CN106564967B - Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof - Google Patents

Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof Download PDF

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CN106564967B
CN106564967B CN201610931894.5A CN201610931894A CN106564967B CN 106564967 B CN106564967 B CN 106564967B CN 201610931894 A CN201610931894 A CN 201610931894A CN 106564967 B CN106564967 B CN 106564967B
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lithium
anode material
presoma
based anode
rich manganese
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CN106564967A (en
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周少雄
李艳萍
闫东伟
况春江
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Advanced Technology and Materials Co Ltd
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
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    • 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 belongs to electrode material preparation fields, are related to a kind of lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof.In this method, metal salt, that is, manganese salt, cobalt salt and nickel salt and surfactant with water are mixed, dissolves and obtains metal salt solution；Precipitating reagent stirring and dissolving soluble in water is taken to obtain precipitant solution；Metal salt solution and precipitant solution are subjected to liquid liquid coprecipitation reaction in super gravity field reactor, filtering, cleaning, vacuum drying can obtain presoma；Calcination processing is carried out after presoma is mixed with lithium salts again, you can obtain lithium-rich manganese-based anode material.The present invention quickly prepares primary particle in below 100nm using the coprecipitation based on high-gravity technology, lithium-rich manganese-based anode material presoma of the second particle between 1 10 μm, and then the positive electrode component distributing and particle diameter distribution of preparation are uniform, granularity is small, active height, can reduce irreversible capacity, the cycle performance of raising lithium rechargeable battery for the first time.

Description

Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof
Technical field
The invention belongs to electrode material preparation fields, and in particular to a kind of lithium-rich manganese-based anode material presoma, anode material Material and preparation method thereof.
Background technology
Lithium-rich manganese-based anode material is a kind of novel anode material succeeded in developing in recent years；It is substantially a kind of layer Shape compound L i [Li1/3Mn2/3]O 2And LiMO2The solid solution cathode material of (M=Ni, Co, Mn) composition, chemical general formula can be with It is written as xLi [Li1/3Mn2/3]O2·(1-x)LiMO2.With traditional anode material for lithium-ion batteries (such as cobalt acid lithium, LiFePO4, LiMn2O4 etc.) it compares, such material has higher working voltage platform (up to more than 4.8V), the high (height of higher specific capacity Up to 300mAh/g), excellent high-temperature electrochemical properties, it is cheap, resourceful the advantages that, be increasingly becoming exploitation high-energy The most promising positive electrode of density lithium ion battery.But lithium-rich manganese-based anode material also has some shortcomings, bag It includes：(1) material circulation process has analysis oxygen, brings security risk, while it is low to also result in coulombic efficiency；(2) cryogenic property is very poor； (3) electron conduction is poor；(4) tap density, compacted density have much room for improvement.In order to further improve its performance, it is overcome Shortcoming by coating, adulterating, surface preparation, constructs the methods of special micro-nano structure, can obtain high performance rich lithium Manganese-based anode material.Xiamen University G.Wei et al. is prepared for lithium-rich manganese-based anode material nanometer by the adjusting to material crystal face Piece, the material show good electrochemistry cycle performance and high rate performance, obtain such material power battery, intelligent grid, The application in the fields such as energy storage is possibly realized.
Lithium-rich manganese base oxide component, structure are complex, extremely difficult to the control of its structure and pattern.Component, knot The complexity of structure causes its synthetic method also complex, and most of document reports are all using lithium salts and containing polynary transition metal Presoma (such as carbonate) carry out high-temperature calcination synthesis.Presoma containing polynary transition metal generally passes through chemical coprecipitation Method, sol-gal process, spray drying process, molte-salt synthesis etc. are prepared.At present, most widely used lithium-rich manganese base material presoma Preparation method be chemical coprecipitation；But due to traditional chemical coprecipitation reaction process usually in stirring reactor into Row, stirring are difficult to be uniformly mixed reactant, are unevenly distributed so as to cause the precipitate component of formation.In addition, chemical precipitation is reacted The precipitation of formation has huge surface energy, contains large quantity of moisture precipitate in addition in, can cause in the precipitation in the drying process Particle there is agglomeration, particle size is big, is unevenly distributed, and finally influences the performance of the material.Therefore chemical coprecipitation Shallow lake method is difficult to control the quality of lithium-rich manganese base material presoma, and the distribution of the product particle diameter of difference processing batch and crystalline phase are deposited In very big difference.In the prior art, the precursor synthesis method of rich lithium manganese advantage and disadvantage that are very much, but having nothing in common with each other：
(1) a kind of preparation method of lithium ion battery lithium-rich manganese-based anode material has been invented by Zhi Xiao sections, Liu Hongguang et al., This method is carbonized by adding starch during precursor synthesis in the sintering process in later stage, improves leading for material Electrical property.But material is not carried out nanosizing processing by this method, so the true capacity of material is difficult to give full play of (most Dawn section, Liu Hongguang, the leaf sea of learning, what likes treasure, and chapter Sue, Shi Jie, the rising sun is positive, a kind of system of lithium ion battery lithium-rich manganese-based anode material Preparation Method, Chinese invention patent application, application number：201210357169.3 the applying date：2012-09-21, publication No.：CN 102881887A)。
(2) Wu Feng, old reality et al. has invented a kind of preparation method of lithium-rich manganese-based ternary composite cathode material, and this method is led to The mode for crossing control co-precipitation obtains presoma, and the particle size distribution of gained persursor material is uniform, and the performance of material obtains Optimization, but the process conditions required by this method are complicated, it is difficult to the control (Wu of grain graininess is realized in the industrial production Cutting edge of a knife or a sword, Chen Shi, Zhong Yunxia, Bai Ying, Wuchuan, Bao Liying, Wu Bairong, a kind of preparation side of lithium-rich manganese-based ternary composite cathode material Method, Chinese invention patent application, application number：201210149592.4 the applying date：2012-05-14, publication No.： CN102655232A)。
(3) Hou Hongjun, Li Shijiang et al. have invented a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode and its preparation Method, this method obtain the rich lithium manganese solid solution material of doping and spherical shape, the performance of material by the modes such as adulterating, being spray-dried Preferably, the technique of the spray drying but used in this method is difficult to amplify, and is equally to be difficult to large batch of system in the industrial production Standby spherical rich lithium manganese solid solution material (Hou Hongjun, Li Shijiang, Luo Chengguo, Luo Chuanjun, Yang Huachun, Li Yunfeng, Xue Xujin, Ding Yun The tinkling of pieces of jade, Zhao Yongfeng, a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode and preparation method thereof, Chinese invention patent application, Shen Please number：201210435110.1 the applying date：2012-11-02, publication No.：CN102916176A).
