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CN106564967A - Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof - Google Patents

Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof Download PDF

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CN106564967A
CN106564967A CN201610931894.5A CN201610931894A CN106564967A CN 106564967 A CN106564967 A CN 106564967A CN 201610931894 A CN201610931894 A CN 201610931894A CN 106564967 A CN106564967 A CN 106564967A
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lithium
rich manganese
manganese
presoma
anode material
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CN106564967B (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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    • 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
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Abstract

The invention belongs to the field of electrode material preparation and relates to a lithium-rich manganese-based cathode material precursor, a cathode material and a preparation method thereof. The preparation method comprises the following steps: mixing metal salts (manganese salt, cobalt salt and nickel salt) and a surfactant and water, and dissolving to obtain a metal salt solution; putting a precipitant in water, stirring and dissolving to obtain a precipitant solution; carrying out liquid-liquid coprecipitation reaction on the metal salt solution and the precipitant solution in a hypergravity field reactor, filtering, cleaning, and carrying out vacuum drying so as to obtain a precursor; mixing the precursor and lithium salt and then calcining so as to obtain the lithium-rich manganese-based cathode material. By the coprecipitation method based on the hypergravity technology, the lithium-rich manganese-based cathode material precursor with primary particle being below 100 nm and secondary particle being 1-10 microns is rapidly prepared, and furthermore the prepared cathode material has advantages of uniform component distribution and particle size distribution, small granularity and high activity. Initial irreversible capacity can be reduced, and cycle performance of a lithium ion secondary battery can be enhanced.

Description

Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof
Technical field
The invention belongs to electrode material preparation field, and in particular to a kind of lithium-rich manganese-based anode material presoma, positive pole material Material and preparation method thereof.
Background technology
Lithium-rich manganese-based anode material, is the class novel anode material succeeded in developing in recent years；It is substantially a class layer Shape compound L i [Li1/3Mn2/3]O 2And LiMO2The solid solution cathode material of (M=Ni, Co, Mn) composition, its 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.) to compare, such material has higher working voltage platform (up to more than 4.8V), higher specific capacity high (high Up to 300mAh/g), excellent high-temperature electrochemical properties, low price, aboundresources the advantages of, 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 part, bag Include：(1) material circulation process has analysis oxygen, brings potential safety hazard, 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 Weak point, by cladding, doping, surface preparation, constructs the methods such as 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 regulation to material crystal face Piece, the material shows good electrochemistry cycle performance and high rate performance, obtain such material electrokinetic cell, 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 with the control of pattern to its structure.Component, knot The complexity of structure causes its synthetic method also complex, and most of document reports are all using lithium salts and containing many element/transition metals Presoma (such as carbonate) carry out high-temperature calcination synthesis.Presoma containing many element/transition metals typically passes through chemical coprecipitation Method, sol-gal process, spray drying method, molte-salt synthesis etc. are prepared from.At present, most widely used lithium-rich manganese base material presoma Preparation method be chemical coprecipitation；But because traditional chemical coprecipitation course of reaction is usually entered in stirring reactor OK, stirring is difficult to make reactant mix homogeneously, so as to the precipitate component skewness for resulting in.Additionally, chemical precipitation reaction The precipitation of formation has huge surface energy, and precipitate in addition in large quantity of moisture is contained, and can cause in the precipitation in dry run Granule there is agglomeration, particle size is big, and skewness finally affects the performance of the material.Therefore chemical coprecipitation Shallow lake method is difficult to control to 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 prior art, the precursor synthesis method of rich lithium manganese is a lot, but the pluses and minuses having nothing in common with each other：
(1) Zhi Xiao sections, Liu Hongguang et al. have invented a kind of preparation method of lithium ion battery lithium-rich manganese-based anode material, The 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 nanorize process by the 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 precious, chapter Sue, Shi Jie, rising sun sun, 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. have invented a kind of preparation method of lithium-rich manganese-based ternary composite cathode material, and the 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 is obtained Optimization, but the process conditions required by the method are complicated, it is difficult to realize the control (Wu of grain graininess 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 microsphere stratiform rich lithium manganese base solid solution positive electrode and its preparation Method, the method is adulterated and spherical rich lithium manganese solid solution material by modes such as doping, spray drying, the performance of material Preferably, but the technique of spray drying used by the method is difficult to amplify, be 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 microsphere 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 with regard to lithium-rich manganese-based anode material presoma and positive electrode also has a lot：
(1) Na ion exchanges are Li ions from the corresponding material containing Na by Kim et al. ion exchanges, and then are obtained Obtained rich lithium manganese solid solution material.The high rate performance of the material is preferable, but the time used by ion-exchange process used by the 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 Close sintering and obtain hollow ball shape richness lithium manganese material, the material has higher specific capacity and high rate performance, but synthesis used is walked It is rapid more, and sinter under hot conditionss 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 sum, the method for the preparation lithium-rich manganese base material presoma and lithium-rich manganese base material of prior art, exists Process conditions are complicated, take longer, it is difficult to realize the control of grain graininess in the industrial production, big in the industrial production to be difficult to The problem of the 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 and the preparation method of positive electrode of production.
