 SeO.sub.4 402 85Mo.sub.0.1 Pb.sub.0.9 SeO.sub.4 394 85V.sub.0.1 Pb.sub.0.9 SeO.sub.4 396 84W.sub.0.1 Pb.sub.0.8 SeO.sub.4 379 86Cr.sub.0.2 Pb.sub.0.7 SeO.sub.4 368 85Ca.sub.0.1 Pb.sub.0.9 SeO.sub.4 408 85Sr.sub.0.1 Pb.sub.0.9 SeO.sub.4 408 85Ba.sub.0.1 Pb.sub.0.9 SeO.sub.4 381 86Mg.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 453 94Zn.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 461 96Ni.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 453 95Fe.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 449 94Co.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 448 95Mn.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 457 92Cu.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 453 94Mo.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 441 95V.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 432 97W.sub.0.1 Sn.sub.0.8 (HSeO.sub.4).sub.2 420 96Cr.sub.0.2 Sn.sub.0.7 (HSeO.sub.4).sub.2 416 95Ca.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 470 95Sr.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 470 95Ba.sub.0.1 Sn.sub.0.9 (HSeO.sub.4).sub.2 448 94Mg.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 385 94Zn.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 389 95Ni.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 391 96Fe.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 371 98Co.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 379 95Mn.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 371 95Cu.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 376 96Mo.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 370 94V.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 369 95W.sub.0.1 Pb.sub.0.8 (HSeO.sub.4).sub.2 349 97Cr.sub.0.2 Pb.sub.0.7 (HSeO.sub.4).sub.2 333 96Ca.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 379 94Sr.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 379 94Ba.sub.0.1 Pb.sub.0.9 (HSeO.sub.4).sub.2 353 96______________________________________ TABLE 20______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________(Mg.sub.0.3 In.sub.0.8).sub.2 (SeO.sub.4).sub.3 398 86(Zn.sub.0.3 In.sub.0.8).sub.2 (SeO.sub.4).sub.3 387 87(Ni.sub.0.3 In.sub.0.8).sub.2 (SeO.sub.4).sub.3 379 86(Co.sub.0.3 Bi.sub.0.8).sub.2 (SeO.sub.4).sub.3 318 80(Fe.sub.0.3 Bi.sub.0.8).sub.2 (SeO.sub.4).sub.3 310 82(Mn.sub.0.3 Bi.sub.0.8).sub.2 (SeO.sub.4).sub.3 320 82Co.sub.0.3 In.sub.0.8 (HSeO.sub.4).sub.3 374 95Fe.sub.0.3 In.sub.0.8 (HSeO.sub.4).sub.3 361 98Mn.sub.0.3 In.sub.0.8 (HSeO.sub.4).sub.3 348 96Mg.sub.0.3 Bi.sub.0.8 (HSeO.sub.4).sub.3 279 91Zn.sub.0.3 Bi.sub.0.8 (HSeO.sub.4).sub.3 284 92Ni.sub.0.3 Bi.sub.0.8 (HSeO.sub.4).sub.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.