Preparation in scientific and technical literature on lithium-rich manganese-based anode material presoma and positive electrode also has very much：
(1) Na ion exchanges from the material accordingly containing Na are Li ions with ion-exchange by Kim et al., and then are obtained Obtained rich lithium manganese solid solution material.The high rate performance of the material is preferable, but the time used in ion-exchange process used in this method It is longer, and yield very limited (Kim D, Kang SH, Balasubramanian M, Johnson CS, High-energy and high-power Li-rich nickel manganese oxide electrode materials.Electrochemistry Communications,2010,12,1618–1621)。
(2) domestic Sun Shigang seminars obtain the lithium-rich manganese-based solid solution of crystal grain oriented growth by hydro-thermal reaction Body material, the material also have excellent high rate performance, but hydro-thermal reaction need high temperature and high pressure condition (Wei GZ, Lu X, Ke FS,Huang L,Li JT,Wang ZX,Zhou ZY,Sun ZG,Crystal Habit-Tuned Nanoplate Material of Li[Li1/3–2x/3NixMn2/3–x/3]O 2for High-Rate Performance Lithium- Ion Batteries,Adv.Mater.2010,4364,22,4364-4367)。
(3) MnCO of Huang Yun brightness seminar synthesizing spherical first3Presoma, then by MnCO3, LiOH and Ni (NO3)2It is mixed It closes sintering and obtains hollow ball shape richness lithium manganese material, which has higher specific capacity and high rate performance, but synthesis used walks It is rapid more, and be sintered under hot conditions and require to keep the hollow ball structure of material, required process conditions are harsh (Jiang Y,Yang Z,Luo W,Hu X,Huang Yunhui,Hollow 0.3Li2MnO3_ 0.7LiNi0.5Mn0.5O2microspheres as a high-performance cathode material for lithium–ion batteries,Phys.Chem.Chem.Phys.,2013,15,22954—2960)。
In conclusion the method for the preparation lithium-rich manganese base material presoma and lithium-rich manganese base material of the prior art, there is Process conditions are complicated, take longer, it is difficult to the control of grain graininess is realized in the industrial production, it is big in the industrial production to be difficult to The problem of preparation of batch.Therefore, in current research and production, it is good to be required to a kind of chemical property, can be with scale The rich lithium manganese base solid solution positive electrode material precursor of production and the preparation method of positive electrode.
Supergravity reactor is then to generate powerful super gravity field using rotation at a high speed, makes fluid reactant in super gravity field It is middle to improve mass transfer and heat transfer efficiency and promote reaction rate.The big I of super gravity field is controlled by by adjustment rotating speed, makes object Material putting in super gravity field stay the time not only very short and also can with stability contorting,
Compared to the traditional reactor reacted under general gravitational field, the equipment volume of supergravity reactor is small, energy efficiency It is high, mass transfer, heat transfer efficiency can be effectively improved, can be applied to the two-phase of gas, liquid, solid or the reaction of three-phase or separation and can be with Product quality is significantly promoted, is a kind of high-efficiency reactor for meeting economic benefit.Such as (1) Zhou Jicheng, Xiao Lingli etc. People (Zhou Jicheng, Xiao Lingli, Xie Fanghua, Meng Xiang, Zeng Min, a kind of method for preparing nano material, Chinese invention patent, application number： 201010517639.9 the applying date：A kind of side for preparing nano material precursor and nano material 2010-10-25) is invented Method.The method for wherein preparing nano material precursor is that reaction raw materials are placed in super gravity field reactor to carry out gas-liquid reaction Or nano material precursor is obtained after liquid-liquid reactions；The method for preparing nano material is to nano material precursor with microwave field Heating and calcining is carried out, nano material is obtained after nano material precursor is made to decompose or turns brilliant.The nano material prepared For the oxide of the nano level metal.The method of the present invention has scientific and reasonable, product quality height, energy saving, without secondary The advantages that pollution.But nano particle prepared by this method, nano particle will not be self-assembled into micron particles, be not suitable for preparing The positive electrode of lithium ion battery.(2) Chen Jianfeng, Wang Yuhong et al. (Chen Jianfeng, Wang Yuhong, Li Yaling, Ji meter Yun, it is overweight Power reaction-crystallization method prepares nano-zinc sulfide, Chinese invention patent, application number：03123308.2, the applying date：2003-04-25) A kind of method that nano-zinc sulfide is prepared using high-gravity reactive precipitation is invented, this method is using zinc nitrate and hydrogen sulfide as original Material, using hypergravity crystallisation, prepares nano-zinc sulfide.Compared with prior art, which it is lower to prepare zinc sulphide cost, Uniform particle sizes, narrow particle size distribution, crystal form are more complete.
The content of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of lithium-rich manganese-based anode material presomas And preparation method thereof, this method uses the progress liquid-liquid co-precipitation fast reaction acquisition presoma in super gravity field reactor micro- Micro-nano structure obtains lithium-rich manganese-based anode material using heat treatment.The efficient quick advantage that the present invention is reacted using hypergravity, With reference to Chemical self-assembly method, a kind of quick method for preparing lithium-rich manganese-based anode material presoma and positive electrode is developed.
Another object of the present invention is to provide a kind of method that lithium-rich manganese-based anode material is prepared using above-mentioned presoma And lithium-rich manganese-based anode material.
The present invention is achieved by the following technical solutions：
A kind of preparation method of lithium-rich manganese-based anode material presoma, this method comprises the following steps：
Metal salt solution preparation process：Metal salt and surfactant are mixed with water, dissolving obtains metal salt solution, The metal salt is made of manganese salt, cobalt salt and nickel salt；
Precipitant solution preparation process：Precipitating reagent stirring and dissolving soluble in water is taken, obtains precipitant solution；
Forerunner's preparation step：The metal salt solution and the precipitant solution are carried out in super gravity field reactor Liquid-liquid coprecipitation reaction, then be filtered processing after obtain sediment, then the sediment is started the cleaning processing, vacuum is done Dry processing obtains the presoma.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, the metal In salting liquid preparation process and precipitant solution preparation process, the water reaches deionized water purity for deionized water or purity Above water.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, the metal In salting liquid preparation process, the manganese salt is：One or more in manganese nitrate, manganese acetate, manganese chloride and manganese sulfate；
The nickel salt is：One or more in nickel nitrate, nickel acetate, nickel chloride and nickel sulfate；
The cobalt salt is：One or more in cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate；
It is highly preferred that the molar ratio of the manganese salt, nickel salt and cobalt salt is y:z:(1-x-y-z), wherein 0.1 ＜ x≤0.3, 0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, the metal In the metal salt solution of salting liquid preparation process, metal cation concentration is 0.01mol/L -2.0mol/L.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, the metal In salting liquid preparation process, the surfactant is polyvinylpyrrolidone；In the metal salt solution, the surface-active The molar ratio of agent and metal cation is 1：(10-50).
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, the precipitation Agent is sodium hydroxide, lithium hydroxide, ammonium hydrogen carbonate, ammonium carbonate or sodium carbonate；Preferably, the concentration of the precipitant solution is 0.0105mol/L~2.1mol/L.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, the forerunner In preparation step, the centrifugal acceleration in the super gravity field is 180-10000m/s2, rotating speed 600-3000rpm is described Metal salt solution and the precipitant solution are pumped into speed as 20ml/min~300ml/min, the liquid-liquid coprecipitation reaction Reaction temperature be 20~60 DEG C；It is highly preferred that the centrifugal acceleration in the super gravity field is 800m/s2, the metal salt The speed that is pumped into of solution and the precipitant solution is 100ml/min~200ml/min, and reaction temperature is 40~60 DEG C, this is anti- The pH value of system is answered to control between 7-12；Further, ammonia spirit and acetum is selected to adjust the pH value of reaction solution.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred embodiment, feature exists In：In forerunner's preparation step, the cleaning treatment is with one in deionized water, ultra-pure water, absolute ethyl alcohol or acetone Kind cleaning is respectively washed with therein more than one.
