CN102120618A - Preparation method of high-tap density manganese carbonate - Google Patents
Preparation method of high-tap density manganese carbonate Download PDFInfo
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- CN102120618A CN102120618A CN2011100275335A CN201110027533A CN102120618A CN 102120618 A CN102120618 A CN 102120618A CN 2011100275335 A CN2011100275335 A CN 2011100275335A CN 201110027533 A CN201110027533 A CN 201110027533A CN 102120618 A CN102120618 A CN 102120618A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of high-tap density manganese carbonate. The preparation method comprises the following steps: preparing an industrial manganese salt and an additive into solution A by using deionized water, wherein the concentration of the manganese salt in the solution A is 0.1M-11M, and the concentration of the additive is 0.05M-6M; preparing an industrial precipitator and a complexing agent into solution B by using the deionized water, wherein in the solution B, the concentration of the precipitator is 0.1M-11M, and the concentration of the complexing agent is 0.05M-6M; putting the deionized water the volume of which is 1/3 of that of a container in a reactor, adding the solution A and the solution B to the container at a volume ratio of (1:1)-(1:11); and carrying out replacement reaction at the pH of 4-13; overflowing the generated precipitate to washing equipment for washing until the pH value of the washing water is 7+/-0.5; and filtering, drying a filter cake for 2-8 hours in a drying oven at the temperature of 40-250 DEG C, so as to obtain the high-tap density manganese carbonate powder. The prepared manganese carbonate is of a sphere particle, is good in flowability and high in tap density; and by using the manganese carbonate, the volume capacity of a material can be effectively increased, the battery processing property of the material is improved, and the electrochemical property of a lithium ion battery is enhanced.
Description
Technical field
The present invention relates to a kind of preparation method of high tap density manganous carbonate, be mainly used in preparation battery electrode manganese dioxide, lithium cell anode material lithium manganate and derived product thereof, belong to lithium electric material industry.
Background technology
At present, the positive electrode material of lithium ion battery is used most often cobalt acid lithium, but cobalt material price costliness, scarcity of resources, and cobalt is poisonous, big for environment pollution.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.
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 microtexture is formed and to be differed greatly, and material is formed inconsistent, has brought the textural defect of material, and the stability that has had a strong impact on material structure is chemical property extremely.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 excellent flowability, dispersiveness and processability, very helps making the coating of 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
The objective of the invention is: a kind of preparation method of high tap density manganous carbonate is provided, makes the manganous carbonate for preparing particle spherical in shape, good fluidity, the tap density height, energy is the auxetic material volume capacity effectively, improves the battery processing characteristics of material, improves the lithium ion battery chemical property.
Technical solution of the present invention is that this preparation method may further comprise the steps:
1. with deionized water the manganese salt and the additive of technical grade is made into A solution, the manganese salt concn is that 0.1M～11M, additive concentration are 0.05M～6M in the A solution;
2. with deionized water the precipitation agent and the complexing agent of technical grade is made into B solution, precipitation agent concentration is that 0.1M～11M, complexing agent concentration are 0.05M～6M in the B solution;
3. open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water as end water, end water is heated to 20 ℃～100 ℃, under violent stirring, A solution and B solution 1:1～1:11 by volume add in the reaction vessel, carry out replacement(metathesis)reaction by input speed control pH value 4～13;
4. the precipitation overflow of reaction generation enters washing plant, and washing of precipitate is qualified to foreign matter content, and washing water PH filters 7 ± 0.5, and filter cake dried by the fire in 40～250 ℃ baking oven 2～8 hours, got high tap density manganous carbonate powder.
Wherein, described manganese salt is a kind of in Manganous chloride tetrahydrate, manganous sulfate, the manganous nitrate.
Wherein, described additive is a kind of of tartarus, Seignette salt.
Wherein, described precipitation agent is a kind of in salt of wormwood, sodium bicarbonate, the bicarbonate of ammonia.
Wherein, described complexing agent is a kind of in ammoniacal liquor, ammonium citrate, the disodium ethylene diamine tetraacetate.
Synthesis technique of the present invention is simple, and production cost is low, effectively controls particulate granularity, density, makes to be shaped as spheroidal particle, is easy to realize industrialization, and the manganous carbonate of preparation can satisfy the requirement of lithium ion battery material lithium manganate Chemical Composition and physicals.
Concrete embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is restriction to technical solution.
Embodiment 1:
With deionized water manganous nitrate is made into 0.1M, tartarus is made into the A solution of 0.05M, with deionized water sodium bicarbonate is made into 0.1M, ammoniacal liquor is made into the B solution of 0.05M, open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water, end water is heated to 20 ℃, A solution joins in the reaction vessel with the flow velocity of 100L/h, B solution joins in the reaction vessel with the flow velocity of 100L/h, by regulating input speed control pH value is 4, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, washing water PH filters 6.5, and filter cake was 40 ℃ of bakings 8 hours, cross 80 mesh sieves, get the high tap density manganous carbonate powder of purity Wei ≧ 99%.
