CN101898796A - High-proportion manganous-manganic oxide and preparation method thereof - Google Patents
High-proportion manganous-manganic oxide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an oxide of manganese and a preparation method thereof, in particular to a high-proportion manganous-manganic oxide and a preparation method thereof. The tap density of the high-proportion manganous-manganic oxide is at least 1.8g/cm<3>, and the specific surface area thereof is 1.5m<2>/g-3.0m<2>/g. The preparation method comprises the following steps of: directly introducing air into a manganese sulfate solution for oxidation, wherein the air flow is controlled to be 800L/h-2500L/h, the oxidation temperature is controlled to be 50-80 DEG C, and the stirring strength in the oxidation process is 75r/min-200r/min; dropwise adding ammonia water in the oxidation process so as to neutralize H<+> generated by oxidization reaction to make the pH value of a reaction system controlled to be 4.5-8.0; repeatedly rinsing manganous-manganic oxide slurry obtained after the reaction is completely ended by using pure water and then drying to obtain the high-proportion manganous-manganic oxide. The high-proportion manganous-manganic oxide not only has higher tap density, smaller specific surface area and even particle size distribution but also has low impurity content and low preparation cost.
Description
Technical field
The present invention relates to compound of a kind of manganese and preparation method thereof, relate in particular to oxide compound of a kind of manganese and preparation method thereof.
Background technology
In recent years, along with of the direction fast development of electronic products such as AV machine, notebook computer towards portability, wireless penetration, this series products is also more and more higher to driving with the requirement of power supply, and legerity type and demand with secondary cell of high-energy-density are also increased thereupon.Meanwhile, people also come to realise low-carbon economy, recycling economy enthusiasm and the importance to the whole ecological environment, pollution-free industries such as the new-energy automobile that arises at the historic moment also begin to be encouraged and praise highly, and the redundant electrical power of new-energy automobile (especially power truck, hybrid vehicle, fuel cell are from motor-car etc.) is the demand rich and influential family of medium-and-large-sized battery.Based on this kind situation, the lithium-ion secondary cell with advantages such as charging/discharging voltage height, charging/discharging voltage are big begins more and more to be subjected to people's attention.Lithium manganate having spinel structure particle powder as one of positive active material in the lithium-ion secondary cell (basic composition is LiMn
2O
4), also begin fast sale gradually with its unique advantage such as abundance, cost is low, safety performance is good of originating, to the also intensification gradually of correlative study of lithium manganate particle powder.
The preparation of existing lithium manganate particle powder mainly is to use manganic compound and lithium compound as raw material and with specific mixed, fires then to form in 500 ℃～1000 ℃ temperature range.Yet, when the lithium manganate particle powder uses as the positive electrode material of lithium-ion secondary cell,, have the unfavorable problem of charge-discharge performance though have the advantage of high-voltage and high-energy-density.Because in discharging and recharging, the stripping that is accompanied by the Mn in the crystal structure causes crumbling of structure, and the component characteristic of lithium manganate has determined the heterogeneity meeting of its composition to cause the structure deterioration.Therefore, the present most important requirement of lithium-ion secondary cell made from the lithium manganate particle powder is exactly the deterioration problem that overcomes charge/discharge capacity after the repeated charge, improves its charge.In order to improve charge, the positive electrode active material that is made of the lithium manganate particle powder should have the size of good filling property and appropriateness, and its basic means has particle diameter and size-grade distribution, the adjusting firing temperature of regulating the lithium manganate particle, adds the xenogenesis element to strengthen the crystalline bonding force and to carry out the methods such as stripping that surface treatment suppresses Mn.
