WO2012111766A1 - 電解二酸化マンガン及びその製造方法、並びにリチウムマンガン系複合酸化物の製造方法 - Google Patents
電解二酸化マンガン及びその製造方法、並びにリチウムマンガン系複合酸化物の製造方法 Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Definitions
- the present invention relates to electrolytic manganese dioxide used as a raw material for a positive electrode active material for a lithium ion secondary battery, for example, and a method for producing the same, and a method for producing a lithium manganese based composite oxide used for the positive electrode active material and the like. Is.
- Lithium manganese composite oxides including lithium manganate mainly containing manganese and having a spinel structure have been studied as positive electrode active materials for lithium ion secondary batteries (hereinafter referred to as “LIB”) (for example, Non-patent document 1).
- Lithium manganese composite oxide not only has high output characteristics and high safety, but also is inexpensive. For this reason, application of lithium manganese based composite oxides not only to portable electronic devices but also to automobiles such as hybrid vehicles (HV) and electric vehicles (EV) is being studied.
- LIB using lithium-manganese composite oxide as a positive electrode active material has a lower discharge capacity per volume, so-called energy density, than LIB using lithium cobaltate as a positive electrode active material. Therefore, improvement of the energy density of the lithium manganese composite oxide is required.
- the filling property of the lithium manganese composite oxide is greatly affected by the filling property of the raw material manganese compound.
- a highly filled manganese compound is used as a manganese raw material.
- electrolytic manganese dioxide and heat-treated products thereof are most used as manganese raw materials for lithium manganese composite oxides because of their high filling properties (for example, Patent Document 1).
- ⁇ -type electrolytic manganese dioxide having a BET specific surface area of 35 m 2 / g or less, which is electrolytically synthesized in a manganese sulfate solution in which manganese oxide is suspended, may be used as a manganese raw material. It has been proposed (Patent Document 2).
- electrolytic manganese dioxide an electrolytic solution obtained from raw materials such as manganese ore and industrial water is electrolyzed (electrolyzed).
- electrolytic manganese dioxide excellent in reactivity with lithium compounds and the like, it is necessary to suppress the incorporation of impurities derived from these raw materials into electrolytic manganese dioxide.
- Patent Document 3 a method using a manganese compound obtained by extracting and removing impurities from manganese ore
- magnesium by adding fluoride in an electrolytic solution treatment step A method of using an electrolytic solution from which water has been removed has been reported (Patent Document 4).
- Electrolytic manganese dioxide has a higher packing property than chemically synthesized manganese dioxide. However, further improvement in packing density is required as a manganese raw material for lithium manganese composite oxide.
- the electrolytic manganese dioxide disclosed in Patent Document 2 has improved fillability by lowering the BET specific surface area.
- the reactivity between the obtained electrolytic manganese dioxide and the lithium compound decreases.
- the electrolytic manganese dioxide of Patent Document 2 has a problem that the reaction between the electrolytic manganese dioxide and the lithium compound becomes non-uniform as the BET specific surface area decreases.
- the present invention provides an electrolytic manganese dioxide suitable for the production of a lithium manganese composite oxide having a high energy density, that is, an electrolytic manganese dioxide having not only high filling properties but also excellent reactivity with lithium compounds.
- Another object of the present invention is to provide a method for producing a lithium manganese composite oxide using the same.
- the present invention prevents impurities such as alkaline earth metals from being mixed without performing an additional impurity treatment step before the electrolytic treatment step or using a highly toxic compound such as fluoride. It is still another object to provide a method for producing electrolytic manganese dioxide that can be suppressed and is suitable for implementation on an industrial scale.
- the gist of the present invention resides in the following (1) to (15).
- Electrolytic manganese dioxide having a BET specific surface area of 20 m 2 / g or more and 60 m 2 / g or less and a pore diameter of pores of 2 nm or more and 200 nm or less of at least 0.023 cm 3 / g.
- a method for producing electrolytic manganese dioxide wherein the manganese oxide particles are mixed in a manganese mixed solution so that the concentration of manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution is 5 mg / L or more and 200 mg / L or less.
- electrolytic current density of 0.8 A / dm 2 or more 1.5A / dm 2 or less, (9) or (10) The method of producing electrolytic manganese dioxide according to.
- the electrolytic manganese dioxide of the present invention has not only high filling properties but also excellent reactivity with lithium compounds.
- this as a manganese raw material for the lithium manganese composite oxide, it is possible to obtain a lithium manganese composite oxide having high filling properties and battery characteristics, in particular, high energy density.
- electrolytic manganese dioxide of the present invention it is possible to provide electrolytic manganese dioxide having not only high filling properties but also excellent reactivity with lithium compounds. Moreover, since electrolytic manganese dioxide is stably electrodeposited during electrolysis, the current efficiency is also excellent.
- the alkaline earth incorporated into the obtained electrolytic manganese dioxide even when an electrolytic solution containing a large amount of impurities, particularly an electrolytic solution containing a large amount of alkaline earth metal, is used, the alkaline earth incorporated into the obtained electrolytic manganese dioxide. Similar metals can be suppressed. As a result, it is not only necessary to perform an additional impurity treatment in the previous stage of electrolysis, but it is also possible to use a low purity electrolytic solution that could not be used conventionally.
- FIG. 3 is a diagram showing a pore size distribution of Example 1.
- 6 is a graph showing the particle size distribution of manganese oxide used in Example 3.
- FIG. 3 is a view showing a pore size distribution of Comparative Example 1.
- the electrolytic manganese dioxide of this embodiment has a BET specific surface area of 20 m 2 / g or more and 60 m 2 / g or less.
- the BET specific surface area is smaller than 20 m 2 / g, the surface area that substantially contributes to the reaction becomes too small.
- partial unevenness occurs in the reaction between the electrolytic manganese dioxide particles and the lithium compound particles, and the composition ratio in the particles becomes non-uniform. For this reason, the battery characteristics, in particular, the energy density, of the lithium manganese composite oxide obtained thereby are lowered.
- BET specific surface area 20 m 2 / g or more, or less 60m 2 / g, 25m 2 / g or more, and preferably not more than 55m 2 / g, 36m 2 / g or more and 50 m 2 / g or less Is more preferable.
- Electrolytic manganese dioxide of this embodiment the pore diameter of 2nm or more 200nm or less pores (hereinafter referred to as "secondary pore") volume of at least 0.023 3 / g, at least 0.025 cm 3 preferably / it is g, and preferably more than is more preferably at least 0.03 cm 3 / g, more preferably at least 0.035cm 3 / g, at least 0.04 cm 3 / g .
- the secondary pores are considered to contribute to the reaction between electrolytic manganese dioxide and the lithium compound during the synthesis of the lithium manganese composite oxide.
- electrolytic manganese dioxide has high reactivity with the lithium compound.
- Electrolytic manganese dioxide having a secondary pore volume of less than 0.023 cm 3 / g has low reactivity with the lithium compound or non-uniform reaction with the lithium compound. As a result, the energy density of the obtained lithium manganese composite oxide is lowered.
- the volume of the secondary pores is preferably at most 0.1 cm 3 / g, more preferably at most 0.05 cm 3 / g.
