CN105417585A - Preparation method of heavy manganous manganic oxide - Google Patents
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Abstract
The invention discloses a preparation method of heavy manganous manganic oxide. The preparation method includes the steps of precipitating a manganese salt solution to generate solid manganese oxalate with a sodium oxalate solution, and dropwisely adding a sodium hydroxide solution to the manganese oxalate slurry to convert the manganese oxalate into manganese hydroxide with pH value of the reaction system controlled to be 6.5-7.5, and meanwhile feeding air to oxidize the manganese hydroxide into the heavy manganous manganic oxide. Reaction equations are: Mn<2+> + Na2C2O4 = MnC2O4 + 2Na<+>, MnC2O4 + 2NaOH = Mn(OH)2 + Na2C2O4, and 6Mn(OH)2 + O2 = 2Mn3O4 + 6H2O. The preparation method is simple in process, is environment-friendly and is easy to carry out, is free of generation of basic salts or other manganese oxides and overcomes a difficult problem that pH value is difficult to control during preparation of the heavy manganous manganic oxide through oxidization of manganese salts in the prior art. Speeds of generating the manganese hydroxide and oxidizing the manganese hydroxide into the manganous manganic oxide are low, which are beneficial to growth of crystals of manganous manganic oxide. The heavy manganous manganic oxide is low in sulfur content, is 5-6 [mu]m in average particle size, is higher than 2.0 g/cm<3> in tap density, is higher than 71.5% in manganese content and is lower than 0.02% in sulfate content, and completely satisfies requirements in preparation of a lithium ion cell anode material lithium manganate having high-rate charge/discharge performance.
Description
Technical field
The present invention relates to a kind of preparation method of heavy trimanganese tetroxide, in particular for preparing the preparation method of the heavy trimanganese tetroxide of anode material of lithium battery lithium manganate.
Background technology
Mn
3o
4be a kind of stable Mn oxide, mainly for the preparation of MnZn iron soft magnetic materials, be widely used in the manufacture of various electronic component, be the base mateiral of the industries such as electromechanics, electronics, information, be widely used in electromagnetism storing unit.Trimanganese tetroxide is also a kind of important source material of synthetic lithium manganate, due to Mn
3o
4have and LiMn
2o
4identical spinel structure, adopts Mn
3o
4as presoma sintering preparation LiMn
2o
4the time of crystal conversion can be reduced, greatly shorten the time of solid state sintering.The lithium manganate trimanganese tetroxide huge market demand, application prospect is wide, is just day by day subject to people and payes attention to.
The method of producing trimanganese tetroxide has the method such as manganese salt or Mn oxide high-temperature decomposition, manganese powder air oxidation process, manganese salt wet oxidation.Manganese salt or Mn oxide pyrolytic decomposition directly prepare Mn
3o
4, has that with low cost, high-temperature calcination technique is simple, process is easy to the advantage that controls, but when lithium manganate prepared by the trimanganese tetroxide that high-temperature calcination obtains, product capacity is low and cycle performance is not good, is not suitable for the production of anode material of lithium battery lithium manganate.Electrolytic metal manganese powder suspension oxidation style take electrolytic metal Mn as raw material, making suspension, utilizing air or oxygen for oxygenant, under certain temperature and additive concentration, preparing trimanganese tetroxide by being pulverized by manganese sheet.With the manganese powder trimanganese tetroxide that atmospheric oxidation is produced under ammonia condition, its microscopic appearance is cotton-shaped, and bulk specific gravity is little, and tap density is about 1.2g/cm
3, foreign matter content is high, can not meet the requirement that anode material of lithium battery lithium manganate is produced.
