CN101110476B - Electrolytic manganese dioxide, positive electrode active material, and battery - Google Patents
Electrolytic manganese dioxide, positive electrode active material, and battery Download PDFInfo
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Abstract
The invention provides an electrolytic manganese dioxide which is characterized by having a surface sulfate (SO4) content of smaller than 0.10% by weight and a JIS-pH value, as measured according to JIS K1467, of at least 1.5 but smaller than 3.5, preferably at least 2.1 but smaller than 3.2 is provided. Preferably 3% to 25% in number of the fine particles of the manganese dioxide have a particle diameter of not larger than 1 mum. A battery provided with a cathode made from the electrolytic manganese dioxide as active material exhibits good high-rate discharge characteristics and good resistance to metal corrosion.
Description
Technical field
The present invention relates to electrolytic manganese dioxide, for example be used for manganese dry cell, particularly the alkaline manganese dry cell as active material of cathode.Electrolytic manganese dioxide among the present invention makes battery demonstrate improved high rate discharge performance, and when the negative electrode of battery was processed by this electrolytic manganese dioxide, this electrolytic manganese dioxide can not cause the corrosion of metals problem.
Background technology
Manganese dioxide is known as the active material of negative electrode, for example is used for manganese dry cell, especially for the alkaline manganese dry cell.Manganese dioxide demonstrates favorable durability and cheap.
Have with electrolytic manganese dioxide as active material the alkaline manganese dry cell of negative electrode when high capacity is discharged, have fabulous discharge performance.Therefore, the alkaline manganese dry cell for example is widely used in Electrofax, portable tape recorder, personal digital assistant, game machine and the toy, thereby its demand is increased sharply in recent years.Yet the alkaline manganese dry cell has following problems, along with the enhancing of discharging current, reduce with the utilization of the manganese dioxide of active material as negative electrode, thereby and discharge voltage reduce discharge capacity significantly reduced.In other words, when the alkaline manganese dry cell is equipped in the instrument that utilizes heavy current in the short time, that is to say and carry out high rate discharge that for the utilization minimizing of the manganese dioxide that is used as cathode active material, and the durability of instrument reduces.Therefore, press for manganese dioxide with improved two-forty performance, just produce at short notice heavy current intermittence high rate discharge condition under can demonstrate big capacity and the manganese dioxide that strengthens durability.
As the manganese dioxide that uses at the active material of cathode that is used for the discharge of intermittent high-speed rate; The open 2002-304990 of japanese unexamined patent publication No. has proposed to have the manganese dioxide of the two-forty performance of enhancing; Its surperficial sulfate radical content is at least 0.10 weight %, and controlled alkali metal content is less than 0.20 weight %.Further, the open 2004-047445 (patent No. is 3712259) of japanese unexamined patent publication No. proposes the electrolytic manganese dioxide of sulphate groups mass contg in 1.3 weight % to 1.6 weight % scopes.Although the two-forty performance of the manganese dioxide that is proposed in the open text of these patents is enhanced to a certain extent, the degree that is strengthened is enough not high.And, owing to contain sulfate groups in the electrolytic manganese dioxide, thereby the problem of reduction of dry cell durability and voltage instability thereof often takes place.
The open 2001-026425 of japanese unexamined patent publication No. has proposed improved manganese dioxide, and controlled sodium content X that it has and controlled JIS-pH value Y satisfy following formula: Y＞4.7X+2.4, and manganese dioxide especially has 3.5 to 5.0 JIS-pH value.Although the two-forty performance of the manganese dioxide that is proposed in the open text of these patents is enhanced to a certain extent, the degree that is strengthened is still enough not high.And, etching problem often takes place in making cell process.
Summary of the invention
Main purpose of the present invention provides the electrolytic manganese dioxide that uses as the active material of cathode that is used for manganese dry cell, especially alkaline manganese dry cell; This battery demonstrates improved high rate discharge performance, and in the manufacturing step of the negative electrode of being processed by this manganese dioxide, can not cause the corrosion of metals problem.
To achieve these goals, the inventor has carried out extensive studies and has found surperficial sulfate radical (SO
4) the JIS-pH value measured less than 0.10 weight %, according to JIS K1467 of content be at least 1.5 but less than 3.5, preferably be at least 2.1 and still make dry cell demonstrate improved high rate discharge performance less than 3.2 electrolytic manganese dioxide.
Further, can find to be not more than under the situation of 1 μ m the improvement high rate discharge performance that can more be strengthened at the fine grain particle diameter of above-mentioned electrolytic manganese dioxide 3% to 25% quantity.
