CN109904402A - A kind of lithium-rich manganese base material and its preparation and application - Google Patents

A kind of lithium-rich manganese base material and its preparation and application Download PDF

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CN109904402A
CN109904402A CN201711305199.9A CN201711305199A CN109904402A CN 109904402 A CN109904402 A CN 109904402A CN 201711305199 A CN201711305199 A CN 201711305199A CN 109904402 A CN109904402 A CN 109904402A
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lithium
base material
soluble
rich manganese
salt
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CN201711305199.9A
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王二东
徐衫
孙公权
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中国科学院大连化学物理研究所
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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

Abstract

A kind of lithium-rich manganese base material, the lithium-rich manganese base material is a kind of multiphase heterojunction structure being made of layer structure and spinelle shape structure, its molecular formula is xLi2MnO3 (1-x) LiMO2yLiNi0.5Mn1.5O4, wherein 0.3 < x <, 1,0 < y < 0.1;M is one of iron, chromium, nickel, cobalt, magnesium, aluminium, zinc, copper or two kinds or more;The micron ball being made of on its is microcosmic the mutually chimeric nano particle of nano particle with lamination structure, spinel structure nano particle and layer structure and spinelle, the size range of nano particle are 20-500 nanometers, and the diameter range of microballoon is 5-20 microns.The preparation process of the lithium-rich manganese base material is without modified work high, the lithium-rich manganese base material of good cycling stability composite spinelle phase that obtains specific discharge capacity such as being doped, coat.Preparation process of the present invention is simple, easily controllable, good product consistency, is suitble to large-scale production.

Description

A kind of lithium-rich manganese base material and its preparation and application

Technical field

The invention belongs to lithium ion battery material technical fields, and in particular to a kind of lithium-rich manganese-based material of composite spinelle phase Expect xLi2MnO3 (1-x) LiMO2 and its preparation and application.

Background technique

The lithium-ion-power cell that the fast development of New-energy electric vehicle needs energy density higher and higher.And lithium ion Positive electrode in battery is then the restraining factors that lithium ion battery energy density is promoted.Therefore, it is desirable to improve lithium ion power The energy density of battery, the task of top priority are to research and develop the high novel anode material of specific capacity.

The positive electrode of existing most common commercialization has LiCoO2、LiMn2O4、LiFePO4, Li-Ni-Co-O and Li-Ni- The actual discharge specific capacity of Mn-Co-O material, these materials is less than 200mAh/g, it is difficult to meet the need of high capacity cell It asks.And the lithium-rich manganese-based xLi occurred in recent years2MnO3·(1-x)LiMO2Material is due to high capacity (practical first circle electric discharge ratio The super 250mAh/g of capacity), high voltage the characteristics of and become the hot spot researched and developed both at home and abroad.But conventional method such as coprecipitation, it is molten The lithium-rich manganese base material that sol-gel obtains leads to first circle coulombic efficiency due to phase transition of the crystal structure from stratiform to spinelle Difference, cyclical stability is poor, and capacity retention ratio is low and is unable to reach the practical application of business.Recently, gold and Wu et al. are using It is doped fluorine ion in the lithium-rich manganese base material of preparation, coats polyvinylpyrrolidone-manganese method to obtain containing sharp brilliant The lithium-rich manganese base material of stone phase, by maintaining stratiform to maintain the cyclical stability of material to the structure not avalanche of Spinel. However, these method of modifying procedure complexities, and some need atom deposition method etc. compared with high-tech means, can not really realize Heavy industrialization.Therefore, and a kind of specific discharge capacity simple there is an urgent need to develop preparation method is high, the richness of good cycling stability Lithium Mn-based material and preparation method thereof come meet large-scale commercial application the needs of.

Summary of the invention

A kind of lithium-rich manganese base material, the microcosmic lithium-rich manganese base material is above to have both layer structure and spinelle shape structure Composite construction, molecular formula is xLi2MnO3 (1-x) LiMO2yLiNi0.5Mn1.5O4, wherein 0.3 < x <, 1,0 < y < 0.1.Layered structure and spinelle shape structure are a kind of relationship of multiphase heterojunction structure.Multiphase refers to layer structure and point Two phases of spinel structure.When two-phase have similar crystal structure, similar atom interlamellar spacing and thermal expansion coefficient, will be in material Multiphase heterojunction structure is formed during material growth.In charge and discharge process, this structure is conducive to different alternate ions and moves It moves and diffusion, especially in the lithium-rich manganese base material, two kinds alternate to complement each other, and traditional lithium-rich manganese-based first lap is made to charge When phase conversion mechanism change, avoid oxygen from escaping, solve restrict the widely applied bottleneck problem of lithium-rich manganese base material.

A kind of preparation method of the lithium-rich manganese base material, includes the following steps,

1) by soluble ferric iron salt, soluble chromic salts, soluble nickel salt, soluble cobalt, soluble magnesium salt, soluble aluminum Salt, soluble zinc salt, one or more of soluble copper salt is soluble in water, and soluble manganese salt is added and forms solution A;

2) it is added sedimentation agent in step 1) acquired solution A, stirring is to dissolving to obtain solution B;

3) the step 2) solution B is placed in reaction vessel, it is made to issue unboiled water thermal response at 150~200 DEG C, reacted After be filtered, washed, dry to obtain presoma C;

4) first time calcining at constant temperature is carried out after grinding smashes in step 3) the presoma C, first time calcination temperature is 300-700 DEG C, calcination time 2-10h;

5) lithium compound is added in first time calcined product and is calcined to obtain the lithium-rich manganese base material for the second time, second Secondary calcination temperature is 500-900 DEG C, calcination time 3-15h;The first time calcination temperature is lower than second of calcination temperature.

