NONAQUEOUS ELECTROLYTE SECONDARY BATTERY

Abstract

The present disclosure provides a technology of eliciting the heat generation suppressing effect of trilithium phosphate (Li.sub.3PO.sub.4) in a 4 V class battery stably. The nonaqueous electrolyte secondary battery disclosed herein includes a positive electrode having a positive electrode mixture material layer, a negative electrode, and a nonaqueous electrolyte. The positive electrode has a region with an open voltage of 4.25 V (Li/Li.sup.+) or less in an operating range of the battery. The positive electrode mixture material layer includes a positive electrode active material, trilithium phosphate (Li.sub.3PO.sub.4), and lithium dihydrogenphosphate (LiH.sub.2PO.sub.4). In the nonaqueous electrolyte secondary battery disclosed herein, in an XRD pattern of the positive electrode mixture material layer, a peak intensity I.sub.A detected near 27 cm.sup.−1, and a peak intensity B detected near 22 cm.sup.−1 satisfy 0<I.sub.A/I.sub.B≤0.03. This prevents decomposition of Li.sub.3PO.sub.4 and gelation of the positive electrode mixture material layer, and the heat generation suppressing effect by Li.sub.3PO.sub.4 can be stably elicited.

Claims

1. A nonaqueous electrolyte secondary battery comprising: a positive electrode having a positive electrode mixture material layer; a negative electrode; and a nonaqueous electrolyte, wherein the positive electrode has a region with an open voltage of 4.25 V (Li/Li.sup.+) or less in an operating range of the battery, the positive electrode mixture material layer includes a positive electrode active material, trilithium phosphate, and lithium dihydrogenphosphate, in an XRD pattern of the positive electrode mixture material layer, a peak intensity I.sub.A detected in the vicinity of 27 cm.sup.−1, and a peak intensity I.sub.B detected in the vicinity of 22 cm.sup.−1 satisfy expression (1) below:
0<I.sub.A/I.sub.B≤0.03  (1).

2. The nonaqueous electrolyte secondary battery according to claim 1, wherein the I.sub.A/I.sub.B is 0.008 or more.

3. The nonaqueous electrolyte secondary battery according to claim 1, wherein a content of the trilithium phosphate is 1 wt % to 15 wt %, with a total solid content mass of the positive electrode mixture material layer being 100 wt %.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] FIG. 1 is a perspective view showing the outside shape of a lithium ion secondary battery in accordance with one embodiment of the present disclosure;

[0014] FIG. 2 is a perspective view schematically showing an electrode body of the lithium ion secondary battery in accordance with one embodiment of the present disclosure; and

[0015] FIG. 3 is a view showing the XRD pattern of the positive electrode mixture material layer of the lithium ion secondary battery in accordance with one embodiment of the present disclosure.

DETAILED DESCRIPTION

[0016] Below, one embodiment of the present disclosure will be described with reference to the accompanying drawings. Incidentally, in the following accompanying drawings, the members/parts providing the same effect are given the same numerals and signs for description. Further, the dimensional relation (such as length, width, or thickness) in each drawing does not reflect the actual dimensional relation. Further, matters other than matters particularly mentioned in this specification, and required for practicing the present disclosure (e.g., the composition of a negative electrode or a general technology concerning construction of a nonaqueous electrolyte secondary battery) can be understood as the design matters of those skilled in the art based on the related art in the present field.

1. Lithium Ion Secondary Battery

[0017] Below, a lithium ion secondary battery will be described as one example of the nonaqueous electrolyte secondary battery disclosed herein. FIG. 1 is a perspective view schematically showing the outside shape of a lithium ion secondary battery in accordance with the present embodiment. FIG. 2 is a perspective view schematically showing an electrode body of the lithium ion secondary battery in accordance with the present embodiment.

