CN102531065A - Spherical manganese carbonate synthetic method - Google Patents
Spherical manganese carbonate synthetic method Download PDFInfo
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- CN102531065A CN102531065A CN2010106245201A CN201010624520A CN102531065A CN 102531065 A CN102531065 A CN 102531065A CN 2010106245201 A CN2010106245201 A CN 2010106245201A CN 201010624520 A CN201010624520 A CN 201010624520A CN 102531065 A CN102531065 A CN 102531065A
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Abstract
The invention relates to a spherical manganese carbonate synthetic method comprising the following concrete steps of: 1) preparing a manganese salt solution, a carbonate solution and an ethanediamine solution; 2) in the presence of inert gas, and adding ammonia water to regulate the pH values of 1-50L of deionized water and 1-1000mL of ethanediamine solution to be 8-10; 3) maintaining the temperature at 30-80 DEG C, metering by adopting a precise electronic pump, respectively adding the manganese salt solution, the carbonate solution and the ammonia water to regulate the pH value, and reacting for 1-70 hours; and 4) stopping heating, carrying out solid-liquid separation, washing condensate with warm water at the temperature of 40-50 DEG C, and drying and sieving at the temperature of 80-1000 DEG C. By adopting the spherical manganese carbonate synthetic method provided by the invention, the content of impurities in the produced manganese carbonate is low, the particle size distribution D10/D90 is narrower and is close to 1, and the specific surface area is small; inert gas is adopted, ethanediamine is added, oxidization of manganese ions is reduced, one intermediate product is added, the reaction process is delayed, and nodular precipitation can be beneficially formed; and the discharge efficiency of the produced manganese carbonate is improved by 17-19%.
Description
Technical field
The present invention relates to lithium battery material, particularly a kind of spheric manganese carbonate compound method.
Background technology
Size distribution uniform spherical MnCO3 is widely used in many high-technology fields such as electronics, pottery, medicine, catalyzer.Prepare in the orderly shell structure material like template, owing to all have a clear superiority at aspects such as preparation, stoning difficulty and prices, spherical MnCO3 is a kind of good template; Prepare size distribution uniform spherical anode material for lithium-ion batteries LiMn with spherical MnCO3
2O
4, have high electrochemical performance and processing characteristics.Therefore, the morphology control technology of MnCO3 comes into one's own day by day.If but directly prepare the manganous carbonate out-of-shape through liquid-phase coprecipitation.Manganese is dissolved in the ionogen easily, and specific surface area is aggravated this phenomenon than conference.And the deposition forming process is very fast, is prone to absorption impurity.In order to obtain size distribution uniform spherical manganous carbonate, many people attempt, and have the people to add tensio-active agent at aqueous phase, or organic solvent, and all the synthesis technique to manganous carbonate improves.
Summary of the invention
Be the synthesizing spherical manganous carbonate, the present invention provides the spheric manganese carbonate compound method.
Spheric manganese carbonate compound method of the present invention, utilize quadrol can with the characteristic of divalent manganesetion complexing, delay the reaction of mn ion and carbonate, reduce the surface that foreign ion is attracted to ball, reduce foreign matter content; And give manganous carbonate certain balling-up time, improve the consistence of manganous carbonate; The quadrol that adopts can be decomposed under the situation of heating, thereby does not influence the various physico-chemical properties of manganous carbonate.
The concrete steps of spheric manganese carbonate compound method of the present invention are following:
1) the preparation manganese salt solution dissolves manganous sulfate with hot deionized water, Manganous chloride tetrahydrate, and manganous nitrate, wherein divalent manganesetion concentration is 1-3mol/L, solution temperature is 40-60 ℃;
The preparation carbonate solution dissolves volatile salt with deionized water at room temperature, bicarbonate of ammonia, and yellow soda ash, salt of wormwood, wherein carbonate content is 1-4mol/L;
The preparation ethylenediamine solution, quadrol content is 1-100mmol/L;
2) add deionized water 1-50L earlier, add ethylenediamine solution 1-1000mL then and rise in the reaction kettle, and the ammoniacal liquor 1-100ml adjusting pH value of adding 1-6mol/L is 8-10 to 10-1000; Feed protection gas such as nitrogen, helium, argon, krypton, xenon; Ventilation speed is 0.5-1.5L/min.
3) keep 30-80 ℃ of temperature, be advisable with 40-60 ℃, use the precise electronic pump, add manganese salt solution with the 1-4000ml/min flow velocity, and n (Mn): n (C)=1: 1.2-1 in molar ratio: 4 usefulness precise electronic pumps adding carbonate solution; Add ammoniacal liquor with the precise electronic pump and regulate the pH value, the reaction times is 1-70 hour.
