# Patent

## Title
Cathode material for lithium ion secondary batteries, cathode member for lithium ion secondary batteries, and lithium ion secondary battery

## Abstract

A cathode material for a lithium ion secondary battery includes an oxide represented by a composition formula Li2-xMIIyM(Si,MB)O4, wherein MII represents a divalent element; M represents at least one element selected from the group consisting of Fe, Mn, Co and Ni; and MB represents, as an optional component, an element substituted for Si to compensate for a difference between an electric charge of [Li2]2+ and an electric change of [Li2-xMIIy]n+ as needed. In the composition formula representing the oxide, x and y are −0.25<x≦0.25 and 0<y≦0.25.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application is a 371 of PCT/JP2012/073598 filed on Sep. 14, 2012 which, in turn, claimed the priority of Japanese Patent Application No. JP2011-212295 filed on Sep. 28, 2011 both applications are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to a cathode material for lithium ion secondary batteries, a cathode member for lithium ion secondary batteries, and a lithium ion secondary battery.
BACKGROUND ART
A lithium ion secondary battery has less weight and more capacity as compared with a conventional lead secondary battery, a nickel-cadmium secondary battery and so forth and hence has been widely used as a power source for electronic devices such as a mobile phone and a notebook type personal computer. It has recently been used also as a battery for an electric vehicle, a plug-in hybrid car, a pedelec and so forth.
The lithium ion secondary battery is basically composed of a cathode, an anode, an electrolyte, and a separator.
For the anode, in general, carbon, lithium titanate or the like which allows metallic lithium or lithium ion intercalation/deintercalation is used. For the electrolyte, lithium salt and an organic solvent or an ionic liquid capable of dissolving the lithium salt are used. The separator is placed between the cathode and the anode so as to keep electrical insulation therebetween and has pores to allow the electrolyte to pass through. For the separator, porous organic resin, glass fiber or the like is used.
The cathode is basically composed of an active material which allows lithium ion intercalation/deintercalation, an electrically conductive auxiliary which ensures an electrical conduction path (electron conduction path) to a current collector, and a binder which binds the active material and the electrically conductive auxiliary. As the electrically conductive auxiliary, a carbon material such as acetylene black, carbon black or graphite is used. As the active material of the cathode material, a metal oxide composed of lithium and a transition metal (s), such as LiCoO2, LiNiO2, LiNi0.8Co0.2O2 or LiMn2O4, is used. Other examples are LiMPO4, derivatives obtained from this lithium metal phosphate as the basic structure by element substitution or compositional change, Li2MSiO4, derivatives obtained from this lithium metal silicate as the basic structure by element substitution or compositional change, LiMBO3, and derivatives obtained from this lithium metal borate as the basic structure by element substitution or compositional change. M mainly contains a transition metal element (s) having a variable valency, such as Fe, Mn, Ni, and Co.
This kind of metal oxide generally has low electron conductivity, and hence, in the cathode which uses the metal oxide as the active material, the metal oxide is mixed with the electrically conductive auxiliary as described above. Efforts have been made to further improve the electron conductivity inside the cathode by coating the surface of the metal oxide as the active material with carbon or by making carbon particles, carbon fiber or the like adhere to the surface of the metal oxide, in addition to mixing the metal oxide with the electrically conductive auxiliary. (Refer to Patent Literatures 1 to 6 and Non-Patent Literature 1, for example.)
In particular, with respect to the metal oxide having significantly low electron conductivity, even if the cathode is configured by making the electrically conductive auxiliary and the metal oxide coexist therein, it is not enough to obtain excellent battery characteristics. Hence, in order to use such metal oxide, the surface of the metal oxide is coated with carbon.
Among the oxides described above, lithium iron silicate Li2FeSiO4, lithium manganese silicate Li2MnSiO4, and derivatives obtained from these as the basic structure by element substitution or compositional change each contain two lithium ions in one composition formula, so that high capacity can be expected theoretically. (Refer to Patent Literatures 7 to 11 and Non-Patent Literature 2.) Since each of these oxides has significantly low electron conductivity, an attempt to coat the oxide grains with carbon has been made in addition to mixing the oxide with the electrically conductive auxiliary in an electrode. (Refer to Non-Patent Literatures 3 to 5.)
RELATED ART LITERATURES
Patent Literatures
Patent Literature 1: Published Patent Application JP 2003-34534 A
Patent Literature 2: Published Patent Application JP 2006-302671 A
Patent Literature 3: Published Patent Application JP 2002-75364 A
Patent Literature 4: Published Patent Application JP 2003-272632 A
Patent Literature 5: Published Patent Application JP 2004-234977 A
Patent Literature 6: Published Patent Application JP 2003-59491 A
Patent Literature 7: Published Patent Application JP 2007-335325 A
Patent Literature 8: Japanese Translation of PCT International Application JP 2005-519451 A
Patent Literature 9: Published Patent Application JP 2001-266882 A
Patent Literature 10: Published Patent Application JP 2010-108678 A
Patent Literature 11: Published Patent Application JP 2009-170401 A
Non-Patent Literatures
Non-Patent Literature 1: J. Moskon, R. Dominko, R. Cerc-Korosec, M. Gaberscek, J. Jamnik, J. Power Sources, 174, (2007) 638-688.
Non-Patent Literature 2: R. Dominko, M. Bele, M. Gaberscek, A. Meden, M. Remskar, J. Jamnik, Electrochem. Commun., 8, (2006)217-222.
Non-Patent Literature 3: Bin SHAO, Izumi TANIGUCHI, Proceedings of The 50th Battery Symposium, (2009)111.
Non-Patent Literature 4: Bin SHAO, Izumi TANIGUCHI, Proceedings of The 51st Battery Symposium, (2010)211.
Non-Patent Literature 5: Yi-Xiao Li, Zheng-Liang Gong, Yong Yang, J. Power Sources, 174, (2007)528-532.
Non-Patent Literature 6: Akira KOJIMA, Toshikatsu KOJIMA, Takuhiro MIYUKI, Yasue OKUMURA, Tetsuo SAKAI, Proceedings of The 51st Battery Symposium, (2010)194.
Non-Patent Literature 7: Yuichi KAMIMURA, Eiji KOBAYASHI, Takayuki DOI, Shigeto OKADA, Jun-ichi YAMAKI, Proceedings of The 50th Battery Symposium, (2009)30.
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
As described above, in lithium iron silicate Li2FeSiO4, lithium manganese silicate Li2MnSiO4, and derivatives obtained from these as the basic structure by element substitution or compositional change, high capacity (330 mAh/g) can be expected theoretically or compositionally. In reality, however, not many reports have described achievement of an actual capacity of 1 Li (165 mAh/g) or more, and no report has described achievement of an actual capacity of 1.5 Li (247 mAh/g) or more. The capacity described in Patent Literature 7 is 60 to 130 mAh/g, and the actual capacities described in Non-Patent Literatures 6 and 7 are 190 mAh/g and 225 mAh/g, respectively.
However, in reality, even if high actual capacity is obtained, the battery cannot obtain high voltage when internal resistance is high, and accordingly actual energy density is low. In addition, when the internal resistance is high, heat generation of a battery is large, and accordingly thermal design of a battery unit and so forth is difficult. Conventionally, because theoretical capacity is high with lithium iron silicate or lithium manganese silicate, efforts have been made to increase the actual capacity. However, the present inventors have found out that not only increase of the actual capacity but also reduction of the internal resistance needs to be tackled.
There is also a problem that when charge/discharge is repeated with a large charge amount, the internal resistance increases and/or the actual capacity decreases. In particular, in lithium manganese silicate, which contains Mn, the actual capacity significantly decreases when charge/discharge is repeated.
The present invention has been conceived in view of the problems, and objects are to provide: a cathode material for lithium ion secondary batteries, containing an oxide for a theoretical capacity of 2 Li or more, the cathode material with which high actual capacity, low internal resistance, and high stability against repetition of charge/discharge in high charge are obtained; and a cathode member for lithium ion secondary batteries and a lithium ion secondary battery each of which uses the cathode material for lithium ion secondary batteries.
Means for Solving the Problems
The present inventors have found out that a new oxide having a divalent element MII existing at a Li site of a composition formula Li2MSiO4, which is typified, for example, by lithium iron silicate and lithium manganese silicate, has the above-described effect.
That is, the present invention is summarized as follows.
(1) A cathode material for a lithium ion secondary battery including an oxide represented by a composition formula Li2-xMIIyM(Si,MB)O4 (wherein MII represents a divalent element; M represents at least one element selected from the group consisting of Fe, Mn, Co and Ni; and MB represents, as an optional component, an element substituted for Si to compensate for a difference between an electric charge of [Li2]2+ and an electric change of [Li2-xMIIy]n+ as needed), wherein in the composition formula representing the oxide, x and y are −0.25<x≦0.25 and 0<y≦0.25.
(2) The cathode material for a lithium ion secondary battery according to (1), wherein the MII exists at a Li site of the composition formula Li2-xMIIyM(Si,MB)O4.
(3) The cathode material for a lithium ion secondary battery according to (1) or (2), wherein a value of the y is a multiple of 0.03125.
(4) The cathode material for a lithium ion secondary battery according to any one of (1) to (3), wherein the represents at least one element selected from Mg, Cu and Zn.
(5) The cathode material for a lithium ion secondary battery according to any one of (1) to (4), wherein the MB represents at least one element selected from B, Al and Ga.
(6) The cathode material for a lithium ion secondary battery according to anyone of (1) to (5), wherein the cathode material is a composite composed of the oxide and a carbon material, and the composite shows a sea-islands structure in which the oxide is scattered like islands in the carbon material, and an average circle-equivalent diameter of the islands of the sea-islands structure is 3 nm or more and 15 nm or less.
(7) The cathode material for a lithium ion secondary battery according to (6), wherein the composite is a grain having a size of 1 μm or more and 20 μm or less, and a void exists inside the grain.
(8) The cathode material for a lithium ion secondary battery according to (7), wherein the void having a size of 200 nm or more and less than the size of the grain exists inside the grain.
(9) The cathode material for a lithium ion secondary battery according to (8), wherein an abundance of the void is 20% or more and 80% or less in terms of an area rate in a section of the grain.
(10) A cathode member for a lithium ion secondary battery including a metal foil provided with a cathode layer including: the cathode material for a lithium ion secondary battery according to any one of (1) to (9); and a binder.
(11) A lithium ion secondary battery including the cathode material for a lithium ion secondary battery according to any one of (1) to (9) or the cathode member for a lithium ion secondary battery according to (10).
Advantageous Effects of the Invention
According to the present invention, a cathode material for lithium ion secondary batteries, a cathode member for lithium ion secondary batteries and a lithium ion secondary battery which can have high actual capacity, reduce the internal resistance and have high stability against repetition of charge/discharge can be provided.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a schematic view of the internal structure of a composite in the present invention and a TEM image of a rupture part thereof.