[0018] The lithium ion secondary battery shown in the present embodiment includes a positive electrode, a negative electrode, and a nonaqueous electrolyte. Specifically, as shown in FIGS. 1 and 2, the lithium ion secondary battery 100 includes an electrode body 80 having a positive electrode 10 and a negative electrode 20, and a nonaqueous electrolyte (not shown) accommodated in the inside of a battery case 50. Below, each configuration will be described.

(1) Battery Case

[0019] As shown in FIG. 1, the battery case 50 has a flat rectangular case main body 52 with an opening formed in the upper surface thereof, and a lid body 54 for closing the opening of the upper surface. Further, the lid body 54 includes a positive electrode terminal 70 and a negative electrode terminal 72 mounted thereon. Although not shown, the positive electrode terminal 70 is connected with the positive electrode 10 of the electrode body 80 in the inside of the battery case 50, and is partially exposed to the outside of the battery case 50. On the other hand, the negative electrode terminal 72 is connected with the negative electrode 20 in the inside of the battery case 50, and is partially exposed to the outside of the battery case 50.

(2) Electrode Body

[0020] As shown in FIG. 2, the electrode body 80 includes the positive electrode 10, the negative electrode 20, and a separator 40. The electrode body 80 in the present embodiment is a wound electrode body. Such a wound electrode body is formed in the following manner. A laminated body in which the positive electrode 10 and the negative electrode 20 each in a long sheet shape are stacked via the separator 40 is manufactured, and the laminated body is wound. Incidentally, for the structure of the electrode body in the technology disclosed herein, a conventionally known structure can be adopted without particular restriction, and the electrode body is not limited to the wound electrode body. Other examples of the structure of the electrode body may include a laminated electrode body in which a plurality of positive electrodes and negative electrodes are alternately stacked with separators interposed therebetween.

(a) Positive Electrode

[0021] The positive electrode 10 includes a foil-shaped positive electrode collector 12, and a positive electrode mixture material layer 14 coated on each surface (each opposite surface) of the positive electrode collector 12. Further, a positive electrode exposed part 16 which is not coated with the positive electrode mixture material layer 14, and from which the positive electrode collector 12 is exposed is formed at one side edge in the width direction of the positive electrode 10. The positive electrode exposed part 16 is the region to be connected with a positive electrode terminal 70 (see FIG. 1). Then, the positive electrode mixture material layer 14 of the lithium ion secondary battery 100 in accordance with present embodiment includes a positive electrode active material, trilithium phosphate (Li.sub.3PO.sub.4), and lithium dihydrogenphosphate (LiH.sub.2PO.sub.4). The constituent components of such a positive electrode mixture material layer 14 will be described in details later.

(b) Negative Electrode

[0022] The negative electrode 20 includes a foil-shaped negative electrode collector 22, and a negative electrode mixture material layer 24 coated on each surface (each opposite surface) of the negative electrode collector 22. Then, a negative electrode exposed part 26 which is not coated with the negative electrode mixture material layer 24, and from which the negative electrode collector 22 is exposed is formed at one side edge in the width direction of the negative electrode 20. The negative electrode exposed part 26 is electrically connected with a negative electrode terminal 72 (see FIG. 1).

[0023] The negative electrode mixture material layer 24 is a layer including a negative electrode active material as the main component. The negative electrode active material is a material capable of reversibly occluding and releasing electric charge carriers (e.g., lithium ions). For such negative electrode active materials, those for use in a general nonaqueous electrolyte secondary battery can be used without particular restriction. As an example thereof, for the negative electrode active material, graphite, non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), or carbon nanotube, or a carbon material of a combination thereof can be used. Incidentally, from the viewpoint of the energy density, of the carbon materials, graphite type materials (such as natural graphite (plumbago) and artificial graphite) can be used. Further, the negative electrode mixture material layer 24 may also include additives (e.g., a binder and a thickener) therein other than the negative electrode active material. Examples of the binder may include styrene butadiene rubber (SBR). Further, examples of the thickener may include carboxymethyl cellulose (CMC). Incidentally, the additives also have no particular restriction, and general additives usable for the negative electrode mixture material layer can be used without particular restriction.