Manganese salt wet oxidation method prepares trimanganese tetroxide development a kind of method faster at present, namely in manganese sulfate solution, adds alkaline matter, manganese salt is converted into manganous hydroxide (Mn (OH)
2), then carry out manganous hydroxide in oxidizing solution with oxygenant, oxygen or air, with obtained trimanganese tetroxide.Publication number CN101948138A, CN103570072A, CN101898797A, CN103739018A, it is raw material that the Chinese invention patent of CN101066780A describes with manganous sulfate, with sodium hydroxide, potassium hydroxide or ammoniacal liquor are that presoma manganous hydroxide prepared by precipitation agent, use air again, oxygen or hydrogen peroxide oxidation prepare trimanganese tetroxide, The method avoids the generation of alkali formula manganous sulfate, the trimanganese tetroxide sulphur content of preparation is low, but because of the oxidized speed of manganous hydroxide quickly, nucleus formation speed is much larger than crystalline growth velocity, therefore be difficult to generate hyperbaric trimanganese tetroxide product (being usually also called heavy trimanganese tetroxide).The Chinese patent of publication number CN102491422A, CN102730762A discloses free Mn
2+the method of trimanganese tetroxide is prepared through air or oxygen oxidation, the method flow process is short, hyperbaric trimanganese tetroxide can be prepared, but need in oxidising process, manganese salt and alkali lye to be added simultaneously, and strict feed rate and the ratio controlling manganese salt and alkali lye, guarantee that the pH value of solution is between 6 ~ 8, general use ammoniacal liquor is as pH buffer reagent, this method is technological operation difficulty not only, ammoniacal liquor volatilization also makes operating environment worsen, if operation is not tight, then easily generate alkali formula manganous sulfate or other Mn oxide, form mixed crystal, reduce Mn
3o
4quality, be difficult to meet the requirement that anode material of lithium battery lithium manganate is produced.
Summary of the invention
The object of this invention is to provide the preparation method of heavy trimanganese tetroxide, be first with water by solubility manganous salt dissolve be mixed with manganese salt solution, by sodium oxalate dissolve be mixed with sodium oxalate solution, by sodium hydroxide dissolve be mixed with sodium hydroxide solution.Then manganese salt solution and sodium oxalate solution carry out precipitin reaction and generate solid oxalic acid manganese, after filtration, with water, solid oxalic acid manganese is deployed into manganous oxalate slurries after washing, then in manganous oxalate slurries, slowly drip sodium hydroxide solution makes manganous oxalate change into manganous hydroxide, the pH value controlling reaction system is 6.5 ~ 7.5, while dropping sodium hydroxide solution, pass into air carry out oxidizing reaction, manganous hydroxide is oxidized to heavy trimanganese tetroxide.Filtration after oxidizing reaction completes, washing, drying, namely obtain heavy trimanganese tetroxide product.Chemical equation is:
Mn
2++Na
2C
2O
4=MnC
2O
4+2Na
+
MnC
2O
4+2NaOH=Mn(OH)
2+Na
2C
2O
4
6Mn(OH)
2+O
2=2Mn
3O
4+6H
2O
The present invention prepares the method for heavy trimanganese tetroxide, comprises the steps:
Step one: by solubility manganous salt pure water or deionized water dissolving, is mixed with the manganese salt solution of 0.5 ~ 2mol/L; Sodium oxalate pure water or deionized water dissolving are mixed with the sodium oxalate solution of 0.2 ~ 0.4mol/L; Sodium hydroxide pure water or deionized water dissolving are mixed with the sodium hydroxide solution of 0.5 ~ 5mol/L;
Step 2: manganese salt solution step one obtained joins in sodium oxalate solution, the ratio being 1: 1 in the mol ratio of mn ion and sodium oxalate feeds intake and carries out precipitin reaction, controlling temperature of reaction is 40 DEG C ~ 90 DEG C, manganese salt solution feed time 10 ~ 120min, add the rear insulation reaction 30 ~ 60min of material, react rear filtration, washing, obtain solid oxalic acid manganese;
Step 3: to step 2 gained solid oxalic acid manganese pure water or deionized water furnishing slurries, the quality liquid-solid ratio of solid oxalic acid manganese and water is 5 ~ 10:1.In manganous oxalate slurries, slowly add the sodium hydroxide solution that step (1) prepares under agitation continuously, make manganous oxalate change into manganous hydroxide.The sodium oxalate solution of manganous oxalate and sodium hydroxide reaction by-product can recycle.
The molar ratio of sodium hydroxide and manganous oxalate is 2: 1.The pH value controlling reaction system is 6.5 ~ 7.5.Sodium hydroxide solution charging reaction time 20 ~ 40h, temperature of reaction 30 DEG C ~ 90 DEG C.While dropping sodium hydroxide solution, pass into air carry out oxidizing reaction, manganous hydroxide is oxidized to heavy trimanganese tetroxide.Air flow quantity is 0.1 ~ 0.5M
3/ h.Material all adds rear continuation reaction 3 ~ 6h.Filtration after oxidizing reaction completes, washing, drying, namely obtain heavy trimanganese tetroxide product.The heavy trimanganese tetroxide product median size obtained is 5 ~ 6 μm, and tap density is greater than 2.0g/cm
3, Mn content is greater than 71.5%, and sulfate radical content is less than 0.02%.