Further; Can find that this electrolytic manganese dioxide makes dry cell demonstrate improved high rate discharge performance and in the step of being processed negative electrode by this electrolytic manganese dioxide, can not cause the corrosion of metals problem as sodium content X (ppm) in the electrolytic manganese dioxide and fine grain median particle diameter Y (μ m) when having particular kind of relationship.
Based on above-mentioned discovery, the present invention is accomplished.
According to the present invention, the electrolytic manganese dioxide of fine particle form is provided, it is characterized in that having surperficial sulfate radical (SO less than 0.10 weight %
4) content and according to JIS K1467 measure be at least 1.5 but less than 3.5, preferably be at least 2.1 but less than 3.2 JIS-pH value.
Description of drawings
Fig. 1 has shown the schematic sectional view of the device that is used for electrolytic manganese dioxide corrosion of metals test; And
Fig. 2 has shown the curve chart that shows sodium content (ppm) relation in fine particle median particle diameter (μ m) and the electrolytic manganese dioxide.
Embodiment
Sulfate radical (the SO that electrolytic manganese dioxide is contained
4) amount be divided into (1) surperficial sulfate radical content, just be present in amount and (2) inner sulfate radical content of the sulfate radical of electrolytic manganese dioxide particle surface, just be present in the amount of the sulfate radical of electrolytic manganese dioxide granule interior.When for example comprising the electrolyte manufacturing electrolytic manganese dioxide of manganese sulfate and sulfuric acid through electrolytic deposition, the employed sulfuric acid of part enters into the electrolytic manganese dioxide inside of deposition.Be present in the form of the inner sulfuric acid of electrolytic manganese dioxide and unclear, even but electrolytic manganese dioxide wash fully or neutralized, still have the part electrolytic manganese dioxide to keep and from electrolytic manganese dioxide, do not remove.This part electrolytic manganese dioxide constitutes inner sulfate radical composition.
Term as used herein " surperficial sulfate radical content " is meant the content that deducts the sulfate radical of inner sulfate radical content calculating with total sulfate radical content.The content of inner sulfate radical is confirmed by following method: will deposit gained manganese dioxide water and clean fully that no longer to change the JIS-pH value that perhaps neutralizes up to JIS-pH value be 4.5, the amount of the sulfate radical that is retained in definite then manganese dioxide that cleaned or neutralized.Total sulfate radical content is the amount of contained sulfate radical in the determined deposition manganese dioxide before washing or the neutralization.The confirming of inner sulfate radical content and total sulfate radical content carries out through atomic absorption spectroscopy or ICP (atomic emission spectrum chemical analysis).
Inner sulfate radical content changes according to the ad hoc approach difference of making electrolytic manganese dioxide, but is generally about 0.90 weight % to about 1.25 weight %.
Electrolytic manganese dioxide among the present invention is characterized in that surperficial sulfate radical (SO
4) content is less than 0.10 weight %, and according to the JIS-pH value that JIS K1467 records be at least 1.5 but less than 3.5, preferably be at least 2.1 but less than 3.2.
Be at least 3.5 JIS-pH value if electrolytic manganese dioxide has, its high rate discharge performance is compared and can't be strengthened with conventional electrolysis manganese dioxide.On the contrary, if electrolytic manganese dioxide has the JIS-pH value less than 1.5, its high rate discharge performance is fine usually, still, because too high acidity makes the durability of battery be easy to variation, and causes the device of manufacturing cathode material and the etching problem of battery case.
JIS-pH value among this paper confirms through the method for the measurement degree of neutralization of routine, just according to the ammonium chloride method of JIS K1467, wherein the manganese dioxide of scheduled volume (10.0g) joined (50ml, 20g NH in the chloride buffer solution of scheduled volume
4Cl/100ml H
2O), in the pH of 25 ± 2 ℃ of definite supernatants value.
The electrolytic manganese dioxide or the JIS-pH value that neutralizes in a usual manner that can use a large amount of water to clean manufacturing are 3.5 or higher; Thus surperficial sulfate radical content is reduced to below the 0.10 weight %, but different among the electrolytic manganese dioxide that so obtains and the present invention.Electrolytic manganese dioxide among the present invention must have the JIS-pH value that is reduced to below 3.5, and is reduced to the surperficial sulphur root salt content below the 0.10 weight %.
Electrolytic manganese dioxide among the present invention exists with the fine particle form usually.Fine grain particle diameter is not specially limited, but the electrolytic manganese dioxide fine particle of preferred 3% to 25% quantity has the particle diameter that is not more than 1 μ m, to strengthen the high rate discharge performance biglyyer.