The lithium-rich manganese-based anode material presoma prepared using the above method, chemical general formula are：MnyNizCo1-x-y-z (OH)2(1-x)Or MnyNizCo1-x-y-z(CO3)1-x, wherein 0.1 ＜ x≤0.3,0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z ≥0；The presoma is the micron ball that nano particle or nano wire are assembled into；Nano particle or nano wire in the presoma A diameter of 2-10nm, the grain size of the micron ball in the presoma is 1-10 μm.
A kind of preparation method of lithium-rich manganese-based anode material, this method comprises the following steps：
Calcination processing step：Calcination processing is carried out after above-mentioned presoma is mixed with lithium salts, obtains lithium-rich manganese-based anode material Material.
In the preparation method of above-mentioned lithium-rich manganese-based anode material, as a kind of preferred embodiment, the calcination processing step In rapid, the temperature of the calcination processing is 600 DEG C~1000 DEG C, time 6h-30h；It is highly preferred that the lithium salts is carbonic acid One or more in lithium, lithium oxalate and lithium hydroxide；The presoma is 1 with the lithium molar ratio in the lithium salts:(1- 1.5) it is more preferably, 1:1.5.
The lithium-rich manganese-based anode material prepared using the above method, the chemical general formula of the lithium-rich manganese-based anode material are Li1+xMnyNizCo1-x-y-zO2, wherein 0.1 ＜ x≤0.3,0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0, the richness lithium Manganese-based anode material is the micron ball that nano particle is assembled into；Nano particle in the lithium-rich manganese-based anode material it is a diameter of 1-30nm, the grain size of the micron ball of the lithium-rich manganese-based anode material is 1-10 μm.
Compared with prior art, the present invention has the advantages that：
1. the present invention quickly prepares primary particle below 100 nanometers using the coprecipitation based on high-gravity technology, and two Lithium-rich manganese-based anode material presoma of the secondary particle between 1-10 μm；The super gravity field that the present invention uses can speed up and strengthen Mass transport process makes the aqueous metal salt in reactor reach being uniformly mixed for molecular scale with precipitant solution, carries out chemistry Reaction, obtains the carbonate of the metal or the nano material presoma of hydroxide species, at further calcining Reason, obtains its lithium-rich manganese-based anode material；Compared with traditional chemical coprecipitation, ageing process is not required in this method, efficiently Energy saving, product quality is homogeneous, reproducible.
2. the present invention by realized in the stainless steel metal silk screen filler material in supergravity reactor metal salt solution with The emulsification of precipitating reagent；The filler material is equivalent to a miniature reactor, is conducive to the nano particle of generation, nano particle is micro- Micron particles are further assembled into type reactor.
3. the liquid-liquid co-precipitation fast reaction of the present invention can accurate artificial control condition, obtain target product.
4. concentration, pH value, temperature and the charging rate of the reactant during the liquid-liquid co-precipitation fast reaction of the present invention The particle size of the material, pattern and chemical property can be made a significant impact, more than parameter synergistic effect can be further It prepares with preferable layered crystal structure, even particle distribution and with the material of higher charge/discharge capacity.
5. the synthesis condition of the present invention is mild, simple for process, it is easy to commercial application.
6. the positive electrode of the present invention has the characteristics that distributed components, granularity are small, particle diameter distribution is uniform, activity is high, The cycle performance of irreversible capacity, raising using the material as the lithium rechargeable battery of positive electrode for the first time can be reduced.
7. the method for the present invention is simple, quickly, solution is uniformly mixed, and the properties of sample of preparation improves very much.Hypergravity reacts Device is then to generate powerful super gravity field using rotation at a high speed, and fluid reactant is made to improve mass transfer and heat transfer effect in super gravity field Rate and promote reaction rate.The big I of super gravity field is controlled by by adjustment rotating speed, makes material putting in super gravity field Stay the time not only very short but also can be with stability contorting, compared to the traditional reactor reacted under general gravitational field, hypergravity is anti- It answers that the equipment volume of device is small, energy efficiency is high, can effectively improve mass transfer, heat transfer efficiency, can be applied to the two-phase of gas, liquid, solid Or three-phase reaction or separation and can significantly promote product quality, be that a kind of high-efficiency for meeting economic benefit is anti- Answer device.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure for the lithium-rich manganese-based anode material presoma that embodiment 1 is prepared Piece, wherein, (a), (b), (c) are different with the amplification factor of (d).
Fig. 2 is the SEM pictures for the lithium-rich manganese-based anode material that embodiment 1 is prepared, wherein, the times magnification of (a), (b) Number is different.
Fig. 3 is X-ray diffraction (XRD) figure for the lithium-rich manganese-based anode material that embodiment 1 is prepared.
Fig. 4 is the lithium rechargeable battery using the lithium-rich manganese-based anode material that embodiment 1 is prepared as positive electrode First charge-discharge graph.
Fig. 5 is the SEM pictures for the lithium-rich manganese-based anode material presoma that embodiment 2 is prepared, wherein, (a), (b), (c) it is different with the amplification factor of (d).
Specific embodiment
A kind of preparation method of lithium-rich manganese-based anode material presoma, includes the following steps：
Step 1: prepared by metal salt solution：By a certain percentage by soluble manganese salt, cobalt salt and nickel salt (i.e. metal salt) with And surfactant is mixed with water, stirring and dissolving obtains metal salt solution.
Above-mentioned manganese salt is：One or more in manganese nitrate, manganese acetate, manganese chloride and manganese sulfate；
Above-mentioned nickel salt is：One or more in nickel nitrate, nickel acetate, nickel chloride and nickel sulfate；
Above-mentioned cobalt salt is：One or more in cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate.
In the metal salt solution, metal cation is made of nickel ion, cobalt ions and manganese ion, total concentration 0.01mol/ L-2.0mol/L (illustratively, can be 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L, Appoint in 0.5mol/L, 0.6mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L etc. Meaning or arbitrary scope between the two)；
The molar ratio (i.e. the molar ratio of nickel ion, cobalt ions and manganese ion) of manganese salt, nickel salt and cobalt salt is y:z:(1-x-y- Z), wherein 0.1 ＜ x≤0.3,0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0；
Above-mentioned surfactant is polyvinylpyrrolidone, dodecyl sodium sulfate etc.；In metal salt solution, surface-active The molar ratio of agent and metal cation is 1：(10-50) (can be illustratively, 1：10、1：15、1：20、1：25、1：30、1： 40、1：45、1：Arbitrary or arbitrary scope between the two in 50 grades).It can be assembled into nano particle using surfactant Micron ball, surfactant is excessive or the very few nano-particles self assemble that is all unfavorable for is into micron ball.