Solubility manganous salt described in the present invention is any one in manganous sulfate or manganous nitrate, Manganous chloride tetrahydrate; Sodium oxalate is the industrial ethanedioic acid sodium of main content 99.5% or the by-product sodium oxalate solution of step 3; Sodium hydroxide is the industrial solid sodium hydroxide of main content 96% or the industrial liquid sodium hydroxide of main content 30%.
Production technique of the present invention is simple, environmental friendliness, easy handling, by controlling sodium hydroxide solution rate of addition, the pH of reaction system is easy to control 6.5 ~ 7.5, do not have subsalt or the generation of other Mn oxide, overcome prior art manganese salt and be oxidized the difficult problem that when preparing heavy trimanganese tetroxide, pH cannot accurately control.The generation of manganous hydroxide and to be oxidized to the speed of trimanganese tetroxide very slow, be conducive to growing up of trimanganese tetroxide crystal, the heavy trimanganese tetroxide sulphur content of production is low, and median size is 5 ~ 6 μm, and product tap density is greater than 2.0g/cm
3, Mn content is greater than 71.5%, and sulfate radical content is less than 0.02%, meets the requirement preparing the lithium cell anode material lithium manganate of high-rate charge-discharge capability completely.
Embodiment 1
Manganous sulfate is dissolved in pure water or deionized water is mixed with the manganese sulfate solution that 2L concentration is 0.5mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 2.5L concentration is 0.4mol/L, under agitation manganese sulfate solution is joined in sodium oxalate solution, keep temperature of reaction 80 DEG C, feed time 60min, add the follow-up continuous insulation reaction 30min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 6:1, slowly adds the sodium hydroxide solution that 2L concentration is 1mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.3M simultaneously
3/ h, charging reaction time 25h, temperature of reaction 70 DEG C, continues reaction 4h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.8 μm, product tap density 2.15g/cm after adding material
3, Mn content 71.56%, sulfate radical content 0.018%.
Embodiment 2
Manganous chloride tetrahydrate is dissolved in pure water or deionized water is mixed with the manganese chloride solution that 1L concentration is 1mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 4L concentration is 0.25mol/L, under agitation manganese chloride solution is joined in sodium oxalate solution, keep temperature of reaction 60 DEG C, feed time 100min, add the follow-up continuous insulation reaction 40min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 7:1, slowly adds the sodium hydroxide solution that 0.5L concentration is 4mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.1M simultaneously
3/ h, charging reaction time 30h, temperature of reaction 30 DEG C, continues reaction 5h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.03 μm, product tap density 2.08g/cm after adding material
3, Mn content 71.60%, sulfate radical content 0.007%.
Embodiment 3
Manganous nitrate is dissolved in pure water or deionized water is mixed with the manganese nitrate solution that 0.5L concentration is 2mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 4L concentration is 0.25mol/L, under agitation manganese nitrate solution is joined in sodium oxalate solution, keep temperature of reaction 65 DEG C, feed time 50min, add the follow-up continuous insulation reaction 30min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 5:1, slowly adds the sodium hydroxide solution that 4L concentration is 0.5mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.15M simultaneously
3/ h, charging reaction time 35h, temperature of reaction 35 DEG C, continues reaction 3h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.47 μm, product tap density 2.17g/cm after adding material
3, Mn content 71.62%, sulfate radical content 0.006%.
Embodiment 4
Manganous chloride tetrahydrate is dissolved in pure water or deionized water is mixed with the manganese chloride solution that 1L concentration is 1mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 2.5L concentration is 0.4mol/L, under agitation manganese chloride solution is joined in sodium oxalate solution, keep temperature of reaction 90 DEG C, feed time 10min, add the follow-up continuous insulation reaction 60min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 10:1, slowly adds the sodium hydroxide solution that 0.67L concentration is 3mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.2M simultaneously
3/ h, charging reaction time 40h, temperature of reaction 40 DEG C, continues reaction 5h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 6.0 μm, product tap density 2.21g/cm after adding material
3, Mn content 71.66%, sulfate radical content 0.009%.