As the main raw material(s) of preparation anode materials for lithium secondary cells lithium manganate, every indexs such as the tap density of trimanganese tetroxide, specific surface area, foreign matter content all will influence the performance of derived product manganate cathode material for lithium.The main method of preparation trimanganese tetroxide is an electrolytic metal manganese powder suspension catalytic oxidation at present, this method method technical maturity, but production cost is higher.Also had in recent years and begin to prepare trimanganese tetroxide with the hydrolyzate oxidation of manganese sulfate solution in alkaline medium, this method is because of preparing without the electrolysis direct oxidation, make the technology cost lower significantly, at home and abroad once came into one's own, but the trimanganese tetroxide specific surface area with the hydrolyzate direct oxidation of manganese preparation is bigger, tap density is difficult to be improved, and easily generates alkali formula manganous sulfate, and oxidization time is also longer relatively.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of tap density is higher, specific surface area is littler, even particle size distribution and the low high-proportion manganous-manganic oxide of foreign matter content, provide also that a kind of cost is low, energy consumption is little, technology is simple, the preparation method of the high-proportion manganous-manganic oxide of good product quality.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of high-proportion manganous-manganic oxide, and the tap density of described high-proportion manganous-manganic oxide is at 1.8g/cm
3More than, its specific surface area is 1.5m
2/ g～3.0m
2/ g.Compare with the trimanganese tetroxide product that the hydrolyzate of existing manganese oxide prepares, the maximum characteristics of high-proportion manganous-manganic oxide of the present invention are that its tap density improves, and the specific surface area of its product pellet reduces, and can be applied to battery material better.
In the technique scheme, described high-proportion manganous-manganic oxide is one-time formed powder particle, and its meta particle diameter is preferably 6 μ m～15 μ m.
In the technique scheme, the Mn content in the described high-proportion manganous-manganic oxide is preferably greater than 70.5%, and S content is preferably less than 0.15%, and various metals content impurities are all preferably below 50ppm.Described metallic impurity preferably include one or more among K, Na, Ca, Mg, Fe, Zn, Cu, the Pb.As further improvement, the content of described metallic impurity Cu, Pb is all below 10ppm.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned high-proportion manganous-manganic oxide, its operation steps is: direct blowing air carries out oxidation in manganese sulfate solution earlier, air flow control is at 800L/h～2500L/h, oxidizing temperature is controlled at 50 ℃～80 ℃, and the stirring intensity in the oxidising process is 75r/min～200r/min; In the oxidising process dropping ammonia with in and the H that produces of oxidizing reaction
+, (according to thermodynamic data, this pH value span of control can make the Mn in the reaction system to make the pH value of reaction system be controlled at 4.5～8.0
2+Be oxidized to Mn
3O
4); The trimanganese tetroxide slip of the back gained that reacts completely (is cleaned free SO in the trimanganese tetroxide slip with pure water rinsing repeatedly
4 2-), drying makes high-proportion manganous-manganic oxide.In oxidising process, Mn ionic concn in the reaction system constantly reduces, can add a certain amount of manganese sulfate solution as required, treat that the trimanganese tetroxide Mn content that generates in the oxidation system reaches 70.5% after, continue insulation reaction 0.5h～2h and promptly obtain described trimanganese tetroxide slip.
The method of the invention described above can abbreviate the direct air blast oxidation of air manganese sulfate solution method as, and this method is by the Mn in the direct oxidation manganese sulfate solution
2+, and air flow quantity is regulated in optimization and stirring velocity is controlled the formation speed of trimanganese tetroxide particle, aforementioned tap density is big, the high-proportion manganous-manganic oxide of even particle size distribution thereby make.
Among the preparation method of above-mentioned high-proportion manganous-manganic oxide, Mn in the described manganese sulfate solution
2+Starting point concentration be preferably 50g/L～120g/L, the concentration of described ammoniacal liquor is preferably 0.03mol/L～0.15mol/L.
Among the preparation method of above-mentioned high-proportion manganous-manganic oxide, described reaction is finished the required time and is preferably 8h～30h.
Processing parameters such as above-mentioned preferred material concentration, oxidization time all have active influence to the performance of trimanganese tetroxide product.
Compared with prior art, the invention has the advantages that: the present invention obtains the trimanganese tetroxide particle of high tap density by direct air blast oxidation manganese sulfate solution method, greatly reduce the content of the specific surface area of trimanganese tetroxide and the foreign matter content in the trimanganese tetroxide, particularly calcium, magnesium; And high-proportion manganous-manganic oxide size distribution of the present invention is even, and preferred meta particle diameter is at 6 μ m～15 μ m, and the complete in crystal formation of product trimanganese tetroxide.In addition, by prepared high-proportion manganous-manganic oxide of the present invention, not only the technology cost is low, energy consumption is little, and product lacks than great, impurity, excellent performance, and this has crucial meaning to the performance of improving the derived product manganate cathode material for lithium.