TABLE 21______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (TeO.sub.4).sub.3 346 82SnTeO.sub.4 426 84SnTe.sub.3 O.sub.8 385 87Sn.sub.3 TeO.sub.6 489 85Si(TeO.sub.4).sub.2 337 83PbTeO.sub.4 405 84PbTe.sub.3 O.sub.8 352 85Pb.sub.3 TeO.sub.6 453 82CdTeO.sub.4 354 79Bi.sub.2 (TeO.sub.4).sub.3 314 79Bi.sub.2 TeO.sub.6 345 77In.sub.2 (TeO.sub.4).sub.3 384 82In.sub.2 TeO.sub.6 405 80Sb.sub.2 TeO.sub.6 384 78Ir.sub.2 TeO.sub.6 351 78ZnTeO.sub.4 302 75MgTeO.sub.4 289 81Ga.sub.2 TeO.sub.6 314 74Ge(TeO.sub.4).sub.2 370 75Ti.sub.2 TeO.sub.6 221 78Cr.sub.2 TeO.sub.6 287 74NiTeO.sub.4 253 76FeTeO.sub.4 254 75MnTeO.sub.4 247 74CoTeO.sub.4 253 75VTeO.sub.4 241 76CuTeO.sub.4 251 75Al(HTeO.sub.4).sub.3 319 89Sn(HTeO.sub.4).sub.2 397 90SnH.sub.4 TeO.sub.6 359 95Sn.sub.2 H.sub.2 TeO.sub.6 459 94Si(HTeO.sub.4).sub.4 307 93Pb(HTeO.sub.4).sub.2 372 92PbH.sub.4 TeO.sub.6 321 94Pb.sub.2 H.sub.2 TeO.sub.6 426 93Cd(HTeO.sub.4).sub.2 320 90Bi(HTeO.sub.4).sub.3 284 87BiH.sub.3 TeO.sub.6 314 87In(HTeO.sub.4).sub.3 359 89InH.sub.3 TeO.sub.6 374 90SbH.sub.3 TeO.sub.6 352 89IrH.sub.3 TeO.sub.6 321 88Zn(HTeO.sub.4).sub.2 275 86Mg(HSeO.sub.4).sub.2 264 89GaH.sub.3 TeO.sub.6 275 86Ge(HTeO.sub.4).sub.4 342 86TiH.sub.3 TeO.sub.6 198 87CrH.sub.3 TeO.sub.6 255 86Ni(HTeO.sub.4).sub.2 234 87Fe(HSeO.sub.4).sub.2 229 86Mn(HTeO.sub.4).sub.2 219 85Co(HSeO.sub.4).sub.2 218 85V(HTeO.sub.4).sub.2 214 87Cu(HTeO.sub.4).sub.2 216 85______________________________________ TABLE 22______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________MoTeO.sub.4 234 73W(TeO.sub.4).sub.2 215 73CaTeO.sub.4 315 74SrTeO.sub.4 315 74BaTeO.sub.4 305 75Mg.sub.0.1 Sn.sub.0.9 TeO.sub.4 402 86Cag.sub.0.1 Sn.sub.0.9 TeO.sub.4 402 86Srg.sub.0.1 Sn.sub.0.9 TeO.sub.4 402 86Zn.sub.0.1 Sn.sub.0.9 TeO.sub.4 405 85Ni.sub.0.1 Sn.sub.0.9 TeO.sub.4 400 86Fe.sub.0.1 Sn.sub.0.9 TeO.sub.4 398 87Co.sub.0.1 Sn.sub.0.9 TeO.sub.4 396 86Mn.sub.0.1 Sn.sub.0.9 TeO.sub.4 389 85Cu.sub.0.1 Sn.sub.0.9 TeO.sub.4 390 85Mo.sub.0.1 Sn.sub.0.9 TeO.sub.4 379 87V.sub.0.1 Sn.sub.0.9 TeO.sub.4 378 88W.sub.0.1 Sn.sub.0.8 TeO.sub.4 369 85Cr.sub.0.2 Sn.sub.0.7 TeO.sub.4 374 86Mg.sub.0.1 Pb.sub.0.9 TeO.sub.4 375 86Ca.sub.0.1 Pb.sub.0.9 TeO.sub.4 375 86Sr.sub.0.1 Pb.sub.0.9 TeO.sub.4 375 86Zn.sub.0.1 Pb.sub.0.9 TeO.sub.4 379 85Ni.sub.0.1 Pb.sub.0.9 TeO.sub.4 370 87Fe.sub.0.1 Pb.sub.0.9 TeO.sub.4 367 88Co.sub.0.1 Pb.sub.0.9 TeO.sub.4 368 87Mn.sub.0.1 Pb.sub.0.9 TeO.sub.4 364 86Cu.sub.0.1 Pb.sub.0.9 TeO.sub.4 362 87Mo.sub.0.1 Pb.sub.0.9 TeO.sub.4 354 87V.sub.0.1 Pb.sub.0.9 TeO.sub.4 352 86W.sub.0.1 Pb.sub.0.8 TeO.sub.4 341 85Mo(HTeO.sub.4).sub.2 215 81W(HTeO.sub.4).sub.4 185 82Ca(HTeO.sub.4).sub.2 289 84Sr(HTeO.sub.4).sub.2 289 84Ba(HTeO.sub.4).sub.2 279 83Mg.