Embodiment 5
Manganous sulfate is dissolved in pure water or deionized water is mixed with the manganese sulfate solution that 0.67L concentration is 1.5mol/L, gained sodium oxalate pure water will be reacted or deionized water is mixed with the sodium oxalate solution that 5L concentration is 0.2mol/L in embodiment 4, under agitation manganese sulfate solution is joined in sodium oxalate solution, keep temperature of reaction 40 DEG C, feed time 30min, add the follow-up continuous insulation reaction 50min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 8:1, slowly adds the sodium hydroxide solution that 1L concentration is 2mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.4M simultaneously
3/ h, charging reaction time 40h, temperature of reaction 90 DEG C, continues reaction 4h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.51 μm, product tap density 2.09g/cm after adding material
3, Mn content 71.81%, sulfate radical content 0.018%.
Embodiment 6
Manganous sulfate is dissolved in pure water or deionized water is mixed with the manganese sulfate solution that 1.33L concentration is 0.75mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 3.33L concentration is 0.33mol/L, under agitation manganese sulfate solution is joined in sodium oxalate solution, keep temperature of reaction 80 DEG C, feed time 120min, add the follow-up continuous insulation reaction 40min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 6:1, slowly adds the sodium hydroxide solution that 0.4L concentration is 5mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.5M simultaneously
3/ h, charging reaction time 35h, temperature of reaction 80 DEG C, continues reaction 6h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.78 μm, product tap density 2.22g/cm after adding material
3, Mn content 71.72%, sulfate radical content 0.020%.
Embodiment 7
Manganous nitrate is dissolved in pure water or deionized water is mixed with the manganese nitrate solution that 1.25L concentration is 0.8mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 4L concentration is 0.25mol/L, under agitation manganese nitrate solution is joined in sodium oxalate solution, keep temperature of reaction 55 DEG C, feed time 80min, add the follow-up continuous insulation reaction 30min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 5:1, slowly adds the sodium hydroxide solution that 2L concentration is 1mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.45M simultaneously
3/ h, charging reaction time 30h, temperature of reaction 70 DEG C, continues reaction 4h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.33 μm, product tap density 2.15g/cm after adding material
3, Mn content 71.53%, sulfate radical content 0.005%.
Embodiment 8
Manganous sulfate is dissolved in pure water or deionized water is mixed with the manganese sulfate solution that 0.83L concentration is 1.2mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 2.5L concentration is 0.4mol/L, under agitation manganese sulfate solution is joined in sodium oxalate solution, keep temperature of reaction 85 DEG C, feed time 20min, add the follow-up continuous insulation reaction 40min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 7:1, slowly adds the sodium hydroxide solution that 1L concentration is 2mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.3M simultaneously
3/ h, charging reaction time 25h, temperature of reaction 40 DEG C, continues reaction 5h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.52 μm, product tap density 2.10g/cm after adding material
3, Mn content 71.50%, sulfate radical content 0.017%.
Embodiment 9
Manganous chloride tetrahydrate is dissolved in pure water or deionized water is mixed with the manganese chloride solution that 0.625L concentration is 1.6mol/L, gained sodium oxalate pure water will be reacted or deionized water is mixed with the sodium oxalate solution that 5L concentration is 0.2mol/L in embodiment 8, under agitation manganese chloride solution is joined in sodium oxalate solution, keep temperature of reaction 70 DEG C, feed time 50min, add the follow-up continuous insulation reaction 50min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 6:1, slowly adds the sodium hydroxide solution that 4L concentration is 0.5mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.2M simultaneously
3/ h, charging reaction time 40h, temperature of reaction 60 DEG C, continues reaction 3h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.74 μm, product tap density 2.18g/cm after adding material
3, Mn content 71.61%, sulfate radical content 0.008%.
Embodiment 10
Manganous sulfate is dissolved in pure water or deionized water is mixed with the manganese sulfate solution that 2L concentration is 0.5mol/L, sodium oxalate pure water or deionized water are mixed with the sodium oxalate solution that 5L concentration is 0.2mol/L, under agitation manganese sulfate solution is joined in sodium oxalate solution, keep temperature of reaction 50 DEG C, feed time 60min, add the follow-up continuous insulation reaction 60min of material, reacted rear filtration, washing, obtained manganous oxalate solid.
Above-mentioned manganous oxalate solid pure water or deionized water are sized mixing, quality liquid-solid ratio is 7:1, slowly adds the sodium hydroxide solution that 2L concentration is 1mol/L under agitation condition, feeds in raw material and passes into air, air capacity 0.25M simultaneously
3/ h, charging reaction time 35h, temperature of reaction 50 DEG C, continues reaction 4h, reacted rear filtration, washing, then drying obtains the heavy trimanganese tetroxide that median size is 5.65 μm, product tap density 2.09g/cm after adding material
3, Mn content 71.53%, sulfate radical content 0.016%.