Supergravity reactor is then to produce 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 lift reaction rate.The big I mat of super gravity field adjusts rotating speed and is controlled by, and makes thing 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 little, energy efficiency It is high, mass transfer, heat transfer efficiency can be effectively improved, can be applicable to gas, liquid, solid biphase or three-phase reaction or separation and can be with Significantly improving product quality, 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 acquisition nano material precursor after liquid-liquid reactions；The method for preparing nano material is to nano material precursor with microwave field Heating and calcining is carried out, is made nano material precursor decompose or is turned to obtain nano material after crystalline substance.The nano material for preparing 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 of pollution.But, nano-particle prepared by the method, nano-particle will not be self-assembled into micron particle, 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 utilization high-gravity reactive precipitation prepares nano-zinc sulfide is invented, the method is with zinc nitrate and hydrogen sulfide as original Material, using hypergravity crystallization process, prepares nano-zinc sulfide.Compared with prior art, to prepare zinc sulfide cost lower for the technology, Uniform particle sizes, narrow particle size distribution, crystal formation is more complete.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of lithium-rich manganese-based anode material presoma And preparation method thereof, the method is micro- using liquid-liquid co-precipitation fast reaction acquisition presoma is carried out in super gravity field reactor Micro-nano structure, then obtain lithium-rich manganese-based anode material through heat treatment.The efficient quick advantage that the present invention is reacted using hypergravity, With reference to Chemical self-assembly method, a kind of method for quickly 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 for preparing lithium-rich manganese-based anode material 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, the method comprises the steps：
Metal salt solution preparation process：Slaine and surfactant are mixed with water, dissolving obtains metal salt solution, The slaine is made up of manganese salt, cobalt salt and nickel salt；
Precipitant solution preparation process：Precipitant stirring and dissolving soluble in water is taken, agent solution is precipitated；
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 carry out being precipitated thing after filtration treatment, then cleaning treatment, vacuum are carried out to the precipitate do Dry process, obtains the presoma.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred implementation, the metal In saline solution preparation process and precipitant solution preparation process, the water is deionized water, or purity reaches deionized water purity Water above.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred implementation, the metal In saline solution 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 dichloride. and nickel sulfate；
The cobalt salt is：One or more in cobalt nitrate, cobalt acetate, cobaltous chloride and cobaltous sulfate；
It is highly preferred that the mol 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 implementation, the metal In the metal salt solution of saline solution 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 implementation, the metal In saline solution preparation process, the surfactant is polyvinylpyrrolidone；In the metal salt solution, the surface activity Agent is 1 with the mol ratio of metal cation：(10-50).
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, as a kind of preferred implementation, the precipitation Agent is sodium hydroxide, Lithium hydrate, 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 implementation, the forerunner In preparation step, the centrifugal acceleration in the super gravity field is 180-10000m/s2, rotating speed is 600-3000rpm, described Metal salt solution and the precipitant solution pump into speed for 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 slaine The speed that pumps into of solution and the precipitant solution is 100ml/min～200ml/min, and reaction temperature is 40～60 DEG C, and this is anti- The pH value for answering system is controlled between 7-12；Further, the pH value of reactant liquor is adjusted from ammonia spirit and acetum.
In the preparation method of above-mentioned lithium-rich manganese-based anode material presoma, used as a kind of preferred implementation, its feature exists In：In forerunner's preparation step, the cleaning treatment is in deionized water, ultra-pure water, dehydrated alcohol or acetone Cleaning is planted, or is respectively washed with therein more than one.
Using the lithium-rich manganese-based anode material presoma of said method preparation, chemical general formula 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；Nano-particle or nano wire in the presoma A diameter of 2-10nm, the particle diameter of the micron ball in the presoma is 1-10 μm.