EMBODIMENT FOR CARRYING OUT THE INVENTION
A cathode material for lithium ion secondary batteries of the present invention contains an oxide represented by a composition formula [1] Li2-xMIIyM(Si,MB)O4, wherein MII represents a divalent element.
M represents at least one element selected from the group consisting of Fe, Mn, Co and Ni. MB represents, as an optional component, an element substituted for Si to compensate for the difference between an electric charge(s) of [Li2]2+ and an electric change (s) of [Li2-xMIIy]n+ as needed. In the composition formula [1], x and y are −0.25<x≦0.25 and 0<y≦0.25. Consequently, the effect of the present invention can be obtained.
The structure of lithium iron silicate, lithium manganese silicate, lithium cobalt silicate or lithium nickel silicate is a structure in which lithium ions are inserted between MSiO4 sheets (layers) composed of M oxygen tetrahedra and Si oxygen tetrahedra sharing the apexes. The sheets are negatively charged in a state in which lithium ions are inserted therebetween, and it is considered that electrostatic attraction acts between the sheets through lithium cations.
As lithium ion deintercalation (delithiation) progresses through charge, the lithium ions existing between the sheets are reduced, and the negatively charged sheets lose the charges, approaching to an electric charge of 0. Accordingly, the electrostatic attraction between the sheets is reduced (or weakens), so that misalignment of the sheets easily occurs. It can be presumed that large misalignment of the sheets makes a path for lithium ions to transfer between the sheets intricate, so that lithium ion transfer becomes difficult and accordingly the internal resistance increases.
It has been considered that if MSiO4 sheets are strongly attracted to each other even when lithium ions between the layers (sheets) are reduced, misalignment of the sheets hardly occurs and accordingly the internal resistance does not increase. Then, it has been considered that a cation(s) having a large electric change strongly attracts the sheets to each other, and an idea of inserting a divalent ion(s) to a Li site (between sheets) has come to mind.
In the case of this kind of layer structure, electron transfer accompanying lithium ion intercalation/deintercalation is mainly performed within the faces of the sheets, so that it can be considered that electron transfer between the sheets is difficult. When an element having a difference between oxygen O in electronegativity smaller than that of Li exists between the layers, localization of electrons at oxygen ions can be reduced, and electrons can be easily conducted between MSiO4 sheets through ions of the element. That is, electrons can easily transfer between the sheets, and accordingly the internal resistance is reduced.
In the case of M being in particular Mn, namely, lithium manganese silicate, there is a problem that when charge/discharge is repeated, discharge capacity rapidly decreases. This is considered because when charge/discharge is repeated, not only misalignment of MnSiO4 sheets occurs but also Mn ions in MnSiO4 sheets transfer to between the sheets, and accordingly Mn tetrahedral coordination changes to Mn octahedral coordination. That is, in the case of lithium manganese silicate, the structure of MnSiO4 sheets itself is broken down. However, if the cations having a higher valency than that of lithium ions exist between the layers, the structure can be prevented from being broken down. This is presumed because when the cations having a high valency exist between the layers, the positive charge between the layers increases, and accordingly Mn ions hardly transfer to between the layers. Therefore, in the case of lithium manganese silicate in particular, the structure broken down by charge/discharge can also be prevented.
The present inventors have found out that the above-described effect can be obtained when a divalent element exists at the Li site within a range of 0<y≦0.25. The divalent element does not exist at the Li site if y is 0 or less, and accordingly the effect of the present invention cannot be obtained. The divalent element cannot be inserted between the sheets in such a way that y is more than 0.25. In other words, the effect of the present invention cannot be obtained if y is more than 0.25.
In the composition formula [1], x is −0.25<x≦0.25. If x is −0.25 or less, Li in the composition formula [1] is more than 2.25. It is impossible to insert so many lithium ions between the sheets, and accordingly the internal resistance cannot be reduced.
In the case where electric-charge compensation for the divalent element MII inserted to the Li site (between layers) is performed only with Li, the composition formula [1] of the present invention can be expressed as a composition formula [2] Li2-yMIIyMSiO4. In this case, MII is substituted for the Li site, and empty sites the number of which is the same as that of MII are formed at the Li site.
In the case where the divalent element MII is excessively inserted to the Li site (between layers), and electric-charge compensation for MII is performed only with MB, the composition formula [1] of the present invention can be expressed as a composition formula [3] Li2MIIyM(Si,MB)O4.
For the electric-charge compensation for MII, MB and Li may be used together. Further, the composition may be Li excessive in addition to the Li site (between layers) being MII excessive. In the present invention, electric-charge compensation is not essential. Further, in the composition formula [1], some compositional variation such as oxygen deficiency is acceptable.
Examples of the divalent element MII include Mg, Ca, Sr, Cu, Zn, Mn, Fe, Co and Ni. Among the elements, Mg, Cu and Zn are preferable. If the MII is a monovalent element, the internal resistance may increase or the effect of the present invention may be unobtainable. If the MII is a trivalent element, the MII is hardly inserted between the layers, and accordingly the effect of the present invention cannot be obtained. Further, in the case where M is Mn or Fe, an element having oxygen ions as ligands and having large ligand field stabilization energy is preferable.
MB to compensate for the difference between an electric change (s) of [Li2]2+ and an electric change (s) of [Li2-xMIIy]n+ is a trivalent element, a divalent element or a monovalent element. Examples thereof include B, Al, Ga, In, Sc, Y, Mg, Ca, Na and K. It is preferable that MB be at least one element selected from B, Al and Ga. Consequently, the internal resistance can be efficiently reduced.
It is preferable that the value of the y be a multiple of 0.03125 within the above-mentioned range. When the value is such a multiple, sublattices are formed and accordingly the structure is more stable. Consequently, even when charge/discharge is repeated, the structure does not change easily and accordingly decrease of the discharge capacity and increase of the internal resistance do not easily progress.
The present invention is a composite composed of the oxide and a carbon material, and it is preferable that the composite show, as shown in FIG. 1, a sea-islands structure in which the oxide is scattered like islands in the carbon material, and an average circle-equivalent diameter of the islands of the sea-islands structure be 3 nm or more and 15 nm or less.
In the composite, a plurality of regions composed of the oxide exist. In other words, the composite has a structure in which the carbon material lies as a matrix (bulk) and the regions composed of the oxide are scattered (discrete). Hence, electron transfer to/from the regions, which occurs accompanying lithium ion intercalation/deintercalation to/from the regions, can be performed through the carbon material, so that all the regions act as an active material. Thereby, higher actual capacity can be realized. When the regions are small, the distance which lithium ion diffuses in solid is short and accordingly the actual capacity tends to be high. The electrical conductivity of the oxide is very low. Hence, in order to obtain high actual capacity with a practical charge/discharge duration, the crystal grain size needs to be equal to or less than the distance which lithium ion can diffuse in solid within the charge/discharge duration.
More specifically, when the circle-equivalent diameter of the projected areas of the regions composed of the oxide in the composite is 15 nm or less, higher actual capacity is obtained. If the diameter is more than 15 nm, the distance which lithium ion diffuses in solid is longer, and lithium ions cannot diffuse within the practical charge/discharge duration, so that high actual capacity is unavailable in some cases. The lower limit of the diameter is the minimum size down to which lithium ions can be easily kept in the oxide structure. That is, if the diameter is less than 3 nm, keeping lithium ions in the oxide structure is difficult in some cases.
The regions composed of the oxide in the composite are observable with a transmission electron microscope. The circle-equivalent diameter of the projected areas thereof can be calculated by observation with a transmission electron microscope and image processing.
More specifically, a transmission electron microscope image is subjected to thresholding, observed regions each are converted to the area of a circle, and the circle-equivalent diameter can be obtained by calculating the average value of the diameters of the circles. The circle-equivalent diameter is a number average value of 20 or more diameters thereof. In general, the circle-equivalent diameter is a number average value of 50 diameters thereof.
It is preferable that the carbon material content be 2 mass % or more and 25 mass % or less in the cathode material for lithium ion secondary batteries of the present invention.
If the carbon material content is less than 2 mass %, a sufficient electron conduction path to a current collector is impossible to secure in some cases, and hence excellent battery characteristics are unavailable in some cases. On the other hand, if the carbon material content is more than 25 mass %, the ratio of the active material content to a produced electrode is small, and hence high battery capacity is unavailable in some cases depending on the way or purpose of battery design. The above-mentioned range secures excellent battery characteristics easily and widens a range of selection of the battery design.