- the volume of pores having pore diameters of 2 nm to 50 nm is preferably at least 0.004 cm 3 / g, and at least 0.005 cm 3. more preferably / a g, more preferably at least 0.01 cm 3 / g, and further preferably from at least 0.015 cm 3 / g.
- the reaction between the manganese raw material and the lithium compound is affected by the pores of the manganese raw material. Since the electrolytic manganese dioxide of this embodiment has mesopores in the above volume range, the reactivity with the lithium compound tends to be higher. If the volume of the mesopore is within the above range, the upper limit value of the volume of the mesopore is not particularly limited. Examples of the upper limit of the mesopore volume include 0.03 cm 3 / g or less.
- the electrolytic manganese dioxide of the present embodiment preferably promotes the reaction with the lithium compound with fine secondary pores, while it is preferable that the volume of large pores having a pore diameter exceeding 200 nm is small.
- the pore volume of the electrolytic manganese dioxide of the present embodiment having a pore diameter exceeding 200 nm is preferably 0.35 cm 3 / g or less. As a result, the electrolytic manganese dioxide of the present embodiment tends to have a higher filling property.
- Apparent particle density of electrolytic manganese dioxide of the present embodiment is preferably at least 3.4 g / cm 3, more preferably at least 3.7 g / cm 3, at least 3.8g / more preferably cm is 3, it is even more preferred of at least 3.9 g / cm 3.
- apparent particle density of electrolytic manganese dioxide is at least 3.4 g / cm 3
- the filling property of the lithium manganese composite oxide obtained using the raw material as a raw material tends to be high.
- the electrolytic manganese dioxide of this embodiment is likely to have high reactivity with the lithium compound. As a result, when the obtained lithium manganese composite oxide is used as a positive electrode active material for a lithium ion secondary battery, the energy density can be increased.
- Electrolytic manganese dioxide of the present embodiment is preferably the bulk density (bulk density) of at least 1.5 g / cm 3, more preferably at least 1.7 g / cm 3, at least 1.8 g / cm 3 More preferably.
- the bulk density is high, the filling property is high, but it is not necessary to be higher than necessary. Therefore, examples of the upper limit of the bulk density of the electrolytic manganese dioxide of the present embodiment include 3.0 g / cm 3 or less, and further 2.5 g / cm 3 or less.
- the apparent particle density is a density calculated based on the actual volume of electrolytic manganese dioxide particles. Note that this volume may include extremely fine cracks or the like that are not filled with mercury even when the pressure of mercury is increased in the mercury intrusion method. However, since these cracks and the like are extremely fine, they do not substantially affect the volume.
- the apparent particle density thus calculated has a high correlation with the reactivity between electrolytic manganese dioxide and the lithium compound, and can be used as an index of reactivity.
- the bulk density is a density obtained by dividing the filling mass by the filling volume.
- the electrolytic manganese dioxide is also filled in the cracks and cracks formed in the particles. The density is calculated from the assumed virtual volume.
- the bulk density is a density that is an index of the filling properties of electrolytic manganese dioxide.
- the bulk density has a low correlation with the reactivity between electrolytic manganese dioxide and the lithium compound, it is difficult to be an index of reactivity. That is, even if the bulk density is high, when the apparent particle density is low, electrolytic manganese dioxide tends to be less reactive with the lithium compound.
- FIG. 1 is a schematic diagram showing the concept of apparent particle density and bulk density in the electrolytic manganese dioxide of the present embodiment.
- Fig.1 (a) is a figure which shows the particulate manganese dioxide used as the basis of bulk density calculation. That is, the bulk density is calculated based on a virtual volume that assumes that electrolytic manganese dioxide particles 1 and all the pores 2 and 3 are also filled with electrolytic manganese dioxide.
- FIG.1 (b) is a figure which shows the virtual volume of the particulate electrolytic manganese dioxide used as the basis of apparent particle density calculation. That is, the apparent particle density is calculated based on the volume of the electrolytic manganese dioxide particles 1.
- the particles 1 may include extremely fine pores not shown. Thus, the volume used when calculating a density differs in both.
- the volume of secondary pores, the volume of mesopores, the apparent particle density, and the bulk density can be measured by, for example, a mercury intrusion method.
- a mercury intrusion method extremely fine pores among the pores 3 having a pore diameter of less than 200 nm in FIG. 1, for example, pores having a pore diameter of less than 2 nm may not be measured.
- the electrolytic manganese dioxide of the present embodiment has a diffraction pattern of (110) plane where 2 ⁇ is around 22 ⁇ 1 ° in a normal X-ray diffraction (hereinafter referred to as “XRD”) measurement pattern using CuK ⁇ rays as a light source.
- XRD normal X-ray diffraction
- the full width at half maximum (hereinafter, the full width at half maximum of the diffraction line is simply referred to as “FWHM”) is preferably 2.1 ° or more and 3.7 ° or less, preferably 2.4 ° or more and 3.5 ° or less. It is more preferable that When the FWHM is 2.1 ° or more, the electrolytic manganese dioxide becomes crystalline that easily reacts with the lithium compound.
- FWHM 3.7 ° or less
- electrolytic manganese dioxide not only the reactivity of electrolytic manganese dioxide is high but also the filling property tends to be high.
- a lithium manganese composite oxide synthesized from such electrolytic manganese dioxide tends to be a positive electrode active material having a high energy density.
- the peak intensity ratio (hereinafter referred to as “(110) / (021)”) between the (110) plane and the (021) plane in the XRD measurement pattern is 0.5 or more, 0 Is preferably 90 or less, more preferably 0.55 or more and 0.65 or less.
- the peak on the (110) plane and the peak on the (021) plane appear at around 22 ⁇ 1 ° and around 37 ⁇ 1 ° in the X-ray diffraction of electrolytic manganese dioxide, respectively. These peaks are the main X-ray diffraction peaks of manganese dioxide crystals.
- the crystal structure of the electrolytic manganese dioxide of the present embodiment is not particularly limited as long as the BET specific surface area and the pore structure (secondary pore volume) of the present embodiment are satisfied.
- the crystal structure of the electrolytic manganese dioxide of this embodiment one or more crystal structures selected from the group of ⁇ -type, ⁇ -type, and ⁇ -type can be exemplified, and a crystal structure including ⁇ -type is preferable. ⁇ -type is more preferable.
- the electrolytic manganese dioxide of this embodiment preferably has a potential (hereinafter referred to as “alkali potential”) of 250 mV or less when measured in a 40 wt% KOH aqueous solution with a mercury / mercury oxide reference electrode as a standard, and 240 mV. More preferably, it is more preferably 235 mV or less. Electrolytic manganese dioxide tends to be stable when the alkali potential is 250 mV or less. That is, even when electrolytic manganese dioxide is stored for a long period of time, the electrochemical characteristics are unlikely to change. In addition, when electrolytic manganese dioxide having an alkali potential of 250 mV or less is electrolytically synthesized, the electrode material is unlikely to corrode.
- the electrolytic manganese dioxide of the present embodiment preferably has an alkaline earth metal content of 500 ppm by weight (0.05% by weight) or less. By reducing the amount of alkaline earth metal, the reaction between electrolytic manganese dioxide and the lithium compound is facilitated. Although the alkaline earth metal content is preferably as small as possible, the alkaline earth metal content in industrially obtained electrolytic manganese dioxide can be exemplified by 100 ppm by weight or more.