A kind of preparation method of lithium-rich manganese-based anode material, the method comprises the steps：
Calcination processing step：Calcination processing is carried out after above-mentioned presoma is mixed with lithium salts, lithium-rich manganese-based anode material is obtained Material.
In the preparation method of above-mentioned lithium-rich manganese-based anode material, as a kind of preferred implementation, the calcination processing step In rapid, the temperature of the calcination processing is 600 DEG C～1000 DEG C, and the time is 6h-30h；It is highly preferred that the lithium salts is carbonic acid One or more in lithium, lithium oxalate and Lithium hydrate；The presoma is 1 with the lithium mol ratio in the lithium salts:(1- 1.5), more preferably 1:1.5.
Using the lithium-rich manganese-based anode material of said method preparation, the chemical general formula of the 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 rich lithium The micron ball that manganese-based anode material is assembled into for nano-particle；Nano-particle in the lithium-rich manganese-based anode material it is a diameter of 1-30nm, the particle diameter of the micron ball of the lithium-rich manganese-based anode material is 1-10 μm.
Compared to existing technology, the present invention has the advantages that：
1. the coprecipitation that employing of the invention is based on high-gravity technology quickly prepares primary particle below 100 nanometers, and two Lithium-rich manganese-based anode material presoma of the secondary granule between 1-10 μm；The super gravity field that the present invention is adopted can speed up and strengthen Mass transport process, makes the aqueous metal salt in reactor reach mixing homogeneously 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, the method does not need ageing process, efficiently Energy-conservation, product quality is homogeneous, reproducible.
2. the present invention by realize in the stainless steel metal silk screen inserts in supergravity reactor metal salt solution with The emulsifying of precipitant；The inserts reactor miniature equivalent to, is conducive to the nano-particle for generating, and nano-particle is micro- Micron particle is further assembled in type reactor.
3. the liquid-liquid co-precipitation fast reaction of the present invention can accurate manual control condition, obtain target product.
4. the liquid-liquid of the present invention is co-precipitated concentration, pH value, temperature and the charging rate of the reactant during fast reaction Size, pattern and chemical property on the material can make a significant impact, and above parameter synergism can be further Prepare 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 gentle, process is simple, it is easy to commercial application.
6. the positive electrode of the present invention have little distributed components, granularity, even particle size distribution, it is active high the characteristics of, The cycle performance of the lithium rechargeable battery of irreversible capacity, raising with the material as positive electrode first can be reduced.
7. the inventive method is simple, and quickly, solution mix homogeneously, the properties of sample of preparation improves a lot.Hypergravity reacts Device is then to produce powerful super gravity field using rotation at a high speed, makes fluid reactant that mass transfer and heat transfer effect are improved in super gravity field Rate and lift reaction rate.The big I mat of super gravity field adjusts rotating speed and is controlled by, and 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- The equipment volume of answering device is little, energy efficiency is high, can effectively improve mass transfer, heat transfer efficiency, can be applicable to the biphase of gas, liquid, solid Or three-phase reaction or separation and can significantly improving 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 of the lithium-rich manganese-based anode material presoma that embodiment 1 is prepared Piece, wherein, (a), (b), (c) it is different with the amplification of (d).
Fig. 2 is the SEM pictures of the lithium-rich manganese-based anode material that embodiment 1 is prepared, wherein, (a), the times magnification of (b) Number is different.
Fig. 3 is X-ray diffraction (XRD) figure of the lithium-rich manganese-based anode material that embodiment 1 is prepared.
Fig. 4 is the lithium rechargeable battery of the lithium-rich manganese-based anode material that prepared using embodiment 1 as positive electrode First charge-discharge curve chart.
Fig. 5 is the SEM pictures of the lithium-rich manganese-based anode material presoma that embodiment 2 is prepared, wherein, (a), (b), C () is different with the amplification of (d).
Specific embodiment
A kind of preparation method of lithium-rich manganese-based anode material presoma, comprises the steps：
It is prepared by step one, metal salt solution：By a certain percentage by the manganese salt of solubility, cobalt salt and nickel salt (i.e. slaine) with And surfactant mixes 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 dichloride. and nickel sulfate；
Above-mentioned cobalt salt is：One or more in cobalt nitrate, cobalt acetate, cobaltous chloride and cobaltous sulfate.
