CN103928679B - A kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma - Google Patents
A kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma Download PDFInfo
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- CN103928679B CN103928679B CN201410086419.3A CN201410086419A CN103928679B CN 103928679 B CN103928679 B CN 103928679B CN 201410086419 A CN201410086419 A CN 201410086419A CN 103928679 B CN103928679 B CN 103928679B
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- Prior art keywords
- lithium
- presoma
- mixed
- formate
- lithium formate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- Manufacturing & Machinery (AREA)
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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma.It is characterized in, comprises the following steps：（1）Prepare lithium formate saturated solution；（2）Precursor material to be mixed is fitted into container, under continuous stirring, keeps temperature of charge at 80 120 DEG C, step is sprayed into the way of spraying（1）The lithium formate saturated solution of preparation, continues to stir, insulation after penetrating, until after material is well mixed and is oven-dried, mixing terminates.The present invention, as lithium salts, makes lithium formate solution uniformly be coated in the surface of presoma using a kind of solubility lithium formate very high with the mode of spraying.Reach mixed uniformly effect.In the case where presoma is stirred continuously, lithium formate solution is uniformly coated in the surface of presoma by the way of spraying, be then sintered.The uniformity of lithium can be ensured using the method for the present invention, be adapted to large-scale production, the uniformity of product can be guaranteed in large-scale production.
Description
Technical field
The present invention relates to a kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma.
Background technology
Present lithium ion anode material is primarily now cobalt acid lithium, LiMn2O4, lithium nickelate, nickle cobalt lithium manganate and ferric phosphate
Lithium etc..The lithium ion anode material its preparation method overwhelming majority for producing on the market now is high-temperature solid-phase sintering method.Its feature
It is：Equipment and technique preparation condition are easy to control, it is easy to accomplish industrialization.Preparation process is generally first by lithium salts and the oxygen of Ni, Co, Mn
Then the mixing of compound, hydroxide or carbonation carries out high temperature sintering so as to obtain lithium ion just under different atmosphere to it again
Pole material.
The lithium salts that sintering producer selects at present is mainly lithium carbonate and lithium hydroxide.The mixed lithium technique for sintering producer is main
It is：Lithium salts loading ball mill is first carried out into ball milling.Lithium salts is set to have small particle diameter as far as possible.Lithium salts after ball milling is pressed with presoma
Ratio mixes in batch mixer.It is sintered after well mixed.Because lithium salts has very big difference with the proportion and particle diameter of presoma,
Same presoma is difficult with the mixed lithium mode of this solid-solid to be well mixed, cause the sample after sintering rich lithium or scarce lithium, batch occur
Between stability it is poor.The electrochemistry of product can be guaranteed.
After anode material precursor needs to be well mixed with lithium salts such as lithium hydroxide or lithium carbonates, obtained by high temperature sintering
Lithium ion anode material.Because this solid-solid blend cannot realize uniform mixing of the lithium in precursor, the product lithium after sintering
The uneven chemical property for having a strong impact on lithium ion anode material of ion distribution.Meanwhile, the lithium salts in existing process generally
It is lithium carbonate and lithium hydroxide, because their solubility is very low, it is impossible to realize that solid-liquid mixes, so the same precursor of lithium salts
Uniform mixing is never resolved.
On the whole, either solid-solid blend or solid-liquid mixing are all unable to reach the same lithium ion of lithium source in the prior art
The uniform mixing of anode material precursor.
The content of the invention
It is an object of the invention to provide a kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma, Neng Goubao
The uniformity of lithium after card mixing.
A kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma, it is particular in that, including as follows
Step：
（1）Prepare lithium formate saturated solution；
（2）Precursor material to be mixed is fitted into container, under continuous stirring, temperature of charge is kept in 80-120
DEG C, spray into step in the way of spraying（1）The lithium formate saturated solution of preparation, continues to stir after penetrating, is incubated, until material is mixed
Close uniform and after being oven-dried, mixing terminates.
Wherein stir speed (S.S.) is 10-100r/min.
Wherein precursor material refer to prepare lithium nickelate presoma nickel hydroxide, cobalt acid lithium presoma cobalt hydroxide,
LiMn2O4 presoma manganese dioxide and ternary material presoma nickel cobalt manganese hydroxide.
It is 1.1-1.2mol with the mixed proportion of precursor material wherein to control lithium formate：1.
Wherein the penetrating speed control of lithium formate saturated solution is in 5-100ml/min.
The present invention, as lithium salts, makes lithium formate solution equal using a kind of solubility lithium formate very high with the mode of spraying
The even surface for being coated in presoma.Reach mixed uniformly effect.Present invention lithium formate prepares equal proportion as lithium source
Lithium formate solution, in the case where presoma is stirred continuously, makes lithium formate solution uniformly be coated in presoma by the way of spraying
Surface, is then sintered.The uniformity of lithium can be ensured using the method for the present invention, be adapted to large-scale production, large-scale production
The uniformity of middle product can be guaranteed.
Brief description of the drawings
Accompanying drawing 1 is the structural representation of mixing apparatus used in the embodiment of the present invention 1；
Accompanying drawing 2 is nickel-cobalt-manganese ternary material precursor Ni used in the embodiment of the present invention 10.5Co0.2Mn0.3(OH)2Electronic Speculum
Schematic diagram；
Accompanying drawing 3 is nickel-cobalt-manganese ternary material precursor Ni used in the embodiment of the present invention 10.5Co0.2Mn0.3(OH)2Electronic Speculum
Schematic diagram；
Accompanying drawing 4 is lithium ion battery nickle cobalt lithium manganate ternary material for the final sample after being sintered in the embodiment of the present invention 1
The Electronic Speculum schematic diagram of material.
