Patent Application
20140170497
The present invention relates to a titanium oxide-based negative electrode material that can be used as a negative electrode for a lithium ion battery. More particularly, it relates to a B-type titanium oxide (TiO2(B)) negative electrode material having a high capacity, a method for producing the same, and a lithium ion battery using the same.
In recent years, from the viewpoints of energy and environmental problems, enlargement of a lithium ion battery is expected to allow the lithium ion battery to be a power source for an electric vehicle or a large secondary battery for power load leveling. However, it is thought that remarkable improvement in cost, safety and life is required in order to put a lithium ion battery into practical use as a large secondary battery.
In order to attain highly enhanced output, reduced cost, high safety and prolonged life of a lithium ion battery, using a high electrical potential negative electrode in which a charge and discharge reaction proceeds at an electrical potential of 1.0 V or more is one of the solutions. As an example of such a high electrical potential negative electrode, the development of a lithium-titanium composite oxide Li4Ti5O12 having a spinel structure has proceeded.
While Li4Ti5O12 has a flat discharge potential at about 1.55 V (vs. Li/Li+) and exhibits extremely good cycle characteristics, it is unattractive from the viewpoint of energy density since the theoretical capacity is low (175 mAh/g, 607 mAh/cm3). There has been published a report in which Li4Ti5O12 is subjected to a surface fluorination treatment (Non-Patent Document 1). This report discloses that by subjecting Li4Ti5O12 pretreated at 120° C. to a fluorination treatment for 2 minutes under heating (70° C., 100° C.) at elevated pressure (3 atm), charge and discharge characteristics at high current densities are enhanced. However, the conditions in which a good effect is exerted by a fluorination treatment are limited, for example, the effect cannot be obtained by the fluorination treatment at 25° C., and enhancement in charge characteristics is attained only in cases of high current densities (300 mA/g, 600 mA/g).
On the other hand, the present inventors focused their attention on B-type titanium oxide [TiO2(B)] which is a type of TiO2 as a negative electrode material, and have conducted research up to the present time. Although B-type titanium oxide is a metastable phase, the theoretical capacity per weight (335 mAh/g) is comparable to that of graphite, and the theoretical capacity per volume (1246 mAh/cm3) exceeds that of graphite. Moreover, B-type titanium oxide is expected as a high capacity high potential negative electrode material since it has excellent cycle characteristics. The present inventors have already been successful in obtaining a B-type titanium oxide powder having a capacity expressed as an average discharge voltage of 1.6 V and a discharge capacity of 200 to 250 mAh/g and having good cycle characteristics and rate characteristics by subjecting K2Ti4O9 as a precursor obtained by a solid phase method to ion exchanging and dehydrating (Non-Patent Document 2) .
However, in order to allow the charge and discharge capacity of a B-type titanium oxide powder obtained in the actual production to approach to the theoretical capacity and effectively use the B-type titanium oxide powder as a negative electrode material, it is expected that further enhancement in charge and discharge characteristics and rate characteristics is attained using a convenient method.
Non-Patent Document 1: T. Nakajima et al./Journal of Fluorine Chemistry 130 (2009) 810-815
Non-Patent Document 2: M. Inaba et al./Journal of Power Sources 189 (2009) 580-584
Thus, in the present invention, a problem to be solved is to enhance the charge and discharge characteristics and rate characteristics of a B-type titanium oxide powder by a simple treatment and to provide a B-type titanium oxide powder that can be suitably used as a negative electrode material for a lithium ion battery.
While the present inventors have repeatedly conducted studies in view of solving the above problems, they have found that by performing a fluorination treatment against a B-type titanium oxide powder, a B-type titanium oxide powder having a high charge and discharge capacity and exhibiting excellent rate characteristics can be obtained, and have completed the present invention.