In the metal salt solution, metal cation is made up of nickel ion, cobalt ion and manganese ion, and total concentration is 0.01mol/ L-2.0mol/L (exemplarily, can for 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 scope arbitrarily between the two)；
The mol ratio (i.e. the mol ratio of nickel ion, cobalt ion 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 activity Agent is 1 with the mol ratio of metal cation：(10-50) (can be exemplarily, 1：10、1：15、1：20、1：25、1：30、1： 40、1：45、1：Scope in 50 grades arbitrarily or arbitrarily between the two).It is assembled into can nano-particle using surfactant Micron ball, surfactant is excessive or very few is all unfavorable for nano-particles self assemble into micron ball.
It is prepared by step 2, precipitant solution：Precipitant stirring and dissolving soluble in water is taken, agent solution is precipitated.
Above-mentioned precipitant is sodium hydroxide, Lithium hydrate, ammonium hydrogen carbonate, ammonium carbonate or sodium carbonate etc.；In the precipitant In solution, its concentration be 0.0105mol/L～4.2mol/L (exemplarily, can for 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. arbitrarily or Scope arbitrarily between the two)；
In step one and step 2, the water for using is deionized water, or purity reaches the water more than purity of deionized water.
It is prepared by step 3, presoma：Metal salt solution and precipitant solution are carried out into liquid-liquid in super gravity field reactor Co-precipitation fast reaction, then carries out being precipitated thing after filtration treatment, then cleaning treatment is carried out to precipitate, 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 high gravity rotating packed bed reactor that the supergravity reactor of any model, such as Beijing University of Chemical Technology are developed, inserts are Stainless steel metal silk screen inserts, the concrete structure of the reactor can be found in the patent text of Application No. 201410188846.2 Offer.
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 Scope in arbitrarily or arbitrarily between the two), rotating speed be 600-3000rpm (exemplarily, can for 600rpm, 700rpm, Appoint in 1000rpm, 1200rpm, 1500rpm, 1800rpm, 2200rpm, 2500rpm, 2800rpm, 2900rpm, 3000rpm etc. Meaning or scope arbitrarily between the two), reactant (i.e. metal salt solution and precipitant solution) pump into speed for 20ml/min～ 300ml/min (exemplarily, can be 20ml/min, 50ml/min, 80ml/min, 90ml/min, 220ml/min, 240ml/ Scope in min, 250ml/min, 260ml/min, 280ml/min, 300ml/min etc. arbitrarily or arbitrarily between the two), reaction 20～60 DEG C of temperature (can be exemplarily, arbitrarily or any 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 pump into speed for 100ml/min～ 200ml/min (exemplarily, can for 100ml/min, 110ml/min, 120ml/min, 130ml/min, 140ml/min, It is both any or any in 150ml/min, 160ml/min, 170ml/min, 180ml/min, 190ml/min, 200ml/min etc. Between scope), 40～60 DEG C of reaction temperature (exemplarily, can for 40 DEG C, 43 DEG C, 45 DEG C, 48 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C, the scope in 60 DEG C etc. arbitrarily or arbitrarily between the two)；The pH value of the reaction system controls the (example between 7-12 Property ground, can be scope in 7,8,9,9.5,10,11,12 etc. arbitrarily or arbitrarily between the two), preferably with ammonia spirit and vinegar Acid solution (0.1mol/L) adjusts the pH value of reactant liquor；
The rotating speed of centrifugal acceleration and reactor, the diameter of reactor have relation, select above-mentioned parameter and on the one hand depend on The size and shape of supergravity reactor, on the other hand also depends on the power of motor and rotating speed of equipment.Reactant pumps into speed Degree depends on the factors such as concentration, the size and shape of reactor of reactant.The selection of reaction temperature is relevant with reactant, reaction If heat absorption, need to improve temperature, but, improving temperature can increase process costs, must consider to determine suitable reaction Temperature range.The pH value of reaction system, determines the OH in reaction system-Content, sphericity of product etc..Select above-mentioned reaction Condition, is mainly determined by equipment and reaction system.
Above-mentioned cleaning treatment, is a kind of cleaning in deionized water, ultra-pure water, dehydrated alcohol or acetone, or uses it One or more of be respectively washed；
Above-mentioned vacuum drying treatment, is that the precipitate after cleaning is placed in vacuum drying oven, is warming up to 80-110 DEG C of (example Property, can be the model in 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C etc. arbitrarily or arbitrarily between the two Enclose), (appoint in being exemplarily, 10Pa, 8Pa, 6Pa, 5Pa, 4Pa, 2Pa, 1Pa, 0.5Pa etc. in vacuum≤10.0Pa Meaning or scope arbitrarily between the two) under be dried, the time be 2h～6h (exemplarily, can for 2h, 2.5h, 3h, 3.5h, 4h, Scope in 5h, 5.5h, 6h etc. arbitrarily or arbitrarily between the two)；
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, reactant liquor residence time in reactor is only 0.001- 0.1s；
In this step, accelerate and strengthen mass transport process using super gravity field, make aqueous metal salt in reactor with it is heavy Shallow lake agent solution reaches the mix homogeneously of molecular scale, carries out chemical reaction, obtains the carbonate material or hydroxide of the metal Species material.