The carbon material in the present invention contains elemental carbon, and it is preferable that the percentage content of graphitic skeletal carbon in the carbon material of the composite grain be 20 to 70%. If the percentage content of graphitic skeletal carbon is less than 20%, the electrical conductivity of the carbon material decreases, and high capacity is difficult to obtain. On the other hand, if the percentage content of graphitic skeletal carbon is more than 70%, permeation of an electrolyte solution is difficult due to increased hydrophobicity, and high capacity is difficult to obtain in some cases.
It is preferable that the composite be a grain having a size of 1 μm or more and 20 μm or less and, as shown in FIG. 1, have a void(s) therein.
Thereby, excellent application performance is obtained without capacity decrease, namely, with high capacity. Because the grain size is large, even dispersion of the cathode material in an applied slurry is easy and the slurry's fluidity is excellent, so that spots by the application are hardly generated. Hence, the applied film shrinks, which occurs in the application process or a drying process, not much and evenly, and cracks are prevented from being generated. In particular, when an application amount thereof is large, the effect is strikingly demonstrated. If the grain size is less than 1 μm, the application performance is bad in some cases. On the other hand, if the grain size is more than 20 μm, the surface of the applied film is rough, i.e. not uniform, caused by the grain in some cases. It is particularly preferable that the shape of the grain be spherical.
Herein, the spherical grain size is a circle-equivalent diameter of the projected areas of spherical grains observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). The circle-equivalent diameter is calculated using a TEM image or a SEM image as follows; observed spherical grains each are converted to the area of a circle, and the average value of the diameters of the circles is calculated. The circle-equivalent diameter is a number average value of 20 or more diameters thereof. In general, the circle-equivalent diameter is a number average value of 50 diameters thereof. When either a TEM image or a SEM image is within the scope of the present invention, the effect of the present invention is obtained.
Further, it is preferable that a void(s) having a size of 200 nm or more and less than the grain diameter exist in the grain.
Existence of the void in the grain makes high capacity possible even under a high discharge rate. This is because the electrolyte solution permeates the grain and a sufficient amount thereof can be kept in the void, so that even under a high rate, Li+ ions can be easily transferred between the grain and the electrolyte solution inside the grain. On the other hand, if no void exists, the electrolyte solution cannot permeate the grain well and a sufficient amount thereof cannot reach the inside of the grain, so that Li+ ions need to diffuse to the surface of the grain through the inside of the solid. Hence, efficient Li+ ion intercalation/deintercalation under a high rate is impossible in some cases. That is, high capacity under a high rate is unavailable in some cases.
The void size is a circle-equivalent diameter of the projected areas of voids observable on a section of a grain with a SEM.
It is preferable that the abundance of the void be 20% or more and 80% or less in terms of an area rate in the section of the grain. The reason why the area rate is 20% or more and 80% or less is that if the area rate is less than 20%, high capacity under a high discharge rate is unavailable in some cases, whereas if the area rate is more than 80%, high capacity under a high discharge rate is available, but increase of the active material content in an electrode is difficult in some cases.
The cathode material for lithium ion secondary batteries of the present invention may be a cathode layer containing at least a binder, and the cathode layer is provided on the surface of a metal foil which serves as a current collector so that a cathode member for lithium ion secondary batteries is produced.
The binder (also referred to as a binding agent) serves to bind an active material and/or an electrically conductive auxiliary.
The binder in the present invention is any of those generally used in producing cathodes of lithium ion secondary batteries. It is preferable that the binder be chemically and electrochemically stable against an electrolyte of a lithium ion secondary battery and a solvent of the electrolyte.
The binder is either of thermoplastic resin and thermosetting resin. Examples thereof include: polyolefin such as polyethylene and polypropylene; fluorine-containing resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer; styrene butadiene rubber (SBR); ethylene-acrylic acid copolymer and Na+ ion crosslinked product of the copolymer; ethylene-methacrylic acid copolymer and Na+ ion crosslinked product of the copolymer; ethylene-methyl acrylate copolymer and Na+ ion crosslinked product of the copolymer; ethylene-methyl methacrylate copolymer and Na+ ion crosslinked product of the copolymer; and carboxymethyl cellulose. Some of these may be used in combination. Among these materials, PVDF and PTFE are particularly preferable.
The binder is generally used in such a way as to be 1 to 20 mass % or around in the total amount of the cathode.
The cathode layer of the cathode member for lithium ion secondary batteries may further contain the electrically conductive auxiliary.
Substantially, there is no special limitation on the electrically conductive auxiliary as long as it is an electron conductive material which is chemically stable. Examples thereof include carbon materials: such as graphites including natural graphite (flaky graphite, etc.) and synthetic graphite; acetylene black; Ketjen black; carbon blacks including channel black, furnace black, lamp black, and thermal black; and carbon fiber, and also include: electro-conductive fibers including metal fiber; carbon fluoride; metal powders of aluminum, etc.; zinc oxide; electro-conductive whiskers of potassium titanate, etc.; electro-conductive metal oxides including titanium oxide; and organic electro-conductive materials including polyphenylene derivative. One of these may be used alone, or two or more thereof may be used in combination. Among these, carbon materials such as acetylene black, Ketjen black, and carbon black are particularly preferable.
The electrically conductive auxiliary is generally used in such a way as to be 1 to 25 mass % or around in the total amount of the cathode.
The cathode layer contains at least the cathode active material and the binder and has a structure having a void(s) which an electrolyte solution can enter. The cathode layer may contain the electrically conductive auxiliary in addition to the cathode active material and the binder.
The metal foil is an electro-conductive metal foil, and a foil made of aluminum, aluminum alloy or the like may be used therefor. The thickness thereof may be 5 μm to 50 μm.
The cathode member for lithium ion secondary batteries is used to produce a lithium ion secondary battery. For example, a lithium ion secondary battery is composed of at least an anode, a separator, and a non-aqueous electrolyte solution in addition to the cathode member for lithium ion secondary batteries.
The anode contains a binder (also referred to as a binding agent) as needed in addition to an anode active material.
The anode active material of the anode is any material which allows metallic lithium or lithium ion doping/de-doping. Examples of the material which allows lithium ion doping/de-doping include carbon materials such as graphite, pyrolytic carbons, cokes, glassy carbons, sintered product of organic polymer compound, mesocarbon microbead, carbon fiber, and activated carbon. Also compounds including: alloys of Si, Sn, In, etc.; oxides of Si, Sn, Ti, etc. capable of charge/discharge at a low potential which is equivalent to that of Li; and nitride of Li and Co such as Li2.6Co0.4N are usable as the anode active material. Metal capable of being alloyed with Li, an oxide or the like may be substituted for a part of graphite.
When graphite is used as the anode active material, the voltage in full-charge can be assumed to be approximately 0.1 V with reference to Li, so that the potential of the cathode can be calculated for convenience by adding 0.1 V to the battery voltage. Hence, graphite is preferable for easy control of the charging potential of the cathode.
The anode may be configured to have an anode layer which contains the anode active material and the binder and is provided on the surface of a metal foil which serves as a current collector.
The metal foil is, for example, a foil of: a simple substance of copper, nickel or titanium; an alloy of any of these; or stainless steel. Preferably used materials for the anode current collector in the present invention include copper and an alloy thereof. Preferable metals capable of being alloyed with cooper include Zn, Ni, Sn, and Al. A small amount of Fe, P, Pb, Mn, Ti, Cr, Si, As or the like may be added thereto.
The separator is any insulating thin film having high ion permeability and a certain level of mechanical strength. Materials used for the separator include olefinic polymer, fluorine-containing polymer, cellulosic polymer, polyimide, nylon, glass fiber, and alumina fiber. Forms used for the separator include non-woven fabric, woven fabric, and micro-porous film.
In particular, polypropylene, polyethylene, mixture of polypropylene and polyethylene, mixture of polypropylene and polytetrafluoroethylene (PTFE), and mixture of polyethylene and polytetrafluoroethylene (PTFE) are preferable materials therefor, and the micro-porous film is a preferable form therefor.
In particular, the micro-porous film having a pore diameter of 0.01 to 1 μm and a thickness of 5 to 50 μm is preferable. The micro-porous film may be a single film or may be a composite film composed of two or more layers having different properties, for example, in pore geometry, pore density and/or material. A composite film configured by bonding a polyethylene film and a polypropylene film is an example thereof.
The non-aqueous electrolyte solution is generally composed of an electrolyte (supporting salt) and a non-aqueous solvent. The supporting salt mainly used for the lithium secondary battery is lithium salt.
Examples of the lithium salt usable in the present invention include LiClO4, LiBF4, LiPF6, LiCF3CO2, LiAsF6, LiSbF6, LiB10Cl10, fluorosulfonate salt represented by LiOSO2CnF2n+1 (n represents a positive integer of 6 or less), imide salt represented by LiN(SO2CnF2n+1) (SO2CmF2m+1) (each of m and n independently represents a positive integer of 6 or less), methide salt represented by LiC(SO2CpF2p+1) (SO2CqF2q+1) (SO2CrF2r+1) (each of p, q and r independently represents a positive integer of 6 or less), and Li salt such as lower aliphatic carboxylate lithium, LiAlCl4, LiCl, LiBr, LiI, chloroborane lithium, and lithium tetraphenylborate. One of these may be used alone, or two or more thereof may be used in a mixed manner. Among them, LiBF4 and/or LiPF6 being dissolved is preferable.