(c) Separator

[0024] The separator 40 is a sheet-shaped member including an insulating resin. The separator 40 is interposed between the positive electrode 10 and the negative electrode 20, and prevents a short-circuit due to the direct contact therebetween. Further, the separator 40 includes a plurality of fine holes for allowing the electric charge carriers to pass therethrough formed therein. Transfer of electric charge carriers during charging and discharging is caused through the fine holes of the separator 40. For the separator 40, an insulating resin such as polyethylene (PE), polypropylene (PP), polyester, or polyamide can be used. Further, a laminated sheet obtained by stacking two or more layers of the resins is also acceptable. Examples of such a laminated sheet may include a three-layer sheet in which PP, PE, and PP are stacked in this order.

(3) Nonaqueous Electrolyte

[0025] Further, in the battery case 50, a nonaqueous electrolyte is accommodated (filled) with the electrode body 80. For the nonaqueous electrolyte, the one obtained by allowing an organic solvent (nonaqueous solvent) to contain a support salt is used. As the nonaqueous solvents, for example, solvents of carbonates, ethers, esters, nitriles, sulfones, and lactones can be used without particular restriction. Specific examples of such a nonaqueous solvent may include ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), monofluoroethylene carbonate (MFEC), difluoroethylene carbonate (DFEC), monofluoromethyl difluoromethyl carbonate (F-DMC), and trifluoro dimethyl carbonate (TFDMC). Further, for the support salt, a lithium salt containing fluorine is used. Examples of such a fluorine-containing lithium salt may include LiPF.sub.6, LiBF.sub.4, and LiCF.sub.3SO.sub.3. Incidentally, the concentration of the support salt in the nonaqueous electrolyte can be set at 0.75 mol/L to 1.25 mol/L (e.g., about 1 mol/L).

2. Constituent Components of Positive Electrode Mixture Material Layer

[0026] As described above, the positive electrode mixture material layer 14 of the lithium ion secondary battery 100 in accordance with the present embodiment includes a positive electrode active material, trilithium phosphate (Li.sub.3PO.sub.4), and lithium dihydrogenphosphate (LiH.sub.2PO.sub.4). Below, the constituent components of the positive electrode mixture material layer 14 will be described.

(1) Positive Electrode Active Material

[0027] The positive electrode active material is a compound capable of reversibly occluding and releasing electric charge carriers. When lithium ions are used as electric charge carriers, as the positive electrode active material, an oxide including lithium and a transition metal element as constituent elements (lithium transition metal oxide) can be used. Incidentally, the lithium ion secondary battery 100 in accordance with the present embodiment is a 4 V class battery having a region in which the open voltage of the positive electrode 10 within the operating range of the battery is 4.25 V or less based on lithium (Li/Li.sup.+). For this reason, for the positive electrode active material, a material implementing an open voltage of 4.25 V or less in the positive electrode 10 is used. Examples of such a positive electrode active material for a 4 V class battery may include a lithium nickel cobalt manganese composite oxide having a layered crystal structure.

[0028] One example of the lithium nickel cobalt manganese composite oxide is shown in the following expression (2).

Li.sub.1+αNi.sub.xCo.sub.yMn.sub.(1-x-y)M.sub.zO.sub.2+β  (2)

[0029] α in the expression is −0.1≤α≤0.7. β is a value determined so as to satisfy the neutralization conditions of electric charges (typically, −0.5≤β, for example, −0.5≤β≤0.5). Further, “x” indicative of the Ni content is 0.1≤x≤0.9. “y” indicative of the Co content is 0.1≤y≤0.4. Further, M is another metal element except for Ni, Co, and Mn, and mention may be made of Zr, Mo, W, Mg, Ca, Na, Fe, Cr, Zn, Si, Sn, Al, or the like. “z” indicative of the content of the another metal element M is 0≤z≤0.1. Namely, the lithium nickel cobalt manganese composite oxide may or may not include another metal element M (0=z).