That is, the present invention is directed to a negative electrode material for a lithium ion battery and the negative electrode material is characterized as including a surface-fluorinated B-type titanium oxide powder. It is preferred that the BET specific surface area of the B-type titanium oxide powder the surface of which is fluorinated by a fluorination treatment is 1 m2/g to 20 m2/g. Moreover, the present invention is directed to a method for producing a surface-fluorinated B-type titanium oxide powder which is a negative electrode material of a lithium ion battery and the method is characterized as including the step of performing a fluorination treatment by allowing a B-type titanium oxide powder to undergo a reaction under a fluorine-containing gas atmosphere at usually 0 to 200° C., preferably 20 to 150° C., for 1 minute to 10 days, preferably 10 minutes to a few hours (for example, 1 hour or 2 hours).
According to the description of the previously stated Non-Patent Document 1, with regard to Li4Ti5O12 subjected to fluorination for 2 minutes at 70° C. or 100° C., enhancement in charge characteristics is observed, and a material obtained by a fluorination treatment at 25° C. shows charge characteristics equivalent to or less than those of an untreated material.
In contrast, in the present invention, a fluorination treatment at a relatively low temperature range including ordinary temperature is possible, and the present invention is characterized as producing a B-type titanium oxide powder in which the degree of surface fluorination is moderately controlled by a widely ranging adjustment for the treating time or treating temperature. With regard to the treatment, since the treatment can be performed at a relatively low temperature range, in particular, in the case of a treatment at ordinary temperature, it is unnecessary to detect and control the temperature in a reaction field and it is possible to diminish the cost of the reaction apparatus and the energy cost required for the treatment.
With regard to a B-type titanium oxide powder subjected to the fluorination treatment, at least the surface thereof is fluorinated, and the shape of the powder is kept almost unchanged before and after the treatment except that the surface is slightly smoothed. Moreover, with regard to a fluorinated B-type titanium oxide powder subjected to the fluorination treatment, the charge and discharge capacity is significantly enhanced compared to an untreated material, and furthermore, the charge and discharge rate characteristics are enhanced at any current densities and good rate characteristics are attained.
It is preferred that the fluorination treatment is performed in the range of 0.01 atm to 2 atm. In the case where the treatment is performed at ordinary pressure, since providing the treatment apparatus with a sealing mechanism and allowing the treatment apparatus to have a pressure-resistant structure are unnecessary, it is advantageous in the point of apparatus cost. In the case of being performed at a pressure higher than ordinary pressure, there is an advantage that the treating time can be reduced compared to the treatment at ordinary pressure.
Furthermore, it has been confirmed that the lithium ion battery having, as a negative electrode material, a material prepared by utilizing a B-type titanium oxide powder bearing fluorine on its surface obtained by the method according to the present invention is capable of attaining an excellent charge and discharge capacity per weight (mAh/g).
Since the surface-fluorinated B-type titanium oxide powder of the present invention has a high discharge capacity per weight and is a B-type titanium oxide powder allowing the charge capacity to be stably enhanced at a wide variety of charging speeds, the powder is very useful as a high electrical potential negative electrode material for a lithium ion battery.
Hereinafter, the surface-fluorinated B-type titanium oxide powder and the method for producing the same according to the present invention will be described in more detail.
The B-type titanium oxide powder contained in the negative electrode material fora lithium ion battery according to the present invention may be produced just before a fluorination treatment, and a B-type titanium oxide powder previously produced and preserved may be subjected to a fluorination treatment, as necessary. The B-type titanium oxide powder to be provided for a fluorination treatment can be prepared by a known production method, and although the production method is not particularly limited, for example, the powder is produced by the following method.
In the calcining step, a known titanium oxide raw material such as rutile type and/or anatase type titanium oxides and an alkali metal salt selected from the group consisting of a carbonate, a nitrate and a hydroxide of an alkali metal (sodium, potassium, rubidium or cesium) are mixed and calcined to obtain an alkali titanate (a precursor). As an alkali metal salt, a carbonate of sodium (Na CO3), a carbonate of potassium (K2CO3) or a carbonate of cesium (Cs CO3) is especially preferred. Although the particle diameter of the titanium oxide raw material is not particularly limited, rutile type and/or anatase type titanium oxides with a particle diameter of about 30 nm to 10 μm can be used.