- calcium (Ca) has a great influence on the reaction between electrolytic manganese dioxide and a lithium compound. Therefore, calcium in electrolytic manganese dioxide is preferably 250 ppm by weight or less, and more preferably 200 ppm by weight or less. The smaller the calcium content, the better. However, the calcium content in the electrolytic manganese dioxide obtained industrially can be exemplified by 50 ppm by weight or more.
- the electrolytic manganese dioxide of the present embodiment is manganese dioxide obtained by electrolysis, and its shape is not limited.
- the agglomerate deposited on the electrode may be used, or a powder obtained by pulverizing the agglomerate may be used.
- the electrolytic manganese dioxide of this embodiment should just have manganese dioxide as a main component, and may contain the trace component different from manganese dioxide as an impurity.
- the electrolytic manganese dioxide of the present embodiment is a method for producing electrolytic manganese dioxide having a step of suspending manganese oxide in a sulfuric acid-manganese sulfate mixed solution to obtain electrolytic manganese dioxide. It can be produced by continuously mixing in a sulfuric acid-manganese sulfate mixed solution and electrolyzing the manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution at a concentration of 5 mg / L to 200 mg / L.
- the manufacturing method of this embodiment is a manufacturing method of electrolytic manganese dioxide in which manganese oxide is suspended in an electrolytic solution, so-called suspension electrolysis. Therefore, this is different from a method for producing electrolytic manganese dioxide in which sulfuric acid-manganese sulfate mixed solution is electrolyzed without using manganese oxide, so-called clarification electrolysis method.
- suspension electrolysis method the electrolytic manganese dioxide of this embodiment in which the pore structure (pore volume of secondary pores) and the BET specific surface area are controlled for the first time can be produced.
- the electrolysis current efficiency is improved in the suspension electrolysis method compared to the clarification electrolysis method not using manganese oxide. Moreover, it is possible to suppress the incorporation of impurities in the electrolytic solution, particularly alkaline earth metals, into electrolytic manganese dioxide, which could not be achieved by the clarification electrolytic method.
- a sulfuric acid-manganese sulfate mixed solution is used as the electrolytic solution.
- the sulfuric acid concentration during the electrolysis period is constant in the electrolysis method using a sulfuric acid-manganese sulfate mixed solution as an electrolytic solution.
- the sulfuric acid-manganese sulfate mixed solution in the present embodiment may be one that does not substantially contain an alkaline earth metal (the alkaline earth metal concentration is 0 g / L to 0.1 g / L).
- the alkaline earth metal concentration in the sulfuric acid-manganese sulfate aqueous solution may be 0.5 g / L or more, 1.0 g / L or more, and further 1.5 g / L or more. Also good. Even when such a high alkaline earth metal concentration sulfuric acid-manganese sulfate mixed solution is used, the alkaline earth metal content in the electrolytic manganese dioxide obtained by the production method of the present embodiment is 500 ppm by weight or less. Furthermore, the content becomes 450 ppm by weight or less, and the alkaline earth metal content has no industrial problem.
- the amount of alkaline earth metal in the sulfuric acid-manganese sulfate mixed solution increases, the amount of alkaline earth metal incorporated into the electrolytic manganese dioxide tends to increase.
- the production method of this embodiment can be obtained even when electrolyzing a sulfuric acid-manganese sulfate mixed solution containing an alkaline earth metal of 5.0 g / L or less, further 3.0 g / L or less.
- the alkaline earth metal concentration of electrolytic manganese dioxide tends to be industrially problematic.
- calcium (Ca) has a saturation concentration as low as 1 g / L or less and is likely to precipitate in a sulfuric acid-manganese sulfate mixed solution. Therefore, calcium is particularly easily taken into the electrolytic manganese dioxide, and the calcium taken into the electrolytic manganese dioxide inhibits the reaction between the electrolytic manganese dioxide and the lithium compound.
- the calcium concentration in the sulfuric acid-manganese sulfate mixed solution may be 0.3 g / L or more, may be 0.5 g / L or more, and is further preferably 0.00. It may be 8 g / L or more.
- manganese oxide is continuously mixed in a sulfuric acid-manganese sulfate mixed solution.
- concentration of the manganese oxide during an electrolysis period can be stabilized, and the physical property of the electrolytic manganese dioxide obtained through the whole electrolysis period, especially the uniformity of a pore improve.
- a method of continuously mixing manganese oxide in a sulfuric acid-manganese sulfate mixed solution a method of mixing manganese oxide particles into a sulfuric acid-manganese sulfate mixed solution, or an electrolyte containing an oxidizing agent mixed with sulfuric acid-manganese sulfate
- a method of generating manganese oxide particles in a mixed solution, or both can be used.
- the continuous mixing in the manufacturing method of the present embodiment means not only mixing manganese oxide into the sulfuric acid-manganese sulfate mixed solution at a constant ratio throughout the entire electrolysis period, but also sulfuric acid-manganese sulfate during the electrolysis period. Intermittently in the sulfuric acid-manganese sulfate mixed solution so that the manganese oxide in the mixed solution is constant (for example, the concentration of manganese oxide in the sulfuric acid-manganese sulfate mixed solution is the target value ⁇ 20%). It also includes mixing manganese oxide.
- manganese oxide particles to be mixed include manganese dioxide (MnO 2 ), manganese trioxide (Mn 2 O 3 ), and manganese trioxide ( Particles containing at least one compound selected from the group of Mn 3 O 4 ) can be used.
- manganese dioxide particles it is preferable to use manganese dioxide particles.
- These manganese oxide particles may be mixed in a sulfuric acid-manganese sulfate mixed solution in advance as a slurry, or the manganese oxide particles may be directly mixed in a sulfuric acid-manganese sulfate mixed solution.
- the type of oxidizing agent is not particularly limited as long as manganese ions in the sulfuric acid-manganese sulfate mixed solution are precipitated as manganese oxide particles.
- An example of the oxidizing agent is persulfate, preferably sodium persulfate (Na 2 S 2 O 8 ).
- the average particle size of the manganese oxide particles is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, still more preferably 1 ⁇ m or less, and even more preferably 0.9 ⁇ m or less.
- the average particle diameter is 5 ⁇ m or less, the manganese oxide particles are less likely to settle and are easily dispersed uniformly in the sulfuric acid-manganese sulfate mixed solution.
- the manganese oxide particles have an average particle size such that the dispersibility does not decrease, but a practical lower limit value is 0.5 ⁇ m or more.
- the average particle diameter in this specification is a 50% diameter (d 50 ) in terms of volume, and can be measured by, for example, a microtrack method.
- the concentration of manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution is 5 mg / L or more and 200 mg / L or less.
- the concentration of the manganese oxide particles exceeds 200 mg / L, the BET specific surface area of the obtained electrolytic manganese dioxide becomes too low.
- the concentration of manganese oxide particles is preferably 150 mg / L or less, more preferably 100 mg / L or less. , 50 mg / L or less is more preferable, and 40 mg / L or less is even more preferable.
- the concentration of manganese oxide particles is less than 5 mg / L, the effect of adding manganese oxide cannot be obtained.