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 375 95Ca.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 375 95Sr.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 375 95Zn.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 379 94Ni.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 374 95Fe.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 370 96Co.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 375 95Mn.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 369 94Cu.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 371 94Mo.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 352 95V.sub.0.1 Sn.sub.0.9 (HTeO.sub.4).sub.2 349 97W.sub.0.1 Sn.sub.0.8 (HTeO.sub.4).sub.2 342 95Cr.sub.0.2 Sn.sub.0.7 (HTeO.sub.4).sub.2 344 94Mg.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 335 95Ca.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 335 95Sr.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 335 95Zn.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 339 94Ni.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 348 95Fe.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 332 96Co.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 321 95Mn.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 322 94Cu.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 337 95Mo.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 326 94V.sub.0.1 Pb.sub.0.9 (HTeO.sub.4).sub.2 322 95W.sub.0.1 Pb.sub.0.8 (HTeO.sub.4).sub.2 320 96______________________________________ TABLE 23______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Cr.sub.0.2 Pb.sub.0.7 TeO.sub.4 361 84(Mg.sub.0.3 In.sub.0.8).sub.2 TeO.sub.6 374 82(Zn.sub.0.3 In.sub.0.8).sub.2 TeO.sub.6 370 83(Fe.sub.0.3 In.sub.0.8).sub.2 TeO.sub.6 364 84(Mg.sub.0.3 Bi.sub.0.8).sub.2 TeO.sub.6 315 79(Zn.sub.0.3 Bi.sub.0.8).sub.2 TeO.sub.6 318 80(Fe.sub.0.3 Bi.sub.0.8).sub.2 TeO.sub.6 308 81Cr.sub.0.2 Pb.sub.0.7 (HTeO.sub.4).sub.2 337 93Co.sub.0.3 In.sub.0.8 H.sub.3 TeO.sub.6 351 93Ni.sub.0.3 In.sub.0.8 H.sub.3 TeO.sub.6 341 92Mn.sub.0.3 In.sub.0.8 H.sub.3 TeO.sub.6 338 92Co.sub.0.3 Bi.sub.0.8 H.sub.3 TeO.sub.6 287 88Ni.sub.0.3 Bi.sub.0.8 H.sub.3 TeO.sub.6 286 90Mn.sub.0.3 Bi.sub.0.8 H.sub.3 TeO.sub.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.