The mixing proportion of the titanium oxide raw material and the alkali metal salt is, for example, 2 to 6:1 in the case where the alkali metal salt is M CO3 (M represents an alkali metal) in terms of the mole ratio (more preferably, 3±0.2:1 in the case of a sodium salt, 4±0.2:1 in the case of a potassium salt, and 5±0.2:1 in the case of a cesium salt). The mixed sample mixed in such a proportion can be calcined at 850° C. to 1100° C., preferably 900 to 1000° C., to obtain an alkali titanate.
Calcining is performed in the air or in an inert gas atmosphere such as nitrogen, and the calcining time can be set to about 30 minutes to 100 hours, preferably about 2 hours to 30 hours.
In the case where Na2CO3 is used as the alkali metal salt in the present step, a precursor obtained after calcining is constituted of Na2Ti3O7, in the case where K2CO3 is used as the alkali metal salt, a precursor obtained after calcining is constituted of K2Ti4O9, and in the case where Cs2CO3 is used as the alkali metal salt, a precursor obtained after calcining is constituted of Cs2Ti5O11.
In the ion exchanging step, alkali metal ions in the alkali titanate (the precursor) obtained in Step 1 are ion-exchanged with hydrogen ions to prepare a titanic acid.
Ion exchanging can be performed by allowing a precursor powder to be immersed in 0.01 to 5 mol/L hydrochloric acid (HCl) for 1 to 300 hours with stirring. Sulfuric acid, nitric acid, perchloric acid or the like may be used as an alternative to HCl. Although ion exchanging may be performed at room temperature, it can be performed under the heating condition at about 30 to 60° C. In the case of being performed under the heating condition, it is possible to shorten the immersion time. After the ion exchanging, it is preferred that the resulting titanic acid powder is filtered, washed and then dried to be used in the next step.
In the dehydrating step, the titanic acid powder obtained in the ion exchanging step is dehydrated to obtain a B-type titanium oxide powder.
Dehydrating can be performed by subjecting a titanic acid powder to a heat treatment for 10 minutes to 10 hours at about 350 to 600° C. A more preferred heat treatment condition is a condition for 30 minutes to 2 hours at about 400 to 550° C.
The B-type titanium oxide powder obtained by the Steps 1 to 3 is basically obtained as an acicular crystal. The shape of the powder is not particularly restricted, and for example, the powder may be a B-type titanium oxide powder with a particulate shape, a mixture of acicular crystals and particles, or a powder with an unspecified shape allowing primary particles with a small particle diameter to be aggregated and to form secondary particles. Furthermore, as the B-type titanium oxide, a metal-doped B-type titanium oxide powder allowing a part of titanium to be substituted with another metal such as niobium (Nb), vanadium (V), chromium (Cr) or another element, or a part of oxygen to be substituted with another element such as nitrogen (N) or sulfur (S) maybe used.
In order to suitably obtain an effect of a fluorination treatment, it is preferred that the BET specific surface area of the B-type titanium oxide powder is 1 m2/g to 20 m2/g. When the specific surface area exceeds 20 m2/g, there occurs a problem that the effective capacity is lowered since the bulk density of an electrode active material is lowered and the electrode density is reduced. When the specific surface area is less than 1 m2/g, there is a problem that the electrode characteristics such as rapid charging performance and rapid discharging performance as the reverse reaction thereof are lowered since the sufficient diffusion and occlusion of lithium ions into the inside of an active material take a long time.
With regard to the fluorination treatment in the present invention, a B-type titanium oxide powder is exposed to a fluorine-containing gas to perform a fluorination treatment. Exposure to a fluorine-containing gas can be performed by a known method. For example, the exposure may be performed by placing a B-type titanium oxide powder in an annular furnace and circulating a fluorine-containing gas through the furnace or may be hermetically performed by filling the furnace with a fluorine-containing gas.
The fluorination treatment is performed at usually 0° C. to 200° C., preferably 20 to 150° C. When the temperature is less than 0° C., there is a problem that sufficient fluorination is not performed. When the temperature exceeds 200° C., there is a problem that the titanium oxide powder is converted to a gas referred to as TiF4 by the fluorination, gradually gasified from its surface, and dissipated. The treating time lies between 1 minute and 10 days, preferably between 1 minute and a few hours (for example, 1 hour or 2 hours). When the treating time is less than 1 minute, sufficient fluorination is not performed, and when the treating time exceeds 10 days, there is a problem that a function as an active material is impaired since the crystal structure of titanium oxide is changed.