It is preferable that the concentration of the supporting salt be 0.2 to 3 mol per liter of an electrolyte solution although not particularly limited.
Examples of the non-aqueous solvent include: aprotic organic solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, trifluoromethyl ethylene carbonate, difluoromethyl ethylene carbonate, monofluoromethyl ethylene carbonate, hexafluoromethyl acetate, trifluoromethyl acetate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, γ-butyrolactone, methyl formate, methyl acetate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, 2,2-bis(trifluoromethyl)-1,3-dioxolane, formamide, dimethyl formamide, dioxolane, dioxane, acetonitrile, nitromethane, ethyl monoglyme, phosphoric triester, boric triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone, 3-alkylsydnone (the alkyl group is propyl group, isopropyl group, butyl group, etc.), propylene carbonate derivative, tetrahydrofuran derivative, ethyl ether, and 1,3-propane sultone; and ionic liquid. One of these may be used alone, or two or more thereof may be used in a mixed manner.
Among them, the carbonate-based solvents are preferable, and it is particularly preferable to use cyclic carbonate and acyclic carbonate in a mixed manner. As cyclic carbonate, ethylene carbonate and propylene carbonate are preferable. As acyclic carbonate, diethyl carbonate, dimethyl carbonate, and methylethyl carbonate are preferable. The ionic liquid is preferable from the viewpoint of wide electrochemical window and heat resistance.
It is preferable that the electrolyte solution contain LiCF3SO3, LiClO4, LiBF4 and/or LiPF6 dissolved in an electrolyte solution prepared by appropriately mixing some of ethylene carbonate, propylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, and diethyl carbonate.
In particular, it is preferable that the electrolyte solution contain LiPF6 and at least one salt selected from LiCF3SO3, LiClO4, and LiBF4 in a mixed solvent of at least one of propylene carbonate and ethylene carbonate and at least one of dimethyl carbonate and diethyl carbonate. The amount of addition of the electrolyte solution to the battery is not particularly limited, and hence an appropriate amount thereof can be used according to the amount of the cathode material and/or the anode material, and to the size of the battery.
Besides the electrolyte solution, a solid electrolyte described below may be used. The solid electrolyte is classified into an inorganic solid electrolyte and an organic solid electrolyte.
Examples of the inorganic solid electrolyte include nitride, halide, and oxysalt of Li. Among them, effective are Li3N, LiI, Li5NI2, Li3N—LiI—LiOH, Li4SiO4, Li4SiO4—LiI—LiOH, xLi3PO4—(1-x)Li4SiO4, Li2SiS3, phosphorus sulfide compound and so forth.
Effective examples of the organic solid electrolyte include polyethylene oxide derivative or polymer containing such derivative; polypropylene oxide derivative or polymer containing such derivative; polymer containing ion dissociative group; mixture of polymer containing ion dissociative group and the above aprotic electrolyte solution; phosphoric ester polymer; and polymer matrix material impregnated with an aprotic polar solvent. Polyacrylonitrile may be added to an electrolyte solution. It is also known to use the inorganic and organic solid electrolytes in combination.
A lithium ion secondary battery can be produced using the material for lithium ion secondary batteries without producing the member for lithium ion secondary batteries. For example, a lithium ion secondary battery is composed of: a cathode configured by forming, on a metal mesh, a cathode layer which contains the material for lithium ion secondary batteries, an electrically conductive auxiliary, and a binder; an anode; a separator; and a non-aqueous electrolyte solution.
The cathode material for lithium ion secondary batteries of the present invention can be produced, for example, by the following methods.
The oxide in the present invention may be produced by any method such as a dry method and a wet method as long as the method can synthesize an oxide. Examples thereof include a solid phase method (a solid phase reaction method), a hydrothermal method (a hydrothermal synthesis method), a coprecipitation method, a sol-gel method, a vapor phase synthetic method (a Physical Vapor Deposition (PVD) method and a Chemical Vapor Deposition (CVD) method), a spray pyrolysis method, a flame method, and a roasting method.
In the following, production thereof using the solid phase method, the spray pyrolysis method, and the roasting method is described as examples.
A source material(s) used in the solid phase method is a compound(s) which contains elements composing the above-mentioned oxide, the compounds being, for example, oxide, carbonate, and/or organic salt such as acetate and oxalate. The compounds are weighed in accordance with a composition ratio and mixed with one another. For the mixing, a wet mixing method, a dry mixing method or the like is used. The obtained mixture is fired to synthesize the oxide. The oxide powder obtained by the firing is grounded as needed. If there is any unreacted substance, further firing may be performed after the grinding.
Asa specific case, in the case of Li1.875Mg0.0625MnSiO4, for example, manganese dioxide, lithium carbonate, magnesium carbonate, and silicon dioxide are weighed in such a way as to be the above chemical composition and mixed. The mixed powder is fired at 700 to 900° C. for 5 to 20 hours in a reductive atmosphere. Thus, Li1.875Mg0.0625MnSiO4 can be produced.
As another specific case, in the case of Li2Mg0.0625Fe(Si0.875Al0.125)O4, for example, lithium carbonate, magnesium carbonate, iron (II) oxalate dihydrate, silicon dioxide, and aluminum oxide are weighed in such a way as to be the above chemical composition and mixed. The mixed powder is fired at 700 to 900° C. for 5 to 20 hours in a reductive atmosphere. Thus, Li2Mg0.0625Fe(Si0.875Al0.125)O4 can be produced.
A source material(s) used in the spray pyrolysis method is a compound(s) which contains elements composing the above-mentioned oxide and is soluble in water or an organic solvent. The solution in which the compound is dissolved is converted into liquid droplets using an ultrasonic wave or a nozzle (a one fluid nozzle, a two fluid nozzle, a four fluid nozzle, etc.). Then, the liquid droplets are introduced into a heating furnace of 400 to 1200° C. to be pyrolyzed. Thus, the oxide can be produced. Further heat treatment and/or grinding are performed as needed. The oxide containing a carbon material can be produced by adding an organic compound to the source material solution.
As a specific case, in the case of Li1.875Mg0.0625MnSiO4, for example, lithium nitrate, magnesium nitrate hexahydrate, manganese (II) nitrate hexahydrate, colloidal silica, and aluminum nitrate are weighted in such a way as to be the above chemical composition and dissolved in water.
Here, an organic compound may be added to the solution. Examples of the organic compound include ascorbic acid, monosaccharides (glucose, fructose, galactose, etc.), disaccharides (sucrose, maltose, lactose, etc.), polysaccharides (amylose, cellulose, dextrin, etc.), polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyvinyl butyral, polyvinyl pyrrolidone, phenol, hydroquinone, catechol, maleic acid, citric acid, malonic acid, ethylene glycol, triethylene glycol, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and glycerin.
For example, the solution in which the compounds are dissolved is converted into liquid droplets using an ultrasonic atomizer, and the liquid droplets are introduced together with nitrogen as a carrier gas into a heating furnace of 400 to 1200° C. to be pyrolyzed. Thus, Li1.875Mg0.0625MnSiO4 can be produced.
As another specific case, in the case of Li2Mg0.0625Fe(Si0.875Al0.125)O4, for example, lithium nitrate, magnesium nitrate hexahydrate, iron (III) nitrate nonahydrate, tetraethoxysilane, and aluminum sec-butoxide are weighted in such a way as to be the above chemical composition and dissolved in water.
Tetraethoxysilane and aluminum sec-butoxide are dissolved in methoxyethanol in advance, and this solution is dissolved in the water. For example, the solution in which the compounds are dissolved is converted into liquid droplets using an ultrasonic atomizer, and the liquid droplets are introduced together with nitrogen as a carrier gas into a heating furnace of 400 to 1200° C. to be pyrolyzed. Thus, Li2Mg0.0625Fe(Si0.875Al0.125)O4 can be produced.
Next, the production method using the roasting method is described as an example.
A source material(s) used in the roasting method is a compound(s) which contains elements composing a desired oxide and is soluble in water. When the oxide contains iron as an element, it is preferable to use for the source material an iron and steel pickling waste liquid or an aqueous solution prepared by dissolving a rolling scale in hydrochloric acid. The aqueous solution in which the compound is dissolved is introduced into a roasting furnace of the Ruthner type, Lurgi type, Chemirite type or the like to be pyrolyzed. Thus, the oxide can be produced. Further heat treatment and/or grinding are performed as needed. The oxide containing a carbon material can be produced by adding an organic compound to the source material solution.
As a specific case, in the case of Li1.875Mg0.0625MnSiO4, for example, lithium carbonate, magnesium carbonate, manganese dioxide, and colloidal silica are weighted in such a way as to be the above chemical composition and dissolved in 18% hydrochloric acid. Glucose is dissolved in the aqueous solution in which the compounds are dissolved, and the resulting solution is, for example, introduced into a Chemirite type roasting furnace to be pyrolyzed at 500 to 1000° C. Thus, Li1.875Mg0.0625MnSiO4 can be produced. Further, the ground grain (s) obtained by wet grinding in a bead mill may be subjected to heat treatment in an inert atmosphere.