Embodiment 2:
With deionized water manganous nitrate is made into 2.8M, Seignette salt is made into the A solution of 1.5M, with deionized water salt of wormwood is made into 2.8M, ammoniacal liquor is made into the B solution of 1.5M, open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water, end water is heated to 40 ℃, A solution joins in the reaction vessel with the flow velocity of 100L/h, B solution joins in the reaction vessel with the flow velocity of 350L/h, by regulating input speed control pH value is 6, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, washing water PH filters 7, and filter cake was 100 ℃ of bakings 7 hours, cross 80 mesh sieves, get the high tap density manganous carbonate powder of purity Wei ≧ 99%.
Embodiment 3:
With deionized water Manganous chloride tetrahydrate is made into 5.5M, Seignette salt is made into the A solution of 3M, with deionized water bicarbonate of ammonia is made into 5.5M, ammonium citrate is made into the B solution of 3M, open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water, end water is heated to 60 ℃, A solution joins in the reaction vessel with the flow velocity of 100L/h, B solution joins in the reaction vessel with the flow velocity of 600L/h, by regulating input speed control pH value is 8.0, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, washing water PH filters 7.5, and filter cake was 160 ℃ of bakings 6 hours, cross 80 mesh sieves, get the high tap density manganous carbonate powder of purity Wei ≧ 99%.
Embodiment 4:
With deionized water manganous sulfate is made into 8.0M, tartarus is made into the A solution of 4.5M, with deionized water bicarbonate of ammonia is made into 8.0M, disodium ethylene diamine tetraacetate is made into the B solution of 4.5M, open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water, end water is heated to 80 ℃, A solution joins in the reaction vessel with the speed speed of 100L/h, B solution joins in the reaction vessel with the speed of 850L/h, by regulating input speed control pH value is 10, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, washing water PH filters 6.5, and filter cake was 200 ℃ of bakings 4 hours, cross 80 mesh sieves, get the high tap density manganous carbonate powder of purity Wei ≧ 99%.
Embodiment 5:
With deionized water manganous sulfate is made into 11.0M, Seignette salt is made into the A solution of 6.0M, with deionized water bicarbonate of ammonia is made into 11.0M, ammonium citrate is made into the B solution of 6.0M, open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water, end water is heated to 100 ℃, A solution joins in the reaction vessel with the speed speed of 100L/h, B solution joins in the reaction vessel with the speed of 1100L/h, by regulating input speed control pH value is 13, the precipitation that reaction generates overflows to washing and filtering equipment, washing of precipitate is qualified to foreign matter content, washing water PH filters 7, and filter cake was 250 ℃ of bakings 2 hours, cross 80 mesh sieves, get the high tap density manganous carbonate powder of purity Wei ≧ 99%.
The high tap density manganous carbonate particle that embodiment 1-5 obtains is the class spheroidal crystal, median size 1～35 μ m, and loose density 1.5～1.9g/cm3, tap density reaches 2.1g/cm
3More than, Meng Han Liang ≧ 47%.
Claims (5)
1. the preparation method of high tap density manganous carbonate is characterized in that this preparation method may further comprise the steps:
1. with deionized water the manganese salt and the additive of technical grade is made into A solution, the manganese salt concn is that 0.1M～11M, additive concentration are 0.05M～6M in the A solution;
2. with deionized water the precipitation agent and the complexing agent of technical grade is made into B solution, precipitation agent concentration is that 0.1M～11M, complexing agent concentration are 0.05M～6M in the B solution;
3. open the stirring of reaction vessel, drop into container 1/3 volumetrical deionized water as end water, end water is heated to 20 ℃～100 ℃, under violent stirring, A solution and B solution 1:1～1:11 by volume add in the reaction vessel, carry out replacement(metathesis)reaction by input speed control pH value 4～13;
4. the precipitation overflow of reaction generation enters washing plant, and washing of precipitate is qualified to foreign matter content, and washing water PH filters 7 ± 0.5, and filter cake dried by the fire in 40～250 ℃ baking oven 2～8 hours, got high tap density manganous carbonate powder.
2. the preparation method of high tap density manganous carbonate according to claim 1 is characterized in that: described manganese salt is a kind of in Manganous chloride tetrahydrate, manganous sulfate, the manganous nitrate.
3. the preparation method of high tap density manganous carbonate according to claim 1 is characterized in that: described additive is a kind of of tartarus, Seignette salt.
4. the preparation method of high tap density manganous carbonate according to claim 1 is characterized in that: described precipitation agent is a kind of in salt of wormwood, sodium bicarbonate, the bicarbonate of ammonia.
5. the preparation method of high tap density manganous carbonate according to claim 1 is characterized in that: described complexing agent is a kind of in ammoniacal liquor, ammonium citrate, the disodium ethylene diamine tetraacetate.
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Cited By (4)
| 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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- 2011-01-26 CN CN2011100275335A patent/CN102120618A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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 |
| 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 |
| 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 |
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Application publication date: 20110713 |