Claims (3)
1. the preparation method of a heavy trimanganese tetroxide, it is characterized in that first with pure water or deionized water, the dissolving of solubility manganous salt being mixed with manganese salt solution, sodium oxalate is dissolved and is mixed with sodium oxalate solution, sodium hydroxide is dissolved and is mixed with sodium hydroxide solution, then manganese salt solution and sodium oxalate solution carry out precipitin reaction and generate solid oxalic acid manganese, after filtration, with water, solid oxalic acid manganese is deployed into manganous oxalate slurries after washing, then in manganous oxalate slurries, slowly drip sodium hydroxide solution makes manganous oxalate change into manganous hydroxide, the pH value controlling reaction system is 6.5 ~ 7.5, while dropping sodium hydroxide solution, pass into air carry out oxidizing reaction, manganous hydroxide is oxidized to heavy trimanganese tetroxide, filtration after oxidizing reaction completes, washing, dry, namely heavy trimanganese tetroxide product is obtained, chemical equation is:
Mn
2++Na
2C
2O
4=MnC
2O
4+2Na
+
MnC
2O
4+2NaOH=Mn(OH)
2+Na
2C
2O
4
6Mn(OH)
2+O
2=2Mn
3O
4+6H
2O。
2. the preparation method of heavy trimanganese tetroxide according to claim 1, is characterized in that, comprise following steps:
Step one: by solubility manganous salt pure water or deionized water dissolving, is mixed with the manganese salt solution of 0.5 ~ 2mol/L; Sodium oxalate pure water or deionized water dissolving are mixed with the sodium oxalate solution of 0.2 ~ 0.4mol/L; Sodium hydroxide pure water or deionized water dissolving are mixed with the sodium hydroxide solution of 0.5 ~ 5mol/L;
Step 2: manganese salt solution step one obtained joins in sodium oxalate solution, the ratio being 1: 1 in the mol ratio of mn ion and sodium oxalate feeds intake and carries out precipitin reaction, controlling temperature of reaction is 40 DEG C ~ 90 DEG C, manganese salt solution feed time 10 ~ 120min, add the rear insulation reaction 30 ~ 60min of material, react rear filtration, washing, obtain solid oxalic acid manganese;
Step 3: to step 2 gained solid oxalic acid manganese pure water or deionized water furnishing slurries, the quality liquid-solid ratio of solid oxalic acid manganese and water is 5 ~ 10:1, the sodium hydroxide solution that step one prepares slowly is added under agitation continuously in manganous oxalate slurries, manganous oxalate is made to change into manganous hydroxide, the by-product sodium oxalate solution of manganous oxalate and sodium hydroxide reaction enters step 2 recycle, the molar ratio of sodium hydroxide and manganous oxalate is 2: 1, the pH value controlling reaction system is 6.5 ~ 7.5, sodium hydroxide solution charging reaction time 20 ~ 40h, temperature of reaction 30 DEG C ~ 90 DEG C, while dropping sodium hydroxide solution, pass into air carry out oxidizing reaction, manganous hydroxide is oxidized to heavy trimanganese tetroxide, air flow quantity is 0.1 ~ 0.5M
3/ h, material all adds rear continuation reaction 3 ~ 6h, filtration after oxidizing reaction completes, washing, drying, and namely obtaining median size is 5 ~ 6 μm, and tap density is greater than 2.0g/cm
3, Mn content is greater than 71.5%, the heavy trimanganese tetroxide product that sulfate radical content is less than 0.02%.
3. the preparation method of heavy trimanganese tetroxide according to claim 1 or 2, is characterized in that described solubility manganous salt is any one in manganous sulfate or manganous nitrate, Manganous chloride tetrahydrate; Sodium oxalate is the industrial ethanedioic acid sodium of main content 99.5% or the by-product sodium oxalate solution of step 3; Sodium hydroxide is the industrial solid sodium hydroxide of main content 96% or the industrial liquid sodium hydroxide of main content 30%.
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| CN110776015A (en) * | 2019-11-05 | 2020-02-11 | 江西智锂科技有限公司 | Synthesis method of battery-grade trimanganese tetroxide |
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