Step 2: prepared by precipitant solution：Precipitating reagent stirring and dissolving soluble in water is taken, obtains precipitant solution.
Above-mentioned precipitating reagent is sodium hydroxide, lithium hydroxide, ammonium hydrogen carbonate, ammonium carbonate or sodium carbonate etc.；In the precipitating reagent In solution, concentration be 0.0105mol/L~4.2mol/L (illustratively, can be 0.0105mol/L, 0.02mol/L, 0.05mol/L、0.1mol/L、0.5mol/L、0.6mol/L、0.8mol/L、1.0mol/L、1.2mol/L、1.5mol/L、 In 1.8mol/L, 2.0mol/L, 2.1mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.1mol/L etc. it is arbitrary or Scope arbitrarily between the two)；
In step 1 and step 2, the water that uses reaches the water more than purity of deionized water for deionized water or purity.
Step 3: prepared by presoma：Metal salt solution and precipitant solution are subjected to liquid-liquid in super gravity field reactor Fast reaction is co-precipitated, then sediment is obtained after being filtered processing, then sediment is started the cleaning processing, at vacuum drying Reason, obtains presoma.
The super gravity field reactor mentioned in step 3 refers to the reactor that can provide super gravity field, can be commercially available The supergravity reactor of any model, such as the high gravity rotating packed bed reactor that Beijing University of Chemical Technology develops, filler material is Stainless steel metal silk screen filler material, the concrete structure of the reactor can be found in the patent text of Application No. 201410188846.2 It offers.
In above-mentioned liquid-liquid co-precipitation fast reaction, the centrifugal acceleration in super gravity field is 180-10000m/s2(example Property, can be 180m/s2、190m/s2、200m/s2、250m/s2、500m/s2、1000m/s2、2000m/s2、3000m/s2、 4000m/s2、5000m/s2、6000m/s2、7000m/s2、8000m/s2、9000m/s2、9500m/s2、9800m/s2、9990m/s2 The arbitrary or arbitrary scope between the two in), rotating speed be 600-3000rpm (illustratively, can be 600rpm, 700rpm, Appoint in 1000rpm, 1200rpm, 1500rpm, 1800rpm, 2200rpm, 2500rpm, 2800rpm, 2900rpm, 3000rpm etc. Meaning or arbitrary scope between the two), reactant (i.e. metal salt solution and precipitant solution) be pumped into speed be 20ml/min~ 300ml/min (illustratively, can be 20ml/min, 50ml/min, 80ml/min, 90ml/min, 220ml/min, 240ml/ Arbitrary or arbitrary scope between the two in min, 250ml/min, 260ml/min, 280ml/min, 300ml/min etc.), reaction 20~60 DEG C of temperature (can be illustratively, arbitrary or arbitrary in 20 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 33 DEG C, 35 DEG C, 38 DEG C etc. Scope between the two)；
Preferably, the centrifugal acceleration in super gravity field is 800m/s2, reactant be pumped into speed for 100ml/min~ 200ml/min (illustratively, can be 100ml/min, 110ml/min, 120ml/min, 130ml/min, 140ml/min, It is both arbitrary or arbitrary in 150ml/min, 160ml/min, 170ml/min, 180ml/min, 190ml/min, 200ml/min etc. Between scope), 40~60 DEG C of reaction temperature (illustratively, can be 40 DEG C, 43 DEG C, 45 DEG C, 48 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C, arbitrary in 60 DEG C etc. or arbitrary scope between the two)；The pH value of the reaction system controls the (example between 7-12 Property, can be arbitrary or arbitrary scope between the two in 7,8,9,9.5,10,11,12 etc.), preferably with ammonia spirit and vinegar Acid solution (0.1mol/L) adjusts the pH value of reaction solution；
The rotating speed of centrifugal acceleration and reactor, the diameter of reactor have relation, on the one hand selected above-mentioned parameter depends on On the other hand the size and shape of supergravity reactor also depends on the power of motor and rotating speed of equipment.Reactant is pumped into speed The factors such as concentration, the size and shape of reactor of the degree depending on reactant.The selection of reaction temperature is related with reactant, reaction , it is necessary to improve temperature if heat absorption, still, process costs can be increased by improving temperature, must consider to determine suitable reaction Temperature range.The pH value of reaction system determines the OH in reaction system-Content, the sphericity of product etc..Select above-mentioned reaction Condition is mainly determined by equipment and reaction system.
Above-mentioned cleaning treatment is with a kind of cleaning in deionized water, ultra-pure water, absolute ethyl alcohol or acetone or uses it One or more of be respectively washed；
Above-mentioned vacuum drying treatment is that the sediment after cleaning is placed in vacuum drying oven, is warming up to 80-110 DEG C of (example Property, can be arbitrary in 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C etc. or arbitrary model between the two Enclose), (can be illustratively, to appoint in 10Pa, 8Pa, 6Pa, 5Pa, 4Pa, 2Pa, 1Pa, 0.5Pa etc. in vacuum degree≤10.0Pa Meaning or arbitrary scope between the two) under it is dry, the time be 2h~6h (illustratively, can be 2h, 2.5h, 3h, 3.5h, 4h, Arbitrary or arbitrary scope between the two in 5h, 5.5h, 6h etc.)；
Above-mentioned liquid-liquid is co-precipitated fast reaction, is to mix above-mentioned metal salt solution and precipitant solution, the rapid pump excess of imports In gravitational field reaction vessel, liquid-liquid moment co-precipitation is carried out, reaction solution residence time in reactor is only 0.001- 0.1s；
In this step, accelerate and strengthen mass transport process using super gravity field, make the aqueous metal salt in reactor with sinking Shallow lake agent solution reaches being uniformly mixed for molecular scale, is chemically reacted, obtains the carbonate substance or hydroxide of the metal Species substance.
Presoma prepared by above method, it is Mn to have following chemical general formulayNizCo1-x-y-z(OH)2(1-x)Or MnyNizCo1-x-y-z(CO3)1-x, wherein 0.1 ＜ x≤0.3,0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0；Before described It is the micron ball that nano particle or nano wire are assembled into drive body；Nano particle or nano wire in the presoma it is a diameter of Below 100nm is preferably 2-10nm, and the grain size of the micron ball in the presoma is 1-10 μm, and the shape of micron ball can be Circular, oval or peanut shape.
It may also be said that above-mentioned presoma is the second particle formed by primary particle self assembly；Primary particle is nano wire Or nano particle, grain size is in below 100nm；Second particle is micron ball, the micron ball can be it is circular, oval or Peanut shape particle, grain size is between 1-10 μm.
A kind of preparation method of lithium-rich manganese-based anode material, includes the following steps：
Calcination processing：Calcination processing is carried out after above-mentioned presoma is mixed with lithium salts, obtains lithium-rich manganese-based anode material.