Description of drawings
The X-Ray diffractogram of the high-proportion manganous-manganic oxide that Fig. 1 makes for the embodiment of the invention 1;
The particle size distribution figure of the high-proportion manganous-manganic oxide that Fig. 2 makes for the embodiment of the invention 1.
The X-Ray diffractogram of the high-proportion manganous-manganic oxide that Fig. 3 makes for the embodiment of the invention 2;
The particle size distribution figure of the high-proportion manganous-manganic oxide that Fig. 4 makes for the embodiment of the invention 2.
The X-Ray diffractogram of the high-proportion manganous-manganic oxide that Fig. 5 makes for the embodiment of the invention 3;
The particle size distribution figure of the high-proportion manganous-manganic oxide that Fig. 6 makes for the embodiment of the invention 3.
Fig. 7 is the X-Ray diffractogram of the trimanganese tetroxide that Comparative Examples makes in the specific embodiment of the invention;
Fig. 8 is the particle size distribution figure of the trimanganese tetroxide that Comparative Examples makes in the specific embodiment of the invention.
Embodiment
Below by specific embodiment the present invention is further described, but therefore do not limit protection scope of the present invention.
A kind of as Fig. 1～high-proportion manganous-manganic oxide of the present invention shown in Figure 2, the tap density of this high-proportion manganous-manganic oxide is 2.25g/cm
3, specific surface area is 1.9419m
2/ g, meta particle diameter are 8.42 μ m.
The high-proportion manganous-manganic oxide of present embodiment is to adopt following method preparation and get:
Prepare Mn at first, respectively
2+Concentration is the manganese sulfate solution of 60g/L, 50g/L, earlier to 5L Mn
2+Starting point concentration be in the manganese sulfate solution of 60g/L directly blowing air carry out oxidation, oxidizing temperature is controlled at 55 ℃, air flow control is at 900L/h～1200L/h, initial pH value is 6.5, stirring intensity is 75r/min; Along with Mn in the reaction system
2+Mn is slowly added in the slow reduction of concentration again
2+Concentration is the manganese sulfate solution of 50g/L, and slow dropping ammonia, makes the slowly increase of pH value of reaction system, and is controlled in 6.5～8.0 the scope; After the manganese sulfate solution for the treatment of 3L, 50g/L is added and finished, continue insulation reaction 1h, the pH value that makes the reaction system terminal point is 7.5, wherein Mn
2+Concentration be 3.2g/L, this reaction process is 18h consuming time altogether, the trimanganese tetroxide slurry that reaction is obtained with pure water repeatedly rinsing to remove free SO
4 2-, filter, dry the finished product trimanganese tetroxide.
The crystalline structure of the finished product that present embodiment is made with the XRD diffractometer characterizes, and with particle size analyzer the finished product of present embodiment is carried out sreen analysis simultaneously, and analytical results respectively as shown in Figure 1 and Figure 2.By Fig. 1, Fig. 2 as seen, the product that present embodiment makes is pure trimanganese tetroxide, and the meta particle diameter is 8.42 μ m.With the proportion instrument this trimanganese tetroxide is carried out than re-detection, its tap density is 2.25g/cm
3It is carried out the element total analysis, the Mn content of this trimanganese tetroxide is 70.76%, and S content is 0.13%, and other elements K, Na, Ca, Mg, Fe, Zn, Cu, Pb content are respectively 8.2ppm, 5.3ppm, 38ppm, 50ppm, 42ppm, 41ppm, 10ppm, 7.5ppm.
A kind of as Fig. 3～high-proportion manganous-manganic oxide of the present invention shown in Figure 4, the tap density of this high-proportion manganous-manganic oxide is 2.10g/cm
3, specific surface area is 2.3276m
2/ g, meta particle diameter are 7.21 μ m.