TABLE 24______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al(PH.sub.2 O.sub.2).sub.3 366 83Al.sub.2 (PHO.sub.3).sub.3 353 84Al.sub.2 (HPO.sub.4).sub.3 348 85Al(H.sub.2 PO.sub.4).sub.3 315 87Sn(PH.sub.2 O.sub.2).sub.4 412 88Sn(PHO.sub.3).sub.2 455 89Sn(HPO.sub.4).sub.2 452 88Sn(H.sub.2 PO.sub.4).sub.4 384 89Sn(PH.sub.2 O.sub.2).sub.2 452 82SnPHO.sub.3 486 92SnHPO.sub.4 485 95Sn(H.sub.2 PO.sub.4).sub.2 402 86Si(PH.sub.2 O.sub.2).sub.4 304 85Si(PHO.sub.3).sub.2 332 86Bi(PH.sub.2 O.sub.2).sub.3 333 82Bi.sub.2 (PHO.sub.3).sub.3 345 83Bi.sub.2 (HPO.sub.4).sub.3 340 83Bi(H.sub.2 PO.sub.4).sub.3 324 85In(PH.sub.2 O.sub.2).sub.3 365 82In.sub.2 (PHO.sub.3).sub.3 380 81In.sub.2 (HPO.sub.4).sub.3 377 83In(H.sub.2 PO.sub.4).sub.3 333 86Zn(PH.sub.2 O.sub.2).sub.2 298 83ZnPHO.sub.3 298 83ZnHPO.sub.4 295 83Zn(H.sub.2 PO.sub.4).sub.2 264 84Mg(PH.sub.2 O.sub.2).sub.2 281 84MgPHO.sub.3 288 83______________________________________ TABLE 25______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Si(HPO.sub.4).sub.2 322 87Si(H.sub.2 PO.sub.4).sub.4 285 88Pb(PH.sub.2 O.sub.2).sub.2 420 85PbPHO.sub.3 425 85PbHPO.sub.4 418 89Pb(H.sub.2 PO.sub.4).sub.2 405 90Cd(PH.sub.2 O.sub.2).sub.2 380 82CdPHO.sub.3 385 83CdHPO.sub.4 384 83Cd(H.sub.2 PO.sub.4).sub.2 375 86Sb.sub.2 (HPO.sub.4).sub.3 321 82Ti.sub.2 (HPO.sub.4).sub.3 275 84V.sub.2 (HPO.sub.4).sub.3 250 85Cr.sub.2 (HPO.sub.4).sub.3 284 84Mn.sub.2 (HPO.sub.4).sub.3 275 85MgHPO.sub.4 286 84Mg(H.sub.2 PO.sub.4).sub.2 267 87Ga(PH.sub.2 O.sub.2).sub.3 321 82Ga.sub.2 (PHO.sub.3).sub.3 335 83Ga.sub.2 (HPO.sub.4).sub.3 325 84Ga(H.sub.2 PO.sub.4).sub.3 305 86Ge(PH.sub.2 O.sub.2).sub.4 367 83Ge(PHO.sub.3).sub.2 382 84Ge(HPO.sub.4).sub.2 375 87Ge(H.sub.2 PO.sub.4).sub.4 342 89Fe.sub.2 (HPO.sub.4).sub.3 264 85CoHPO.sub.4 264 84NiHPO.sub.4 261 84CuHPO.sub.4 275 85______________________________________ TABLE 26______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________SrHPO.sub.4 332 85Ca.sub.0.2 Sn.sub.0.8 HPO.sub.4 451 88Sr.sub.0.2 Sn.sub.0.8 HPO.sub.4 451 88Ba.sub.0.2 Sn.sub.0.8 HPO.sub.4 432 89Zn.sub.0.2 Sn.sub.0.8 HPO.sub.4 437 92Fe.sub.0.2 Sn.sub.0.8 HPO.sub.4 441 91Ni.sub.0.2 Sn.sub.0.8 HPO.sub.4 438 92Co.sub.0.2 Sn.sub.0.8 HPO.sub.4 442 92Mn.sub.0.2 Sn.sub.0.8 HPO.sub.4 429 90Ti.sub.0.2 Sn.sub.0.7 HPO.sub.4 415 91Cu.sub.0.2 Sn.sub.0.8 HPO.sub.4 429 92Cr.sub.0.2 Sn.sub.0.7 HPO.sub.4 418 93V.sub.0.2 Sn.sub.0.8 HPO.sub.4 404 91W.sub.0.1 Sn.sub.0.8 HPO.sub.4 406 90BaHPO.sub.4 312 86Ca.sub.0.2 Pb.sub.0.8 HPO.sub.4 372 90Sr.sub.0.2 Pb.sub.0.8 HPO.sub.4 372 90Ba.sub.0.2 Pb.sub.0.8 HPO.sub.4 359 91Zn.sub.0.2 Pb.sub.0.8 HPO.sub.4 382 93Fe.sub.0.2 Pb.sub.0.8 HPO.sub.4 374 94Ni.sub.0.2 Pb.sub.0.8 HPO.sub.4 368 93Co.sub.0.2 Pb.sub.0.8 HPO.sub.4 376 92Mn.sub.0.2 Pb.sub.0.8 HPO.sub.4 374 93Ti.sub.0.2 Pb.sub.0.7 HPO.sub.4 369 94Cu.sub.0.2 Pb.sub.0.8 HPO.sub.4 371 93Cr.sub.0.2 Pb.sub.0.7 HPO.sub.4 368 95V.sub.0.2 Pb.sub.0.8 HPO.sub.4 365 93W.sub.0.1 Pb.sub.0.8 HPO.sub.4 345 93______________________________________ TABLE 27______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Sn.sub.2 (P.sub.2 O.sub.7).sub.0.9 (HPO.sub.4).sub.0.2 495 82Sn.sub.2 (P.sub.2 O.sub.7).sub.0.8 (HPO.sub.4).sub.0.4 490 88Pb.sub.2 (P.sub.2 O.sub.7).sub.0.9 (HPO.sub.4).sub.0.2 425 80Pb.sub.2 (P.sub.2 O.sub.7).sub.0.8 (HPO.sub.4).sub.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.