Above-mentioned lithium salts is the one or more in lithium carbonate, lithium oxalate and lithium hydroxide；The presoma and the lithium in lithium salts Molar ratio is 1:(1-1.5) (such as 1:1.1、1:1.2、1:1.3、1:1.4) it is preferably, 1:1.5；
The temperature of above-mentioned calcination processing be 600 DEG C~1000 DEG C (illustratively, can be 600 DEG C, 650 DEG C, 700 DEG C, Arbitrary or arbitrary scope between the two in 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 1000 DEG C etc.), the time is 6-30h (examples Property, can be arbitrary in 6h, 8h, 10h, 15h, 18h, 20h, 23h, 25h, 28h, 30h etc. or arbitrary model between the two It encloses).Temperature is too low, it is impossible to form the crystalline phase of needs；Temperature is excessively high, has dephasign appearance, performance is undesirable, in addition, temperature mistake High product is also easily lumpd.
The lithium-rich manganese-based anode material prepared using the above method has following chemical general formula：Li1+xMnyNizCo1-x-y- zO2, wherein 0.1 ＜ x≤0.3,0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0, the lithium-rich manganese-based anode material are to receive The micron ball that rice grain is assembled into；A diameter of 1-30nm of nano particle in the lithium-rich manganese-based anode material, the richness lithium The grain size of the micron ball of manganese-based anode material is 1-10 μm.
This method quickly prepares primary particle below 100 nanometers using the coprecipitation based on high-gravity technology, secondary Lithium-rich manganese-based anode material presoma of the particle between 1-10 μm；The super gravity field that this method uses can speed up and strengthen biography Matter process makes the aqueous metal salt in reactor reach being uniformly mixed for molecular scale with liquid precipitation agent, it is anti-to carry out chemistry Should, the carbonate of the metal or the nano material presoma of hydroxide species are obtained, by further calcination processing, Obtain its lithium-rich manganese-based anode material；Compared with traditional chemical coprecipitation, ageing process is not required in this method, efficiently saves Can, product quality is homogeneous, reproducible.
This method in the filler material in supergravity reactor such as stainless steel metal silk screen filler material by realizing metal salt The emulsification of solution and precipitating reagent；The filler material is equivalent to a miniature reactor, is conducive to the nano particle of generation, nanometer Grain is further assembled into micron particles in microreactor.
The liquid-liquid co-precipitation fast reaction of this method can accurate artificial control condition, obtain target product.
Concentration, pH value, temperature and the charging rate pair of reactant during the liquid-liquid co-precipitation fast reaction of this method Particle size, pattern and the chemical property of the material can make a significant impact, and more than parameter synergistic effect can further be made It is standby go out with preferable layered crystal structure, even particle distribution, and the material with compared with high charge-discharge capacity.
The synthesis condition of this method is mild, simple for process, is easy to commercial application.
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments be only used for the present invention without For limiting the scope of the invention.Externally it is to be understood that after present disclosure has been read, those skilled in the art are to this hair Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.With Under embodiment in, the high gravity rotating packed bed reactor developed with Beijing University of Chemical Technology provides the super gravity field, turns Fast general control is 600-3000rpm, and the centrifugal acceleration control in super gravity field is 180-10000m/s2。
Embodiment 1：
Using hypergravity method, lithium-rich manganese-based anode material presoma and positive electrode are prepared.Richness manufactured in the present embodiment Lithium Mn-based material presoma, molecular formula Mn0.4Ni0.24Co0.16(CO3)0.8；Lithium-rich manganese-based anode material manufactured in the present embodiment The chemical formula of material is Li1.2Mn0.4Ni0.24Co0.16O2, specific preparation method is as follows：
(1), prepared by metal salt solution：The nitre of the manganese nitrate of 0.2mol, the nickel nitrate of 0.12mol, 0.08mol are weighed respectively The polyvinylpyrrolidone (PVP) of sour cobalt, 0.04mol, is dissolved in ultra-pure water, is configured to 2 liters of solution, so as to obtain The metal salt solution of 0.2mol/L.
(2), prepared by precipitant solution：The sodium carbonate of 0.42mol is weighed, is dissolved in ultra-pure water, is configured to 2 liters water-soluble Liquid obtains the precipitant solution that concentration is 0.21mol/L.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carried out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, obtains precipitation reaction product；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, reactant are pumped into speed as 300ml/min, and 25 DEG C of reaction temperature, the pH value of reaction system is controlled between 8-9, is used Ammonium hydroxide and acetic acid (0.1mol/L) adjust the pH value of reaction solution；
After the precipitation reaction product is filtered, sediment is obtained, the sediment is cleaned with ultra-pure water；By the precipitation after cleaning Object is placed in vacuum drying oven, is warming up to 110 DEG C, and dry 2h, obtains presoma, molecular formula is under vacuum degree≤10.0Pa Mn0.5Ni0.3Co0.2CO3。
(4), calcination processing：After 0.1mol presomas are mixed with the lithium carbonate of 0.075mol, in 900 DEG C of calcination processings 12 Hour, obtain lithium-rich manganese-based anode material Li1.2Mn0.4Ni0.24Co0.16O2。
Fig. 1 is lithium-rich manganese-based anode material presoma Mn0.4Ni0.24Co0.16(CO3)0.8Scanning electron microscope (SEM) Picture.Gained presoma Mn is can be seen that from above-mentioned picture0.4Ni0.24Co0.16(CO3)0.8Most of is in micron " peanut " shape knot Structure sphere ((a) and (b) in Fig. 1), it is a small amount of in micron spherical shape structure, the long axis scope of micron " peanut " for 1-3 μm, Short axle is from hundreds of nanometers to several microns etc..The fine structure of micron " peanut " is shown in (c) and (d) in Fig. 1, from figure The upper micron " peanut " that can be seen that is formed by nano wire self assembly, and nano wire thickness is more homogeneous, in 10nm or so.
Fig. 2 is lithium-rich manganese-based anode material Li1.2Mn0.4Ni0.24Co0.16O2SEM pictures.Compared with the pattern of presoma, Lithium-rich manganese-based anode material Li1.2Mn0.4Ni0.24Co0.16Pattern change, micron " peanut " structural evolution is into micron ball With micron ellipsoid structure.Main cause is the primary particle after high-temperature heat treatment --- nano wire fusion is nano particle, Granular size is at 50nm or so ((b) in Fig. 2)；And the secondary structure being made of primary particle --- the pattern of micron ball particle Also change, the particle size of micron ball particle is between 1-4 μm.
Fig. 3 is lithium-rich manganese-based anode material Li1.2Mn0.4Ni0.24Co0.16O2X-ray diffractogram (XRD).The figure is typical case α-NaFeO2Type layer structure XRD spectrum, without other miscellaneous peaks, it is single pure phase to illustrate the material obtained.