- the concentration of the manganese oxide particles is preferably 8 mg / L or more, more preferably 10 mg / L or more, and 15 mg / L or more. More preferably, it is still more preferably 20 mg / L or more.
- an aqueous manganese sulfate solution is supplied to the sulfuric acid-manganese sulfate mixed solution.
- the manganese ion concentration of the manganese sulfate aqueous solution used for replenishment is, for example, 30 g / L or more and 110 g / L or less, preferably 30 g / L or more and 60 g / L or less.
- the sulfuric acid-manganese sulfate mixed solution preferably has a sulfuric acid concentration of 18 g / L or more and 50 g / L or less, more preferably 20 g / L or more and 40 g / L or less, and 20 g / L or more and 30 g / L or less. More preferably.
- the sulfuric acid concentration here is a value excluding the divalent anion of manganese sulfate.
- the electrolysis current density is 0.8 A / dm 2 or more 1.5A / dm 2 or less.
- the electrolytic current density is 1.5 A / dm 2 or less, an increase in electrolytic voltage during electrolytic synthesis can be suppressed. Thereby, it becomes easy to manufacture the electrolytic manganese dioxide of this embodiment efficiently and stably.
- the electrolytic current density is more preferably 1.0 A / dm 2 or more and 1.5 A / dm 2 or less, and 1.2 A / dm 2 or more and 1. and more preferably 4A / dm 2 or less.
- the electrolysis temperature may be 90 ° C or higher and 98 ° C or lower. Since the production efficiency of electrolytic manganese dioxide increases as the electrolysis temperature increases, the electrolysis temperature preferably exceeds at least 95 ° C.
- the electrolytic manganese dioxide of the present embodiment can be mixed with a lithium compound and heat-treated to obtain a lithium manganese-based composite oxide having a high filling property and uniformity.
- the electrolytic manganese dioxide of the present embodiment When used as a manganese raw material for a lithium manganese composite oxide, it can be produced by a general method. Moreover, you may grind
- Any lithium compound may be used, and examples include lithium hydroxide, lithium oxide, lithium carbonate, lithium iodide, lithium nitrate, lithium oxalate, and alkyl lithium.
- examples of preferable lithium compounds include lithium hydroxide, lithium oxide, and lithium carbonate.
- the electrolytic manganese dioxide to be measured was dried at 80 ° C. as a pretreatment. Thereafter, the pressure range of mercury was measured in steps from atmospheric pressure to 414 MPa, and the pore distribution (volume distribution) was determined.
- a pore having a pore diameter of 2 nm or more and 200 nm or less was designated as “secondary pore”, and a pore having a pore diameter of 2 nm or more and 50 nm or less was designated as “mesopore”.
- pores having a pore diameter of less than 2 nm are not filled with mercury, and therefore the pore distribution in a range of less than 2 nm cannot be measured.
- FIG. 1 is a schematic diagram showing the concept of apparent particle density and bulk density of particulate electrolytic manganese dioxide.
- mercury when measuring the bulk density, mercury is introduced at atmospheric pressure, so that mercury (4 nm or more) 2 and pores (less than 200 nm) 3 in electrolytic manganese dioxide 1 have mercury 4. Is not filled.
- mercury when measuring the apparent particle density, mercury is introduced at a high pressure, so that the pores (200 nm or more) 2 and the pores (less than 200 nm) 3 in the electrolytic manganese dioxide are filled with mercury 4. Will be.
- mercury 4 is not filled up to extremely fine pores (less than 2 nm) among the pores (less than 200 nm) 3 in electrolytic manganese dioxide.
- the BET specific surface area of electrolytic manganese dioxide was measured by nitrogen adsorption using the BET one-point method.
- a gas adsorption specific surface area measuring device (trade name: Flowsorb III, manufactured by Shimadzu Corporation) was used as the measuring device. Prior to the measurement, the measurement sample was deaerated by heating at 150 ° C. for 40 minutes.
- FWHM full width at half maximum
- the alkaline potential of electrolytic manganese dioxide was measured in a 40% KOH aqueous solution as follows.
- a mixed powder was prepared by adding 0.9 g of carbon as a conductive agent to 3 g of electrolytic manganese dioxide. To this mixed powder, 4 ml of 40% KOH aqueous solution was added and mixed to obtain a mixture slurry containing electrolytic manganese dioxide, carbon and KOH aqueous solution. The potential of this mixture slurry was measured using a mercury / mercury oxide reference electrode as a reference, and the alkaline potential of electrolytic manganese dioxide was determined.
- Example 1 A sulfuric acid-manganese sulfate mixed solution was used as the electrolytic solution. This electrolytic solution is put into an electrolytic cell, and a replenished manganese sulfate solution with a manganese ion concentration of 40.0 g / L and an aqueous sodium persulfate solution containing 200 g / L of sodium persulfate are continuously added to the electrolytic cell. Electrolysis was performed while adding, and electrolytic manganese dioxide was electrodeposited on the electrode. During electrolysis, the electrolysis current density 1.2A / dm 2, and the electrolysis temperature was 96 ° C..
- the replenished manganese sulfate solution was added so that the sulfuric acid concentration in the electrolytic cell was 25.0 g / L, and electrolysis was performed for 8 days. Moreover, the sodium persulfate aqueous solution was continuously added so that the density
- the electrolysis voltage at the end of electrolysis in Example 1 was 3.35V.
- the production conditions of the electrolytic manganese dioxide of Example 1 are shown in Table 1, the evaluation results of the obtained electrolytic manganese dioxide are shown in Table 2, and the pore size distribution is shown in FIG.
- the volume of pores exceeding 200 nm of the obtained electrolytic manganese dioxide was 0.26 cm 3 / g.
- manganese oxide particles having an average particle size of 1 to 3 ⁇ m were produced in the sulfuric acid-manganese sulfate mixed solution by adding an aqueous sodium persulfate solution. The resulting particles were collected and analyzed for crystal phase and composition.
- FIG. 2 shows a powder X-ray diffraction pattern of the obtained particles. These manganese oxides were confirmed to be crystalline manganese oxides (MnO 1.96 ) showing a clear diffraction peak.
- Example 2 Manufacture electrolytic manganese dioxide under the same conditions as in Example 1 except that an aqueous sodium persulfate solution was continuously added to the electrolytic bath so that the concentration of manganese oxide particles in the electrolytic solution was 15 mg / L. did.
- the electrolysis voltage at the end of electrolysis in Example 2 was 3.35V.
- the production conditions of the electrolytic manganese dioxide of Example 2 are shown in Table 1, and the evaluation results of the obtained electrolytic manganese dioxide are shown in Table 2.
- the volume of the pores having a pore diameter exceeding 200 nm was 0.23 cm 3 / g.
- Example 3 Commercially available electrolytic manganese dioxide (trade name: HH-S, manufactured by Tosoh Corporation) was pulverized with a jet mill to produce electrolytic manganese dioxide particles having an average particle size (volume average particle size) of 0.63 ⁇ m. This was made into manganese oxide particles. The particle size distribution of the manganese oxide particles is shown in FIG. The manganese oxide particles were dispersed in water at a concentration of 30 g / L to prepare a slurry liquid. The slurry was continuously added to the electrolytic solution so that the concentration of manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution was 60 mg / L.