Presoma prepared by above method, is Mn with 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 Drive the micron ball that body is that nano-particle or nano wire are assembled into；Nano-particle or nano wire in the presoma it is a diameter of Below 100nm, preferably 2-10nm, the particle diameter 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 by the second particle of primary particle self assembly；Primary particle is nano wire Or nano-particle, particle diameter is in below 100nm；Second particle is micron ball, the micron ball can be it is circular, oval or Peanut shape granule, particle diameter is between 1-10 μm.
A kind of preparation method of lithium-rich manganese-based anode material, comprises the steps：
Calcination processing：Calcination processing is carried out after above-mentioned presoma is mixed with lithium salts, lithium-rich manganese-based anode material is obtained.
Above-mentioned lithium salts is one or more in lithium carbonate, lithium oxalate and Lithium hydrate；Lithium in the presoma and lithium salts Mol ratio is 1:(1-1.5) (such as 1:1.1、1:1.2、1:1.3、1:1.4), preferably 1:1.5；
The temperature of above-mentioned calcination processing be 600 DEG C～1000 DEG C (exemplarily, can for 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, the scope in 1000 DEG C etc. arbitrarily or arbitrarily between the two), the time is 6-30h (examples Property, can be the model in 6h, 8h, 10h, 15h, 18h, 20h, 23h, 25h, 28h, 30h etc. arbitrarily or arbitrarily between the two Enclose).Temperature is too low, it is impossible to form the crystalline phase for needing；Temperature is too high, has dephasign appearance, and performance is undesirable, additionally, temperature mistake High product is also easily lumpd.
The lithium-rich manganese-based anode material prepared using said method, with 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 is to receive The micron ball that rice grain is assembled into；A diameter of 1-30nm of the nano-particle in the lithium-rich manganese-based anode material, the rich lithium The particle diameter of the micron ball of manganese-based anode material is 1-10 μm.
The 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 granule between 1-10 μm；The super gravity field that the method is adopted can speed up and strengthen biography Matter process, makes the aqueous metal salt in reactor reach mixing homogeneously for molecular scale with liquid precipitation agent, carries out chemical anti- 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, the method does not need ageing process, efficiently section Can, product quality is homogeneous, reproducible.
The method in the inserts in supergravity reactor such as stainless steel metal silk screen inserts by realizing slaine The emulsifying of solution and precipitant；The inserts reactor miniature equivalent to, is conducive to the nano-particle for generating, nanometer Grain is further assembled into micron particle in microreactor.
The liquid-liquid co-precipitation fast reaction of the method can accurate manual control condition, obtain target product.
The liquid-liquid of the method is co-precipitated concentration, pH value, temperature and the charging rate pair of the reactant during fast reaction The size of the material, pattern and chemical property can make a significant impact, and above parameter synergism can further be made It is standby go out with preferable layered crystal structure, even particle distribution, and with the material compared with high charge-discharge capacity.
The synthesis condition of the method is gentle, process is simple, it is easy to commercial application.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments be only used for the present invention and not For limiting the scope of the present invention.Externally it should be understood that after present disclosure has been read, those skilled in the art are to this Bright to make various changes or modifications, these equivalent form of values equally fall within the application appended claims limited range.With Under embodiment in, the high gravity rotating packed bed reactor developed with Beijing University of Chemical Technology turns providing the super gravity field Fast general control is 600-3000rpm, and the centrifugal acceleration in super gravity field is controlled to 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, its molecular formula is 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, concrete preparation method is as follows：
(1), prepared by metal salt solution：Manganese nitrate, the nickel nitrate of 0.12mol, the nitre of 0.08mol of 0.2mol are weighed respectively The polyvinylpyrrolidone (PVP) of sour cobalt, 0.04mol, in being 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, in being dissolved in ultra-pure water, 2 liters water-soluble is configured to Liquid, obtains the precipitant solution that concentration is 0.21mol/L.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carry out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, is precipitated product；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, it is 300ml/min that reactant pumps into speed, and 25 DEG C of reaction temperature, the pH value of reaction system controls between 8-9, to use Ammonia and acetic acid (0.1mol/L) adjust the pH value of reactant liquor；
After the precipitation product is filtered, thing is precipitated, the precipitate is cleaned with ultra-pure water；By the precipitation after cleaning Thing is placed in vacuum drying oven, is warming up to 110 DEG C, and under vacuum≤10.0Pa 2h is dried, and obtains presoma, and its molecular formula is 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)0.8Great majority are in micron " Semen arachidis hypogaeae " shape knot Structure spheroid ((a) and (b) in Fig. 1), it is a small amount of in micron spherical shape structure, the major axis scope of micron " Semen arachidis hypogaeae " for 1-3 μm, Short axle is from hundreds of nanometer to several microns.(c) and (d) in Fig. 1 is shown the fine structure of micron " Semen arachidis hypogaeae ", from figure The upper micron " Semen arachidis hypogaeae " 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 " Semen arachidis hypogaeae " 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 up of primary particle --- the pattern of micron ball particle Also change, the 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, illustrates that the material for obtaining is single pure phase.