4) stop to carry out solid-liquid separation after the heating, 40-50 ℃ of warm water washs cured article, 80-100 ℃ of oven dry screening.
Spheric manganese carbonate compound method of the present invention, the manganous carbonate foreign matter content of production is low, the narrower D of size distribution
10/ D
90Approach very much 1, specific surface area is little; Owing in mn ion and the carbanion reaction process, adopted rare gas element simultaneously, added quadrol; It is oxidized to have reduced mn ion on the one hand, adopts quadrol on the other hand, with the divalent manganesetion complexing; Be equivalent in reaction process, add an intermediate product, delayed reaction process; In the situation of high-speed stirring, help forming nodular precipitation.Can reduce the free force field action and the specific surface area of precipitation surface thus; Reduce its adsorption, reduce foreign matter content; The manganous carbonate that produces, its discharging efficiency has improved 17%-19%.
Embodiment
Embodiment one:
(1) the 3L deionized water is poured in the 10L reaction kettle, added 10mmol/L ethylenediamine solution 40ml again, regulate pH=9.5 with the ammoniacal liquor of 1mol/L, controlled temperature is 35 ℃, and stirring velocity is 1200r/min, feeds nitrogen with 0.6L/min;
(2) adopt the precise electronic pump with 10ml/min and the adding of 12ml/min speed the manganese sulfate solution of 1mol/L and sal volatile respectively;
(3) come the pH ≈ 9.5 of conditioned reaction and with 2mol/L ammoniacal liquor;
(4) reaction is 4.5 hours, stops to add;
(5) carry out solid-liquid separation, washing, oven dry, screening.
(6) particle diameter of test gained manganous carbonate, main content, BET;
(7) press Li: Mn=1: 2 with Quilonum Retard and manganous carbonate mixing, fully grinds mixing with ball mill, and compacting is spent high temperature sinterings 3 hours with 900 in flakes in the oxygen atmosphere.Grind after cooling, promptly get lithium manganate material, carry out secondary cell and detect.
Embodiment two:
(1) the 40L deionized water is poured in the 100L reaction kettle, adding 10mmol/L diethylamine solution 510ml, regulated pH ≈ 9.0 with the ammoniacal liquor of 1mol/L, controlled temperature is 45 ℃, and stirring velocity is 800r/min, feeds argon gas with 0.8L/min;
(2) adopt the precise electronic pump with 100ml/min and the adding of 140ml/min speed the manganese chloride solution of 2mol/L and ammonium bicarbonate soln respectively;
(3) come the pH ≈ 9.0 of conditioned reaction and with 2mol/L ammoniacal liquor;
(4) reaction is 10 hours, stops to add;
(5) carry out solid-liquid separation, washing, oven dry screening.
Embodiment three:
(1) the 450L deionized water is poured in the 1000L reaction kettle, added 10mmol/L ethylenediamine solution 1L again, regulate pH ≈ 8.0 with the ammoniacal liquor of 1mol/L, controlled temperature is 65 ℃, and stirring velocity is 600r/min, feeds nitrogen and argon gas mixing with 0.7L/min;
(2), adopt the precise electronic pump to add with 4L/min and 5.5L/min speed respectively with manganese nitrate solution, volatile salt and the bicarbonate of ammonia mixing solutions of 1mol/L;
(3) come the pH ≈ 8.0 of conditioned reaction and with 2mol/L ammoniacal liquor;
(4) reaction is 40 hours, stops to add;
(5) carry out solid-liquid separation, washing, oven dry screening.
Comparative Examples
(1) the 3L deionized water is poured in the 10L reaction kettle, regulated pH ≈ 9.5 with the ammoniacal liquor of 1mol/L, controlled temperature is 35 ℃, and stirring velocity is 1200r/min, feeds nitrogen with 0.6L/min;
(2) manganous sulfate and the bicarbonate of ammonia with 1mol/L adopts the precise electronic pump to add with 10ml/min and 12ml/min speed;
(3) come the pH ≈ 9.5 of conditioned reaction and with 2mol/L ammoniacal liquor;
(4) reaction is 4.5 hours, stops to add, and stops heating.
(5) carry out solid-liquid separation, washing, oven dry, screening.
More than the various data of each instance gained manganous carbonate
Table 1. manganous carbonate physical and chemical indexes
Table 2. electric performance test result
| Charging capacity | 114 | 121 | 115 | 114 |
| Loading capacity | 110 | 118 | 112 | 90 |
| Discharging efficiency | 0.96 | 0.98 | 0.97 | 0.79 |
Conclusion:
Can find out that from table 1 foreign matter content is low, the narrower D of size distribution
10/ D
90Approach very much 1, specific surface area is little.Owing in mn ion and the carbanion reaction process, adopted rare gas element simultaneously, added quadrol.It is oxidized to have reduced mn ion on the one hand, adopts quadrol on the other hand, with the divalent manganesetion complexing, is equivalent in reaction process, add an intermediate product, has delayed reaction process.In the situation of high-speed stirring, help forming nodular precipitation.Can reduce the free force field action and the specific surface area of precipitation surface thus.Reduce its adsorption, reduce foreign matter content.