The test method of the chemical property of the lithium-rich manganese-based anode material of the present embodiment is as follows：
The Li prepared with this example1.2Mn0.4Ni0.24Co0.16O2CR2025 button cells are assembled into for positive electrode active materials： First, it is in mass ratio 8:1:1 by Li1.2Mn0.4Ni0.24Co0.16O2Microballoon, acetylene black and PVDF are scattered in N- crassitudes Slurry is made in ketone (NMP)；Then, with scraper plate coating machine by slurry coating in forming electrode slice on aluminium foil, electrode slice is in vacuum In 120 DEG C of dry 12h in drying box, 1cm is stamped out on electrode slice2Cathode disk；Battery pack is mounted in full of high-purity argon gas Glove box in complete, using lithium piece as cathode, Celgard2300 polypropylene porous films be membrane, electrolyte 1mol/L LiPF6Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1:1) mixed solution.It is assembled into button cell, It is tested.Tested using performance of lithium ion battery test cabinet, with the electric current of 25mA/g first by each constant-current charging of battery extremely 4.7V, then with 25mA/g by battery constant-current discharge to 2.0V, record discharge capacity for the first time, according to first discharge specific capacity= Positive active material quality, obtains first discharge specific capacity in discharge capacity/positive plate.
Fig. 4 is prepared lithium-rich manganese-based anode material Li1.2Mn0.4Ni0.24Co0.16O2First charge-discharge curve, test Voltage range is 2.0V to 4.6V, and under conditions of 25mA/g, discharge capacity is 251.2mAh/g for the first time, and initial charge capacity is 328.1mAh/g, for the first time efficiency reach 76.6%, after cycle 200 times, discharge capacity 224.6mAh/g, capacity retention ratio is 89.4%.
Embodiment 2：
Using hypergravity method, lithium-rich manganese base material presoma is prepared.Lithium-rich manganese base material forerunner manufactured in the present embodiment Body, molecular formula Mn0.58Ni0.18Co0.04(OH)1.6；The expression formula of lithium-rich manganese-based anode material manufactured in the present embodiment is Li1.2Mn0.4Ni0.24Co0.16O2, specific method is as follows：
(1) prepared by metal salt solution：The manganese nitrate of 0.725mol, the nickel nitrate of 0.225mol, 0.05mol are weighed respectively The PVP of cobalt nitrate, 0.08mol, is dissolved in ultra-pure water, is configured to 1 liter of solution, so as to obtain the metal salt solution of 1mol/L.
(2) prepared by precipitant solution：The sodium hydroxide of 2.1mol is weighed, is dissolved in ultra-pure water, is configured to 1 liter water-soluble Liquid obtains the precipitant solution that concentration is 2.1mol/L.
(3) prepared by presoma：Above-mentioned metal salt solution and precipitant solution are subjected to liquid-liquid in super gravity field reactor Fast reaction is co-precipitated, obtains precipitation reaction product；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, reactant are pumped into speed as 260ml/min, and 25 DEG C of reaction temperature, the pH value of reaction system is controlled between 11-12, The pH value of reaction solution is adjusted with ammonium hydroxide and acetic acid (0.1mol/L)；
After the precipitation reaction product is filtered, sediment is obtained, the sediment is cleaned with deionized water；It will be heavy after cleaning Starch is placed in vacuum drying oven, is warming up to 80 DEG C, is dried under vacuum degree≤10.0Pa, and vacuum drying time 6h is obtained To presoma, molecular formula Mn0.58Ni0.18Co0.04(OH)1.6。
(4), calcination processing：After 0.1mol presomas are mixed with the lithium carbonate of 0.15mol, in 850 DEG C of calcination processings 20 Hour, obtain lithium-rich manganese-based anode material Li1.2Mn0.58Ni0.18Co0.04O2。
Fig. 5 is presoma Mn prepared by the embodiment0.58Ni0.18Co0.04(OH)1.6SEM pictures.It can from picture Go out, gained presoma Mn0.58Ni0.18Co0.04(OH)1.6In micron chondritic, particle is than more uniform, and size is at 1-2 μm.Fig. 5 In (d) be shown micron ball fine structure, from figure as can be seen that micron ball be to be formed by nano-particles self assemble , granular size is more homogeneous, and grain size is in 10nm or so.
The primary particle of lithium-rich manganese-based anode material manufactured in the present embodiment is nano particle, and granular size is left in 20nm It is right；The particle size of the and secondary structure being made of primary particle --- micron ball is between 3-4 μm.
The test method of the chemical property of the lithium-rich manganese-based anode material of the present embodiment with embodiment 1, wherein, test electricity Pressure scope is 2.0V to 4.6V, and under conditions of 40mA/g, discharge capacity is 272.5mAh/g for the first time, and initial charge capacity is 332.5mAh/g, for the first time efficiency reach 81.9%.After cycle 100 times, discharge capacity 256.7mAh/g, capacity retention ratio is 91%.
Embodiment 3：
Using hypergravity method, lithium-rich manganese base material presoma is prepared.Lithium-rich manganese base material forerunner manufactured in the present embodiment Body, molecular formula Mn0.4Ni0.24Co0.16(CO3)0.8；The expression formula of lithium-rich manganese-based anode material manufactured in the present embodiment is Li1.2Mn0.4Ni0.24Co0.16O2, specific method is as follows：
(1), prepared by metal salt solution：The sulfuric acid of the manganese sulfate of 1mol, the nickel sulfate of 0.6mol, 0.4mol are weighed respectively Cobalt, the polyvinylpyrrolidone (PVP) of 0.04mol, is dissolved in ultra-pure water, is configured to 1 liter of solution, so as to obtain 2mol/L's Metal salt solution.
(2), prepared by precipitant solution：The sodium carbonate of 2.1mol is weighed, it is soluble in water, 1 liter of aqueous solution is configured to, is obtained Concentration is the precipitant solution of 2.1mol/L.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carried out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, obtains precipitation reaction object；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, reactant are pumped into speed as 200ml/min, 50 DEG C of reaction temperature, the pH value control of reaction system 8, with ammonium hydroxide and Acetic acid (0.1mol/L) adjusts the pH value of reaction solution；
After the precipitation reaction product is filtered, sediment is obtained, the sediment is cleaned with deionized water；It will be heavy after cleaning Starch is placed in vacuum drying oven, is warming up to 100 DEG C, is dried under vacuum degree≤10.0Pa, and vacuum drying time 6h is obtained To presoma, molecular formula Mn0.4Ni0.24Co0.16(CO3)0.8。
(4), calcination processing：After 0.1mol presomas are mixed with the lithium carbonate of 0.15mol, 800 DEG C of calcination processings are carried out 20 it is small when, obtain a kind of lithium-rich manganese-based anode material Li1.2Mn0.4Ni0.24Co0.16O2。
Above-mentioned presoma is in micron chondritic, and size is 4-5 μm, and micron ball is formed by nano-particles self assemble, Grain diameter is 8-10nm.
The primary particle of lithium-rich manganese-based anode material manufactured in the present embodiment is nano particle, and granular size is in 8nm or so； The particle size of the and secondary structure being made of primary particle --- micron ball is between 3-4 μm.
The test method of the chemical property of the lithium-rich manganese-based anode material of the present embodiment with embodiment 1, wherein, test electricity Pressure scope is 2.0V to 4.7V, and under conditions of 25mA/g, discharge capacity is 245.4mAh/g for the first time, and initial charge capacity is 272.3mAh/g, for the first time efficiency reach 90.1%；Test voltage scope is 2.0V to 4.6V, under conditions of 25mA/g, cycles 200 After secondary, capacity 214.5mAh/g, capacity retention ratio 87.4%.