As another specific case, in the case of Li2Mg0.0625Fe(Si0.875Al0.125)O4, for example, lithium carbonate, magnesium carbonate, colloidal silica, and aluminum (III) chloride hexahydrate are dissolved in an iron and steel pickling waste liquid (for example, hydrochloric acid waste liquid with a concentration of 3.0 mol (Fe)/L) to be prepared in such a way as to be a concentration equivalent to the above chemical composition ratio. In order to fully dissolve lithium carbonate and magnesium carbonate, an appropriate amount of 18% hydrochloric acid is added to the iron and steel pickling waste liquid in advance. Glucose is dissolved in the aqueous solution in which the compounds are dissolved, and the resulting solution is, for example, introduced into a Ruthner type roasting furnace to be pyrolyzed at 500 to 1000° C. Thus, Li2Mg0.0625Fe(Si0.875Al0.125)O4 can be produced. Further, the ground grain (s) obtained by wet grinding in a bead mill may be subjected to heat treatment in an inert atmosphere.
Examples of the organic compound, which produces the carbon material, include ascorbic acid, monosaccharides (glucose, fructose, galactose, etc.), disaccharides (sucrose, maltose, lactose, etc.), polysaccharides (amylose, cellulose, dextrin, etc.), polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyvinyl butyral, polyvinyl pyrrolidone, phenol, hydroquinone, catechol, maleic acid, citric acid, malonic acid, ethylene glycol, triethylene glycol, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and glycerin.
Examples of the compound, which contains elements composing the metal oxide, include metal, hydroxide, nitrate, chloride, organic acid salt, oxide, carbonate, and metal alkoxide.
EXAMPLES
First Example
Starting materials used were lithium nitrate (LiNO3), manganese (II) nitrate hexahydrate (Mn(NO3)2.6H2O), colloidal silica, aluminum nitrate nonahydrate (Al(NO3)3.9H2O), magnesium nitrate hexahydrate (Mg(NO3)2.6H2O), copper nitrate trihydrate (Cu(NO3)2.3H2O), zinc nitrate hexahydrate (Zn(NO3)2.6H2O), iron (III) nitrate nonahydrate (Fe(NO3)3.9H2O), boric acid (H3BO3), gallium nitrate (Ga(NO3)3.nH2O), yttrium nitrate hexahydrate (Y(NO3)3.6H2O), sodium nitrate (NaNO3), and potassium nitrate (KNO3). The materials were dissolved in water in such a way as to be each composition ratio shown in Table 1-1, so that aqueous solutions were prepared. Further, glucose as the organic compound, which produces a carbon material, was added to the aqueous solutions. Each of these aqueous solutions was subjected to spray pyrolysis in a heating furnace heated at 450 to 700° C. using a carrier gas composed of nitrogen gas. Thereby, samples were produced.
Samples 1-1 to 1-2 and 1-4 to 1-25 were further subjected to wet grinding and then heat treatment at 700° C. for 5 hours in 1% H2/Ar after the aqueous solutions were sprayed in the heating furnace of 600° C. As to Sample 1-3, the heat treatment was performed at 900° C. for 3 hours in 1% H2/Ar. For Sample 1-26, the aqueous solution was sprayed in the heating furnace of 700° C. Samples 1-27 to 1-29 were subjected to neither wet grinding nor heat treatment. For Sample 1-28, the aqueous solution was sprayed in the heating furnace of 500° C. For Sample 1-29, the aqueous solution was sprayed in the heating furnace of 450° C. Sample 1-30 was produced by subjecting Sample 1-27 to grinding and then granulation.
The solutions each were prepared in such a way that the concentration of metal ions in the solution was 0.21 or 0.33 mol/L when the composition of the oxide was converted to moles. The glucose was added in such a way that a mole ratio of glucose/oxide was 2 or 3. Each sample produced without grinding was a spherical grain(s), and the spherical grain size was controlled through the concentration of metal ions in the liquid droplets and the glucose content.
<Analysis of Individual Samples>
The individual samples obtained as described above were analyzed as follows.
Phase check was performed using a powder X-ray diffractometer (Ultima II manufactured by Rigaku Corporation). Because Samples 1-1 to 1-26 were subjected to the heat treatment, they had a diffraction pattern similar to that of a Li2MnSiO4 crystal phase. However, in the samples which were divalent-element-added or element-substituted, diffraction peak shift was observed. Samples 1-27 to 1-30 had no diffraction peak within 2θ=15 to 18° but had a broad diffraction peak within 2θ=33±2° with Cu-Kα line and hence were crystalline.
Samples 1-1 to 1-30 were observed under a transmission electron microscope (H-9000UHR III manufactured by Hitachi Ltd.). All of the samples were composites having the sea-islands structure. The circle-equivalent diameter of the islands (oxide) was calculated using the method described above. The obtained circle-equivalent diameter of each sample is shown in Table 1-3.
The grains of Samples 1-1 to 1-30 were observed under a scanning electron microscope (JSM-7000F manufactured by JEOL Ltd.), and the circle-equivalent diameter was calculated as the grain size using the images. The values are shown in the “Grain Size” column in Table 1-3. Each of Samples 1-1 to 1-26 was grounded to be a size of 0.2 μm, so that each of Samples 1-1 to 1-26 was a nonuniformity-shaped fine grain(s) having the mentioned size, not a spherical grain(s). Each of Samples 1-27 to 1-29 was a spherical grain(s) and had a void(s) of 200 nm or more in the grain. Sample 1-30 was produced by grinding Sample 1-27 and then granulating, so that the size thereof was the size of a spherically-granulated grain(s). The spherical grains were observable under a transmission electron microscope too. The obtained values of the spherical grain size under a transmission electron microscope were the same as those shown therein.
Sections of Samples 1-27 to 1-30, which were the spherical grains, were also observed under a scanning electron microscope. Using the images, a void(s) of 200 nm or more in the spherical grains was picked, and the area rate was calculated as the abundance of the void. Samples 1-27 to 1-29 had the values shown in the “Area Rate” column of the “Void in Grain” column in Table 1-3. Sample 1-30 was the spherical grain produced by grinding Sample 1-27 and then granulating, so that the inside of the spherical grain was dense, and no large void such as a void of 200 nm or more existed.
The carbon material content in each sample was determined using a carbon/sulfur analyzer EMIA-320V manufactured by Horiba Ltd. and is shown in Table 1-2.
<Evaluation of Battery Characteristics>
Battery characteristics of each sample were evaluated as follows.
First, a sample, acetylene black powder, and polytetrafluoroethylene powder were mixed in a weight ratio of 70:25:5 in a mortar, and the mixture was compressed onto a titanium mesh. Thereby, cathodes were produced.
For anodes, metallic lithium foils were used, and for anode current collectors, 20 μm thick nickel foils were used.
As each of electrolyte solutions, a non-aqueous electrolyte solution was used, in which LiPF6 was dissolved in a mixed solvent of ethyl carbonate and dimethyl carbonate mixed in a volume ratio of 1:2 at a concentration of 1.0 mol/L, and as each of separators, porous polypropylene with a thickness of 25 μm was used. CR2032 type coin batteries were assembled in an argon-filled glove box by using these.
Five coin batteries were produced using each sample, and the produced coin batteries were subjected to a charge/discharge test in a thermostat chamber at 25° C. to measure the initial charge/discharge capacity. In the initial charge/discharge test, preliminary charge-and-discharge was performed one time under a CC-CV condition over a voltage range of 1.0 to 5.0 V at a rate of 0.1 C, and thereafter charge was performed under the CC-CV condition at a rate of 0.1 C to 250 mAh/g, and the discharge capacity was measured to obtain the initial charge/discharge capacity. The initial charge/discharge capacity of the five coin batteries of each sample was measured. The average value of the obtained values of the initial charge/discharge capacity of three coin batteries without those having the maximum value and the minimum value is shown in the “Initial Charge/Discharge Capacity” column in Table 1-4.
Regarding the internal resistance reduction effect, a voltage at 140 mAh/g was obtained from the discharge curve from which the initial discharge capacity was obtained. It was determined that the internal resistance was reduced when the voltage was high. The voltage of the five coin batteries of each sample was obtained from the discharge curve. The average value of the obtained values of the voltage of three coin batteries without those having the maximum value and the minimum value is shown in Table 1-3.
In addition, charge-and-discharge was repeated 10 cycles, and a slope of voltage change (voltage change per cycle) at 140 mAh/g in the discharge curve from the 5th cycle to the 10th cycle was obtained, and the obtained value regarding each sample is shown in Table 1-4 as stability of the internal resistance reduction effect.
Further, as a discharge capacity maintenance rate, values obtained by “(discharge capacity at 2 V in the 10th cycle/discharge capacity at 2 V in the 2nd cycle)×100” are shown in Table 1-4.
As shown in Table 1-3, the discharge voltage at 140 mAh/g of Samples 1-2 to 1-5, 1-9 to 1-19, 1-22 to 1-23, and 1-25 to 1-30 having a divalent ion as MII was higher than that of Sample 1-1 having nothing as MII and Samples 1-6 to 1-8 having a non-divalent ion as MII, and Samples 1-2 to 1-5, 1-9 to 1-19, 1-22 to 1-23, and 1-25 to 1-30 showed the internal resistance reduction effect. Sample 1-20 had more than 0.25 as the value of y and did not show the internal resistance reduction effect. Sample 1-21 had −0.25 as the value of x and did not show the internal resistance reduction effect. Sample 1-24 had more than 0.25 as the value of x and as the value of y and did not show the internal resistance reduction effect.
In addition, the samples having a multiple of 0.03125 as the value of y had better stability of the internal resistance reduction effect. The samples having a divalent ion other than Mg ion as MII showed the same tendency about the stability.
The application performance was evaluated regarding Samples 1-27 to 1-30. Into a dispersion medium (N-methylpyrrolidone, i.e. NMP), 80 mass % of a sample, 10 mass % of polyvinylidene difluoride (PVDF), and 10 mass % of acetylene black were mixed to prepare a slurry. The slurry was applied onto a 20 μm thick aluminum foil using a Baker-type applicator in which a clearance was set at 300 μm and dried using a dryer of 100° C. The surface of the dried applied film was visually observed. Samples having conspicuous surface roughness or a crack(s) were evaluated as “bad application performance”, and samples having flat surface and no crack were evaluated as “excellent application performance”.
Samples 1-27 to 1-30 were evaluated as “excellent application performance”. The samples each having an appropriate amount of the void in the spherical grain showed excellent discharge capacity even under a high rate.