If the particle diameter that thin electrolytic manganese dioxide particle comprises is not more than the quantity of particle of 1 μ m less than 3%, the powder molding spare that makes through the thin electrolytic manganese dioxide particle of pressure forming is highly brittle and is broken easily.On the contrary; If the particle diameter that thin electrolytic manganese dioxide particle comprises is not more than the amount of particle of 1 μ m greater than 25% of quantity; When adding carbon when improving conductivity, can make the minimizing that contacts of electrolytic manganese dioxide and carbon, and the utilance step-down of electrolytic manganese dioxide in the battery.
The maximum gauge of thin electrolytic manganese dioxide particle is not specially limited, but preferably is not more than 100 μ m.If parts of fine electrolytic manganese dioxide particle has the particle diameter greater than 100 μ m, the dry cell inner surface of container is easy to damage, thereby the metal that inner surface of container plated is easy to damage and the iron that exposes is easy to react and produce gas.And, the slider generation chemical damage between anode of processing by for example zinc and the negative electrode processed by electrolytic manganese dioxide powder molding spare that is used to insulate, thus begin directly to contact as the Powdered electrolytic manganese dioxide of active material of cathode with zinc anode.Thereby the self discharge that occurs takes place not hope in battery electric power storage process, cause capacity to reduce.
Thin electrolytic manganese dioxide particle preferably has the median particle diameter in 15 μ m and 70 mu m ranges.If median particle diameter is greater than 70 μ m, the total surface area of this thin electrolytic manganese dioxide particle can desirably not reduce, thereby weakens cell reaction.On the contrary, if median particle diameter is lower than 15 μ m, the fine grain amount that is filled in the battery case reduces to a great extent.
Confirm that through following optical scatter counting method particle diameter is not more than the fine grain amount of 1 μ m, fine grain maximum particle diameter and fine grain median particle diameter.
Wherein be dispersed with the liquid of thin electrolytic manganese dioxide particle with laser beam irradiation, use can be purchased the Co. in Nikkiso, and the optical scatter counting device of Ltd. " Micro-trac particle size distribution measurement mechanism " is measured scattered light to confirm particle diameter and amounts of particles.
Contained sodium comprises the sodium compound of sodium ion and for example NaOH in the thin electrolytic manganese dioxide particle of the present invention.
Sodium contained in the thin electrolytic manganese dioxide particle is from the NaOH nertralizer that is used to regulate fine particle pH value.Most of sodium is adsorbed on the particle surface.The discharge battery reaction is that proton is from the reaction of particle surface to the granule interior diffusion.If it is too high to be present in the amount of sodium of particle surface, the diffusion of protons reaction is suppressed, and causes the high rate discharge performance to weaken.On the contrary, if be present in particle surface sodium amount very little, can obtain good relatively discharge performance usually, but when dry cell is processed by this electrolytic manganese dioxide, owing to the minimizing of sodium content causes other Corrosion of Metallic Materials.
Sodium content X (ppm) in this electrolytic manganese dioxide and fine particle median particle diameter Y (μ m) preferably have the relation that satisfies following formula (1):
-0.016X+56.8≤Y≤-0.04X+134 (1)
When electrolytic manganese dioxide satisfied above-mentioned formula (1), resulting battery demonstrated improved high rate discharge performance, and in the manufacturing step of being processed negative electrode by this manganese dioxide, can not cause the corrosion of metals problem.
In addition, the sodium content X (ppm) in the electrolytic manganese dioxide preferably has the relation that satisfies following formula (2) with fine particle median particle diameter Y (μ m):
-0.016X+56.8≤Y≤-0.016X+71.2 (2)
When electrolytic manganese dioxide satisfied above-mentioned formula (2), resulting battery demonstrated more improved high rate discharge performance, and in the manufacturing step of being processed negative electrode by this manganese dioxide, can not cause the corrosion of metals problem.When the battery of the AA specification with negative electrode of being processed by this active material stood the discharge test of 1A pulse under the cut-ff voltage of the time of repose of 10 seconds discharge time, 50 seconds and 0.9V, resulting battery demonstrated at least 425 times discharge time.
Electrolytic manganese dioxide is through the reason that satisfies above-mentioned formula (1) and/or (2) and obtain improved high rate discharge performance and good metal resistance to corrosion and unclear.But, think that the content of the sodium that the electrolytic manganese dioxide particle surface is adsorbed and the intergranular pore-size that changes according to specific median particle diameter influence particle surface hydrophily and water retention property thereof.Therefore between electrolytic manganese dioxide, electrolyte and metal material, do not form solid-liquid-liquid/solid interface, stop thus or reduced corrosion of metal as far as possible.
