CN101269840A - Spherical manganese carbonate and preparing method thereof - Google Patents
Spherical manganese carbonate and preparing method thereof Download PDFInfo
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- CN101269840A CN101269840A CNA2008100266014A CN200810026601A CN101269840A CN 101269840 A CN101269840 A CN 101269840A CN A2008100266014 A CNA2008100266014 A CN A2008100266014A CN 200810026601 A CN200810026601 A CN 200810026601A CN 101269840 A CN101269840 A CN 101269840A
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Abstract
The invention relates to a spherical manganese carbonate and the preparation method thereof, and mainly relates to the spherical manganese carbonate for preparing a manganese compound (manganese dioxide, etc.) of a dry battery, lithium manganese oxide of cathode materials for lithium ion batteries and derivatives, and the spherical manganese carbonate belongs to a chemical product. On the premise of easy industrial production realization, a method for simply preparing the spherical manganese carbonate with good fluidity is provided, and the spherical manganese carbonate is synthetized through controlling a synthesis technology. Particles of the manganese carbonate powder are spherical crystallization, the average particle size ranges from 2 to 30microns, the apparent density ranges from 1.3 to 1.8g per cm <3>, the tap density can reach over 2.0g per cm<3>, and the manganese content is equal to and larger than 47 percent. Experimental results indicate that the lithium manganese oxide synthetized by the manganese carbonate used as a precursor has better performance, and can improve electrochemical properties of lithium ion batteries. The lithium manganese oxide has good fluidity and highest bulk density, and can effectively improve the tap density of powder to cause materials to obtain higher specific capacity, thereby improving the electrochemical properties of the lithium ion batteries.
Description
Technical field
The present invention relates to a kind of spheric manganese carbonate, the particularly preparation of high-density spherical manganous carbonate is mainly used in a kind of manganic compound (Manganse Dioxide etc.) for preparing drying battery, and lithium cell anode material lithium manganate and derived product thereof belong to Chemicals.
Background technology
Lithium ion battery is a kind of emerging power supply, and therefore plurality of advantages such as it has, and voltage height, capacity are big, safety and environmental protection are subjected to widespread use in the secondary cell field.The positive electrode material of lithium ion battery is used most often cobalt acid lithium at present, but cobalt material price costliness, scarcity of resources, and cobalt is poisonous, big for environment pollution.At present the exploitation high-performance, anode material for lithium-ion batteries is the fundamental starting point that this field develops rapidly cheaply.In existing positive electrode material, advantages such as lithium manganate is cheap because of it, environmentally safe, safety performance are good, high-energy-density become one of focus of current anode material for lithium-ion batteries research.This material has the fast shortcoming of capacity attenuation when cycle charge-discharge, to this, people are devoted to improve the research of its cyclical stability from optimization synthesis technique, the aspects such as different elements and finishing of mixing.
As everyone knows, the pattern of powder has significant effects to the performance of material.Now, common high temperature solid-state synthetic material granule is not of uniform size, and the microtexture composition differs greatly, and occurs the different components that top layer " rich lithium " and center " lack lithium " in the material.It is inconsistent that material is formed, and brought the textural defect of material, and the stability that has had a strong impact on material structure is chemical property extremely.We think, the spheric powder granule and the synthetic positive electrode material of lithium salts in can lithium ion be spread between crystal, to form the thing phase of homogeneous.Simultaneously, the granule-morphology of powder, particle diameter and its tap density are closely related, and erose powder particle has serious reunion and particle arch formation when mixing, and have bigger space when particle packing is filled between particle, and the powder tap density is lower.The spheroidal particle of rule is piled up when filling, and contact surface is little between particle, does not reunite and the particle arch formation, and interparticle space is less, and the powder tap density is higher.Therefore, the spheroidization by the positive electrode material powder granule is the effective way that improves material tap density and volume and capacity ratio.Moreover, with respect to random particle, the spheroidal particle surface ratio of rule is easier to coat complete, even, firm decorative layer, therefore sphere material more is hopeful further to improve over-all properties by finishing, and, spherical product also has the coating that excellent flowability, dispersiveness and processability extremely help making electrode materials slurry and electrode slice, improves the electrode slice quality.We estimate in view of the above, and spheroidization is the important development direction of anode material for lithium-ion batteries.