TABLE 1-1









TEMPERATURE





OF
ADDED AMOUNT




SPRAY
OF GLUCOSE



Li2−xMyIIM(SinMmB)O4
FURNACE
MOLE RATIO
















No.
x
MII
y
M
n
MB
m
[° C.]
(GLUCOSE/OXIDE)



















1-1
0
—
0
Mn
1
—
0
600
2


1-2
0.125
Mg(II)
0.0625
Mn
1
—
0
600
2


1-3
0.125
Mg(II)
0.0625
Mn
1
—
0
600
2


1-4
0
Mg(II)
0.0625
Mn
0.875
Al
0.125
600
2


1-5
−0.03125
Mg(II)
0.0625
Mn
0.9063
Al
0.09375
600
2


1-6
0.0625
K(I)
0.0625
Mn
1
—
0
600
2


1-7
0.0625
Na(I)
0.0625
Mn
1
—
0
600
2


1-8
0.1875
Al(III)
0.0625
Mn
1
—
0
600
2


1-9
0.125
Cu(II)
0.0625
Mn
1
—
0
600
2


1-10
0
Cu(II)
0.0625
Mn
0.875
Al
0.125
600
2


1-11
0.125
Zn(II)
0.0625
Mn
1
—
0
600
2


1-12
0
Zn(II)
0.0625
Mn
0.875
Al
0.125
600
2


1-13
0
Ca(II)
0.0625
Mn
0.875
Al
0.125
600
2


1-14
0
Mn(II)
0.0625
Mn
0.875
Al
0.125
600
2


1-15
0
Fe(II)
0.0625
Mn
0.875
Al
0.125
600
2


1-16
0.04
Mg(II)
0.02
Mn
1
—
0
600
2


1-17
0
Mg(II)
0.03125
Mn
0.9375
B
0.0625
600
2


1-18
0
Mg(II)
0.125
Mn
0.75
Al
0.25
600
2


1-19
0
Mg(II)
0.25
Mn
0.5
Al
0.5
600
2


1-20
0
Mg(II)
0.28
Mn
0.44
Al
0.56
600
2


1-21
−0.25
Mg(II)
0.0625
Mn
0.625
Al
0.375
600
2


1-22
0.03125
Mg(II)
0.03125
Mn
0.9688
Ga
0.03125
600
2


1-23
0.25
Mg(II)
0.25
Mn
0.75
Al
0.25
600
2


1-24
0.26
Mg(II)
0.26
Mn
0.74
Al
0.26
600
2


1-25
0
Mg(II)
0.09735
Mn
0.8053
Y
0.1947
600
2


1-26
0.03125
Mg(II)
0.03125
Mn
0.9688
Al
0.03125
700
2


1-27
0.0625
Mg(II)
0.0625
Mn
0.9375
Al
0.0625
700
2


1-28
0.0625
Mg(II)
0.0625
Mn
0.9375
Al
0.0625
500
2


1-29
0.0625
Mg(II)
0.0625
Mn
0.9375
Al
0.0625
450
3


1-30
0.0625
Mg(II)
0.0625
Mn
0.9375
Al
0.0625
700
2



















TABLE 1-2






CONCENTRATION





OF METAL ION

CARBON



OXIDE

CONTENT


No.
mol/L
GRINDING AND HEAT TREATMENT
[mass %]


















1-1
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-2
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-3
0.33
GRINDING AND HEAT TREATMENT AT 900° C. FOR 3 h.
8


1-4
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-5
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-6
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-7
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-8
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-9
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-10
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-11
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-12
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-13
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-14
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-15
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-16
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-17
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-18
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-19
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-20
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-21
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-22
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-23
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-24
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-25
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-26
0.33
GRINDING AND HEAT TREATMENT AT 700° C. FOR 5 h.
9


1-27
0.33
NEITHER GRINDING NOR HEAT TREATMENT
11


1-28
0.33
NEITHER GRINDING NOR HEAT TREATMENT
12


1-29
0.21
NEITHER GRINDING NOR HEAT TREATMENT
15


1-30
0.33
GRIND 1-27 AND GRANULATE
11




















TABLE 1-3








CIRCLE-EQUIVALENT






DIAMETER OF

VOID IN GRAIN
INTERNAL RESISTANCE



OXIDE IN

(200 nm OR MORE)
REDUCTION EFFECT













COMPOSITE
GRAIN SIZE

AREA RATE
(VOLTAGE AT 140 mAh/g)


No.
[nm]
[μm]
PRESENCE
[%]
[V]















1-1
14
0.2
NO
—
2.75


1-2
14
0.2
NO
—
3.30


1-3
18
0.2
NO
—
3.20


1-4
14
0.2
NO
—
3.29


1-5
14
0.2
NO
—
3.30


1-6
14
0.2
NO
—
2.25


1-7
14
0.2
NO
—
2.30


1-8
14
0.2
NO
—
2.70


1-9
14
0.2
NO
—
3.32


1-10
14
0.2
NO
—
3.31


1-11
14
0.2
NO
—
3.21


1-12
14
0.2
NO
—
3.20


1-13
14
0.2
NO
—
3.00


1-14
14
0.2
NO
—
3.15


1-15
14
0.2
NO
—
3.12


1-16
14
0.2
NO
—
3.13


1-17
14
0.2
NO
—
3.20


1-18
14
0.2
NO
—
3.24


1-19
14
0.2
NO
—
3.00


1-20
14
0.2
NO
—
2.75


1-21
14
0.2
NO
—
2.70


1-22
14
0.2
NO
—
2.98


1-23
14
0.2
NO
—
3.01


1-24
14
0.2
NO
—
2.75


1-25
14
0.2
NO
—
2.95


1-26
14
0.2
NO
—
3.19


1-27
8
4
YES
46
3.26


1-28
4
5
YES
40
3.29


1-29
2
3
YES
35
3.23


1-30
8
20
NO
—
2.95




















TABLE 1-4







STABILITY
DIS-





OF
CHARGE





INTERNAL
CAPACITY




INITIAL
RESISTANCE
MAINTE-




DISCHARGE
REDUCTION
NANCE




CAPACITY
EFFECT
RATE



No.
[mAh/g]
[V/cycle]
[%]
REMARK







1-1
240
−0.12
78
COMPARATIVE






EXAMPLE


1-2
245
−0.05
90
EXAMPLE


1-3
241
−0.06
89
EXAMPLE


1-4
243
−0.05
92
EXAMPLE


1-5
242
−0.05
91
EXAMPLE


1-6
175
−0.15
65
COMPARATIVE






EXAMPLE


1-7
178
−0.21
66
COMPARATIVE






EXAMPLE


1-8
205
−0.12
70
COMPARATIVE






EXAMPLE


1-9
246
−0.05
86
EXAMPLE


1-10
245
−0.05
85
EXAMPLE


1-11
242
−0.06
83
EXAMPLE


1-12
242
−0.06
82
EXAMPLE


1-13
241
−0.07
79
EXAMPLE


1-14
233
−0.06
80
EXAMPLE


1-15
232
−0.06
81
EXAMPLE


1-16
241
−0.08
80
EXAMPLE


1-17
242
−0.06
87
EXAMPLE


1-18
243
−0.05
91
EXAMPLE


1-19
242
−0.06
89
EXAMPLE


1-20
240
−0.13
75
COMPARATIVE






EXAMPLE


1-21
198
−0.18
72
COMPARATIVE






EXAMPLE


1-22
242
−0.06
88
EXAMPLE


1-23
242
−0.05
87
EXAMPLE


1-24
239
−0.14
68
COMPARATIVE






EXAMPLE


1-25
240
−0.07
82
EXAMPLE


1-26
242
−0.05
89
EXAMPLE


1-27
241
−0.05
90
EXAMPLE


1-28
242
−0.05
91
EXAMPLE


1-29
240
−0.06
86
EXAMPLE


1-30
240
−0.06
87
EXAMPLE









Second Example
Starting materials used were lithium nitrate (LiNO3), iron (III) nitrate nonahydrate (Fe(NO3)3.9H2O), tetraethoxysilane (hereinafter TEOS), aluminum sec-butoxide, magnesium nitrate hexahydrate (Mg(NO3)2.6H2O), copper nitrate trihydrate (Cu(NO3)2.3H2O), zinc nitrate hexahydrate (Zn(NO3)2.6H2O), manganese (II) nitrate hexahydrate (Mn(NO3)2.6H2O), boric acid (H3BO3), gallium nitrate (Ga(NO3)3.nH2O), yttrium isopropoxide, sodium nitrate (NaNO3), and potassium nitrate (KNO3). The materials were dissolved in water in such a way as to be each composition ratio shown in Table 2-1, so that aqueous solutions were prepared.
TEOS was dissolved in methoxyethanol in advance, and this solution was dissolved in the water. When aluminum sec-butoxide or yttrium isopropoxide was used, aluminum sec-butoxide or yttrium isopropoxide chemically modified with ethyl acetoacetate was added to and dissolved in the methoxyethanol, in which TEOS was dissolved, and the resulting solution was dissolved in the water. Further, glucose as the organic compound, which produces a carbon material, was added to the aqueous solutions. Each of these aqueous solutions was subjected to spray pyrolysis in a heating furnace heated at 450 to 900° C. using a carrier gas composed of nitrogen gas. Thereby, samples were produced.
Samples 2-1 to 2-18 and 2-20 to 2-26 were further subjected to wet grinding and then heat treatment at 500° C. for 12 hours in 1% H2/Ar after the aqueous solutions were sprayed in the heating furnace of 800° C. As to Sample 2-19, the heat treatment was performed at 800° C. for 5 hours in 1% H2/Ar. Samples 2-27 to 2-29 were subjected to neither wet grinding nor heat treatment. For Sample 2-27, the aqueous solution was sprayed in the heating furnace of 900° C. For Sample 2-28, the aqueous solution was sprayed in the heating furnace of 500° C. For Sample 2-29, the aqueous solution was sprayed in the heating furnace of 400° C. Sample 2-30 was produced by subjecting Sample 2-27 to grinding and then granulation. The solutions each were prepared in such a way that the concentration of metal ions in the solution was 0.2 or to 0.3 mol/L when the composition of the oxide was converted to moles. The glucose was added in such a way that a mole ratio of glucose/oxide was 2 or 3. Each sample produced without grinding was a spherical grain(s), and the spherical grain size was controlled through the concentration of metal ions in the liquid droplets and the glucose content.
<Analysis of Individual Samples>
The individual Samples 2-1 to 2-30 obtained as described above were analyzed in the same manner as that of the first example.
Samples 2-1 to 2-30 were subjected to X-ray diffraction. Because Samples 2-1 to 2-26 were subjected to the heat treatment, they had a diffraction pattern similar to that of a Li2FeSiO4 crystal phase. However, in the samples which were divalent-element-added or element-substituted, diffraction peak shift was observed. Samples 2-27 to 2-30 had no diffraction peak within 2θ=15 to 18° but had a broad diffraction peak within 2θ=33±2° with Cu-Kα line and hence were crystalline.
According to observation under a TEM, all of Samples 2-1 to 2-30 were composites having the sea-islands structure. The circle-equivalent diameter of the islands (oxide) was calculated using the method described above. The obtained circle-equivalent diameter of each sample is shown in Table 2-3.
The spherical grains of Samples 2-27 to 2-30 were observed under a SEM, and the circle-equivalent diameter was calculated as the grain size using the images. The values are shown in the “Grain Size” column in Table 2-3. Each of Samples 2-1 to 2-26 was grounded to be a size of 0.15 μm, so that each of Samples 2-1 to 2-26 was a nonuniformity-shaped fine grain (s) having the mentioned size, not a spherical grain(s). Sample 2-30 was produced by grinding Sample 2-27 and then granulating, so that the size thereof was the size of a spherically-granulated grain(s).
Sections of Samples 2-27 to 2-30, which were the spherical grains, were also observed under a SEM. Using the images, a void (s) of 200 nm or more in the grains was picked, and the area rate was calculated as the abundance of the void. Samples 2-27 to 2-29 had the values shown in the “Area Rate” column of the “Void in Grain” column in Table 2-3. Sample 2-30 was the grain produced by grinding Sample 2-27 and then granulating, so that the inside of the grain was dense, and no large void such as a void of 200 nm or more existed.
<Evaluation of Battery Characteristics>
Battery characteristics were evaluated in the same manner as that of the first example except for the following point.
In the initial charge/discharge test, preliminary charge-and-discharge was repeated four times under a CC-CV condition over a voltage range of 1.5 to 5.0 V at a rate of 0.1 C, and thereafter charge was performed under the CC-CV condition at a rate of 0.1 C to 250 mAh/g, and the discharge capacity was measured to obtain the initial charge/discharge capacity.
Regarding the internal resistance reduction effect, a voltage at 140 mAh/g was obtained from the discharge curve from which the initial discharge capacity was obtained. It was determined that the internal resistance was reduced when the voltage was high. In addition, charge-and-discharge was repeated 25 cycles, and a slope of voltage change (voltage change per cycle) at 140 mAh/g in the discharge curve from the 20th cycle to the 25th cycle was obtained as stability of the internal resistance reduction effect.
Further, the discharge capacity maintenance rate was obtained by “(discharge capacity at 1.5 V in the 10th cycle/discharge capacity at 1.5 V in the 2nd cycle)×100”.
As shown in Table 2-3, the discharge voltage at 140 mAh/g of Samples 2-2 to 2-4, 2-8 to 2-20, 2-23 to 2-24, and 2-26 to 2-30 having a divalent ion as MII was higher than that of Sample 2-1 having nothing as MII and Samples 2-5 to 2-7 having a non-divalent ion as MII, and Samples 2-2 to 2-4, 2-8 to 2-20, 2-23 to 2-24, and 2-26 to 2-30 showed the internal resistance reduction effect. Sample 2-21 had more than 0.25 as the value of y and did not show the internal resistance reduction effect. Sample 2-22 had −0.25 as the value of x and did not show the internal resistance reduction effect. Sample 2-25 had more than 0.25 as the value of x and as the value of y and did not show the internal resistance reduction effect.
In addition, the samples having a multiple of 0.03125 as the value of y had better stability of the internal resistance reduction effect. The samples having a divalent ion other than Mg ion as MII showed the same tendency about the stability.
The application performance was evaluated regarding Samples 2-27 to 2-30. They were evaluated as “excellent application performance”. The samples each having an appropriate amount of the void in the grain showed excellent discharge capacity even under a high rate.