Can find out that from table 2 by the manganous carbonate that generates under the quadrol condition, its discharging efficiency has improved 17%-19% than Comparative Examples.
Claims (5)
1. spheric manganese carbonate compound method, it is characterized in that: the concrete steps of said compound method are following:
1) preparation manganese salt solution, with hot deionized water dissolving soluble manganese salt, wherein divalent manganesetion content is 1-3mol/L, solution temperature is 40-60 ℃;
Prepare carbonate with deionized water at room temperature, wherein carbonate content is 1-4mol/L;
The preparation ethylenediamine solution, quadrol content is 1-100mol/L;
2) add deionized water 1-50L earlier, add ethylenediamine solution 1-1000mL then and rise in the reaction kettle, and the ammoniacal liquor 1-100ml adjusting pH value of adding 1-6mol/L is 8-10 to 10-1000; It is 0.5-1.5L/min that rare gas element, ventilation speed are used in the feeding protection.
3) keep 30-80 ℃ of temperature of reaction, use the precise electronic pump, add manganese salt solution with the 1-4000ml/min flow velocity, and by Mn: the C mol ratio is 1: 1.2-1: 4 usefulness precise electronic pumps adding carbonate solution; Add ammoniacal liquor with the precise electronic pump and regulate the pH value, the reaction times is 1-70 hour.
4) stop to carry out solid-liquid separation after the heating, 40-50 ℃ of warm water washs cured article, 80-100 ℃ of oven dry screening.
2. according to the spheric manganese carbonate compound method of claim said 1, it is characterized in that: said soluble manganese salt comprises manganous sulfate, Manganous chloride tetrahydrate, manganous nitrate.
3. according to the spheric manganese carbonate compound method of claim said 2, it is characterized in that: said carbonate comprises volatile salt, bicarbonate of ammonia, yellow soda ash, salt of wormwood.
4. according to the spheric manganese carbonate compound method of claim said 3, it is characterized in that: said rare gas element comprises nitrogen, helium, argon, krypton, one or more of xenon.
5. according to the spheric manganese carbonate compound method of claim said 4, it is characterized in that: the temperature of reaction preferred value of said compound method in the 3rd step is 40-60 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103991907A (en) * | 2014-05-08 | 2014-08-20 | 洛阳理工学院 | Preparation method for manganese carbonate nano-fiber ball |
| CN104724760A (en) * | 2015-03-25 | 2015-06-24 | 大连瑞源动力有限公司 | Method for synthesizing spherical manganese carbonate by use of ionic liquid |
| CN109437309A (en) * | 2018-11-26 | 2019-03-08 | 郝新丽 | A kind of synthetic method of shuttle-type structure manganese carbonate nano material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106784785A (en) * | 2016-12-12 | 2017-05-31 | 大连瑞源动力股份有限公司 | The synthesis of high decentrality submicron level spheric manganese carbonate |
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| CN101269840A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | Spherical manganese carbonate and preparing method thereof |
| CN101704553A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
| CN101857278A (en) * | 2010-06-25 | 2010-10-13 | 浙江华友钴业股份有限公司 | Method for preparing spherical carbonate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101269840A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | Spherical manganese carbonate and preparing method thereof |
| CN101704553A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
| CN101857278A (en) * | 2010-06-25 | 2010-10-13 | 浙江华友钴业股份有限公司 | Method for preparing spherical carbonate |
Non-Patent Citations (1)
| Title |
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| DONG-MEI SUN等: "Synthesis and Design of MnCO3 Crystals with Different Morphologies by Supported Liquid Membrane", 《J CHEM CRYSTALLOGR》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103991907A (en) * | 2014-05-08 | 2014-08-20 | 洛阳理工学院 | Preparation method for manganese carbonate nano-fiber ball |
| CN103991907B (en) * | 2014-05-08 | 2015-08-19 | 洛阳理工学院 | A kind of preparation method of manganous carbonate nanofiber ball |
| CN104724760A (en) * | 2015-03-25 | 2015-06-24 | 大连瑞源动力有限公司 | Method for synthesizing spherical manganese carbonate by use of ionic liquid |
| CN109437309A (en) * | 2018-11-26 | 2019-03-08 | 郝新丽 | A kind of synthetic method of shuttle-type structure manganese carbonate nano material |
| CN109437309B (en) * | 2018-11-26 | 2021-04-30 | 河北地质大学 | Synthetic method of shuttle-shaped structure manganese carbonate nano material |
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