The treating temperature and the treating time are set according to the shape of the B-type titanium oxide powder to be used, the amount of powder treated, the flow rate of the fluorine-containing gas and the like, and a preliminary experiment can be performed as necessary to set a suitable treatment condition. In general, there is a tendency that the higher the treating temperature is, the more shortened the treating time is.
As the fluorine-containing gas used for the fluorination treatment, a nitrogen trifluoride (NF3) gas, a perfluorotrimethylamine (N(CF3)3) gas, a chlorine trifluoride (ClF3) gas and the like, as well as a fluorine (F2) gas, can be used. In the fluorination treatment, these gases maybe used alone and may be mixed and diluted with inert gas (for example, nitrogen gas, argon gas) to be used. Although it is suitable that the concentration of a fluorine-containing compound in the gas used for the fluorination treatment is 100%, a gas which is diluted with a nitrogen gas, an argon gas or the like and containing a fluorine-containing compound of 0.01% by volume or more, preferably 0.1% by volume or more and more preferably 1% by volume or more can also be used. When the concentration of the fluorine-containing compound is less than 0.01% by volume, the fluorination is not performed efficiently since the treatment efficiency is low.
Hereinafter, a production method of a surface-fluorinated B-type titanium oxide powder according to the present invention, and the case of preparing a negative electrode for a lithium secondary battery using the resulting fluorinated B-type titanium oxide powder will be described with reference to Examples, but the present invention is not limited to these Examples.
As starting materials, TiO2 anatase (available from Sigma-Aldrich Japan K.K., purity of 99% or more) and K2CO3 (available from Wako Pure Chemical Industries, Ltd., purity of 99.8%) were used. First, TiO2 anatase and K2CO3 were weighed so as to allow the mole ratio to be 4:1, and mixing was performed so that the raw materials as a sample were uniformly mixed for 1 hour at 400 rpm using a planetary ball mill. Subsequently, the sample was placed in an alumina crucible, and calcination was performed in two batches in the air at 1000° C. for 24 hours. Each of the resulting samples was immersed in 1 M HCl, and ion exchanging was performed for 72 hours at ordinary temperature. After ion exchanging, the sample was washed and filtered, and drying was performed for about 24 hours in a vacuum desiccator. After drying, dehydrating was performed by subjecting the sample to a heat treatment for 30 minutes at 500° C. to synthesize B-type titanium oxide. Afterward, the synthesized B-type titanium oxide was transferred to a Ni-made tray and was placed in a 3-L annular furnace. After the inside pressure of the annular furnace was reduced to 0.001 atm, the titanium oxide was exposed to a 100% fluorine gas for 1 hour at ordinary temperature and a treatment pressure of 1 atm to obtain a fluorinated B-type titanium oxide powder.
The resulting fluorinated B-type titanium oxide powder, carbon (available from Lion Corporation, KETJENBLACK EC600JD) as a conductive assistant and polyvinylidene fluoride (PVdF) (available from KUREHA CORPORATION, KF Polymer) as a binding agent were weighed and mixed at a weight ratio of 8:1:1. A planetary ball mill was used for mixing, and mixing was performed for 40 minutes at 400 rpm. The mixed material was applied onto a copper plate using a doctor blade to obtain a test electrode. At the time of applying the mixed material containing the fluorinated B-type titanium oxide powder, the thickness thereof and the electrode area were set to about 50 μm and about 1.54 cm2, respectively.
A B-type titanium oxide powder was obtained in the same manner as that in Example 1 except that a fluorination treatment is not performed. Moreover, a test electrode was produced in the same manner as that in Example 1 using the B-type titanium oxide powder.
With regard to the B-type titanium oxide powders obtained in Example 1 and Comparative Example 1, the bulk was analyzed for the crystal structure using the powder X-ray diffraction (XRD) method. As a powder X-ray diffractometer, Rint2500 (available from Rigaku Corporation) was used. As an X-ray source, CuKa was used, and the measurement was performed under the conditions of the tube voltage of 40 kV, the tube current of 200 mA, the measurement range of 5°≦2θ≦60°, the light receiving slit of 0.3 mm, the divergence slit of 1°, and the scattering slit of 1°.