TABLE 2-1









TEMPERATURE





OF
ADDED AMOUNT




SPRAY
OF GLUCOSE



Li2−xMyIIM(SinMmB)O4
FURNACE
MOLE RATIO
















No.
x
MII
y
M
n
MB
m
[° C.]
(GLUCOSE/OXIDE)



















2-1
0
—
0
Fe
1
—
0
800
2


2-2
0.1875
Cu(II)
0.09375
Fe
1
—
0
800
2


2-3
0
Cu(II)
0.09375
Fe
0.8125
Al
0.1875
800
2


2-4
−0.0625
Cu(II)
0.09375
Fe
0.875
Al
0.125
800
2


2-5
0.09375
K(I)
0.09375
Fe
1
—
0
800
2


2-6
0.09375
Na(I)
0.09375
Fe
1
—
0
800
2


2-7
0.09375
Al(III)
0.03125
Fe
1
—
0
800
2


2-8
0.1875
Mg(II)
0.09375
Fe
1
—
0
800
2


2-9
0
Mg(II)
0.09375
Fe
0.8125
Al
0.1875
800
2


2-10
0
Mg(II)
0.07
Fe
0.86
Al
0.14
800
2


2-11
0.1875
Zn(II)
0.09375
Fe
1
—
0
800
2


2-12
0
Zn(II)
0.09375
Fe
0.8125
Al
0.1875
800
2


2-13
0
Ca(II)
0.09375
Fe
0.8125
Al
0.1875
800
2


2-14
0
Mn(II)
0.09375
Fe
0.8125
Al
0.1875
800
2


2-15
0
Fe(II)
0.09375
Fe
0.8125
Al
0.1875
800
2


2-16
0.08
Cu(II)
0.04
Fe
1
—
0
800
2


2-17
0
Cu(II)
0.03125
Fe
0.9375
Al
0.0625
800
2


2-18
0
Cu(II)
0.0625
Fe
0.875
Al
0.125
800
2


2-19
0
Cu(II)
0.0625
Fe
0.875
Al
0.125
800
2


2-20
0
Cu(II)
0.25
Fe
0.5
Al
0.5
800
2


2-21
0
Cu(II)
0.27
Fe
0.46
Al
0.54
800
2


2-22
−0.25
Cu(II)
0.03125
Fe
0.6875
Al
0.3125
800
2


2-23
0.03125
Cu(II)
0.03125
Fe
0.9688
Ga
0.03125
800
2


2-24
0.25
Cu(II)
0.25
Fe
0.75
B
0.25
800
2


2-25
0.27
Cu(II)
0.27
Fe
0.73
Al
0.27
800
2


2-26
0
Cu(II)
0.03125
Fe
0.9375
Y
0.0625
800
2


2-27
0.125
Cu(II)
0.09375
Fe
0.9688
Al
0.03125
900
2


2-28
0.125
Cu(II)
0.09375
Fe
0.9688
Al
0.03125
500
2


2-29
0.125
Cu(II)
0.09375
Fe
0.9688
Al
0.03125
400
3


2-30
0.125
Cu(II)
0.09375
Fe
0.9688
Al
0.03125
900
2



















TABLE 2-2






CONCENTRATION





OF METAL ION

CARBON



OXIDE

CONTENT


No.
mol/L
GRINDING AND HEAT TREATMENT
[mass %]







2-1
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-2
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-3
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-4
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-5
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-6
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-7
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-8
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-9
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-10
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-11
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-12
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-13
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-14
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-15
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-16
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-17
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-18
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-19
0.3
GRINDING AND HEAT TREATMENT AT 800° C. FOR 5 h.
10


2-20
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-21
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-22
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-23
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-24
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-25
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-26
0.3
GRINDING AND HEAT TREATMENT AT 500° C. FOR 12 h.
10


2-27
0.3
NEITHER GRINDING NOR HEAT TREATMENT
12


2-28
0.3
NEITHER GRINDING NOR HEAT TREATMENT
13


2-29
0.2
NEITHER GRINDING NOR HEAT TREATMENT
18


2-30
0.3
GRIND 2-27 AND GRANULATE
12




















TABLE 2-3








CIRCLE-EQUIVALENT






DIAMETER OF

VOID IN GRAIN
INTERNAL RESISTANCE



OXIDE IN

(200 nm OR MORE)
REDUCTION EFFECT













COMPOSITE
GRAIN SIZE

AREA RATE
(VOLTAGE AT 140 mAh/g)


No.
[nm]
[μm]
PRESENCE
[%]
[V]