TABLE 28______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al(CN).sub.3 382 76Al(SCN).sub.3 286 82Al(ONC).sub.3 364 80Sn(CN).sub.4 529 85Sn(SCN).sub.4 326 92Sn(ONC).sub.4 436 90Sn(CN).sub.2 537 82Sn(SCN).sub.2 487 95Sn(ONC).sub.2 506 93Si(CN).sub.4 315 76Si(SCN).sub.4 292 82Si(ONC).sub.4 310 79Pb(CN).sub.2 454 82Pb(SCN).sub.2 346 88Pb(ONC).sub.2 386 87Cd(CN).sub.2 372 75Cd(SCN).sub.2 315 79Cd(ONC).sub.2 340 79Bi(CN).sub.3 324 75Bi(SCN).sub.3 286 86Bi(ONC).sub.3 316 80In(CN).sub.3 412 82In(SCN).sub.3 375 89In(ONC).sub.3 369 86Zn(CN).sub.2 315 76Zn(SCN).sub.2 285 83Zn(ONC).sub.2 310 79Ga(CN).sub.3 348 74Ga(SCN).sub.3 302 79Ga(ONC).sub.3 326 76Ge(CN).sub.4 390 78Ge(SCN).sub.4 352 86Ge(ONC).sub.4 389 82Mg(CN).sub.2 320 79Mg(SCN).sub.2 289 89Mg(ONC).sub.2 341 85______________________________________ TABLE 29______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Ti(CN).sub.3 265 75Ti(SCN).sub.3 251 77Ti(ONC).sub.3 263 75V(CN).sub.2 275 81V(SCN).sub.2 245 82V(ONC).sub.2 263 80Mn(CN).sub.2 278 82Mn(SCN).sub.2 261 87Mn(ONC).sub.2 275 85Sb(CN).sub.3 315 76Sb(SCN).sub.3 281 80Sb(ONC).sub.3 298 78Cr(CN).sub.3 301 82Cr(SCN).sub.3 275 84Cr(ONC).sub.3 280 83Fe(CN).sub.2 269 75Fe(SCN).sub.2 245 79Fe(ONC).sub.2 257 79W(CN).sub.4 215 81W(SCN).sub.4 201 82W(ONC).sub.4 210 81Co(CN).sub.2 269 78Co(SCN).sub.2 245 84Co(ONC).sub.2 253 80Ni(CN).sub.2 275 82Ni(SCN).sub.2 257 86Ni(ONC).sub.2 261 81Cu(CN).sub.2 251 77Cu(SCN).sub.2 235 80Cu(ONC).sub.2 246 78Mo(CN).sub.3 235 77Mo(SCN).sub.3 211 79Mo(ONC).sub.3 225 77Ca(CN).sub.2 325 78Ca(SCN).sub.2 314 84Ca(ONC).sub.2 322 80Ba(CN).sub.2 333 79Ba(SCN).sub.2 301 87Ba(ONC).sub.2 311 81Nb(CN).sub.2 222 82Nb(SCN).sub.2 201 83Nb(ONC).sub.2 216 81Sr(SCN).sub.2 314 84Sr(ONC).sub.2 322 80______________________________________ TABLE 30______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________ZnSn(CN).sub.4 402 87MgSn(SCN).sub.4 382 92CaSn(SCN).sub.4 382 92Sr(SCN).sub.4 382 92FeSn(ONC).sub.4 376 91NiSn(CN).sub.4 398 88CoSn(SCN).sub.4 375 93MnSn(ONC).sub.4 390 92TiSn(CN).sub.5 385 87CuSn(SCN).sub.4 360 93NiPb(CN).sub.4 382 83CoPb(SCN).sub.4 362 85MnPb(ONC).sub.4 375 84ZnPb(CN).sub.4 395 84MgPb(SCN).sub.4 376 89CaPb(SCN).sub.4 376 89SrPb(SCN).sub.4 376 89FePb(ONC).sub.4 375 89TiPb(CN).sub.5 376 84CuPb(SCN).sub.4 326 89CuIn(CN).sub.5 355 84FeIn(SCN).sub.5 335 91CoIn(ONC).sub.5 345 88MgIn(CN).sub.5 365 85CuBi(CN).sub.5 324 78FeBi(SCN).sub.5 315 87BaBi(ONC).sub.5 320 83CaBi(CN).sub.3 321 77MgBi(CN).sub.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.