Embodiment 4
Using hypergravity method, lithium-rich manganese base material presoma is prepared.Lithium-rich manganese base material forerunner manufactured in the present embodiment Body, molecular formula Mn0.58Ni0.18Co0.04(CO3)1.6；The expression formula of lithium-rich manganese-based anode material manufactured in the present embodiment is Li1.2Mn0.58Ni0.18Co0.04O2, specific method is as follows：
(1), prepared by metal salt solution：The manganese chloride of 0.725mol, the nickel sulfate of 0.225mol, 0.05mol are weighed respectively Cobalt nitrate, the PVP of 0.08mol, be dissolved in ultra-pure water, be configured to 1 liter of solution, so as to obtain 1mol/L metal salt solutions.
(2), prepared by precipitant solution：The sodium carbonate of 1.05mol is weighed, it is soluble in water, 1 liter of aqueous solution is configured to, is obtained It is 1.05mol/L precipitant solutions to concentration.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carried out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, obtains precipitation reaction object；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, reactant are pumped into speed as 300ml/min, and 55 DEG C of reaction temperature, the pH value of reaction system is controlled between 8-9, is used Ammonium hydroxide and acetic acid (0.1mol/L) adjust the pH value of reaction solution；
After the precipitation reaction product is filtered, sediment is obtained, the sediment is cleaned with deionized water；It will be heavy after cleaning Starch is placed in vacuum drying oven, is warming up to 110 DEG C, is dried under vacuum degree≤10.0Pa, and vacuum drying time 2h is obtained To presoma, molecular formula Mn0.58Ni0.18Co0.04(CO3)1.6。
(4), calcination processing：After 0.1mol presomas are mixed with the lithium carbonate of 0.15mol, in 1000 DEG C of calcination processings 8 Hour, obtain a kind of lithium-rich manganese-based anode material Li1.2Mn0.58Ni0.18Co0.04O2。
Above-mentioned presoma is in micron chondritic, and size is 3-4 μm, and micron ball is formed by nano-particles self assemble, Grain diameter is 8-10nm.
The primary particle of lithium-rich manganese-based anode material manufactured in the present embodiment is nano particle, and granular size is left in 20nm It is right；The particle size of the and secondary structure being made of primary particle --- micron ball is between 3-4 μm.
The test method of the chemical property of the lithium-rich manganese-based anode material of the present embodiment with embodiment 1, wherein, test electricity Pressure scope is 2.0V to 4.6V, and under conditions of 25mA/g, discharge capacity is 282.6mAh/g for the first time, and initial charge capacity is 341.2mAh/g, for the first time efficiency reach 82.8%.After cycle 100 times, discharge capacity 272.1mAh/g, capacity retention ratio is 96.3%.
Embodiment 5
Using hypergravity method, lithium-rich manganese base material presoma is prepared.Lithium-rich manganese base material forerunner manufactured in the present embodiment Body, molecular formula Mn0.54Ni0.13Co0.13(CO3)1.6；The expression formula of lithium-rich manganese-based anode material manufactured in the present embodiment is Li1.2Mn0.54Ni0.13Co0.13O2, specific method is as follows：
(1), prepared by metal salt solution：Weigh respectively the manganese nitrate of 0.135mol, 0.0325mol nickel nitrate, The cobalt nitrate of 0.0325mol, the PVP of 0.08mol, are dissolved in ultra-pure water, are configured to 2 liters of solution, so as to obtain 0.1mol/L Metal salt solution.
(2), prepared by precipitant solution：The sodium carbonate of 0.21mol is weighed, it is soluble in water, 2 liters of aqueous solution is configured to, is obtained It is 0.105mol/L precipitant solutions to concentration；
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carried out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, obtains precipitation reaction object；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, reactant are pumped into speed as 300ml/min, and 60 DEG C of reaction temperature, the pH value of reaction system is controlled between 8-9, is used Ammonium hydroxide and acetic acid (0.1mol/L) adjust the pH value of reaction solution；
After the precipitation reaction product is filtered, sediment is obtained, the sediment is cleaned with deionized water；It will be heavy after cleaning Starch is placed in vacuum drying oven, is warming up to 100 DEG C, is dried under vacuum degree≤10.0Pa, and vacuum drying time 3h is obtained To presoma, molecular formula Mn0.54Ni0.13Co0.13(CO3)1.6；
(4), calcination processing：After 0.1mol presomas are mixed with the lithium carbonate lithium of 0.15mol, carry out at 950 DEG C of calcinings Manage 12 it is small when, obtain a kind of lithium-rich manganese-based anode material Li1.2Mn0.54Ni0.13Co0.13O2.Above-mentioned presoma is in the spherical knot of micron Structure, size are 1-2 μm, and micron ball is formed by nano-particles self assemble, grain diameter 4-5nm.
The microstructure of lithium-rich manganese-based anode material manufactured in the present embodiment is：Primary particle is nano particle, and particle is big It is small in 6-8nm or so；And the particle size for the secondary structure-micron ball being made of primary particle is between 1-3 μm.
The test method of the chemical property of the lithium-rich manganese-based anode material of the present embodiment with embodiment 1, wherein, test electricity Pressure scope is 2.0V to 4.6V, and under conditions of 25mA/g, discharge capacity is 268.4mAh/g for the first time, and initial charge capacity is 301.2mAh/g, for the first time efficiency reach 89.1%.After cycle 100 times, discharge capacity 256.1mAh/g, capacity retention ratio is 95.4%.
Embodiment 6
Using hypergravity method, lithium-rich manganese base material presoma is prepared.Lithium-rich manganese base material forerunner manufactured in the present embodiment Body, molecular formula Mn0.54Ni0.13Co0.13(OH)1.6；The chemical formula of lithium-rich manganese-based anode material manufactured in the present embodiment is Li1.2Mn0.54Ni0.13Co0.13O2, specific method is as follows：
(1), prepared by metal salt solution：The manganese chloride of 1.35mol, the nickel chloride of 0.325mol, 0.325mol are weighed respectively Cobalt chloride, the PVP of 0.2mol, be dissolved in ultra-pure water, be configured to 1 liter of solution, so as to obtain 2mol/L metal salt solutions.