[0030] Incidentally, the battery performances tend to be improved with an increase in content of the positive electrode active material directly contributing to the charging and discharging reaction. From such a viewpoint, the content of the positive electrode active material for every 100 wt % of the total solid content mass of the positive electrode mixture material layer 14 can be set at 75 wt % or more, can be set at 80 wt % or more, can be set at 82 wt % or more, and can be set at 85 wt % or more. On the other hand, from the viewpoint of allowing the effects of the additives such as Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 described later to be sufficiently exhibited, the upper limit value of the content ratio of the positive electrode active material can be set at 99 wt % or less, can be set at 97 wt % or less, can be set at 95 wt % or less, and can be set at 90 wt % or less.

(2) Trilithium Phosphate

[0031] The positive electrode mixture material layer 14 in the present embodiment includes trilithium phosphate (Li.sub.3PO.sub.4). The Li.sub.3PO.sub.4 reacts with hydrogen fluoride (HF) generated by decomposition of the nonaqueous electrolyte during overcharging, resulting in phosphate ions (PO.sub.4.sup.3−), which form a phosphoric acid film on the surface of the negative electrode 20. This stabilizes the charging and discharging reaction at the negative electrode 20, and hence can suppress the heat generation of the negative electrode 20 during overcharging. As shown in FIG. 3, when the positive electrode mixture material layer 14 containing Li.sub.3PO.sub.4 is subjected to X-ray diffraction (XRD), a peak B derived from Li.sub.3PO.sub.4 occurs in the vicinity of 22 cm.sup.−1 (typically, 22±1 cm.sup.−1). In the present specification, the intensity of the peak B derived from Li.sub.3PO.sub.4 is referred to as “peak intensity I.sub.B”.

[0032] Incidentally, from the viewpoint of allowing the heat generation suppressing effect to be more preferably exhibited, the content of Li.sub.3PO.sub.4 for every 100 wt % of the total solid content mass of the positive electrode mixture material layer 14 can be set at 0.5 wt % or more, can be set at 0.75 wt % or more, can be set at 1 wt % or more, and can be set at 1.5 wt % or more. On the other hand, from the viewpoint of preventing the reduction of the battery performances due to the reduction of the content of the positive electrode active material, the upper limit value of the content of the Li.sub.3PO.sub.4 can be set at 15 wt % or less, can be set at 10 wt % or less, can be set at 7.5 wt % or less, and can be set at 5 wt % or less.

(3) Lithium Dihydrogenphosphate

[0033] To the positive electrode mixture material layer 14 in the present embodiment, lithium dihydrogenphosphate (LiH.sub.2PO.sub.4) is added. As shown in FIG. 3, when the positive electrode mixture material layer 14 containing LiH.sub.2PO.sub.4 is subjected to XRD, a peak A derived from LiH.sub.2PO.sub.4 occurs in the vicinity of 27 cm.sup.−1 (typically, 27±1 cm.sup.−1). In the present specification, the intensity of the peak A derived from LiH.sub.2PO.sub.4 is referred to as “peak intensity I.sub.A”. Then, in the present specification, the abundance proportions of Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 in the positive electrode mixture material layer 14 are specified as “the ratio (I.sub.A/I.sub.B) of the peak intensity I.sub.A derived from LiH.sub.2PO.sub.4 to the peak intensity In derived from Li.sub.3PO.sub.4”.