TABLE 31______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.3 (WO.sub.4).sub.3 292 86AlWO.sub.4 301 83SnWO.sub.4 477 94Sn.sub.2 W.sub.3 O.sub.8 436 95Sn(WO.sub.4).sub.2 402 96Si(WO.sub.4).sub.2 282 95PbWO.sub.4 405 95PbWO.sub.3 419 94CdWO.sub.4 326 91CdWO.sub.3 345 90Bi.sub.2 WO.sub.6 382 90Bi.sub.2 (WO.sub.4).sub.3 368 92In.sub.2 (WO.sub.4).sub.3 426 90In(WO.sub.3).sub.3 398 94Sb.sub.2 (WO.sub.4).sub.3 350 90ZnWO.sub.4 208 86ZnWO.sub.3 226 89Ga.sub.2 (WO.sub.4).sub.3 321 89Ga.sub.2 (WO.sub.3).sub.3 333 88Ge(WO.sub.4).sub.2 341 89Ge(WO.sub.3).sub.2 353 86MgWO.sub.4 301 87MgWO.sub.3 313 86CaWO.sub.4 301 87CaWO.sub.3 313 86SrWO.sub.4 301 87SrWO.sub.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.

TABLE 32______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (MoO.sub.4).sub.3 302 87SnMo.sub.2 O.sub.8 426 94SnMoO.sub.4 472 92SiMo.sub.2 O.sub.8 340 90PbMoO.sub.4 456 94CdMoO.sub.4 346 91Bi.sub.2 (MoO.sub.4).sub.3 402 93In.sub.2 (MoO.sub.4).sub.3 436 94InMo.sub.4 O.sub.6 398 96Sb.sub.2 (MoO.sub.4).sub.3 348 90ZnMoO.sub.4 268 87Ga.sub.2 (MoO.sub.4).sub.3 359 89GeMoO.sub.4 371 90MgMoO.sub.4 324 88CaMoO.sub.4 324 88SrMoO.sub.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.