The method of testing of the chemical property of the lithium-rich manganese-based anode material of the present embodiment is as follows：
With Li prepared by 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 Li1.2Mn0.4Ni0.24Co0.16O2Microsphere, acetylene black and PVDF are scattered in N- crassitudes Slurry is made in ketone (NMP)；Then, slurry coating is formed into electrode slice on aluminium foil with scraper plate coating machine, electrode slice is in vacuum 12h is dried in 120 DEG C in drying baker, 1cm is stamped out on electrode slice2Negative pole disk；Battery is assembled in full of high-purity argon gas Glove box in complete, with lithium piece as negative pole, Celgard2300 polypropylene porous films be barrier film, electrolyte is 1mol/L LiPF6Ethylene carbonate (EC)/(volume ratio is 1 to dimethyl carbonate (DMC):1) mixed solution.It is assembled into button cell, 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 first, 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, first discharge capacity is 251.2mAh/g, and initial charge capacity is 328.1mAh/g, first efficiency reach 76.6%, after circulation 200 times, discharge capacity is 224.6mAh/g, and capability retention 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, its molecular formula is 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, concrete grammar 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, in being 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, in being dissolved in ultra-pure water, 1 liter water-soluble is configured to Liquid, obtains the precipitant solution that concentration is 2.1mol/L.
(3) prepared by presoma：Above-mentioned metal salt solution and precipitant solution are carried out into liquid-liquid in super gravity field reactor Co-precipitation fast reaction, is precipitated product；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, it is 260ml/min that reactant pumps into speed, and 25 DEG C of reaction temperature, the pH value of reaction system is controlled between 11-12, The pH value of reactant liquor is adjusted with ammonia and acetic acid (0.1mol/L)；
After the precipitation product is filtered, thing is precipitated, deionized water cleans the precipitate；It is heavy after by cleaning Starch is placed in vacuum drying oven, is warming up to 80 DEG C, is dried under vacuum≤10.0Pa, and vacuum drying time is 6h, is obtained To presoma, its molecular formula is 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.Can from picture Go out, gained presoma Mn0.58Ni0.18Co0.04(OH)1.6In micron chondritic, than more uniform, size is at 1-2 μm for granule.Fig. 5 In (d) it is shown that 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 particle diameter 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；And the secondary structure being made up of primary particle --- the size of micron ball is between 3-4 μm.
The method of testing 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, first discharge capacity is 272.5mAh/g, and initial charge capacity is 332.5mAh/g, first efficiency reach 81.9%.After circulation 100 times, discharge capacity is 256.7mAh/g, and capability retention 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, its molecular formula is 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, concrete grammar is as follows：
(1), prepared by metal salt solution：Manganese sulfate, the nickel sulfate of 0.6mol, the sulphuric acid of 0.4mol of 1mol are weighed respectively Cobalt, the polyvinylpyrrolidone (PVP) of 0.04mol, in being 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, obtain Concentration is the precipitant solution of 2.1mol/L.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carry out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, is precipitated reactant；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, reactant pumps into speed for 200ml/min, 50 DEG C of reaction temperature, the pH value control of reaction system 8, with ammonia and Acetic acid (0.1mol/L) adjusts the pH value of reactant liquor；
After the precipitation product is filtered, thing is precipitated, deionized water cleans the precipitate；It is heavy after by cleaning Starch is placed in vacuum drying oven, is warming up to 100 DEG C, is dried under vacuum≤10.0Pa, and vacuum drying time is 6h, is obtained To presoma, its molecular formula is 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 hours, 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； And the secondary structure being made up of primary particle --- the size of micron ball is between 3-4 μm.