The content of the sodium in the thin electrolytic manganese dioxide particle is confirmed through following method: thin electrolytic manganese dioxide particle is dissolved in the aqueous solution of hydrochloric acid and hydrogen peroxide, measures sodium content through atomic absorption spectroscopy then.
When sodium content in the electrolytic manganese dioxide and fine grain median particle diameter satisfy above-mentioned formula (1) and/or (2), can obtain improved high rate discharge performance and good metal resistance to corrosion, still, sodium content especially preferably is not more than 2000ppm.
The active material that is used for cell cathode of the present invention comprises above-mentioned electrolytic manganese dioxide.
Active material of cathode can contain other composition, this is not had special restriction.Other composition comprises, for example, and such as the electric conducting material and the potassium hydroxide aqueous solution of graphite.
Active material of cathode of the present invention makes battery have improved high rate discharge performance and good metal resistance to corrosion.When this active material of cathode is used to make the battery of AA specification; When resulting battery stands the discharge test of 1A pulse under the cut-ff voltage of the time of repose of 10 seconds discharge time, 50 seconds and 0.9V; Resulting battery demonstrates at least 400 times discharge time, preferably at least 425 times.
The present invention will describe in detail in following instance that does not limit invention scope and comparison example.
In these instances, have the two-forty performance of battery of the AA specification of the negative electrode of processing by the manganese dioxide active material, the electric power storage stability of manganese dioxide and the corrosion of metals of electrolytic manganese dioxide are through following method evaluation.
The two-forty performance of battery
5g comprises that powder mixture compression molding under 2 tons molding pressure of the potassium hydroxide electrolyte of the Powdered manganese dioxide of 85.8 weight %, 7.3 weight % graphite and 6.9 weight %40% is the annular die product.Two moulded parts as cathode material, are assembled into zinc the dry cell of AA specification as anode material.After battery at room temperature placed 24 hours, under following discharging condition, carry out discharge test.Repeat to comprise the circulation that discharge 10 seconds under 1000mA and time of repose as a pulse are 50 seconds, reach 0.9V up to final voltage.Discharge performance is estimated through the quantity of pulse.
The electric power storage stability of manganese dioxide
Above-mentioned AA specification dry cell was placed 20 days in the air of 60 ℃ of maintenances, then through said method test two-forty performance.
The corrosion of metals of electrolytic manganese dioxide
The powder mixture compression molding under 2.5 tons molding pressure of potassium hydroxide electrolyte that comprises the 40 weight % of the Powdered electrolytic manganese dioxide of 10g, 0.7g graphite and 0.3g is spherical moulded parts (diameter 20mm).As shown in Figure 1, moulded parts 2 is placed fully the bottom of the test container of processing by polyvinyl chloride 1.The SKD-11 plate that is used for molded cell cathode 3 polishings with routine place on the spherical moulded parts 2 then.Further, will process ground perforated plate 4 by polyvinyl chloride places on the SKD-11 plate 3.Have the spiral sleeve 5 of sillicon rubber blocking 6 through the top, the assembly of moulded parts 2, SKD-11 plate 3 and perforated plate 4 is exerted pressure with the torque of 5Nm.
The test container 1 that will comprise the pressurized assembly is that 50 ℃, relative humidity are to place 3 days in 95% the temperature-adjusting device keeping temperature.Take out SKD-11 plate 3 then, subsequently with sodium bicarbonate aqueous solution treatment S KD-11 plate 3 to remove spherical moulded parts fully.Water is used acetone after cleaning SKD-11 plate 3 again, dry 1 hour then.The difference of the weight of measuring after the weight through the SKD-11 plate 3 measured before the corrosion test and its corrosion test is estimated corrosion rate.Corrosion rate is represented (mm/y) through the slip of annual thickness.
Instance 1
The internal capacity that heater is equipped with in use is that 20 liters electrolytic vessel is made electrolytic manganese dioxide, wherein will as the titanium plate of negative electrode and as the graphite cake suspension of anode so that the two each other over against.Use manganese sulfate solution as electrolyte.The composition of adjustment electrolyte is so that the concentration of bivalent manganese is 40g/l, and the concentration of sulfuric acid is 50g/l.The temperature of electrolyte remains on 95 ℃, and current density is 60A/m
2
After electrolysis is accomplished, clean the electrolytic manganese dioxide of deposition thus, it is separated through compacting with pure water.It is powder that the electrolytic manganese dioxide piece is pulverized.In reach 3.14 with powder up to its JIS-pH value, the powder that water cleaning neutralized, drying obtains Powdered electrolytic manganese dioxide then.