2-1
12
0.15
NO
—
2.25


2-2
12
0.15
NO
—
2.70


2-3
12
0.15
NO
—
2.70


2-4
12
0.15
NO
—
2.71


2-5
12
0.15
NO
—
1.60


2-6
12
0.15
NO
—
1.60


2-7
12
0.15
NO
—
2.20


2-8
12
0.15
NO
—
2.65


2-9
12
0.15
NO
—
2.65


2-10
12
0.15
NO
—
2.60


2-11
12
0.15
NO
—
2.70


2-12
12
0.15
NO
—
2.69


2-13
12
0.15
NO
—
2.30


2-14
12
0.15
NO
—
2.53


2-15
12
0.15
NO
—
2.54


2-16
12
0.15
NO
—
2.66


2-17
12
0.15
NO
—
2.70


2-18
12
0.15
NO
—
2.70


2-19
17
0.15
NO
—
2.69


2-20
12
0.15
NO
—
2.69


2-21
12
0.15
NO
—
2.25


2-22
12
0.15
NO
—
2.20


2-23
12
0.15
NO
—
2.65


2-24
12
0.15
NO
—
2.67


2-25
12
0.15
NO
—
2.00


2-26
12
0.15
NO
—
2.30


2-27
7
3
YES
43
2.70


2-28
3
4
YES
40
2.70


2-29
2
2
YES
33
2.68


2-30
7
20
NO
—
2.65




















TABLE 2-4







STABILITY
DIS-





OF
CHARGE





INTERNAL
CAPACITY




INITIAL
RESISTANCE
MAINTE-




DISCHARGE
REDUCTION
NANCE




CAPACITY
EFFECT
RATE



No.
[mAh/g]
[V/cycle]
[%]
REMARK



















2-1
250
−0.18
100
COMPARATIVE






EXAMPLE


2-2
250
−0.04
100
EXAMPLE


2-3
250
−0.04
100
EXAMPLE


2-4
250
−0.04
100
EXAMPLE


2-5
220
−0.21
90
COMPARATIVE






EXAMPLE


2-6
220
−0.22
90
COMPARATIVE






EXAMPLE


2-7
250
−0.18
100
COMPARATIVE






EXAMPLE


2-8
250
−0.04
100
EXAMPLE


2-9
250
−0.04
100
EXAMPLE


2-10
250
−0.08
100
EXAMPLE


2-11
250
−0.04
100
EXAMPLE


2-12
250
−0.04
100
EXAMPLE


2-13
250
−0.04
100
EXAMPLE


2-14
250
−0.04
100
EXAMPLE


2-15
250
−0.04
100
EXAMPLE


2-16
250
−0.08
100
EXAMPLE


2-17
250
−0.04
100
EXAMPLE


2-18
250
−0.04
100
EXAMPLE


2-19
250
−0.04
100
EXAMPLE


2-20
250
−0.04
100
EXAMPLE


2-21
245
−0.18
95
COMPARATIVE






EXAMPLE


2-22
230
−0.18
93
COMPARATIVE






EXAMPLE


2-23
250
−0.04
100
EXAMPLE


2-24
250
−0.05
100
EXAMPLE


2-25
228
−0.18
92
COMPARATIVE






EXAMPLE


2-26
250
−0.05
100
EXAMPLE


2-27
250
−0.04
100
EXAMPLE


2-28
250
−0.04
100
EXAMPLE


2-29
250
−0.04
100
EXAMPLE


2-30
250
−0.05
100
EXAMPLE









Third Example
Starting materials used were lithium carbonate (Li2CO3), magnesium carbonate (MgCO3), zinc oxide (ZnO), copper oxide (CuO), iron (II) oxalate dihydrate (FeC2O4.2H2O), manganese carbonate (MnCO3), cobalt oxide (CoO), silicon dioxide (SiO2), boric acid (H3BO3), gamma-alumina (Al2O3), gallium oxide (Ga2O3), yttrium oxide (Y2O3), sodium carbonate (Na2CO3), and potassium carbonate (K2CO3). With the solid phase method, powders of the oxides shown in the composition column in Table 3-1 were prepared.
First, the materials were combined and weighted in such a way as to be each composition ratio shown in the composition column in Table 3-1 and then wet-mixed using methanol for 12 hours in a ball mill. However, when boric acid was used, the materials were dry-mixed. Each of the obtained mixtures was fired at 850° C. for 24 hours in a nitrogen atmosphere and then grounded in a planetary ball mill. The grounded powder(s) was fired at 950° C. for 10 hours in a nitrogen atmosphere. Thus, the oxide powders shown in Table 3-1 were prepared.
With each prepared oxide powder, 10 mass % of acetylene black was mixed. In order to mix acetylene black therewith, each prepared oxide powder and acetylene black were wet-mixed using methanol for 12 hours in a ball mill. Each of the obtained mixtures was fired at 400° C. for 5 hours in a nitrogen atmosphere.
<Analysis of Individual Samples>
The individual Samples 3-1 to 3-17 obtained as described above were analyzed in the same manner as that of the first example.
Samples 3-1 to 3-17 were subjected to X-ray diffraction. Samples 3-1 to 3-17 had, as a main phase, a diffraction pattern similar to that of a Li2CoSiO4 crystal phase. However, in the samples which were divalent-element-added or element-substituted, diffraction peak shift was observed.
<Evaluation of Battery Characteristics>
Battery characteristics were evaluated in the same manner as that of the first example except for the following point.
In the initial charge/discharge test, preliminary charge-and-discharge was repeated four times under a CC-CV condition over a voltage range of 1.0 to 5.0 V at a rate of 0.1 C, and thereafter charge was performed under the CC-CV condition at a rate of 0.1 C to 200 mAh/g, and the discharge capacity was measured to obtain the initial charge/discharge capacity.
Regarding the internal resistance reduction effect, a voltage at 140 mAh/g was obtained from the discharge curve from which the initial discharge capacity was obtained. It was determined that the internal resistance was reduced when the voltage was high. In addition, charge-and-discharge was repeated 20 cycles, and a slope of voltage change (voltage change per cycle) at 140 mAh/g in the discharge curve from the 15th cycle to the 20th cycle was obtained as stability of the internal resistance reduction effect.
As shown in Table 3-1, the discharge voltage at 140 mAh/g of Samples 3-2 to 3-4, 3-7 to 3-11, 3-14 to 3-15, and 3-17 having a divalent ion as MII was higher than that of Sample 3-1 having nothing as MII and Samples 3-5 to 3-6 having a non-divalent ion as MII, and Samples 3-2 to 3-4, 3-7 to 3-11, 3-14 to 3-15, and 3-17 showed the internal resistance reduction effect. Sample 3-12 had more than 0.25 as the value of y and did not show the internal resistance reduction effect. Sample 3-13 had −0.25 as the value of x and did not show the internal resistance reduction effect. Sample 3-16 had more than 0.25 as the value of x and as the value of y and did not show the internal resistance reduction effect.
Regarding the case of the value of y being a multiple of 0.03125 and the case of the value of y being not a multiple of 0.03125, it is shown therein that stability of the internal resistance reduction effect is excellent in the case of the value of y being a multiple of 0.03125.
Samples of Li2-xMIIyFe(Si,MB)O4, Li2-xMIIyMn(Si,MB)O4, and Li2-xMIIyNi(Si,MB)O4 were also produced using nickel oxide (NiO) as starting materials with the solid phase method described above. It was confirmed that they had the same effects as those of the above samples.









TABLE 3-1









INTERNAL RESISTANCE




REDUCTION EFFECT



Li2−xMyIIM(SinMmB)O4
(VOLTAGE AT















No.
x
MII
y
M
n
MB
m
140 mAh/g) [V]


















3-1
0
—
0
Co
1
—
0
3.00


3-2
0.125
Cu(II)
0.0625
Co
1
—
0
3.40


3-3
0
Zn(II)
0.0625
Co
0.875
Al
0.125
3.38


3-4
−0.0625
Cu(II)
0.0625
Co
0.9375
Al
0.0625
3.41


3-5
0.09375
Na(I)
0.0625
Co
1
—
0
2.01


3-6
0.1875
Al(III)
0.0625
Co
1
—
0
2.20


3-7
0.125
Mg(II)
0.0625
Co
1
—
0
3.40


3-8
0
Mn(II)
0.0625
Co
0.875
Al
0.125
3.39


3-9
0
Ca(II)
0.07
Co
0.86
Al
0.14
3.34


3-10
0.08
Fe(II)
0.04
Co
1
—
0
3.35


3-11
0
Cu(II)
0.25
Co
0.5
Al
0.5
3.38


3-12
0
Cu(II)
0.27
Co
0.46
Al
0.54
2.56


3-13
−0.25
Cu(II)
0.03125
Co
0.6875
Al
0.3125
2.51


3-14
0.03125
Cu(II)
0.03125
Co
0.9688
Ga
0.03125
3.37


3-15
0.25
Cu(II)
0.25
Co
0.75
B
0.25
3.38


3-16
0.27
Cu(II)
0.27
Co
0.73
Al
0.27
1.90


3-17
0
Cu(II)
0.03125
Co
0.9375
Y
0.0625
3.35




















TABLE 3-2







STABILITY
DIS-





OF
CHARGE





INTERNAL
CAPACITY




INITIAL
RESISTANCE
MAINTE-




DISCHARGE
REDUCTION
NANCE




CAPACITY
EFFECT
RATE



No.
[mAh/g]
[V/cycle]
[%]
REMARK







3-1
160
−0.10
80
COMPARATIVE






EXAMPLE


3-2
180
−0.05
90
EXAMPLE


3-3
179
−0.05
90
EXAMPLE


3-4
181
−0.04
90
EXAMPLE


3-5
142
−0.18
70
COMPARATIVE






EXAMPLE


3-6
158
−0.14
76
COMPARATIVE






EXAMPLE


3-7
180
−0.04
91
EXAMPLE


3-8
178
−0.05
88
EXAMPLE


3-9
175
−0.07
87
EXAMPLE


3-10
178
−0.07
88
EXAMPLE


3-11
179
−0.05
89
EXAMPLE


3-12
159
−0.15
78
COMPARATIVE






EXAMPLE


3-13
148
−0.17
77
COMPARATIVE






EXAMPLE


3-14
178
−0.05
89
EXAMPLE


3-15
178
−0.05
88
EXAMPLE


3-16
135
−0.18
75
COMPARATIVE






EXAMPLE


3-17
174
−0.05
87
EXAMPLE









INDUSTRIAL APPLICABILITY
The present invention is usable in the field of lithium ion secondary batteries.

## Claims

1. A cathode material for a lithium ion secondary battery comprising an oxide represented by a composition formula Li2-xMIIyM(Si,MB)O4,
wherein MII represents a divalent element; M represents at least one element selected from the group consisting of Fe, Mn, Co and Ni; and MB represents, as an optional component, a monovalent, divalent, or trivalent element substituted for Si to compensate for a difference between an electric charge of [Li2]2+ and an electric change of [Li2-xMIIy]n+ as needed,
wherein in the composition formula representing the oxide, x and y are −0.25<x≦0.25 and 0<y≦0.25, and
wherein the MII exists at a Li site of the composition formula Li2-xMIIyM(Si,MB)O4.

2. The cathode material for a lithium ion secondary battery according to claim 1, wherein a value of the y is a multiple of 0.03125.

3. The cathode material for a lithium ion secondary battery according to claim 1, wherein the MII represents at least one element selected from Mg, Cu and Zn.

4. The cathode material for a lithium ion secondary battery according to claim 1, wherein the MB represents at least one element selected from B, Al and Ga.

5. The cathode material for a lithium ion secondary battery according to claim 1, wherein
the cathode material is a composite composed of the oxide and a carbon material, and
the composite shows a sea-islands structure in which the oxide is scattered like islands in the carbon material, and an average circle-equivalent diameter of the islands of the sea-islands structure is 3 nm or more and 15 nm or less.

6. The cathode material for a lithium ion secondary battery according to claim 5, wherein
the composite is a grain having a size of 1 μm or more and 20 μm or less, and
a void exists inside the grain.

7. The cathode material for a lithium ion secondary battery according to claim 6, wherein the void having a size of 200 nm or more and less than the size of the grain exists inside the grain.

8. The cathode material for a lithium ion secondary battery according to claim 7, wherein an abundance of the void is 20% or more and 80% or less in terms of an area rate in a section of the grain.

9. A cathode member for a lithium ion secondary battery comprising a metal foil provided with a cathode layer including: the cathode material for a lithium ion secondary battery according to claim 1; and a binder.

10. A lithium ion secondary battery comprising the cathode material for a lithium ion secondary battery according to claim 1.