The method of testing 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, first discharge capacity is 245.4mAh/g, and initial charge capacity is 272.3mAh/g, first efficiency reach 90.1%；Test voltage scope is 2.0V to 4.6V, under conditions of 25mA/g, circulation 200 After secondary, capacity is 214.5mAh/g, and capability retention is 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, its molecular formula is 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, concrete grammar is as follows：
(1), prepared by metal salt solution：Manganese chloride, the nickel sulfate of 0.225mol, the 0.05mol of 0.725mol are weighed respectively Cobalt nitrate, the PVP of 0.08mol, in being dissolved in ultra-pure water, 1 liter of solution is configured to, 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, obtain It is 1.05mol/L precipitant solutions to concentration.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carry out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, is precipitated reactant；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, it is 300ml/min that reactant pumps into speed, and 55 DEG C of reaction temperature, the pH value of reaction system controls between 8-9, to use Ammonia and acetic acid (0.1mol/L) adjust the pH value of reactant liquor；
After the precipitation product is filtered, thing is precipitated, deionized water cleans the precipitate；It is heavy after by cleaning Starch is placed in vacuum drying oven, is warming up to 110 DEG C, is dried under vacuum≤10.0Pa, and vacuum drying time is 2h, is obtained To presoma, its molecular formula is 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；And the secondary structure being made up of primary particle --- the size of micron ball is between 3-4 μm.
The method of testing 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, first discharge capacity is 282.6mAh/g, and initial charge capacity is 341.2mAh/g, first efficiency reach 82.8%.After circulation 100 times, discharge capacity is 272.1mAh/g, and capability retention 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, its molecular formula is 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, concrete grammar is as follows：
(1), prepared by metal salt solution：Weigh respectively the manganese nitrate of 0.135mol, the nickel nitrate of 0.0325mol, The cobalt nitrate of 0.0325mol, the PVP of 0.08mol, in being 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, obtain It is 0.105mol/L precipitant solutions to concentration；
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carry out in super gravity field reactor liquid- Liquid is co-precipitated fast reaction, is precipitated reactant；Centrifugal acceleration wherein in super gravity field is 800m/s2, rotating speed is 1200rpm, it is 300ml/min that reactant pumps into speed, and 60 DEG C of reaction temperature, the pH value of reaction system controls between 8-9, to use Ammonia and acetic acid (0.1mol/L) adjust the pH value of reactant liquor；
After the precipitation product is filtered, thing is precipitated, deionized water cleans the precipitate；It is heavy after by cleaning Starch is placed in vacuum drying oven, is warming up to 100 DEG C, is dried under vacuum≤10.0Pa, and vacuum drying time is 3h, is obtained To presoma, its molecular formula is 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 Reason 12 hours, obtains 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 is 1-2 μm, and micron ball is formed by nano-particles self assemble, and grain diameter is 4-5nm.
The microstructure of lithium-rich manganese-based anode material manufactured in the present embodiment is：Primary particle is nano-particle, and granule is big It is little in 6-8nm or so；And the size of the secondary structure-micron ball being made up of primary particle is between 1-3 μm.
The method of testing 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, first discharge capacity is 268.4mAh/g, and initial charge capacity is 301.2mAh/g, first efficiency reach 89.1%.After circulation 100 times, discharge capacity is 256.1mAh/g, and capability retention 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, its molecular formula is 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, concrete grammar is as follows：
(1), prepared by metal salt solution：Manganese chloride, the Nickel dichloride. of 0.325mol, the 0.325mol of 1.35mol are weighed respectively Cobaltous chloride, the PVP of 0.2mol, in being dissolved in ultra-pure water, 1 liter of solution is configured to, 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, obtain It is 4.2mol/L precipitant solutions to concentration.
(3), prepared by presoma：By above-mentioned metal salt solution and precipitant solution carry 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 pumps into speed Min, rotating speed is 1200rpm, and 60 DEG C of reaction temperature, the pH value of reaction system is controlled between 11-12, with ammonia and acetic acid (0.1mol/L) pH value of reactant liquor is adjusted；
After the precipitation product is filtered, thing is precipitated, deionized water or ultra-pure water clean the precipitate；Will be clear Precipitate after washing is placed in vacuum drying oven, is warming up to 100 DEG C, is dried under vacuum≤10.0Pa, during vacuum drying Between be 3h, obtain presoma, its molecular formula be 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 granule is big It is little in 10-12nm or so；And the size of the secondary structure-micron ball being made up of primary particle is between 8-12 μm.