Summary of the invention
Purpose of the present invention is just in order to improve the shortcoming and defect of existing Technology now, a kind of preparation method with manganous carbonate of spherical morphology is provided, make the spherical in shape or spherical particle of the manganous carbonate for preparing, have good fluidity, the highest tap density, the tap density that can effectively improve powder makes material obtain high gram specific storage, thereby improves the lithium ion battery chemical property.
The present invention is a prerequisite with easy realization industrial production, and the method that provides a kind of easy manufacture to have the spheric manganese carbonate of good fluidity by the control synthesis technique, has been synthesized the spheric manganese carbonate powder.Experimental result shows to be that presoma synthetic lithium manganate demonstrates better properties with this manganous carbonate, can improve the lithium ion battery chemical property.
The objective of the invention is to realize by following technical proposal:
A kind of spheric manganese carbonate, this manganous carbonate powder granule is a spheroidal crystal, 2～30 microns of median sizes (can adjust according to actual needs), loose density 1.3～1.8g/cm
3(can adjust according to actual needs), tap density can reach 2.0g/cm
3More than, manganese content 〉=47%.
A kind of preparation method of spheric manganese carbonate, undertaken by following step:
1., at first respectively the manganese salt of technical grade and additive being mixed with the manganese salt concn with deionized water is that 0.1M～10M, additive concentration are the solution of 0.05M～5M;
2., with deionized water alkaline precipitating agent, the complexing agent of technical grade being made into alkaline precipitating agent concentration is that 0.1M～10M, complexing agent concentration are the solution of 0.05M～5M;
3., the stirring of opening reaction vessel, drop into container 1/10～2/3 volumetrical deionized water or precipitation agent earlier and do end water (end water can be heated to 30 ℃～100 ℃ according to actual needs).Under violent stirring, press 1.: 2.=1: 1～1: 10, make 1.: 2. two kinds of solution carry out replacement(metathesis)reaction simultaneously in reaction vessel, control pH value 5～12;
4. the precipitation overflow of reaction generation enters filtration unit, uses the deionized water wash several of 1～10 times of weight of filter cake,,, filter then after each impurity ion content is up to standard near neutral up to PH, filter cake dried by the fire in 50～200 ℃ baking oven 2～10 hours, can dry.
Above-mentioned used cobalt salt is one or more in Manganous chloride tetrahydrate, manganous sulfate, the manganous nitrate.
Above-mentioned used additive is one or more in ammonium citrate, the ammonium oxalate.
Above-mentioned used alkaline precipitating agent is one or more in yellow soda ash, sodium bicarbonate, the bicarbonate of ammonia.
Above-mentioned used complexing agent is one or more among ammoniacal liquor, citric acid, the EDTA.
The manganous carbonate of present method preparation is that a kind of density height, crystalline structure are complete, particle shape is sphere or class spheric manganic compound, and this manganic compound synthesis technique is simple, cost is low, particle diameter can be controlled, and realize industrialization easily.
The present invention has following advantage:
1, adopts special depositing technology, prepare a kind of compound of manganese, in the process of preparation, can effectively control granularity, the density of product, make to be shaped as sphere or spherical particle, show as Fig. 1.
2, the Chemical Composition of the manganous carbonate of present method preparation and the requirement that physicals all can satisfy lithium ion battery material lithium manganate Chemical Composition and physicals.
Concrete embodiment
Embodiment 1:
With deionized water Manganous chloride tetrahydrate is made into 0.5M, ammonium citrate is made into the mixing solutions of 0.5M, with deionized water yellow soda ash is made into 1M, ammoniacal liquor is made into the mixing solutions of 0.5M, open the stirring of reaction vessel, drop into container 2/3 volumetrical deionized water, and end water is heated to 40 ℃, Manganous chloride tetrahydrate joins in the reaction vessel with the flow velocity of 5ml/min, alkaline precipitating agent yellow soda ash joins in the reaction vessel with the flow velocity of 4～6ml/min, by regulating the flow velocity of yellow soda ash, the control pH value is 7 ± 0.5, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, and washing water PH filters then 7 ± 0.5,100 ℃ of oven dry, oven dry back is crossed 80 mesh sieves and is got purity and be 〉=99% spheric manganese carbonate powder filter cake.