The high-proportion manganous-manganic oxide of present embodiment is to adopt following method preparation and get:
At first, preparation Mn
2+Concentration is the manganese sulfate solution of 50g/L, to 5L, Mn
2+Starting point concentration be in the manganese sulfate solution of 50g/L directly blowing air carry out oxidation, oxidizing temperature is controlled at 70 ℃, air flow control is at 800L/h～1000L/h, initial pH value is 6.0, stirring intensity is 85r/min; Along with Mn in the reaction system
2+The slow reduction of concentration, slow dropping ammonia makes the slowly increase of pH value of reaction system again, and is controlled in 6.5～7.5 the scope; Mn in reaction system
2+Change in concentration stop dropping ammonia when very little, continue insulation reaction 2h, the pH value that makes the reaction system terminal point is 7.5, wherein Mn
2+Concentration be 2.8g/L, this reaction process is 14h consuming time altogether, the trimanganese tetroxide slurry that reaction is obtained with pure water repeatedly rinsing to remove free SO
4 2-, filter, dry the finished product trimanganese tetroxide.
The crystalline structure of the finished product that present embodiment is made with the XRD diffractometer characterizes, and with particle size analyzer the finished product of present embodiment is carried out sreen analysis simultaneously, and analytical results respectively as shown in Figure 3, Figure 4.By Fig. 3, Fig. 4 as seen, the product that present embodiment makes is pure trimanganese tetroxide, and the meta particle diameter is 7.21 μ m.With the proportion instrument this trimanganese tetroxide is carried out than re-detection, its tap density is 2.10g/cm
3It is carried out the element total analysis, the Mn content of this trimanganese tetroxide is 70.63%, and S content is 0.09%, and other elements K, Na, Ca, Mg, Fe, Zn, Cu, Pb content are respectively 10.4ppm, 7.8ppm, 40ppm, 12ppm, 37ppm, 43ppm, 8ppm, 7ppm.
A kind of as Fig. 5～high-proportion manganous-manganic oxide of the present invention shown in Figure 6, the tap density of this high-proportion manganous-manganic oxide is 1.95g/cm
3, specific surface area is 2.9015m
2/ g, meta particle diameter are 10.72 μ m.
The high-proportion manganous-manganic oxide of present embodiment is to adopt following method preparation and get:
At first, preparation 5L, Mn
2+Concentration is the manganese sulfate solution of 80g/L, to Mn
2+Starting point concentration be in the manganese sulfate solution of 80g/L directly blowing air carry out oxidation, oxidizing temperature is controlled at 80 ℃, air flow control is at 800L/h～1000L/h, initial pH value is 5.5, stirring intensity is 85r/min; Along with Mn in the reaction system
2+The slow reduction of concentration, slow dropping ammonia makes the slowly increase of pH value of reaction system again, and is controlled in 6.0～7.0 the scope; Mn in reaction system
2+Change in concentration stop dropping ammonia when very little, continue insulation reaction 2h, the pH value that makes the reaction system terminal point is 7.0, wherein Mn
2+Concentration be 4.1g/L, this reaction process is 12h consuming time altogether, the trimanganese tetroxide slurry that reaction is obtained with pure water repeatedly rinsing to remove free SO
4 2-, filter, dry the finished product trimanganese tetroxide.
The crystalline structure of the finished product that present embodiment is made with the XRD diffractometer characterizes, and with particle size analyzer the finished product of present embodiment is carried out sreen analysis simultaneously, and analytical results is respectively as Fig. 5, shown in Figure 6.By Fig. 5, Fig. 6 as seen, the product that present embodiment makes is pure trimanganese tetroxide, and the meta particle diameter is 10.72 μ m.With the proportion instrument this trimanganese tetroxide is carried out than re-detection, its tap density is 1.95g/cm
3It is carried out the element total analysis, the Mn content of this trimanganese tetroxide is 70.52%, and S content is 0.14%, and other elements K, Na, Ca, Mg, Fe, Zn, Cu, Pb content are respectively 9.5ppm, 4.4ppm, 45ppm, 8.7ppm, 41ppm, 49ppm, 9ppm, 6ppm.
Comparative Examples
A kind of as Fig. 7～trimanganese tetroxide shown in Figure 8, the tap density of this trimanganese tetroxide is 1.35g/cm
3, specific surface area is 9.4532m
2/ g, meta particle diameter are 1.38 μ m.