As a result of the analysis, as shown in
With regard to the B-type titanium oxide powders obtained in Example 1 and Comparative Example 1, the surface shape observation was performed using a field emission type scanning electron microscope (FE-SEM). As an electron microscope, JSM7001FD available from JEOL Ltd. was used. The sample was subjected to sputtering of gold since the sample has low electron conductivity, after which the surface observation was performed at an acceleration voltage of 15 kV.
As a result of the observation, as shown in
Moreover, with regard to the B-type titanium oxide powders obtained in Example 1 and Comparative Example 1, the specific surface area measurement was performed using a BET specific surface meter. As a measuring apparatus, the automated specific surface area and porosity analyzer TriStar 3000 available from Shimadzu Corporation was used. The sample powder was dried under vacuum for 40 minutes at 80° C., after which a helium gas was used as a filling gas, liquid nitrogen was used as an adsorbing gas, and the sample powder was evaluated.
As a result of the measurement, the BET specific surface area of Example 1 was determined to be 7.3 (m2/g) , the BET specific surface area of Comparative Example 1 was determined to be 8.6 (m2/g), and it has been observed that the specific surface area of the sample powder of Example 1 is slightly reduced compared to Comparative Example 1 by the etching effect of the fluorination treatment.
Analysis of Elemental Composition on Powder Surface
With regard to the B-type titanium oxide powder obtained in Example 1, an energy dispersive X-ray spectroscopic analysis (EDS) was performed using the electron microscope JSM7001FD available from JEOL Ltd. described in the above-mentioned Example 3 to investigate fluorine atoms which are present on the surface. Moreover, with regard to the B-type titanium oxide powders obtained in Example 1 and Comparative Example 1, an X-ray photoelectron spectroscopic analysis (XPS) was performed to confirm the presence of fluorine atoms on the sample surface, and furthermore, to research the change in chemical and electronic state of titanium and oxygen in the sample surface layer.
As a result of the analysis, as shown in
The charge and discharge characteristics of the B-type titanium oxide powders obtained in Example 1 and Comparative Example 1 were evaluated by a bipolar half-cell method described below. In this connection, electrical potentials shown below are based on that of the lithium metal foil which is a counter electrode.
By using a bipolar coin type cell shown in
With regard to the test electrode of the B-type titanium oxide powder obtained in Comparative Example 1, a coin battery was prepared in the same manner as above.
In the charge and discharge cycle test, charging was started in a constant current charging method (CC mode) at the end of 24 hours after the assembly of the coin battery. The current value at the time of constant current charging was set so that the rate becomes C/6 (a current value with which the theoretical capacity is attained at the end of 6 hours) on the basis of a capacity calculated from the weight of each of working electrode powders when the theoretical capacity of B-type titanium oxide is assumed to be 335.6 mAh/g.
First, constant current charging was performed at a current value determined by the above method until the charging potential reached 1.4 V. After the elapse of a pause time of minutes, discharging was performed until the cut-off potential of 3.0 V was attained. All subsequent pause times between charging and discharging were set to 30 minutes.
The evaluation of the charge and discharge rate characteristics was performed with C/6 rate for the first 3 cycles, after which the current density was sequentially changed to C/30, C/10, C/6, C/3, C, 3C and 6C every 3 cycles, while the discharge capacity was measured under the same other conditions as those described above.
The results of the charge and discharge characteristics test of Example 1 and Comparative Example 1 are shown in
The results of rate characteristics test are shown in
From the test results stated above, with regard to the B-type titanium oxide powder subjected to a fluorination treatment by the method according to the present invention, compared to the B-type titanium oxide powder not subjected to the treatment, it is possible to allow the discharge capacity to be significantly enhanced, and moreover, the rate characteristics are also significantly enhanced and it has been experimentally demonstrated that the present invention contributes to attaining highly enhanced capacity of the B-type titanium oxide negative electrode material.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-167046 | Jul 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/068921 | 7/26/2012 | WO | 00 | 1/28/2014 |