- Example 1 except that the above manganese oxide particles were added instead of the sodium persulfate aqueous solution, the electrolysis current density during electrolysis was 1.37 A / dm 2 , and electrolysis was performed for 7 days. Similarly, electrolytic manganese dioxide was produced.
- the production conditions of the electrolytic manganese dioxide of Example 3 are shown in Table 1, and the evaluation results of the obtained electrolytic manganese dioxide are shown in Table 2.
- the electrolysis voltage at the end of electrolysis in Example 3 was 3.05V.
- the manganese oxide particles used in Example 3 had a content of particles of 1 ⁇ m or less of 93% by weight, an iron content of 45 ppm, and an Mn valence of 3.92.
- Electrolytic manganese dioxide was produced under the same conditions as in Example 3 except that the electrolytic current density during electrolysis was 1.5 A / dm 2 and electrolysis was performed for 6 days.
- the production conditions of the electrolytic manganese dioxide of Example 4 are shown in Table 1, and the evaluation results of the obtained electrolytic manganese dioxide are shown in Table 2.
- the electrolysis voltage at the end of electrolysis was 3.48V.
- Example 5 Manganese oxidation so that the electrolysis current density during electrolysis was 1.5 A / dm 2 , electrolysis was performed for 4 days, and the concentration of manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution was 30 mg / L. Electrolytic manganese dioxide was produced under the same conditions as in Example 3 except that the product particles were added to the sulfuric acid-manganese sulfate mixed solution.
- the production conditions of the electrolytic manganese dioxide of Example 5 are shown in Table 1, and the evaluation results of the obtained electrolytic manganese dioxide are shown in Table 2.
- the electrolysis voltage at the end of electrolysis was 3.59V.
- Example 6 A sulfuric acid-manganese sulfate mixed solution was used as the electrolytic solution. To this, a replenished manganese sulfate solution having a manganese ion concentration of 43 g / L and a slurry solution in which electrolytic manganese dioxide particles obtained by the same method as in Example 3 were dispersed in water at a concentration of 30 g / L were continuously added. Electrolysis was performed while producing electrolytic manganese dioxide.
- the slurry was added so that the concentration of manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution was 45 mg / L.
- the replenished manganese sulfate solution was added to the electrolyte so that the sulfuric acid concentration in the sulfuric acid-manganese sulfate mixed solution was 25.0 g / L.
- the electrolysis current density during electrolysis was 1.39 A / dm 2 , and the electrolysis temperature was 96 ° C. Electrolysis was performed for 7 days.
- the electrolysis voltage at the end of electrolysis in Example 6 was 2.77V.
- Example 7 A manganese sulfate aqueous solution and a sodium hydroxide (NaOH) aqueous solution were mixed while blowing air to obtain a precipitate. The obtained precipitate was filtered, washed, and dried and then pulverized to obtain manganese oxide particles having an average particle size of 0.61 ⁇ m. The obtained manganese oxide particles were trimanganese tetraoxide particles composed of a single phase of trimanganese tetraoxide.
- NaOH sodium hydroxide
- electrolytic manganese dioxide particles instead of the electrolytic manganese dioxide particles, the use of the trimanganese tetraoxide particles, the use of a supplemental manganese sulfate solution having a manganese ion concentration of 42 g / L, and the electrolysis current density during electrolysis of 1.5 A / dm 2
- Electrolytic manganese dioxide (trade name: HH-S, manufactured by Tosoh Corporation) was baked at 620 ° C. for 12 hours to obtain manganese oxide particles having an average particle size of 0.96 ⁇ m.
- the obtained manganese oxide particles were manganese dioxide particles composed of a single phase of manganese dioxide (Mn 2 O 3 ).
- Electrolytic manganese dioxide was obtained under the same conditions as in Example 7 except that the manganese trioxide particles were used instead of the electrolytic manganese dioxide particles.
- Electrolytic manganese dioxide was produced by electrolysis for 12 days while continuously adding a supplemental manganese sulfate solution having a manganese ion concentration of 40.0 g / L into the electrolytic cell.
- the electrolysis current density during electrolysis was 0.8 A / dm 2 , and the electrolysis temperature was 92 ° C.
- the sulfuric acid concentration in the electrolytic cell during electrolysis was adjusted to 25.0 g / L, and the concentration of manganese oxide particles in the sulfuric acid-manganese sulfate mixed solution was adjusted to 3 mg / L.
- the electrolysis voltage at the end of electrolysis was 3.2V.
- Electrolytic manganese dioxide was produced in the same manner as in Comparative Example 1 except that the amount was adjusted to 2 mg / L and electrolysis was performed for 15 days.
- the electrolysis voltage at the end of electrolysis was 2.8V.
- Table 3 shows the production conditions of the electrolytic manganese dioxide of Comparative Example 2, and Table 4 shows the evaluation results of the obtained electrolytic manganese dioxide.
- Electrolysis was performed in the same manner as Comparative Example 1 except that the electrolysis current density during electrolysis was 1.2 A / dm 2 and the electrolysis temperature was 96 ° C. The electrolysis voltage rapidly increased immediately after the incoming power, and the electrolysis voltage exceeded 4.0 V after 2 hours. Therefore, electrolysis was stopped 2 hours after the incoming call. Since the electrodeposited electrodeposit deposited on the electrode was too thin, the electrolytic manganese dioxide electrodeposit could not be peeled off from the electrode, and electrolytic manganese dioxide could not be obtained.
- Table 3 shows the production conditions for the electrolytic manganese dioxide of Comparative Example 3.
- Electrolytic manganese dioxide was produced in the same manner as in Comparative Example 1 except that the electrolysis current density during electrolysis was 0.2 A / dm 2 , the electrolysis temperature was 96 ° C., and electrolysis was performed for 30 days. The electrolysis voltage at the end of electrolysis was 2.3V.
- Table 3 shows the production conditions of the electrolytic manganese dioxide of Comparative Example 4, and Table 4 shows the evaluation results of the obtained electrolytic manganese dioxide.
- Example 9 A sulfuric acid-manganese sulfate mixed solution having a calcium concentration of 600 mg / L, a magnesium concentration of 1800 mg / L, and a sulfuric acid concentration of 25.0 g / L was used as the electrolytic solution.
- a slurry in which a manganese sulfate solution having a manganese ion concentration of 43 g / L and electrolytic manganese dioxide particles having an average particle diameter of 0.63 ⁇ m dispersed at a concentration of 30 g / L is continuously added to the electrolyte solution. Then, electrolytic manganese dioxide was produced by electrolysis.
- the replenishment manganese sulfate solution was continuously added to the electrolyte solution so that the sulfuric acid concentration of the electrolyte solution was 25.0 g / L, and the slurry solution had a manganese oxide particle concentration of 55 mg / L in the electrolyte solution.
- Electrolysis was performed while continuously adding to the electrolyte solution. During electrolysis, the current density was 1.39 A / dm 2 , the electrolysis temperature was 96 ° C., and the electrolysis period was 7 days.
- Table 5 shows the production conditions of the electrolytic manganese dioxide of Example 9, and Table 6 shows the evaluation results of the obtained electrolytic manganese dioxide.
- the electrolysis voltage at the end of electrolysis in Example 9 was 2.75V.