TABLE 33______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________AlTiO.sub.5 326 73SnTiO.sub.4 443 82SiTiO.sub.6 321 75PbTiO.sub.3 476 80PbTi.sub.3 O.sub.7 402 81CdTiO.sub.3 354 76Bi.sub.2 TiO.sub.5 498 81Bi.sub.2 Ti.sub.2 O.sub.7 424 82In.sub.2 TiO.sub.5 478 83Sb.sub.3 Ti.sub.2 O.sub.10 369 80ZnTiO.sub.3 324 76GaTiO.sub.5 371 75GeTiO.sub.3 380 74MgTiO.sub.4 334 71CaTiO.sub.4 334 71SrTiO.sub.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.

TABLE 34______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 (ZrO.sub.3).sub.3 304 71SnZrO.sub.3 484 78SiZrO.sub.4 342 76PbZrO.sub.3 466 77CdZrO.sub.3 357 71Bi.sub.2 (ZrO.sub.3).sub.3 419 77In.sub.2 (ZrO.sub.3).sub.3 443 78Sb.sub.2 (ZrO.sub.3).sub.3 354 75ZnZrO.sub.3 294 73Ga.sub.2 (ZrO.sub.3).sub.3 372 74GeZrO.sub.3 379 72MgZrO.sub.3 339 73CaZrO.sub.3 339 73SrZrO.sub.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.

TABLE 35______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________AlVO.sub.4 319 82SnV.sub.2 O.sub.6 452 89Sn.sub.2 V.sub.2 O.sub.6 489 87SiV.sub.2 O.sub.7 324 84Pb.sub.2 V.sub.2 O.sub.6 477 86PbV.sub.2 O.sub.6 427 88CdV.sub.2 O.sub.6 326 83BiVO.sub.4 436 86Bi.sub.2 VO.sub.5 496 85InVO.sub.4 498 85In.sub.2 VO.sub.5 504 83SbVO.sub.4 354 83ZnV.sub.2 O.sub.6 311 81GaVO.sub.4 368 83GeV.sub.2 O.sub.6 341 84MgV.sub.2 O.sub.6 312 79CaV.sub.2 O.sub.6 312 79SrV.sub.2 O.sub.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.

TABLE 36______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________AlCrO.sub.3 342 87SnCrO.sub.4 463 94Sn.sub.2 CrO.sub.6 504 92Si(CrO.sub.4).sub.2 341 89Pb.sub.3 CrO.sub.6 511 91PbCrO.sub.4 484 93CdCr.sub.2 O.sub.4 324 87BiCrO.sub.3 432 91Bi.sub.2 CrO.sub.6 426 93InCrO.sub.3 445 92In.sub.2 CrO.sub.6 486 90Sb.sub.2 (CrO.sub.4).sub.3 352 88ZnCrO.sub.4 336 87Ga.sub.3 (CrO.sub.4).sub.2 381 86GeCrO.sub.4 382 85MgCr.sub.2 O.sub.7 304 87CaCr.sub.2 O.sub.7 304 87SrCr.sub.2 O.sub.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.

TABLE 37______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________AlNbO.sub.4 324 71SnNb.sub.2 O.sub.6 424 75Sn.sub.2 Nb.sub.2 O.sub.7 468 74SiNbO.sub.4 342 71PbNb.sub.2 O.sub.6 403 74Pb.sub.2 Nb.sub.2 O.sub.7 426 72Cd.sub.2 Nb.sub.2 O.sub.7 314 71BiNbO.sub.4 415 73InNbO.sub.4 445 74SbNbO.sub.4 370 73ZnNb.sub.2 O.sub.6 204 71GaNbO.sub.4 364 72GeNb.sub.2 O.sub.6 368 73MgNb.sub.2 O.sub.6 301 72CaNb.sub.2 O.sub.6 301 72SrNb.sub.2 O.sub.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.

