CN102502850A - Preparation method of lithium manganate precursor spherical manganese hydroxide - Google Patents
Preparation method of lithium manganate precursor spherical manganese hydroxide Download PDFInfo
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- CN102502850A CN102502850A CN2011103443968A CN201110344396A CN102502850A CN 102502850 A CN102502850 A CN 102502850A CN 2011103443968 A CN2011103443968 A CN 2011103443968A CN 201110344396 A CN201110344396 A CN 201110344396A CN 102502850 A CN102502850 A CN 102502850A
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Abstract
The invention relates to the field of lithium ion batteries, in particular to a preparation method of precursor spherical manganese hydroxide of lithium manganate. The method comprises the following steps of: raising the temperature to 40-80 DEG C by taking pure water as a base solution; adding ammonia water and an alkaline liquor, adjusting the alkalinity and pH of the base solution, and keeping the alkalinity and pH of the base solution at 10-40 and 8.5-10.5 respectively; adding an antioxidant of which the volume ratio is 0.5-2.0 percent, continually introducing ammonia gas, starting stirring, and controlling the stirring rotating speed at 60-180 revolutions per minute; adding a manganese salt solution, the alkaline liquor and ammonia water into the base solution in a parallel flow way, and undergoing a precipitation reaction at the temperature of 40-80 DEG C; and controlling the slurry solid content, pH value and alkalinity of a reaction system to produce a manganese hydroxide crystal nucleus, and gradually growing the crystal nucleus into a spherical or sphere-like manganese hydroxide crystal. Manganese hydroxide powder with high crystallinity is obtained in a parallel flow feeding way, and a product is easy to filter and wash and has high oxidation resistance simultaneously.
Description
Technical field
The present invention relates to the lithium ion battery material field, particularly the preparation method of the spherical manganous hydroxide of a kind of presoma of lithium manganate.
Background technology
It is anodal lithium ion battery field that spherical manganous hydroxide is mainly used in the lithium manganate, is one of important source material of lithium manganate.And China's manganese resource is abundanter, and the relative cobalt of price is cheap and environmentally friendly with its lithium manganate battery that makes, and security is good.Therefore lithium manganate is acknowledged as one of the most promising new green power material, and spherical manganous hydroxide is one of its presoma.
Simultaneously; Because spheroidal particle has minimum porosity and relatively little sliding friction factor; Have superior extendability and ductility, can make it have higher tap density, mix with Quilonum Retard by the presoma manganous hydroxide so manganous hydroxide is processed sphere; The lithium manganate that makes also has sphericity and higher tap density preferably, and the battery of finally making also has higher specific storage and long cycle life.
Summary of the invention
In order to solve the technical problem that exists in the prior art, the object of the present invention is to provide the preparation method of the spherical manganous hydroxide of manganate precursor for lithium that a kind of sphericity is better and scale resistance is stronger.
The technical scheme that the present invention adopts is following:
The preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium is characterized in that, may further comprise the steps:
With the pure water is end liquid, and temperature rises to 40～80 ℃;
Add ammoniacal liquor and alkali lye, regulate the basicity and the pH of end liquid, make it maintain 10～40 and 8.5～10.5 respectively;
Add 0.5～2.0% long-pending oxidation inhibitor of end liquid then, continue to feed nitrogen, open and stir, the control mixing speed is at 60～180r/min;
Manganese salt solution, alkali lye and ammoniacal liquor and stream are added in the end liquid, at 40～80 ℃ precipitin reaction takes place, crystalline growth velocity is very fast under this temperature, forms crystal particle easily.
Slip solid content, pH value and the basicity of control reaction system, thus the manganous hydroxide nucleus produced, and nucleus grows up into sphere or type spherical manganous hydroxide xln gradually.
The manganous hydroxide slurry that reaction generates is dry through washing press washing and Vacuumdrier, obtains spherical manganous hydroxide.
Preferably, said manganese salt is manganous sulfate, Manganous chloride tetrahydrate or manganous nitrate.
Further, the concentration of metal ions of said manganese salt solution is 60～140g/l.
Preferably, said alkali lye is sodium hydroxide or potassium hydroxide solution.
Further, the mass percentage concentration of said alkali lye is 10～40%.
Preferably, said oxidation inhibitor is one or more in Hydrazine Hydrate 80, sodium ascorbate, butylated hydroxytoluene, the Tenox PG.
Preferably, the concentration of said ammoniacal liquor is 10～30%, and the flow that feeds nitrogen is 20～2000ml/min.
Preferably, during the terminal point of said precipitin reaction, the pH value of solution is controlled at 10～13, and basicity is controlled at 15～45, and the slurry solid content is controlled at 60～200g/l.