The JIS-pH value confirms through the method for conventional measurement degree of neutralization, just according to the ammonium chloride method of JIS K1467, wherein the manganese dioxide of scheduled volume (10.0g) joined (50ml, NH in the chloride buffer solution of scheduled volume
4Cl 20g/100ml H
2O), 25 ℃ of pH values of measuring supernatant down.
Powdered electrolytic manganese dioxide is dissolved in the aqueous solution of hydrochloric acid and hydrogen peroxide, and passes through atomic absorption spectroscopy and measure the sulphate groups mass contg.Reach in the JIS-pH value that sulfate radical content is 1.18 weight % in the electrolytic manganese dioxides of measuring 3.14 backs.Reach in the JIS-pH value that sulfate radical content is 1.17 weight % in the electrolytic manganese dioxides of measuring 4.5 backs.Thereby surperficial sulfate radical content is 0.01 weight %.
5g is comprised the Powdered manganese dioxide of 85.8 weight %, and powder mixture compression molding under 2 tons molding pressure of the potassium hydroxide electrolyte of the 40 weight % of 7.3 weight % graphite and 6.9 weight % is the annular die product.Two moulded parts as cathode material, are assembled into zinc the dry cell of AA specification as anode material.Carry out the discharge test of battery through said method.Discharge time is 474.
Provided evaluation result in the table 1 to manganese dioxide performance and battery performance.Confirm AA specification dry cell performance after 20 hours 60 ℃ of held, do not find deterioration condition.
Through with the instance 1 described identical operation shape electrolytic manganese dioxide that makes powder, reach 1.56 to 3.44 scope with the Powdered electrolytic manganese dioxide of manufacturing up to the JIS-pH value in wherein, rather than 3.14.All other conditions keep identical.Evaluation result is shown in table 1.
Comparison example 1
Through with the instance 1 described identical operation shape electrolytic manganese dioxide that makes powder, reach 1.44 with the Powdered electrolytic manganese dioxide of manufacturing up to JIS-pH value in wherein, rather than 3.14, all other conditions maintenances are identical.Sulfate radical content is 1.28 weight % in the electrolytic manganese dioxide.Reach in the JIS-pH value that sulfate radical content is 1.16 weight % in the electrolytic manganese dioxides of measuring 4.5 backs.Thereby surperficial sulfate radical content is 0.12 weight %.Evaluation result is shown in table 1.
Comparison example 2
Through with the instance 1 described identical operation shape electrolytic manganese dioxide that makes powder, wherein neutralizing reaches 3.78 up to the JIS-pH value, rather than 3.14, all other conditions keep identical.The surface sulfate radical content is 0.00 weight %.Evaluation result is shown in table 1.
Table 1
| Surface sulfate radical content (weight %) | JIS-pH(-) | Discharge test *1 (number of times) | |
| Instance 1 |
0.01 0.09 0.07 0.08 0.05 0.02 | 3.14 2.10 1.56 1.76 2.26 3.44 | 474 462 463 427 445 428 |
| Comparison example 1 comparison example 2 | 0.12 0.00 | 1.44 3.78 | 395 360 |
*The period that 1AA specification dry cell discharges under the 1A pulse
Instance 7
Through with the instance 1 described identical operation shape electrolytic manganese dioxide that makes powder, wherein use the electrolytic manganese dioxide of pure water clean deposition, it is separated through compacting.Then the electrolytic manganese dioxide piece is pulverized for powder and through above-mentioned optical scatter counting device " Micro-trac particle size distribution measurement mechanism " and measured particle diameter.Clean and the resulting powder that neutralizes reaches 2.98 up to JIS-pH value, and the powder that the water cleaning neutralized carries out drying then, and obtain Powdered electrolytic manganese dioxide.
Powdered electrolytic manganese dioxide comprises the fine powder of the particle diameter of 13.8 quantity % less than 1 μ m.Median particle diameter is 45 μ m.
This Powdered electrolytic manganese dioxide is dissolved in the aqueous solution of hydrochloric acid and hydrogen peroxide, measures the sulphate groups mass contg through atomic absorption spectroscopy then.Reach in the JIS-pH value that sulfate radical content is 1.13 weight % in the electrolytic manganese dioxides of measuring 2.98 backs.Reach in the JIS-pH value that sulfate radical content is 1.11 weight % in the electrolytic manganese dioxides of measuring 4.5 backs.Thereby surperficial sulfate radical content is 0.02 weight %.Sodium content through with instance 1 described same procedure measurement is 1250ppm.