- Example 10 A sulfuric acid-manganese sulfate mixed solution having a calcium concentration of 800 mg / L, a magnesium concentration of 1000 mg / L, and a sulfuric acid concentration of 25 g / L was used as the electrolytic solution.
- electrolytic solution By electrolyzing the electrolytic solution while continuously adding a slurry in which a manganese sulfate solution having a manganese ion concentration of 42 g / L and electrolytic manganese dioxide particles having an average particle diameter of 0.8 ⁇ m are dispersed to the electrolytic solution Electrolytic manganese dioxide was produced.
- the supplemental manganese sulfate solution is continuously added to the electrolyte so that the sulfuric acid concentration in the electrolytic cell is 25.0 g / L, and the electrolytic manganese dioxide particles have a manganese oxide particle concentration of 9 in the electrolyte. It was continuously added to the electrolyte so as to be 6 mg / L.
- Electrolysis was carried out with an electrolysis current density of 1.5 A / dm 2 , an electrolysis temperature of 96 ° C., and an electrolysis period of one day to obtain electrolytic manganese dioxide.
- the electrolysis voltage at the end of electrolysis in Example 6 was 2.26V.
- Table 5 shows the production conditions of the electrolytic manganese dioxide of Example 10, and Table 6 shows the evaluation results of the obtained electrolytic manganese dioxide.
- Electrolytic manganese dioxide was produced in the same manner as in Example 10 except that manganese oxide was not added to the electrolytic solution.
- Table 5 shows the production conditions of the electrolytic manganese dioxide of Comparative Example 5, and Table 6 shows the evaluation results of the obtained electrolytic manganese dioxide.
- Example 11 Manufacture of lithium manganate
- the electrolytic manganese dioxide obtained in Example 1 was mixed with commercially available lithium carbonate and fired at 850 ° C. to produce lithium manganate.
- the obtained lithium manganate was molded at a pressure of 2 t / cm 2 to produce a molded body.
- the molding density of the compact was 2.7 g / cm 3 , and this lithium manganate showed high filling properties.
- all the samples had the same composition ratio of Li, and the electrolytic manganese dioxide of the present invention was uniform with the lithium compound. It was confirmed that the reaction occurred.
- the lithium ion secondary battery is an ethylene carbonate containing lithium manganate obtained in this example as a positive electrode active material, metal lithium as a negative electrode, and 1 mol / L lithium hexafluorophosphate (LiPF 6 ) as an electrolyte. / Dimethyl carbonate (volume ratio 1: 2) mixed solution was used.
- the prepared lithium ion secondary battery was charged and discharged, and the energy density was determined from the discharge capacity and the average voltage during discharge.
- the charge / discharge current was 1 C rate, and the charge / discharge voltage was 3 V to 4.3 V (charge: 3 V to 4.3 V, discharge 4.3 V to 3 V).
- the energy density of the lithium manganate of Example 11 was 445 mWh / g.
- Table 7 The results are shown in Table 7.
- Example 12 The electrolytic manganese dioxide obtained in Example 2 and lithium carbonate were mixed and baked at 850 ° C. to produce lithium manganate.
- the obtained lithium manganate was molded at a pressure of 2 t / cm 2 to produce a molded body.
- the molding density of the molded body was 2.72 g / cm 3 , and this lithium manganate showed high filling properties.
- the electrolytic manganese dioxide of the present invention was a lithium compound. It was confirmed that they reacted uniformly.
- the energy density was measured by the same method as in Example 11 except that the obtained lithium manganate was used as the positive electrode active material. As a result, the energy density of the lithium manganate of Example 12 was 448 mWh / g. The results are shown in Table 7.