Preferably, said washing adopt 50～80 ℃ hot deionized water wash to pH 8～10; Said drying temperature is 80～120 ℃.
Comparatively perfect is, the manganous hydroxide of the present invention's preparation is regular spherical, and tap density is 1.5～2.5g/cm
3, granularity is 5～30um
The present invention has following beneficial effect:
1, reaction conditions is simple and easy to control, can adapt to industriallization, continuous production.
Conditions such as size that 2, can be through adjustment temperature of reaction, pH, basicity and mixing speed, thus realize product granularity and tap density etc. is controlled.
3, the present invention adopts the cocurrent adding material mode, obtains the good manganous hydroxide spherical powder of crystallinity, and product is easy to filtration washing, and resistance of oxidation is stronger simultaneously.
Description of drawings
For the ease of it will be appreciated by those skilled in the art that the present invention is further described below in conjunction with accompanying drawing.
Fig. 1 is the electronic scanning Electronic Speculum figure of the product that obtains of the present invention.
Embodiment
Embodiment 1
With the pure water is end liquid, and temperature rises to 40 ℃, adds 10% ammoniacal liquor and 15% sodium hydroxide solution, makes that end liquid caustic soda degree maintains 10, pH maintains 9.5.
Add volume ratio then and be 0.5% Hydrazine Hydrate 80, continue to feed the nitrogen of 20ml/min, open and stir, the control mixing speed is at 80r/min.
The manganese sulfate solution of 120g/l, 15% sodium hydroxide solution and 10% ammoniacal liquor and stream are added in the end liquid, at 40 ℃ precipitin reaction take place, the pH value of control reaction system is 10, and basicity is controlled at 15, and the slurry solid content is controlled at 100g/l.
Slip continues to add reaction raw materials, serialization production through the riser overflow at reaction vessel top in the reaction vessel.
Slurry is through the press filtration of washing press repetitive scrubbing, washing adopt 80 ℃ hot deionized water wash to pH be 8.
Dry at Vacuumdrier, drying temperature is 120 ℃.
Obtain spherical manganous hydroxide, its tap density is 1.5g/cm
3, granularity is 5～10um.
The electron-microscope scanning figure of product is as shown in Figure 1, and the spherical ball looks are better, and particle is even relatively, good sphericity, and spherome surface is smooth, and mobility of particle is good.
Embodiment 2
With the pure water is end liquid, and temperature rises to 80 ℃, adds 20% ammoniacal liquor and 20% potassium hydroxide solution, makes that end liquid caustic soda degree maintains 15, pH maintains 8.5.
Add volume ratio then and be 1% sodium ascorbate, continue to feed the nitrogen of 2000ml/min, open and stir, the control mixing speed is at 60r/min.
The manganese chloride solution of 100g/l, 20% potassium hydroxide solution and 20% ammoniacal liquor and stream are added in the end liquid, at 80 ℃ precipitin reaction take place, the pH value of control reaction system is 12.5, and basicity is controlled at 20, and the slurry solid content is controlled at 200g/l.
Slip continues to add reaction raw materials, serialization production through the riser overflow at reaction vessel top in the reaction vessel.
Slurry is through the press filtration of washing press repetitive scrubbing, washing adopt 70 ℃ hot deionized water wash to pH be 8.5.
Dry at Vacuumdrier, drying temperature is 110 ℃.
Obtain spherical manganous hydroxide, its tap density is 2.5g/cm
3, granularity is 7～12um.
Embodiment 3
With the pure water is end liquid, and temperature rises to 50 ℃, adds 15% ammoniacal liquor and 25% sodium hydroxide solution, makes that end liquid caustic soda degree maintains 30, pH maintains 9.
Add volume ratio then and be 1.5% butylated hydroxytoluene, continue to feed the nitrogen of 500ml/min, open and stir, the control mixing speed is at 120r/min.
The manganese nitrate solution of 60g/l, 25% sodium hydroxide solution and 15% ammoniacal liquor and stream are added in the end liquid, at 50 ℃ precipitin reaction take place, the pH value of control reaction system is 10.5, and basicity is controlled at 45, and the slurry solid content is controlled at 60g/l.
Slip continues to add reaction raw materials, serialization production through the riser overflow at reaction vessel top in the reaction vessel.
Slurry is through the press filtration of washing press repetitive scrubbing, washing adopt 60 ℃ hot deionized water wash to pH be 8.7.
Dry at Vacuumdrier, drying temperature is 100 ℃.