Powder mixture compression molding under 2.5 tons molding pressure of potassium hydroxide electrolyte that will comprise the 40 weight % of the Powdered electrolytic manganese dioxide of 10g, 0.7g graphite and 0.3g is spherical moulded parts (diameter 20mm).Through carrying out corrosion test with instance 1 described identical method.Corrosion rate is less than 0.01mm/y.
5g is comprised the Powdered manganese dioxide of 85.8 weight %, and powder mixture compression molding under 2 tons molding pressure of the potassium hydroxide electrolyte of the 40 weight % of 7.3 weight % graphite and 6.9 weight % is the annular die product.Use two moulded parts to process the dry cell of AA specification, through carrying out the battery discharge test with instance 1 described identical method as cathode material.Discharge time is 472.
Provided evaluation result in the table 2 to manganese dioxide performance and battery performance.Confirm AA specification dry cell performance after 20 hours 60 ℃ of held, do not find deterioration condition.
Instance 8 to 11
Through with the instance 7 described identical operations shape electrolytic manganese dioxide that makes powder, reach 1.69 to 2.76 scope with the Powdered electrolytic manganese dioxide of manufacturing up to the JIS-pH value in wherein, rather than 2.98.All other conditions keep identical.Evaluation result is shown in table 2.
Instance 12
Through with the instance 7 described identical operations shape electrolytic manganese dioxide that makes powder, reach 2.19 with the Powdered electrolytic manganese dioxide of manufacturing up to JIS-pH value in wherein, rather than 2.98, all other conditions maintenances are identical.The surface sulfate radical content is 0.04 weight %.Sodium content is 1500ppm.Powdered electrolytic manganese dioxide comprises the fine powder of the particle diameter of 2.8 quantity % less than 1 μ m.Median particle diameter is 70 μ m.
Powder mixture compression molding under 2.5 tons molding pressure of potassium hydroxide electrolyte that will comprise the 40 weight % of the Powdered electrolytic manganese dioxide of 10g, 0.7g graphite and 0.3g is spherical moulded parts (diameter 20mm).Through carrying out corrosion test with instance 7 described identical methods.Corrosion rate is less than 0.01mm/y.
5g is comprised the Powdered manganese dioxide of 85.8 weight %, and powder mixture compression molding under 2 tons molding pressure of the potassium hydroxide electrolyte of the 40 weight % of 7.3 weight % graphite and 6.9 weight % is the annular die product.Use two moulded parts to process the dry cell of AA specification, through carrying out the battery discharge test with instance 7 described identical methods as cathode material.Discharge time is 418.Evaluation result is shown in table 2.
Instance 13 to 16
Through with the instance 12 described identical operations shape electrolytic manganese dioxide that makes powder, reach 1.99 to 3.28 scope with the Powdered electrolytic manganese dioxide of manufacturing up to the JIS-pH value in wherein, rather than 2.19.All other conditions keep identical.Evaluation result is shown in table 2.
Comparison example 3
Through with the instance 12 described identical operations shape electrolytic manganese dioxide that makes powder, reach 3.55 with the Powdered electrolytic manganese dioxide of manufacturing up to JIS-pH value in wherein, rather than 2.19, all other conditions maintenances are identical.The surface sulfate radical content is 0.02 weight %.Sodium content is 2000ppm.Powdered electrolytic manganese dioxide comprises the fine powder of the particle diameter of 20.5 quantity % less than 1 μ m.Median particle diameter is 60 μ m.
Powder mixture compression molding under 2.5 tons molding pressure of potassium hydroxide electrolyte that will comprise the 40 weight % of the Powdered electrolytic manganese dioxide of 10g, 0.7g graphite and 0.3g is spherical moulded parts (diameter 20mm).Through carrying out corrosion test with instance 12 described identical methods.Corrosion rate is less than 0.01mm/y.
The powder mixture compression molding under 2 tons molding pressure of potassium hydroxide electrolyte that 5g is comprised the 40 weight % of the Powdered manganese dioxide of 85.8 weight %, 7.3 weight % graphite and 6.9 weight % is the annular die product.Use two moulded parts to process the dry cell of AA specification, through carrying out the battery discharge test with instance 12 described identical methods as cathode material.Discharge time is 392.Evaluation result is shown in table 2.
Comparison example 4
Through with the instance 12 described identical operations shape electrolytic manganese dioxide that makes powder, reach 3.52 with the Powdered electrolytic manganese dioxide of manufacturing up to JIS-pH value in wherein, rather than 2.19, all other conditions maintenances are identical.Evaluation result is shown in table 2.