(2), prepared by precipitant solution：The sodium hydroxide of 4.2mol is weighed, it is soluble in water, 1 liter of aqueous solution is configured to, is obtained It is 4.2mol/L precipitant solutions to concentration.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carried out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, and the wherein centrifugal acceleration in super gravity field is 800m/s2, it is 300ml/ that reactant, which is pumped into speed, Min, rotating speed are 1200rpm, and 60 DEG C of reaction temperature, the pH value of reaction system is controlled between 11-12, with ammonium hydroxide and acetic acid (0.1mol/L) adjusts the pH value of reaction solution；
After the precipitation reaction product is filtered, sediment is obtained, the sediment is cleaned with deionized water or ultra-pure water；It will be clear Sediment after washing is placed in vacuum drying oven, is warming up to 100 DEG C, is dried under vacuum degree≤10.0Pa, during vacuum drying Between for 3h, obtain presoma, molecular formula Mn0.54Ni0.13Co0.13(OH)1.6。
(4), calcination processing：After 0.1mol presomas are mixed with the lithium carbonate of 0.15mol, in 850 DEG C of calcination processings 12 Hour, obtain a kind of lithium-rich manganese-based anode material Li1.2Mn0.54Ni0.13Co0.13O2。
Above-mentioned presoma is in micron chondritic, and size is 8-10 μm, and micron ball is formed by nano-particles self assemble, Grain diameter is 8-10nm.
The microstructure of lithium-rich manganese-based anode material manufactured in the present embodiment is：Primary particle is nano particle, and particle is big It is small in 10-12nm or so；And the particle size for the secondary structure-micron ball being made of primary particle is between 8-12 μm.
The test method of the chemical property of the lithium-rich manganese-based anode material of the present embodiment with embodiment 1, wherein, test electricity Pressure scope is 2.0V to 4.6V, and under conditions of 25mA/g, discharge capacity is 282.6mAh/g for the first time, and initial charge capacity is 351.1mAh/g, for the first time efficiency reach 81.5%.After cycle 100 times, discharge capacity 252.1mAh/g, capacity retention ratio is 89.2%.

Claims (14)

1. a kind of preparation method of lithium-rich manganese-based anode material presoma, which is characterized in that this method comprises the following steps：
Metal salt solution preparation process：Metal salt and surfactant are mixed with water, dissolving obtains metal salt solution, described Metal salt is made of manganese salt, cobalt salt and nickel salt；The molar ratio of the manganese salt, nickel salt and cobalt salt is y:z:(1-x-y-z), wherein 0.1 ＜ x≤0.3,0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0；In the metal salt solution, metal cation is dense It spends for 0.01mol/L-2.0mol/L；
Precipitant solution preparation process：Precipitating reagent stirring and dissolving soluble in water is taken, obtains precipitant solution；The precipitant solution Concentration be 0.0105mol/L~2.1mol/L；
Forerunner's preparation step：The metal salt solution and the precipitant solution are carried out in super gravity field reactor liquid- Liquid coprecipitation reaction, then sediment is obtained after being filtered processing, then the sediment is started the cleaning processing, at vacuum drying Reason, obtains the presoma；In forerunner's preparation step, the centrifugal acceleration in the super gravity field is 180- 10000m/s2, rotating speed 600-3000rpm, the metal salt solution and the precipitant solution are pumped into speed as 20ml/ Min~300ml/min, the reaction temperature of the liquid-liquid coprecipitation reaction is 20~60 DEG C；In the liquid-liquid coprecipitation reaction, Reaction solution residence time in reactor is only 0.001-0.1s.
2. the preparation method of lithium-rich manganese-based anode material presoma according to claim 1, it is characterised in that：
In metal salt solution preparation process, the manganese salt is：One kind or more in manganese nitrate, manganese acetate, manganese chloride and manganese sulfate Kind；
The nickel salt is：One or more in nickel nitrate, nickel acetate, nickel chloride and nickel sulfate；
The cobalt salt is：One or more in cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate.
3. the preparation method of lithium-rich manganese-based anode material presoma according to claim 1 or claim 2, it is characterised in that：
In the metal salt solution preparation process, the surfactant is polyvinylpyrrolidone；In the metal salt solution, The molar ratio of the surfactant and metal cation is 1：(10-50).
4. the preparation method of lithium-rich manganese-based anode material presoma according to claim 1 or claim 2, it is characterised in that：It is described heavy Shallow lake agent is sodium hydroxide, lithium hydroxide, ammonium hydrogen carbonate, ammonium carbonate or sodium carbonate.
5. the preparation method of lithium-rich manganese-based anode material presoma according to claim 1 or claim 2, it is characterised in that：It is described super Centrifugal acceleration in gravitational field is 800m/s2, the speed that is pumped into of the metal salt solution and the precipitant solution is 100ml/min~200ml/min, reaction temperature are 40~60 DEG C, and the pH value of the reaction system is controlled between 7-12.
6. the preparation method of lithium-rich manganese-based anode material presoma according to claim 5, it is characterised in that：The presoma In preparation process, the pH value of reaction solution is adjusted with ammonia spirit and acetum.
7. the preparation method of lithium-rich manganese-based anode material presoma according to claim 5, it is characterised in that：The presoma In preparation process, the cleaning treatment is with a kind of cleaning in deionized water, ultra-pure water, absolute ethyl alcohol or acetone or uses it One or more of be respectively washed.
8. the preparation method of lithium-rich manganese-based anode material presoma according to claim 7, it is characterised in that：The metal salt In solution preparation step and precipitant solution preparation process, the water for deionized water or purity reach deionized water purity with On water.
9. the lithium-rich manganese-based anode material presoma prepared using any the methods of claim 1-8, which is characterized in that described The chemical general formula of presoma is：MnyNizCo1-x-y-z(OH)2(1-x)Or MnyNizCo1-x-y-z(CO3)1-x, wherein 0.1 ＜ x≤0.3, 0.33≤y≤0.6,0<Z≤0.5 and 1-x-y-z >=0；The presoma is the micron ball that nano particle or nano wire are assembled into； A diameter of 2-10nm of nano particle or nano wire in the presoma, the grain size of the micron ball in the presoma is 1-10 μm。
10. a kind of preparation method of lithium-rich manganese-based anode material, it is characterised in that：This method comprises the following steps：
Calcination processing step：Calcination processing is carried out after presoma described in claim 9 is mixed with lithium salts, obtain it is lithium-rich manganese-based just Pole material.
11. the preparation method of lithium-rich manganese-based anode material according to claim 10, it is characterised in that：The calcination processing step In rapid, the temperature of the calcination processing is 600 DEG C~1000 DEG C, time 6h-30h.
12. the preparation method of lithium-rich manganese-based anode material according to claim 11, it is characterised in that：The lithium salts is carbonic acid One or more in lithium, lithium oxalate and lithium hydroxide；The presoma is 1 with the lithium molar ratio in the lithium salts:(1- 1.5)。
13. the preparation method of lithium-rich manganese-based anode material according to claim 12, it is characterised in that：The presoma and institute It is 1 to state the lithium molar ratio in lithium salts:1.5.
14. the lithium-rich manganese-based anode material prepared using method any one of claim 10-13, it is characterised in that：Institute The chemical general formula for stating lithium-rich manganese-based anode material is Li1+xMnyNizCo1-x-y-zO2, wherein 0.1 ＜ x≤0.3,0.33≤y≤ 0.6,0<Z≤0.5 and 1-x-y-z >=0, the lithium-rich manganese-based anode material are the micron ball that nano particle is assembled into；The richness A diameter of 1-30nm of nano particle in lithium manganese-based anode material, the grain size of the micron ball of the lithium-rich manganese-based anode material are 1-10μm。
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