[0034] The experiments and the studies by the present inventors indicate as follows: when Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 are allowed to coexist at proper proportions in the positive electrode mixture material layer 14, decomposition of Li.sub.3PO.sub.4 and gelation of the positive electrode mixture material layer 14 are suppressed, which stabilizes the heat generation suppressing effect due to Li.sub.3PO.sub.4. Specifically, when Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 coexist in the positive electrode mixture material layer 14 (I.sub.A/I.sub.B>0), gelation of the positive electrode mixture material layer 14 is preferably suppressed. On the other hand, when the abundance proportion of LiH.sub.2PO.sub.4 to Li.sub.3PO.sub.4 is too large, decomposition of Li.sub.3PO.sub.4 may rather proceed. For this reason, in the present embodiment, the abundance proportion (I.sub.A/I.sub.B) of LiH.sub.2PO.sub.4 to Li.sub.3PO.sub.4 is adjusted at 0.03 or less. In other words, for the lithium ion secondary battery 100 in accordance with the present embodiment, the peak intensity I.sub.A in the vicinity of 27 cm.sup.−1 derived from Li.sub.3PO.sub.4, and the peak intensity I.sub.B in the vicinity of 22 cm.sup.−1 derived from LiH.sub.2PO.sub.4 satisfy the following expression (1) in the XRD pattern of the positive electrode mixture material layer 14. This can properly suppress the decomposition of Li.sub.3PO.sub.4 and the gelation of the positive electrode mixture material layer 14. For this reason, the heat generation suppressing effect of Li.sub.3PO.sub.4 can be preferably exhibited, which can preferably suppress the heat generation of a 4 V class battery during overcharging.

0<I.sub.A/I.sub.B≤0.03  (1)

[0035] Incidentally, from the viewpoint of more preferably suppressing the decomposition of Li.sub.3PO.sub.4, the upper limit value of the peak intensity ratio (I.sub.A/I.sub.B) can be set at 0.027 or less, can be set at 0.025 or less, and can be set at 0.02 or less. On the other hand, from the viewpoint of more surely preventing the gelation of the positive electrode mixture material layer 14, the lower limit value of the peak intensity ratio (I.sub.A/I.sub.B) can be set at 0.008 or more, can be set at 0.01 or more, can be set at 0.012 or more, and can be set at 0.015 or more.

(3) Other Additives

[0036] The positive electrode mixture material layer 14 may include prescribed additives other than the essential components added therein. As such other additives, conventionally known materials can be used without particular restriction, and hence a detailed description thereon is omitted. As one example, for the purpose of improving the adhesion of the positive electrode mixture material layer 14 to the surface of the positive electrode collector 12, a binder can be added to the positive electrode mixture material layer 14. As the binder, a resin material commonly used as the binder of the nonaqueous electrolyte secondary battery can be used without particular restriction. Examples of such a binder may include carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVdF), polyvinylidene chloride (PVdC), and polyethylene oxide (PEO). Further, other examples of the additive to the positive electrode mixture material layer 14 may include a conductive material. For the conductive material, a carbon material such as carbon black can be used.

[0037] Up to this point, a description has been given to the lithium ion battery in accordance with one embodiment of the present disclosure. Incidentally, the embodiment is merely an example, and the disclosure herein includes various modifications and changes of the embodiment.

Test Example

[0038] Below, Test Example on the present disclosure will be described. Incidentally, the contents of Test Example described below is not intended to limit the present disclosure.

[0039] In the present Test Example, four kinds of lithium ion secondary batteries (samples 1 to 4) having different abundance ratios (I.sub.A/I.sub.B) of Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 in the positive electrode mixture material layer were prepared, and the heating value upon overcharging each sample was evaluated.

1. Manufacturing of Each Sample

[0040] First, a mixture including a positive electrode active material, Li.sub.3PO.sub.4, LiH.sub.2PO.sub.4, a conductive material, and a binder mixed therein was manufactured. Then, the mixture was dispersed in a disperse medium, thereby preparing a paste-shaped positive electrode mixture material paste. Incidentally, in the present Test Example, as a positive electrode active material, lithium nickel cobalt manganese composite oxide (LiNi.sub.0.33Co.sub.0.33Mn.sub.0.33O.sub.2) was used. Further, acetylene black (AB) was used as a conductive material, and polyvinylidene fluoride (PVdF) was used as a binder. Then, water was used as the disperse medium for paste preparation. Then, the positive electrode mixture material paste was applied to each opposite surface of the positive electrode collector (aluminum foil), followed by drying/rolling, thereby manufacturing a sheet-shaped positive electrode. Incidentally, in the present Test Example, the amounts of the Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 added were varied for each sample.