- the lithium manganate obtained from the electrolytic manganese dioxide of Comparative Example 1 has a high density of the compact, the energy density is higher than that of the lithium manganate obtained from the electrolytic manganese dioxide of Examples 11 and 12. It was also confirmed that it was lowered.
- Electrolytic manganese dioxide particle
- 2 Pore in electrolytic manganese dioxide (pore diameter 200 nm or more)
- 3 Pore in electrolytic manganese dioxide (pore diameter less than 200 nm)
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Abstract
Description
(1)BET比表面積が20m2/g以上60m2/g以下であり、細孔直径が2nm以上200nm以下の細孔の容積が少なくとも0.023cm3/gである、電解二酸化マンガン。
(2)細孔直径が2nm以上200nm以下の細孔の容積が少なくとも0.025cm3/gである、上記(1)に記載の電解二酸化マンガン。
(3)細孔直径が2nm以上50nm以下の細孔の容積が少なくとも0.004cm3/gである、上記(1)又は(2)に記載の電解二酸化マンガン。
(4)細孔直径が2nm以上50nm以下の細孔の容積が少なくとも0.005cm3/gである、上記(1)~(3)のいずれか一つに記載の電解二酸化マンガン。
(5)見掛粒子密度が少なくとも3.4g/cm3である、上記(1)~(4)のいずれか一つに記載の電解二酸化マンガン。
(6)見掛粒子密度が少なくとも3.8g/cm3である、上記(1)~(5)のいずれか一つに記載の電解二酸化マンガン。
(7)嵩密度が少なくとも1.5g/cm3である、上記(1)~(6)のいずれかに記載の電解二酸化マンガン。
(8)アルカリ土類金属の含有量が500重量ppm以下である、上記(1)~(7)のいずれか一つに記載の電解二酸化マンガン。
(9)硫酸-硫酸マンガン混合溶液中にマンガン酸化物を懸濁させて電解二酸化マンガンを得る工程を有する電解二酸化マンガンの製造方法において、前記工程において、マンガン酸化物粒子を連続的に硫酸-硫酸マンガン混合溶液に混合し、硫酸-硫酸マンガン混合溶液中のマンガン酸化物粒子の濃度を5mg/L以上200mg/L以下とする、電解二酸化マンガンの製造方法。
(10)硫酸-硫酸マンガン混合溶液中の硫酸濃度が20g/L以上30g/L以下である、上記(9)に記載の電解二酸化マンガンの製造方法。
(11)電解電流密度が0.8A/dm2以上1.5A/dm2以下である、上記(9)又は(10)に記載の電解二酸化マンガンの製造方法。
(12)電解電流密度が1.2A/dm2以上1.4A/dm2以下である、上記(9)~(11)のいずれか一つに記載の電解二酸化マンガンの製造方法。
(13)マンガン酸化物粒子の平均粒子径が5μm以下である、上記(9)~(12)のいずれか一つに記載の電解二酸化マンガンの製造方法。
(14)硫酸-硫酸マンガン混合溶液のアルカリ土類金属濃度が0.5g/L以上である、上記(9)~(13)のいずれか一つに記載の電解二酸化マンガンの製造方法。
(15)上記(1)~(8)のいずれか一つに記載の電解二酸化マンガンとリチウム化合物とを混合して熱処理しリチウムマンガン系複合酸化物を得る工程を有するリチウムマンガン系複合酸化物の製造方法。
電解二酸化マンガンの二次細孔及びメソポアの細孔容積、見掛粒子密度及び嵩密度は市販の装置(商品名:ポアサイザー9510,マイクロメリティクス社製)を用いた水銀圧入法によって測定した。
電解二酸化マンガンのBET比表面積はBET1点法の窒素吸着により測定した。測定装置にはガス吸着式比表面積測定装置(商品名:フローソーブIII,島津製作所製)を用いた。測定に先立ち、150℃で40分間加熱することで測定試料を脱気処理した。
電解二酸化マンガンの2θが22±1°付近の回折線のFWHMを、一般的なX線回折装置(商品名:MXP-3,マックサイエンス社製)を使用して測定した。線源にはCuKα線(λ=1.5405Å)を用い、測定モードはステップスキャン、スキャン条件は毎秒0.04°、計測時間は3秒間、および測定範囲は2θとして5°から80°の範囲で測定した。
FWHMと同様にして得られたXRD図において、2θが22±1°付近の回折線を(110)面に対応するピークとし、37±1°付近の回折線を(021)面に対応するピークとした。(110)面のピーク強度を(021)面のピーク強度で除することにより(110)/(021)を求めた。
電解二酸化マンガンのアルカリ電位は、40%KOH水溶液中で次のように測定した。
電解二酸化マンガン0.5gを純水50mL中に投入し、10秒間超音波照射を行って分散スラリーを調製した。この分散スラリーを測定装置(商品名:マイクロトラックHRA,HONEWELL製)に所定量投入し、レーザー回折法で粒度分布を測定した。得られた粒度分布データから、マンガン酸化物粒子の粒子径の分布及び平均粒子径を求めた。測定に際し、純水の屈折率を1.33、二酸化マンガンの屈折率を2.20とした。
電解液として硫酸-硫酸マンガン混合溶液を用いた。電解槽内にこの電解液を投入し、この電解槽内に、マンガンイオン濃度40.0g/Lの補給硫酸マンガン液と、過硫酸ナトリウムを200g/L含む過硫酸ナトリウム水溶液と、を連続的に添加しながら電解し、電極上に電解二酸化マンガンを電着させた。電解中は、電解電流密度を1.2A/dm2、電解温度を96℃とした。なお、補給硫酸マンガン液は電解槽内の硫酸濃度が25.0g/Lとなるよう添加し、8日間電解した。また、過硫酸ナトリウム水溶液は電解液中のマンガン酸化物粒子の濃度が5mg/Lとなるように連続的に添加した。実施例1の電解終了時の電解電圧は、3.35Vであった。
電解液中のマンガン酸化物粒子の濃度が15mg/Lとなるように、過硫酸ナトリウム水溶液を電解槽内に連続的に添加したこと以外は、実施例1と同様の条件で電解二酸化マンガンを製造した。実施例2の電解終了時の電解電圧は3.35Vであった。
市販の電解二酸化マンガン(商品名:HH-S,東ソー株式会社製)をジェットミルで粉砕し、平均粒子径(体積平均粒子径)が0.63μmの電解二酸化マンガン粒子を製造した。これをマンガン酸化物粒子とした。当該マンガン酸化物粒子の粒子径分布を図4に示した。このマンガン酸化物粒子を30g/Lの濃度で水に分散させてスラリー液を調製した。硫酸-硫酸マンガン混合溶液中のマンガン酸化物粒子の濃度が60mg/Lとなるように、当該スラリー液を電解液中に連続的に添加した。
電解中の電解電流密度を1.5A/dm2としたこと、及び電解を6日間行ったこと以外は、実施例3と同様の条件で電解二酸化マンガンを製造した。
電解中の電解電流密度を1.5A/dm2としたこと、電解を4日間行ったこと、及び硫酸-硫酸マンガン混合溶液中のマンガン酸化物粒子の濃度が30mg/Lとなるようにマンガン酸化物粒子を硫酸-硫酸マンガン混合溶液中に添加したこと以外は、実施例3と同様の条件で電解二酸化マンガンを製造した。
電解液として硫酸-硫酸マンガン混合溶液を用いた。これに、マンガンイオン濃度43g/Lの補給硫酸マンガン液と、実施例3と同様の方法で得られた電解二酸化マンガン粒子を30g/Lの濃度で水に分散させたスラリー液を連続的に添加しながら電解を行って、電解二酸化マンガンを製造した。
硫酸マンガン水溶液と水酸化ナトリウム(NaOH)水溶液を、空気を吹き込みながら混合して析出物を得た。得られた析出物をろ過、洗浄、及び乾燥した後に粉砕し、平均粒子径0.61μmのマンガン酸化物粒子を得た。得られたマンガン酸化物粒子は、四三酸化マンガンの単相からなる四三酸化マンガン粒子であった。
電解二酸化マンガン(商品名:HH-S,東ソー株式会社製)を620℃で12時間焼成して、平均粒子径0.96μmのマンガン酸化物粒子を得た。得られたマンガン酸化物粒子は三二酸化マンガン(Mn2O3)の単相からなる三二酸化マンガン粒子であった。
実施例1と同様に電解液として硫酸-硫酸マンガン溶液を用いた。電解槽内に、マンガンイオン濃度が40.0g/Lの補給硫酸マンガン液を連続的に添加しながら12日間電解して、電解二酸化マンガンを製造した。電解中の電解電流密度は0.8A/dm2、電解温度は92℃とした。電解時の電解槽内の硫酸濃度は25.0g/L、硫酸-硫酸マンガン混合溶液中のマンガン酸化物粒子の濃度は3mg/Lに調整した。電解終了時の電解電圧は3.2Vであった。
電解時の電解電流密度を0.6A/dm2及び電解温度を96℃としたこと、電解槽内の硫酸濃度を35.0g/L、硫酸-硫酸マンガン混合溶液中のマンガン酸化物粒子の濃度を2mg/Lに調整したこと、並びに15日間電解を行ったこと以外は、比較例1と同様にして電解二酸化マンガンを製造した。電解終了時の電解電圧は2.8Vであった。
電解時の電解電流密度を1.2A/dm2、及び電解温度を96℃としたこと以外は、比較例1と同様にして電解を行った。入電直後から電解電圧が急上昇し、2時間後に電解電圧が4.0Vを超えた。そのため、入電から2時間後に電解を停止した。電極上に電析した電着物の電着厚みが薄すぎるため、電極から電解二酸化マンガン電着物を剥離させることができず、電解二酸化マンガンを得ることができなかった。