The trimanganese tetroxide of this Comparative Examples is to adopt following method preparation and get:
At first, preparation Mn
2+Concentration is the manganese sulfate solution of 50g/L, dropping ammonia neutralizes to it in this solution, the neutralization reaction temperature is 40 ℃, the pH value of neutralization reaction terminal point is 9.5～10.0, in and the time stirring intensity be 85r/min, after neutralization reaction is finished the manganous hydroxide suspension liquid, be air blast oxidation 18h under the 85r/min condition with the manganous hydroxide suspension liquid at 75 ℃ of temperature, stirring intensity again, the endpoint pH of oxidizing reaction system is 5.5, Mn in the solution
2+Concentration be 4.3g/L.The trimanganese tetroxide slurry that oxidizing reaction is made with pure water repeatedly rinsing to remove free SO
4 2-, filter, obtain the finished product trimanganese tetroxide after the oven dry.
The crystalline structure of the finished product that present embodiment is made with the XRD diffractometer characterizes, and with particle size analyzer the finished product of present embodiment is carried out sreen analysis simultaneously, and analytical results is respectively as Fig. 7, shown in Figure 8.By Fig. 7, Fig. 8 as seen, the product that present embodiment makes is pure trimanganese tetroxide, and the meta particle diameter is 1.38 μ m.With the proportion instrument this trimanganese tetroxide is carried out than re-detection, its tap density is 1.35g/cm
3It is carried out the element total analysis, and the Mn content of this trimanganese tetroxide is 70.05%, SO
4 2-Content is 0.73%, and other elements K, Na, Ca, Mg, Fe, Zn, Cu, Pb content are respectively: 35ppm, 23ppm, 228ppm, 86ppm, 109ppm, 45ppm, 21ppm, 20ppm.
Therefore, the trimanganese tetroxide that the processing method in the Comparative Examples makes, not only tap density is little, specific surface area big, the meta particle diameter is little, and the content of other foreign metals is higher relatively in the finished product, and its product quality obviously is inferior to product of the present invention.
Claims (8)
1. high-proportion manganous-manganic oxide, it is characterized in that: the tap density of described high-proportion manganous-manganic oxide is at 1.8g/cm
3More than, its specific surface area is 1.5m
2/ g～3.0m
2/ g.
2. high-proportion manganous-manganic oxide according to claim 1 is characterized in that: the meta particle diameter of described high-proportion manganous-manganic oxide is 6 μ m～15 μ m.
3. high-proportion manganous-manganic oxide according to claim 1 and 2 is characterized in that: the Mn content in the described high-proportion manganous-manganic oxide is greater than 70.5%, and S content is less than 0.15%, and various metals content impurities are all below 50ppm.
4. high-proportion manganous-manganic oxide according to claim 3 is characterized in that: described metallic impurity comprise one or more among K, Na, Ca, Mg, Fe, Zn, Cu, the Pb.
5. high-proportion manganous-manganic oxide according to claim 4 is characterized in that: the content of described metallic impurity Cu, Pb is all below 10ppm.
6. preparation method as each described high-proportion manganous-manganic oxide in the claim 1～5, its operation steps is: directly blowing air carries out oxidation in manganese sulfate solution, air flow control is at 800L/h～2500L/h, oxidizing temperature is controlled at 50 ℃～80 ℃, and the stirring intensity in the oxidising process is 75r/min～200r/min; In the oxidising process dropping ammonia with in and the H that produces of oxidizing reaction
+, make the pH value of reaction system be controlled at 4.5～8.0; With pure water rinsing repeatedly, drying makes high-proportion manganous-manganic oxide with the trimanganese tetroxide slip that obtains after reacting completely.
7. the preparation method of high-proportion manganous-manganic oxide according to claim 6 is characterized in that: Mn in the described manganese sulfate solution
2+Starting point concentration be 50g/L～120g/L, the concentration of described ammoniacal liquor is 0.03mol/L～0.15mol/L.
8. according to the preparation method of claim 6 or 7 described high-proportion manganous-manganic oxides, it is characterized in that: it is 8h～30h that the required time is finished in described reaction.
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