[0041] On the other hand, in the present Test Example, the negative electrodes with the same configuration were used for respective samples. The negative electrode used in the present Test Example is a sheet-shaped negative electrode obtained by applying a negative electrode mixture material layer on the surface of a negative electrode collector (foil). Incidentally, the negative electrode mixture material layer is obtained by drying/rolling a paste of a mixture of a negative electrode active material (graphite), a binder (styrene-butadiene copolymer (SBR)), and a thickener (carboxymethyl cellulose (CMC)).

[0042] Then, a positive electrode and a negative electrode were stacked via a separator, thereby forming a laminated body. The laminated body was wound, thereby manufacturing a wound electrode body. Then, the wound electrode body was accommodated with a nonaqueous electrolyte in a battery case, thereby constructing a battery assembly. The battery assembly was subjected to initial charging and discharging, and an aging treatment, thereby constructing a 4 V class lithium ion secondary battery for evaluation test. Incidentally, for the nonaqueous electrolyte, the one obtained by allowing a mixed solvent including EC, DMC, and EMC at a volume ratio of 3:4:3 to contain a support salt (LiPF.sub.6) with a concentration of about 1 mol/L was used.

2. Overcharge Test

[0043] An overcharge test of compulsorily continuing charging at a constant current of 3 C up to 12 V under environment of 25° C. was conducted on the batteries for evaluation test (samples 1 to 4). Then, the measurement was carried out with the battery temperature after the voltage reached 12 V as the “battery temperature during overcharging”. The results are shown in Table 1. Incidentally, the battery temperature during overcharging in Table 1 is the relative value when the battery temperature of the sample 4 is assumed as 100%.

3. Measurement of Abundance Ratio of Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4

[0044] The battery for evaluation test of each sample was disassembled, to collect the positive electrode mixture material layer. The positive electrode mixture material layer was subjected to XRD analysis using an X-ray diffraction device (model: ULtima IV manufactured by Rigaku Corporation). Then, the peak intensity I.sub.B in the vicinity of 22 cm.sup.−1 and the peak intensity I.sub.A in the vicinity of 27 cm.sup.−1 in the XRD pattern of each sample were measured. Then, the ratio (I.sub.A/I.sub.B) of the peak intensity I.sub.A to the peak intensity I.sub.B was calculated as the “abundance ratio of Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 in the positive electrode mixture material layer”. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Battery temperature during overcharging I.sub.A/I.sub.B (%) Sample 1 0.0002 107 Sample 2 0.008 97 Sample 3 0.03 98 Sample 4 0 100 (No peak A)

[0045] As shown in Table 1, for each of the samples 1 to 3, the peak derived from LiH.sub.2PO.sub.4 was observed in the vicinity of 27 cm.sup.−1, and I.sub.A/I.sub.B exceeded 0. Thus, for the samples 1 to 3 in which the presence of LiH.sub.2PO.sub.4 was observed with XRD, the gelation of the positive electrode mixture material layer was suppressed. On the other hand, for the sample 4 in which the presence of LiH.sub.2PO.sub.4 could not be observed with XRD, gelation of the positive electrode mixture material layer occurred. On the other hand, comparison among the battery temperatures of the samples 1 to 3 indicated that the heat generation during overcharging was preferably suppressed in the samples 2 and 3. The results have indicated as follows: LiH.sub.2PO.sub.4 is added in an amount enough to allow observation of the peak B derived from LiH.sub.2PO.sub.4 with XRD, and the positive electrode mixture material layer is formed so that the abundance proportion (I.sub.A/I.sub.B) of Li.sub.3PO.sub.4 and LiH.sub.2PO.sub.4 becomes 0.03 or less; this enables the construction of a lithium ion secondary battery capable of preferably suppressing the heat generation during overcharging.

[0046] Up to this point, the present disclosure was described in details, and the description is merely an example, and the technology disclosed herein includes various modifications and changes of the specific examples.