Comparison example 5
Through with the instance 12 described identical operations shape electrolytic manganese dioxide that makes powder, reach 1.44 with the Powdered electrolytic manganese dioxide of manufacturing up to JIS-pH value in wherein, rather than 2.19, all other conditions maintenances are identical.The surface sulfate radical content is 0.10 weight %.Sodium content is 360ppm.Powdered electrolytic manganese dioxide comprises the fine powder of the particle diameter of 18.8 quantity % less than 1 μ m.Median particle diameter is 45 μ m.
Powder mixture compression molding under 2.5 tons molding pressure of potassium hydroxide electrolyte that will comprise the 40 weight % of the Powdered electrolytic manganese dioxide of 10g, 0.7g China ink and 0.3g is spherical moulded parts (diameter 20mm).Through carrying out corrosion test with instance 12 described identical methods.Corrosion rate is greater than 0.1mm/y.
5g is comprised the Powdered manganese dioxide of 85.8 weight %, and powder mixture compression molding under 2 tons molding pressure of the potassium hydroxide electrolyte of the 40 weight % of 7.3 weight % graphite and 6.9 weight % is the annular die product.Use two moulded parts to process the dry cell of AA specification, through carrying out the battery discharge test with instance 12 described identical methods as cathode material.Discharge time is 436.Evaluation result is shown in table 2.
Comparison example 6 and 7
Through with the instance 12 described identical operations shape electrolytic manganese dioxide that makes powder, reach 1.35 to 1.39 scope with the Powdered electrolytic manganese dioxide of manufacturing up to JIS-pH value in wherein, rather than 2.19, all other conditions maintenances are identical.Evaluation result is shown in table 2.
The median particle diameter (μ m) of the Powdered electrolytic manganese dioxide that is obtained by instance 7-16 and comparison example 3-7 ties up among Fig. 2 with the pass of sodium content (ppm) and shows.In Fig. 2, (1) to (15) refers to the data that obtained by following instance.
(1) instance 7 (6) instances 12 (11) comparison example 3
(2) instance 8 (7) instances 13 (12) comparison example 4
(3) instance 9 (8) instances 14 (13) comparison example 5
(4) instance 10 (9) instances 15 (14) comparison example 6
(5) instance 11 (10) instances 16 (15) comparison example 7
In Fig. 2, be clipped in line
aAnd line
bBetween regional A comprise the data that obtain by instance 7 to 11, wherein demonstrate fabulous two-forty performance down in 1A pulsed discharge test, have at least 425 period, and find to corrode.Be clipped in line
bAnd line
cBetween area B comprise the data that obtain by instance 12 to 16, wherein demonstrate good two-forty performance down in 1A pulsed discharge test, have at least 400 period, and find to corrode.Online
cOn zone C comprise the data that obtain by comparison example 3 and 4, wherein find corrosion, but the period of the two-forty performance that shows down in 1A pulsed discharge test is lower than 400.Online
aUnder region D comprise the data that obtain by comparison example 5-7, wherein demonstrate fabulous two-forty performance down in 1A pulsed discharge test, have at least 425 period, corrosion, corrosion rate＞0.1mm/y have still taken place.
Table 2
| Sodium content (ppm) | Surface sulfate radical content (weight %) | JIS-pH (-) | Fine grain amount *1 (％) | Median diameter (μ m) | Discharge test *2 (umber of pulses) | Corrosion rate (mm/ y) | |
| Instance 7 instances 8 |
1250 1800 740 1160 220 1500 440 1720 2000 1200 | 0.02 0.05 0.08 0.04 0.09 0.04 0.08 0.04 0.01 0.03 | 2.98 2.68 2.11 2.76 1.69 2.19 1.99 3.18 3.28 2.88 | 13.8 17.6 10.8 9.8 6.6 2.8 2.3 2.9 25.4 25.8 | 45 39 52 50 58 70 66 59 49 56 | 472 470 450 468 438 418 405 419 412 422 | ＜0.01 ＜0.01 ＜0.01 ＜0.01 ＜0.01 ＜0.01 ＜0.01 ＜0.01 ＜0.01 ＜0.01 |
| Comparison example 3 comparison example 4 comparison example 5 comparison example 6 comparison example 7 | 2000 1660 360 700 1450 | 0.02 0.05 0.10 0.14 0.09 | 3.55 3.52 1.44 1.35 1.39 | 20.5 25.3 18.8 19.9 23.8 | 60 70 45 43 32 | 392 345 436 438 442 | ＜0.01 ＜0.01 ＞0.1 ＞0.1 ＞0.1 |
*1 particle diameter is less than the fine grain amount of 1 μ m
*The period that 2AA specification dry cell discharges under the 1A pulse
Claims (9)
1. the electrolytic manganese dioxide of a fine particle form; It is characterized in that having less than the surperficial sulfate radical content of 0.10 weight % and according to JIS K1467 measure be at least 1.5 but less than 3.5 JIS-pH value, wherein said surperficial sulfate radical content is the amount that is present in the sulfate radical of electrolytic manganese dioxide particle surface.