The method of testing 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, first discharge capacity is 282.6mAh/g, and initial charge capacity is 351.1mAh/g, first efficiency reach 81.5%.After circulation 100 times, discharge capacity is 252.1mAh/g, and capability retention is 89.2%.

Claims (10)

1. a kind of preparation method of lithium-rich manganese-based anode material presoma, it is characterised in that the method comprises the steps：
Metal salt solution preparation process：Slaine and surfactant are mixed with water, dissolving obtains metal salt solution, described Slaine is made up of manganese salt, cobalt salt and nickel salt；
Precipitant solution preparation process：Precipitant stirring and dissolving soluble in water is taken, agent solution is precipitated；
Forerunner's preparation step：By the metal salt solution and the precipitant solution carry out in super gravity field reactor liquid- Liquid coprecipitation reaction, then carry out being precipitated thing after filtration treatment, then cleaning treatment is carried out to the precipitate, at vacuum drying Reason, obtains the presoma.
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 many in manganese nitrate, manganese acetate, manganese chloride and manganese sulfate Kind；
The nickel salt is：One or more in nickel nitrate, nickel acetate, Nickel dichloride. and nickel sulfate；
The cobalt salt is：One or more in cobalt nitrate, cobalt acetate, cobaltous chloride and cobaltous sulfate；
Preferably, the mol 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.
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, in the metal salt solution, metal cation concentration is 0.01mol/L- 2.0mol/L；
Preferably, in the metal salt solution preparation process, the surfactant is polyvinylpyrrolidone；The slaine In solution, the surfactant is 1 with the mol ratio of metal cation：(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 hydrate, ammonium hydrogen carbonate, ammonium carbonate or sodium carbonate；Preferably, the concentration of the precipitant solution is 0.0105mol/L～2.1mol/L.
5. the preparation method of lithium-rich manganese-based anode material presoma according to claim 1 or claim 2, it is characterised in that：Before described In driving preparation step, the centrifugal acceleration in the super gravity field is 180-10000m/s2, rotating speed is 600-3000rpm, institute The speed that pumps into for stating metal salt solution and the precipitant solution is 20ml/min～300ml/min, and the liquid-liquid co-precipitation is anti- The reaction temperature answered is 20～60 DEG C；Preferably, the centrifugal acceleration in the super gravity field is 800m/s2, the slaine The speed that pumps into of solution and the precipitant solution is 100ml/min～200ml/min, and reaction temperature is 40～60 DEG C, and this is anti- The pH value for answering system is controlled between 7-12；The pH value of reactant liquor is more preferably adjusted with ammonia spirit and acetum.
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 cleaning treatment is a kind of cleaning in deionized water, ultra-pure water, dehydrated alcohol or acetone, or uses it One or more of be respectively washed；
Preferably, in the metal salt solution preparation process and precipitant solution preparation process, the water is deionized water, or pure Degree reaches water more than deionized water purity.
7. the lithium-rich manganese-based anode material presoma for being prepared using the arbitrary methods described of claim 1-6, it is characterised 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 particle diameter of the micron ball in the presoma is 1-10 μm。
8. a kind of preparation method of lithium-rich manganese-based anode material, it is characterised in that：The method comprises the steps：
Calcination processing step：Calcination processing is carried out after presoma described in claim 8 is mixed with lithium salts, obtain it is lithium-rich manganese-based just Pole material.
9. the preparation method of lithium-rich manganese-based anode material according to claim 8, it is characterised in that：The calcination processing step In, the temperature of the calcination processing is 600 DEG C～1000 DEG C, and the time is 6h-30h；Preferably, the lithium salts is lithium carbonate, grass One or more in sour lithium and Lithium hydrate；The presoma is 1 with the lithium mol ratio in the lithium salts:(1-1.5), preferably For 1:1.5.
10. the lithium-rich manganese-based anode material for being prepared using the methods described of claim 8 or 9, it is characterised in that：It is described lithium-rich manganese-based The chemical general formula of positive electrode 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 micron ball that the lithium-rich manganese-based anode material is assembled into for nano-particle；The lithium-rich manganese-based anode material A diameter of 1-30nm of the nano-particle in material, the particle diameter of the micron ball of the lithium-rich manganese-based anode material is 1-10 μm.
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