Specific embodiment
Precursor material in the inventive method refers to positive electrode material precursor, and this positive electrode material precursor includes preparing
Lithium nickelate presoma nickel hydroxide, cobalt acid lithium presoma cobalt hydroxide, LiMn2O4 presoma manganese dioxide and ternary material
Material presoma nickel cobalt manganese hydroxide etc..The mixed process of such presoma and lithium salts is mainly uses soluble lithium salt.It is right
The physical indexs such as particle diameter, the specific surface area of presoma are without clearly requiring.But existing various presomas in the market will
Ask and possess certain particle size, such as：D50：It is 8-10 microns, spherical, tap density 1.8-2.4cm3/ g, it is therefore an objective to increase positive pole
The density of material.It is exactly this to possess certain sphericity and granularity, density presoma higher, using the mixing side of this patent
Method, it is easier to highlight this solid-liquid mixed uniformly advantage to be reached.
Embodiment 1：
The 523 type nickel cobalt manganese hydroxide precursors that following presoma material is produced using Ningxia east Tan Ye Co., Ltds
Ni0.5Co0.2Mn0.3（OH）2Presoma.
Concrete operations are as follows：
In 100L containers（Referring to Fig. 1）In, the 523 type nickel cobalt manganese hydroxide precursor materials for adding 20Kg to dry
Ni0.5Co0.2Mn0.3（OH）2, stirring is opened, its speed is 35r/min, and opens chuck heating, particular by heating heat conduction
Oil is heated in the chuck of container, material temperature is controlled at 100 DEG C, by the shower nozzle of container top spray into 1.5 moles prepared/
L lithium formate solution 160L.Penetrating flow is 25ml/min, treats that lithium formate solution has all sprayed, and continues to stir, dries 30min, is treated
Stop stirring after drying materials and heat, you can be well mixed.
The material that will be mixed is put into sintering furnace and is calcined 12 hours, and it is 950 DEG C to control temperature, you can obtain functional
Lithium ion anode material nickle cobalt lithium manganate（LiNi0.5Co0.2Mn0.3O2）.
Its performance detection data is as follows：
Half-cell detection, room temperature, 1C（2.75-4.2V）Specific capacity>160mAh/g, first efficiency be more than 88%, 50 times circulation
Capability retention is more than 95%.
Remarks 1, the Ni0.5Co0.2Mn of 20Kg0.3（OH）2The Lithium formate hydrate of 1.1 times of the corresponding mol ratio of presoma
Consumption be 16.9Kg；Remarks 2, lithium formate only can just be configured to the saturation of 1.5 moles/L in temperature more than 90 DEG C or more
Solution, and before penetrating, should remain that lithium formate solution is not less than 90 DEG C.
As shown in figure 1, reaction vessel includes upper lid 2, bottom rabbling mechanism 3, side rabbling mechanism 4 connects lithium formate solution
The atomizer 5 of tank, chuck 6, chuck 6 can pass to chuck and be circulated by external heat conduction oil, play heating
The effect of material.Wherein atomizer 5 may be selected spraying company of U.S. spraying systems Co high-efficient atomizing shower nozzles.
Claims (1)
1. a kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma, it is characterised in that comprise the following steps：
（1）Prepare lithium formate saturated solution；
（2）Presoma material to be mixed is fitted into container, under continuous stirring, temperature of charge is kept at 80-120 DEG C, with
The mode of spraying sprays into step（1）The lithium formate saturated solution of preparation, continues to stir after penetrating, is incubated, until material mixing is equal
Even and after being oven-dried, mixing terminates；
Wherein stir speed (S.S.) is 10-100 r/min；
Wherein presoma material refers to prepare lithium nickelate presoma nickel hydroxide, cobalt acid lithium presoma cobalt hydroxide, mangaic acid
Lithium presoma manganese dioxide and ternary material presoma nickel cobalt manganese hydroxide；
The molar ratio for wherein controlling lithium formate to mix with presoma material is 1.1-1.2：1；
Wherein the penetrating speed control of lithium formate saturated solution is in 5-100 ml/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410086419.3A CN103928679B (en) | 2014-03-11 | 2014-03-11 | A kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma |
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| CN201410086419.3A CN103928679B (en) | 2014-03-11 | 2014-03-11 | A kind of lithium salts and the mixed uniformly method of lithium ion anode material presoma |
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| CN103928679A CN103928679A (en) | 2014-07-16 |
| CN103928679B true CN103928679B (en) | 2017-06-20 |
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| CN106299254B (en) * | 2016-08-15 | 2018-12-14 | 北方奥钛纳米技术有限公司 | A kind of preparation method of nickel-cobalt lithium manganate cathode material |
| CN106410138A (en) * | 2016-10-09 | 2017-02-15 | 多氟多（焦作）新能源科技有限公司 | Lithium mixing method for lithium battery positive electrode ternary material |
| CN113178565B (en) * | 2021-03-29 | 2023-06-16 | 广东邦普循环科技有限公司 | Mixing process for preparing high-nickel anode material and application thereof |
| CN113903908B (en) * | 2021-10-09 | 2023-05-09 | 合肥国轩高科动力能源有限公司 | High-nickel multi-element positive electrode material and preparation method and application thereof |
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| JP5863525B2 (en) * | 2012-03-21 | 2016-02-16 | 古河電気工業株式会社 | Fine particle mixture production method and aqueous solution used for fine particle mixture production method |
| CN102891288B (en) * | 2012-09-24 | 2016-08-31 | 上海锦众信息科技有限公司 | A kind of preparation method of lithium battery surface clad anode material |
| CN102891308A (en) * | 2012-09-25 | 2013-01-23 | 上海锦众信息科技有限公司 | Preparation method for li-rich cathode material for lithium ion battery |
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