電解時の電解電流密度を0.2A/dm2、及び電解温度を96℃としたこと、並びに30日間電解を行ったこと以外は、比較例1と同様にして電解二酸化マンガンを製造した。電解終了時の電解電圧は2.3Vであった。
電解液としてカルシウム濃度が600mg/L、マグネシウム濃度が1800mg/L、硫酸濃度が25.0g/Lである硫酸-硫酸マンガン混合溶液を用いた。当該電解液に、マンガンイオン濃度が43g/Lの補給硫酸マンガン液、及び、平均粒子径0.63μmの電解二酸化マンガン粒子を濃度30g/Lで分散させたスラリーを電解液に連続的に添加しながら電解することにより、電解二酸化マンガンを製造した。
電解液として、カルシウム濃度800mg/L、及びマグネシウム濃度1000mg/L、及び硫酸濃度25g/Lである硫酸-硫酸マンガン混合溶液を用いた。当該電解液に、マンガンイオン濃度が42g/Lの補給硫酸マンガン液、及び、平均粒子径0.8μmの電解二酸化マンガン粒子を分散させたスラリーを電解液に連続的に添加しながら電解することにより、電解二酸化マンガンを製造した。
マンガン酸化物を電解液に添加しなかったこと以外は、実施例10と同様な方法により電解二酸化マンガンを製造した。比較例5の電解二酸化マンガンの製造条件を表5に、得られた電解二酸化マンガンの評価結果を表6に示した。
(マンガン酸リチウムの製造)
実施例1で得られた電解二酸化マンガンを市販の炭酸リチウムと混合し、850℃で焼成してマンガン酸リチウムを製造した。得られたマンガン酸リチウムを2t/cm2の圧力で成形して成形体を作製した。成形体の成形密度は2.7g/cm3であり、このマンガン酸リチウムは高い充填性を示した。また、このマンガン酸リチウムからサンプルを3個分取して、それぞれのサンプルの組成分析をしたところ、いずれのサンプルもLiの組成比が同じであり、本発明の電解二酸化マンガンがリチウム化合物と均一に反応したことが確認できた。
得られたマンガン酸リチウムを用いたリチウムイオン二次電池を作製し、エネルギー密度を測定した。リチウムイオン二次電池は、正極活物質として本実施例で得られたマンガン酸リチウム、負極として金属リチウム、並びに、電解液として1mol/Lの六フッ化リン酸リチウム(LiPF6)を含むエチレンカーボネート/ジメチルカボネート(体積比1:2)混合溶液を用いて、作製した。
実施例2で得られた電解二酸化マンガンと炭酸リチウムとを混合し、850℃で焼成してマンガン酸リチウムを製造した。得られたマンガン酸リチウムを2t/cm2の圧力で成形して成形体を作製した。成形体の成形密度は2.72g/cm3であり、このマンガン酸リチウムは高い充填性を示した。また、得られたマンガン酸リチウムからサンプルを3個分取して、それぞれのサンプルの組成分析をしたところ、いずれのサンプルもLiの組成比が同じであり、本発明の電解二酸化マンガンがリチウム化合物と均一に反応したことが確認できた。
比較例1で得られた電解二酸化マンガンを炭酸リチウムと混合し、850℃で焼成してマンガン酸リチウムを製造した。得られたマンガン酸リチウムを2t/cm2の圧力で成形して成形体を作製した。成形体の成形密度は2.73g/cm3であり、実施例11,12のマンガン酸リチウムよりも高い充填性を示した。得られたマンガン酸リチウムを正極活物質としたこと以外は実施例11と同様の方法でエネルギー密度を測定した。その結果、比較例6のマンガン酸リチウムのエネルギー密度は432mWh/gであった。結果を表7に示す。
Claims (15)
- BET比表面積が20m2/g以上60m2/g以下であり、
細孔直径が2nm以上200nm以下の細孔の容積が少なくとも0.023cm3/gである、電解二酸化マンガン。 - 細孔直径が2nm以上200nm以下の細孔の容積が少なくとも0.025cm3/gである、請求項1に記載の電解二酸化マンガン。
- 細孔直径が2nm以上50nm以下の細孔の容積が少なくとも0.004cm3/gである、請求項1又は2に記載の電解二酸化マンガン。
- 細孔直径が2nm以上50nm以下の細孔の容積が少なくとも0.005cm3/gである、請求項1~3のいずれか一項に記載の電解二酸化マンガン。
- 見掛粒子密度が少なくとも3.4g/cm3である、請求項1~4のいずれか一項に記載の電解二酸化マンガン。
- 見掛粒子密度が少なくとも3.8g/cm3である、請求項1~5のいずれか一項に記載の電解二酸化マンガン。
- 嵩密度が少なくとも1.5g/cm3である、請求項1~6のいずれか一項に記載の電解二酸化マンガン。
- アルカリ土類金属の含有量が500重量ppm以下である、請求項1~7のいずれか一項に記載の電解二酸化マンガン。
- 硫酸-硫酸マンガン混合溶液中にマンガン酸化物を懸濁させて電解二酸化マンガンを得る工程を有する電解二酸化マンガンの製造方法において、
前記工程において、マンガン酸化物粒子を連続的に硫酸-硫酸マンガン混合溶液に混合し、硫酸-硫酸マンガン混合溶液中のマンガン酸化物粒子の濃度を5mg/L以上200mg/L以下とする、電解二酸化マンガンの製造方法。 - 前記工程における硫酸-硫酸マンガン混合溶液中の硫酸濃度が20g/L以上30g/L以下である、請求項9に記載の電解二酸化マンガンの製造方法。
- 前記工程における電解電流密度が0.8A/dm2以上1.5A/dm2以下である、請求項9又は10に記載の電解二酸化マンガンの製造方法。
- 前記工程における電解電流密度が1.2A/dm2以上1.4A/dm2以下である、請求項9~11のいずれか一項に記載の製造方法。
- 前記マンガン酸化物粒子の平均粒子径が5μm以下である、請求項9~12のいずれか一項に記載の電解二酸化マンガンの製造方法。
- 前記硫酸-硫酸マンガン混合溶液のアルカリ土類金属濃度が0.5g/L以上である、請求項9~13のいずれか一項に記載の電解二酸化マンガンの製造方法。
- 請求項1~8のいずれか一項に記載の電解二酸化マンガンとリチウム化合物とを混合して熱処理しリチウムマンガン系複合酸化物を得る工程を有する、リチウムマンガン系複合酸化物の製造方法。
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EP2811556A1 (en) * | 2013-02-19 | 2014-12-10 | Panasonic Intellectual Property Management Co., Ltd. | Manganese dioxide, and alkaline dry cell using same |
EP2811556A4 (en) * | 2013-02-19 | 2014-12-10 | Panasonic Ip Man Co Ltd | MANGANO DIOXIDE AND ALKALI DRY BATTERY THEREWITH |
WO2015028718A1 (en) * | 2013-08-28 | 2015-03-05 | Inkron Ltd | Transition metal oxide particles and method of producing the same |
CN105940145A (zh) * | 2013-08-28 | 2016-09-14 | 英克罗恩有限公司 | 过渡金属氧化物颗粒及其制备方法 |
US10385464B2 (en) | 2013-08-28 | 2019-08-20 | Inkron Ltd | Transition metal oxide particles and method of producing the same |
EP3889322A4 (en) * | 2018-11-29 | 2022-11-09 | Tosoh Corporation | ELECTROLYTIC MANGANE DIOXIDE, PROCESS FOR PRODUCTION THEREOF AND USE THEREOF |
Also Published As
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ES2691630T3 (es) | 2018-11-28 |
EP2677066A1 (en) | 2013-12-25 |
TWI518208B (zh) | 2016-01-21 |
JP5998510B2 (ja) | 2016-09-28 |
EP2677066B1 (en) | 2018-08-29 |
CN103370448A (zh) | 2013-10-23 |
EP2677066A4 (en) | 2014-08-13 |
JP2012184504A (ja) | 2012-09-27 |
CN103370448B (zh) | 2016-08-10 |
KR20130096754A (ko) | 2013-08-30 |
US9214675B2 (en) | 2015-12-15 |
US20130330268A1 (en) | 2013-12-12 |
TW201245494A (en) | 2012-11-16 |
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