TABLE 38______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________AlTaO.sub.4 302 81Sn.sub.2 Ta.sub.2 O.sub.7 476 88SiTa.sub.2 O.sub.7 272 82Pb.sub.2 Ta.sub.2 O.sub.7 406 87Cd.sub.2 Ta.sub.2 O.sub.7 314 84BiTaO.sub.4 404 86InTaO.sub.4 446 85SbTaO.sub.4 364 85Zn.sub.2 Ta.sub.2 O.sub.7 246 83GaTaO.sub.4 356 81Ge.sub.2 Ta.sub.2 O.sub.7 346 81Mg.sub.2 Ta.sub.2 O.sub.7 304 79Ca.sub.2 Ta.sub.2 O.sub.7 304 79Sr.sub.2 Ta.sub.2 O.sub.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.

TABLE 39______________________________________ Capacity Discharge capacity maintenance rateSalt (mAh/g) (%)______________________________________Al.sub.2 MnO.sub.6 326 80SnMnO.sub.3 486 89SnMn.sub.2 O.sub.4 424 90SiMnO.sub.3 314 81PbMnO.sub.3 443 87CdMnO.sub.3 369 82Bi.sub.2 MnO.sub.4 424 84Bi.sub.2 MnO.sub.6 412 86In.sub.2 MnO.sub.4 461 84In.sub.2 MnO.sub.6 452 84Sb.sub.2 MnO.sub.4 392 83Sb.sub.2 MnO.sub.6 376 84ZnMnO.sub.3 314 81Ga.sub.2 MnO.sub.4 386 81GeMnO.sub.3 349 82MgMnO.sub.3 326 78CaMnO.sub.3 326 78SrMnO.sub.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 as coin-type, rectangular-type, and cylinder-type.

In the above examples, LiMn.sub.1.8 Co.sub.0.2 O.sub.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.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.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 and has a higher energy density and a high reliability.

Although the present invention has been described in terms of the presently preferred embodiments, it is to be understood that such disclosure is not to be interpreted as limiting. Various alterations and modifications will no doubt become apparent to those skilled in the art to which the present invention pertains, after having read the above disclosure. Accordingly, it is intended that the appended claims be interpreted as covering all alterations and modifications as fall within the true spirit and scope of the invention.

Claims

1. 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 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 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.

2. 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.

3. The non-aqueous electrolyte secondary battery in accordance with claim 1, 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.

4. 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.

5. 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.

6. 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.

7. 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.

8. 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.sub.2 (SeO.sub.4).sub.m, selenites M.sub.2 (SeO.sub.3).sub.m, M.sub.2 (SeO.sub.5).sub.m, M(HSeO.sub.4).sub.m, and M(HSeO.sub.3).sub.m, where M denotes a metal or semi-metal having a valence m.

9. 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.sub.6 (TeO.sub.6).sub.m, M.sub.2 (TeO.sub.4).sub.m, M.sub.5 (H.sub.5 TeO.sub.6), M.sub.4 (H.sub.2 TeO.sub.6).sub.m, M.sub.2 (H.sub.3 TeO.sub.6).sub.m, and M.sub.2 (H.sub.4 TeO.sub.6).sub.m, where M denotes a metal or semi-metal having a valence m.

10. 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 of a metal or a semi-metal and an oxo-acid of an element selected from the group consisting of nitrogen, sulfur, carbon, boron, phosphorus, selenium, and tellurium, salts of said oxo-acids of phosphorus and boron being restricted to hydrogenphosphates and hydrogenborates.

11. The non-aqueous electrolyte secondary battery in accordance with claim 10, 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.

12. 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 of a metal or a semi-metal and an oxo-acid of a transition element selected from the group consisting of tungsten, molybdenum, titanium, chromium, zirconium, niobium, tantalum, manganese, and vanadium.

13. The non-aqueous electrolyte secondary battery in accordance with claim 12, 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.

14. 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 of a metal or a semi-metal and an oxo-acid, wherein said metal or semi-metal is at least one selected from the group consisting of Sn and Si, wherein said oxo-acid comprises an element selected from the group consisting of sulfur, phosphorus and boron and wherein salts of said oxo-acids of phosphorus and boron are restricted to hydrogenphosphates and hydrogenborates.