Embodiment 2:
With deionized water Manganous chloride tetrahydrate is made into 2M, ammonium citrate is made into the mixing solutions of 1M, with deionized water bicarbonate of ammonia is made into 2M, ammoniacal liquor is made into the mixing solutions of 1M, open the stirring of reaction vessel, drop into container 2/3 volumetrical deionized water, and end water is heated to 40 ℃, Manganous chloride tetrahydrate joins in the reaction vessel with the flow velocity of 5ml/min, alkaline precipitating agent bicarbonate of ammonia joins in the reaction vessel with the flow velocity of 8～12ml/min, by regulating the flow velocity of bicarbonate of ammonia, the control pH value is 7 ± 0.5, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, and washing water PH filters then 7 ± 0.5,100 ℃ of oven dry, oven dry back is crossed 80 mesh sieves and is got purity and be 〉=99% spheric manganese carbonate powder filter cake.
Embodiment 3:
With deionized water manganous nitrate is made into 3M, ammonium citrate is made into the mixing solutions of 1M, with deionized water bicarbonate of ammonia is made into 2M, ammoniacal liquor is made into the mixing solutions of 0.5M, open the stirring of reaction vessel, drop into container 2/3 volumetrical deionized water, and end water is heated to 50 ℃, manganous nitrate joins in the reaction vessel with the flow velocity of 5ml/min, alkaline precipitating agent sodium hydroxide joins in the reaction vessel with the flow velocity of 7.5～15ml/min, by regulating the flow velocity of bicarbonate of ammonia, the control pH value is 6.5 ± 0.5, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, and washing water PH filters then 7 ± 0.5,100 ℃ of oven dry, oven dry back is crossed 80 mesh sieves and is got purity and be 〉=99% spheric manganese carbonate powder filter cake.
Embodiment 4:
With deionized water manganous sulfate is made into 1M, ammonium oxalate is made into the mixing solutions of 0.3M, with deionized water yellow soda ash is made into 1M, EDTA is made into the mixing solutions of 1M, open the stirring of reaction vessel, drop into container 2/3 volumetrical deionized water, and end water is heated to 50 ℃, manganous sulfate joins in the reaction vessel with the flow velocity of 10ml/min, alkaline precipitating agent yellow soda ash joins in the reaction vessel with the flow velocity of 10～15ml/min, by regulating the flow velocity of yellow soda ash, the control pH value is 8 ± 0.5, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, and washing water PH filters then 7 ± 0.5,100 ℃ of oven dry, oven dry back is crossed 80 mesh sieves and is got purity and be 〉=99% spheric manganese carbonate powder filter cake.
Embodiment 5:
With deionized water manganous nitrate is made into 2M, ammonium oxalate is made into the mixing solutions of 1M, with deionized water bicarbonate of ammonia is made into 2M, ammoniacal liquor is made into the mixing solutions of 1M, open the stirring of reaction vessel, drop into container 2/3 volumetrical alkaline precipitating agent ammonium bicarbonate soln, manganous nitrate joins in the reaction vessel with the flow velocity of 5ml/min, drop at 7 ± 0.5 o'clock up to pH value, begin into alkaline precipitating agent ammonium bicarbonate soln, flow velocity is 5～15ml/min, by regulating the flow velocity of alkaline precipitating agent, the control pH value is 7 ± 0.5, and the precipitation that reaction generates overflows to washing and filtering equipment, and washing of precipitate is qualified to foreign matter content, washing water PH is 7 ± 0.5, filter then, 100 ℃ of oven dry, the oven dry back is crossed 80 mesh sieves and is got purity and be 〉=99% spheric manganese carbonate powder filter cake.