2. electrolytic manganese dioxide according to claim 1, the JIS-pH value of wherein measuring according to JIS K1467 are at least 2.1 still less than 3.2.
3. electrolytic manganese dioxide according to claim 1, wherein the fine particle of 3 quantity % to 25 quantity % has the particle diameter that is not more than 1 μ m.
4. according to each described electrolytic manganese dioxide in the claim 1 to 3, sodium content X (ppm) in the wherein said electrolytic manganese dioxide and fine grain median particle diameter Y (μ m) have the relation that satisfies following formula (1):
-0.016X+56.8≤Y≤-0.04X+134 (1)
5. according to each described electrolytic manganese dioxide in the claim 1 to 3, sodium content X (ppm) in the wherein said electrolytic manganese dioxide and fine grain median particle diameter Y (μ m) have the relation that satisfies following formula (2):
-0.016X+56.8≤Y≤-0.016X+71.2 (2)
6. active material that is used for cell cathode; The electrolytic manganese dioxide that comprises the fine particle form; It is characterized in that having less than the surperficial sulfate radical content of 0.10 weight % and according to JIS K1467 measure be at least 1.5 but less than 3.5 JIS-pH value, wherein said surperficial sulfate radical content is the amount that is present in the sulfate radical of electrolytic manganese dioxide particle surface.
7. the active material that is used for cell cathode according to claim 6; When the battery to AA specification with negative electrode of being processed by said active material carries out the discharge test of the 1A pulse under the cut-ff voltage of time of repose and 0.9V of discharge time, 50 seconds at 10 seconds, show at least 400 times discharge time.
8. according to claim 6 or the 7 described active materials that are used for cell cathode; When the battery to AA specification with negative electrode of being processed by said active material carries out the discharge test of the 1A pulse under the cut-ff voltage of time of repose and 0.9V of discharge time, 50 seconds at 10 seconds, show at least 425 times discharge time.
9. battery with negative electrode; Wherein said negative electrode comprises the active material that is used for cell cathode; This active material comprises the electrolytic manganese dioxide of fine particle form; It is characterized in that having less than the surperficial sulfate radical content of 0.10 weight % and according to JIS K1467 measure be at least 1.5 but less than 3.5 JIS-pH value, wherein said surperficial sulfate radical content is the amount that is present in the sulfate radical of electrolytic manganese dioxide particle surface.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP158283/2006 | 2006-06-07 | ||
| JP2006158283 | 2006-06-07 | ||
| JP2006324908A JP4888088B2 (en) | 2006-06-07 | 2006-11-30 | Electrolytic manganese dioxide |
| JP324908/2006 | 2006-11-30 |
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| CN101110476A CN101110476A (en) | 2008-01-23 |
| CN101110476B true CN101110476B (en) | 2012-04-11 |
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| KR20130096754A (en) | 2011-02-18 | 2013-08-30 | 도소 가부시키가이샤 | Electrolytic manganese dioxide and method for producing same, and method for producing lithium-manganese complex oxide |
| WO2017087404A1 (en) * | 2015-11-16 | 2017-05-26 | HHeLI, LLC | Synthesized surface-functionalized, acidified metal oxide materials for energy storage, catalytic, photovoltaic, and sensor applications |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| EP0782972A2 (en) * | 1996-01-08 | 1997-07-09 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic manganese dioxide, process for preparing the same, and manganese dry cell |
| CN1290657A (en) * | 1999-09-30 | 2001-04-11 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
-
2007
- 2007-06-07 CN CN2007101388086A patent/CN101110476B/en active Active
- 2007-07-02 ZA ZA200705037A patent/ZA200705037B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| EP0782972A2 (en) * | 1996-01-08 | 1997-07-09 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic manganese dioxide, process for preparing the same, and manganese dry cell |
| CN1290657A (en) * | 1999-09-30 | 2001-04-11 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
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| CN101110476A (en) | 2008-01-23 |
| ZA200705037B (en) | 2008-05-28 |
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