Obtain spherical manganous hydroxide, its tap density is 1.6g/cm
3, granularity is 15～20um.
Embodiment 4
With the pure water is end liquid, and temperature rises to 70 ℃, adds 25% ammoniacal liquor and 10% potassium hydroxide solution, makes that end liquid caustic soda degree maintains 40, pH maintains 10.
Add volume ratio then and be 2.0% Tenox PG, continue to feed the nitrogen of 1000ml/min, open and stir, the control mixing speed is at 140r/min.
The manganese sulfate solution of 80g/l, 10% potassium hydroxide solution and 25% ammoniacal liquor and stream are added in the end liquid, at 70 ℃ precipitin reaction take place, the pH value of control reaction system is 13, and basicity is controlled at 25, and the slurry solid content is controlled at 150g/l.
Slip continues to add reaction raw materials, serialization production through the riser overflow at reaction vessel top in the reaction vessel.
Slurry is through the press filtration of washing press repetitive scrubbing, washing adopt 50 ℃ hot deionized water wash to pH be 9.
Dry at Vacuumdrier, drying temperature is 105 ℃.
Obtain spherical manganous hydroxide, its tap density is 2.4g/cm
3, granularity is 5～15um.
Embodiment 5
With the pure water is end liquid, and temperature rises to 60 ℃, adds 30% ammoniacal liquor and 30% sodium hydroxide solution, makes that end liquid caustic soda degree maintains 25, pH maintains 10.5.
Add volume ratio then and be 1.3% Hydrazine Hydrate 80 and sodium ascorbate mixed solution, continue to feed the nitrogen of 1500ml/min, open and stir, the control mixing speed is at 180r/min.
The manganese chloride solution of 115g/l, 30% sodium hydroxide solution and 30% ammoniacal liquor and stream are added in the end liquid, at 70 ℃ precipitin reaction take place, the pH value of control reaction system is 12, and basicity is controlled at 35, and the slurry solid content is controlled at 170g/l.
Slip continues to add reaction raw materials, serialization production through the riser overflow at reaction vessel top in the reaction vessel.
Slurry is through the press filtration of washing press repetitive scrubbing, washing adopt 55 ℃ hot deionized water wash to pH be 9.5.
Dry at Vacuumdrier, drying temperature is 90 ℃.
Obtain spherical manganous hydroxide, its tap density is 1.8g/cm
3, granularity is 15～30um.
Embodiment 6
With the pure water is end liquid, and temperature rises to 65 ℃, adds 28% ammoniacal liquor and 40% potassium hydroxide solution, makes that end liquid caustic soda degree maintains 35, pH maintains 10.
Add volume ratio then and be 1.8% butylated hydroxytoluene and Tenox PG mixed solution, continue to feed the nitrogen of 1800ml/min, open and stir, the control mixing speed is at 160r/min.
The manganese nitrate solution of 140g/l, 40% potassium hydroxide solution and 28% ammoniacal liquor and stream are added in the end liquid, at 75 ℃ precipitin reaction take place, the pH value of control reaction system is 11, and basicity is controlled at 30, and the slurry solid content is controlled at 135g/l.
Slip continues to add reaction raw materials, serialization production through the riser overflow at reaction vessel top in the reaction vessel.
Slurry is through the press filtration of washing press repetitive scrubbing, washing adopt 75 ℃ hot deionized water wash to pH be 10.
Dry at Vacuumdrier, drying temperature is 80 ℃.
Obtain spherical manganous hydroxide, its tap density is 2.2g/cm
3, granularity is 10～25um.
Above content only is to give an example and explanation to what structure of the present invention was done; Under the technician in present technique field described specific embodiment is made various modifications or replenish or adopt similar mode to substitute; Only otherwise depart from the structure of invention or surmount the defined scope of these claims, all should belong to protection scope of the present invention.
Claims (10)
1. the preparation method of the spherical manganous hydroxide of manganate precursor for lithium is characterized in that, may further comprise the steps:
With the pure water is end liquid, and temperature rises to 40～80 ℃;
Add ammoniacal liquor and alkali lye, regulate the basicity and the pH of end liquid, make it maintain 10～40 and 8.5～10.5 respectively;
Add volume ratio then and be 0.5～2.0% oxidation inhibitor, continue to feed nitrogen, open and stir, the control mixing speed is at 60～180r/min;
Manganese salt solution, alkali lye and ammoniacal liquor and stream are added in the end liquid, precipitin reaction takes place, slip solid content, pH value and the basicity of control reaction system at 40～80 ℃;
The manganous hydroxide slurry that reaction generates is dry through washing press washing and Vacuumdrier, obtains spherical manganous hydroxide.
2. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 1 is characterized in that said manganese salt is manganous sulfate, Manganous chloride tetrahydrate or manganous nitrate.
3. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 2 is characterized in that the concentration of said manganese salt solution is 60～140g/l.
4. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 1 is characterized in that said alkali lye is sodium hydroxide or potassium hydroxide solution.
5. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 4 is characterized in that the concentration of said alkali lye is 10～40%.
6. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 1 is characterized in that said oxidation inhibitor is one or more in Hydrazine Hydrate 80, sodium ascorbate, butylated hydroxytoluene, the Tenox PG.
7. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 1 is characterized in that the concentration of said ammoniacal liquor is 10～30%, and the flow that feeds nitrogen is 20～2000ml/min.
8. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 1; It is characterized in that during the terminal point of said precipitin reaction, the pH value of solution is controlled at 10～13; Basicity is controlled at 15～45, and the slurry solid content is controlled at 60～200g/l.
9. the preparation method of the spherical manganous hydroxide of a kind of manganate precursor for lithium according to claim 1 is characterized in that, said washing adopt 50～80 ℃ hot deionized water wash to pH 8～10; Said drying temperature is 80～120 ℃.
10. according to the preparation method of the spherical manganous hydroxide of each described a kind of manganate precursor for lithium of claim 1～9, it is characterized in that the tap density of the manganous hydroxide of preparation is 1.5～2.5g/cm
3, granularity is 5～30um.
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Cited By (7)
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| CN102820462A (en) * | 2012-08-24 | 2012-12-12 | 安徽亚兰德新能源材料股份有限公司 | Preparation process of anode material lithium manganate of spherical structure for lithium ion battery |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
| CN105399154A (en) * | 2015-11-25 | 2016-03-16 | 兰州金川新材料科技股份有限公司 | Method for producing Ni-Co-Mn ternary hydroxide |
| CN105439212A (en) * | 2014-09-30 | 2016-03-30 | 荆门市格林美新材料有限公司 | Preparation method for cell grade cobalt hydroxide |
| CN106745336A (en) * | 2016-12-28 | 2017-05-31 | 杉杉能源（宁夏）有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide of nanometer sheet reunion second particle and preparation method thereof |
| CN115028201A (en) * | 2022-05-23 | 2022-09-09 | 荆门市格林美新材料有限公司 | Preparation method and application of spherical MnOOH |
| CN115286051A (en) * | 2022-08-09 | 2022-11-04 | 荆门市格林美新材料有限公司 | Quaternary positive electrode precursor and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102820462A (en) * | 2012-08-24 | 2012-12-12 | 安徽亚兰德新能源材料股份有限公司 | Preparation process of anode material lithium manganate of spherical structure for lithium ion battery |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
| CN103606654B (en) * | 2012-12-21 | 2016-01-06 | 燕山大学 | The preparation method of the coated manganese oxide composite material of a kind of carbon |
| CN105439212A (en) * | 2014-09-30 | 2016-03-30 | 荆门市格林美新材料有限公司 | Preparation method for cell grade cobalt hydroxide |
| CN105439212B (en) * | 2014-09-30 | 2017-05-17 | 荆门市格林美新材料有限公司 | Preparation method for cell grade cobalt hydroxide |
| CN105399154A (en) * | 2015-11-25 | 2016-03-16 | 兰州金川新材料科技股份有限公司 | Method for producing Ni-Co-Mn ternary hydroxide |
| CN106745336A (en) * | 2016-12-28 | 2017-05-31 | 杉杉能源（宁夏）有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide of nanometer sheet reunion second particle and preparation method thereof |
| CN106745336B (en) * | 2016-12-28 | 2018-02-13 | 杉杉能源（宁夏）有限公司 | A kind of precursor of nickel-cobalt-lithium-manganese-oxide of nanometer sheet reunion second particle and preparation method thereof |
| CN115028201A (en) * | 2022-05-23 | 2022-09-09 | 荆门市格林美新材料有限公司 | Preparation method and application of spherical MnOOH |
| CN115028201B (en) * | 2022-05-23 | 2023-11-21 | 荆门市格林美新材料有限公司 | Spherical MnOOH preparation method and application thereof |
| CN115286051A (en) * | 2022-08-09 | 2022-11-04 | 荆门市格林美新材料有限公司 | Quaternary positive electrode precursor and preparation method and application thereof |
| CN115286051B (en) * | 2022-08-09 | 2023-06-27 | 荆门市格林美新材料有限公司 | Quaternary positive electrode precursor and preparation method and application thereof |
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Application publication date: 20120620 |