Claims (6)
1, a kind of spheric manganese carbonate is characterized in that this manganous carbonate powder granule is a spheroidal crystal, median size 2～30 μ m, loose density 1.3～1.8g/cm
3, tap density can reach 2.0g/cm
3More than, manganese content 〉=47%.
2, a kind of preparation method of spheric manganese carbonate is characterized in that it is undertaken by following step:
1., at first respectively the manganese salt of technical grade and additive being mixed with the manganese salt concn with deionized water is that 0.1M～10M, additive concentration are the solution of 0.05M～5M;
2., with deionized water alkaline precipitating agent, the complexing agent of technical grade being made into alkaline precipitating agent concentration is that 0.1M～10M, complexing agent concentration are the solution of 0.05M～5M;
3., open the stirring of reaction vessel, drop into container 1/10～2/3 volumetrical deionized water or precipitation agent earlier and do end water, end water can be heated to 30 ℃～100 ℃ according to actual needs, under violent stirring, press 1.: 2.=1: 1～1: 10, make 1.: 2. two kinds of solution carry out replacement(metathesis)reaction simultaneously in reaction vessel, control pH value 5～12;
4., the precipitation overflow that generates of reaction, enter filtration unit, for several times with the deionized water wash of 1～10 times of weight of filter cake,,, filter then after each impurity ion content is up to standard near neutral up to PH, filter cake dried by the fire in 50～200 ℃ baking oven 2～10 hours, can dry.
3, the preparation method of spheric manganese carbonate according to claim 2 is characterized in that used cobalt salt is one or more in Manganous chloride tetrahydrate, manganous sulfate, the manganous nitrate.
4, the preparation method of spheric manganese carbonate according to claim 2 is characterized in that used additive is one or more in ammonium citrate, the ammonium oxalate.
5, the preparation method of spheric manganese carbonate according to claim 2 is characterized in that used alkaline precipitating agent is one or more in yellow soda ash, sodium bicarbonate, the bicarbonate of ammonia.
6, the preparation method of spheric manganese carbonate according to claim 2 is characterized in that used complexing agent is one or more among ammoniacal liquor, citric acid, the EDTA.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805024A (en) * | 2010-04-27 | 2010-08-18 | 江苏大学 | Preparation method of manganese carbonate nanorod |
| CN102070197A (en) * | 2011-01-26 | 2011-05-25 | 江苏方舟新能源股份有限公司 | Preparation method of spherical manganous oxide |
| CN102120618A (en) * | 2011-01-26 | 2011-07-13 | 江苏方舟新能源股份有限公司 | Preparation method of high-tap density manganese carbonate |
| CN102502854A (en) * | 2011-10-17 | 2012-06-20 | 四川大学 | Preparation method of high-purity manganese sulfate solution |
| CN102531065A (en) * | 2010-12-30 | 2012-07-04 | 河南科隆集团有限公司 | Spherical manganese carbonate synthetic method |
| CN102795669A (en) * | 2011-05-23 | 2012-11-28 | 湖北开元化工科技股份有限公司 | Process method for producing high-pure spherical heavy manganese carbonate |
| CN102931393A (en) * | 2012-11-15 | 2013-02-13 | 北京工业大学 | Lithium manganate anode material with porous spherical structure and preparation method of lithium manganate anode material |
| CN103991907A (en) * | 2014-05-08 | 2014-08-20 | 洛阳理工学院 | Preparation method for manganese carbonate nano-fiber ball |
| CN106006745A (en) * | 2016-05-19 | 2016-10-12 | 烟台佳隆纳米产业有限公司 | Method for continuously preparing soft agglomerated nano manganese carbonate |
| CN106315683A (en) * | 2016-08-22 | 2017-01-11 | 武汉科技大学 | Method for preparing manganese ferrite by using waste zinc manganese dry cell as manganese source |
| 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 |
| CN106745280A (en) * | 2016-12-29 | 2017-05-31 | 中信大锰矿业有限责任公司 | The production system of high density mangano-manganic oxide presoma high-purity manganese carbonate |
| CN106887606A (en) * | 2017-02-23 | 2017-06-23 | 广西大学 | One kind " peach-shaped " Mn2 O3The preparation method of/C particles |
| CN107082452A (en) * | 2017-04-28 | 2017-08-22 | 潍坊泰兴生物化工有限责任公司 | A kind of production technology for preparing manganese carbonate |
| CN110408192A (en) * | 2019-06-28 | 2019-11-05 | 深圳大学 | A kind of manganese carbonate/polyamino acid component and preparation method thereof |
| CN113582234A (en) * | 2021-08-11 | 2021-11-02 | 南方锰业集团有限责任公司 | Preparation method of battery-grade spheroidal manganese carbonate |
| CN115304103A (en) * | 2022-08-23 | 2022-11-08 | 荆门市格林美新材料有限公司 | Aluminum-doped manganese carbonate and preparation method and application thereof |
-
2008
- 2008-03-05 CN CNA2008100266014A patent/CN101269840A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805024A (en) * | 2010-04-27 | 2010-08-18 | 江苏大学 | Preparation method of manganese carbonate nanorod |
| CN102531065A (en) * | 2010-12-30 | 2012-07-04 | 河南科隆集团有限公司 | Spherical manganese carbonate synthetic method |
| CN102531065B (en) * | 2010-12-30 | 2014-12-10 | 河南科隆集团有限公司 | Spherical manganese carbonate synthetic method |
| CN102070197A (en) * | 2011-01-26 | 2011-05-25 | 江苏方舟新能源股份有限公司 | Preparation method of spherical manganous oxide |
| CN102120618A (en) * | 2011-01-26 | 2011-07-13 | 江苏方舟新能源股份有限公司 | Preparation method of high-tap density manganese carbonate |
| CN102795669A (en) * | 2011-05-23 | 2012-11-28 | 湖北开元化工科技股份有限公司 | Process method for producing high-pure spherical heavy manganese carbonate |
| CN102502854A (en) * | 2011-10-17 | 2012-06-20 | 四川大学 | Preparation method of high-purity manganese sulfate solution |
| CN102931393A (en) * | 2012-11-15 | 2013-02-13 | 北京工业大学 | Lithium manganate anode material with porous spherical structure and preparation method of lithium manganate anode material |
| 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 |
| CN106006745A (en) * | 2016-05-19 | 2016-10-12 | 烟台佳隆纳米产业有限公司 | Method for continuously preparing soft agglomerated nano manganese carbonate |
| CN106315683A (en) * | 2016-08-22 | 2017-01-11 | 武汉科技大学 | Method for preparing manganese ferrite by using waste zinc manganese dry cell as manganese source |
| 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 |
| CN106745280A (en) * | 2016-12-29 | 2017-05-31 | 中信大锰矿业有限责任公司 | The production system of high density mangano-manganic oxide presoma high-purity manganese carbonate |
| CN106887606A (en) * | 2017-02-23 | 2017-06-23 | 广西大学 | One kind " peach-shaped " Mn2 O3The preparation method of/C particles |
| CN106887606B (en) * | 2017-02-23 | 2019-12-13 | 广西大学 | Peach-shaped Mn2O3preparation method of/C particles |
| CN107082452A (en) * | 2017-04-28 | 2017-08-22 | 潍坊泰兴生物化工有限责任公司 | A kind of production technology for preparing manganese carbonate |
| CN110408192A (en) * | 2019-06-28 | 2019-11-05 | 深圳大学 | A kind of manganese carbonate/polyamino acid component and preparation method thereof |
| CN110408192B (en) * | 2019-06-28 | 2021-11-23 | 深圳大学 | Manganese carbonate/polyamino acid compound and preparation method thereof |
| CN113582234A (en) * | 2021-08-11 | 2021-11-02 | 南方锰业集团有限责任公司 | Preparation method of battery-grade spheroidal manganese carbonate |
| CN115304103A (en) * | 2022-08-23 | 2022-11-08 | 荆门市格林美新材料有限公司 | Aluminum-doped manganese carbonate and preparation method and application thereof |
| CN115304103B (en) * | 2022-08-23 | 2023-11-03 | 荆门市格林美新材料有限公司 | Aluminum-doped manganese carbonate and preparation method and application thereof |
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