The preparation method of another lithium-rich manganese base material, includes the following steps,

1) by soluble ferric iron salt, soluble chromic salts, soluble nickel salt, soluble cobalt, soluble magnesium salt, soluble aluminum Salt, soluble zinc salt, one or more of soluble copper salt is soluble in water, and soluble manganese salt is added and forms solution A;

2) it is added sedimentation agent in step 1) acquired solution A, stirring is to dissolving to obtain solution B;

3) the step 2) solution B is placed in reaction vessel, it is made to issue unboiled water thermal response at 150~200 DEG C, reacted After be filtered, washed, dry to obtain presoma C;

4) described to presoma C progress first time calcining in step 3), first time calcination temperature is 300-400 DEG C, calcining Time is 2-5h;Second of calcination temperature is the calcination time 2-10h greater than 400-600 DEG C;To the mixing after addition lithiumation object Object is calcined, and first time calcination temperature is 500-800 DEG C, calcination time 3-10h;Second of calcination temperature is greater than 800- 900 DEG C, calcination time 8-15h.

The present invention has obtained the micro- of the nano particle composition that the diameter of core-shell structure is 5~20 μm by calcining presoma Ball is separated core with shell by grinding, and it is anti-with lithium salts that the difference of core and the distribution of shell parts nickel manganese element ratio results in core part Spinel should be formed, shell parts react to form the lithium-rich manganese-based phase of stratiform with lithium salts.To the richness that product is composite spinelle phase Lithium Mn-based material.

Step 1) the soluble ferric iron salt is one or more of ferric nitrate, ferric acetate, ferric sulfate, iron chloride; Soluble chromic salts is one or more of chromic nitrate, chromium acetate, chromium sulfate, chromium chloride;Soluble nickel salt be nickel nitrate, One or more of nickel acetate, nickel sulfate, nickel chloride;Soluble cobalt is cobalt nitrate, cobalt acetate, cobaltous sulfate, chlorination One or more of cobalt;Soluble magnesium salt be one or both of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride with On;Aluminum soluble salt is one or more of alchlor, aluminum sulfate, aluminum nitrate, aluminium chloride;Soluble zinc salt is nitre One or more of sour zinc, zinc acetate, zinc sulfate, zinc chloride;Soluble copper salt be copper nitrate, copper acetate, copper sulphate, One or more of copper chloride;Soluble manganese salt is one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride or two Kind or more.

Alkalescent substance containing ammonium root described in step 2) is hexa, hexamethylene diamine, ammonium hydrogen carbonate, urea One or more of.

Reversible hydrolysis can occur in aqueous solution for these alkalescent substances, cause reaction can be in 7 PH≤10 < Weakly alkaline environment persistently carry out and do not generate concentration gradient, ensure that the pattern in presoma forming process, structure and element The consistency of distribution.Hydrolysis is as follows:

Hexa hydrolysis

Hexamethylene diamine hydrolysis

The double hydrolysis of ammonium hydrogen carbonate (degree of ionization of ammonium hydroxide is eager to excel than bicarbonate radical, and alkalescent is presented in hydrolysis)

Hydrolysis of urea reaction

NH2CONH2+H2O→2NH3+CO2

The total concentration of metal ion is 0.2~1mol/L in the step 1) solution A;

The concentration for the sedimentation agent being added in step 2) is 0.02~0.2molL-1

The molar ratio of metal ion and precipitating reagent in step 2) (in ammonium ion) is 0.1~0.5.

Lithium compound described in step 4) be one or both of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride with On;The amount for the substance that the lithium compound is added is so that the mass ratio of the material of lithium and manganese element is 3:2-4:1.

The time of the step 3) hydro-thermal reaction is 6-24 hours;The washing is to be cleaned using deionized water 2 times or more. Purpose is to wash presoma C to neutrality not introduce impurity.

Layer structure is on [001] crystal face, including by stacking lithium layer, oxygen layer, transition metal layer as stratiform repetitive unit The stratiform cobalt acid lithium structure of composition, and the stratiform Asia manganese being made of stacking lithium layer, oxygen layer, lithium manganese layer as stratiform repetitive unit Sour lithium structure;

The present invention is provided compared with other precipitating reagents such as sodium hydroxide using hexa etc. as precipitating reagent A kind of solution rich in ammonium ion, the hydrolysis of ammonium ion make to obtain a reaction environment without PH concentration gradient. When hydro-thermal method synthesizes lithium-rich manganese base material, 150 DEG C spinel structure material, 200 DEG C of whens, obtain layer structure material, therefore it is of the invention Hydrothermal temperature at 160~190 DEG C, obtain the stratiform lithium-rich manganese base material of composite spinelle phase.The present invention be different from et al. The method of coating spinelle phase material in existing stratiform lithium-rich manganese base material, also different from simply mixing two kinds of substance physics The method of conjunction.The present invention is directed to by grinding presoma manganese composite oxide, be allowed to disperse nano particle out, make during calcining At Elemental redistribution unevenness.After lithium salts is added using this feature, product a part forms stratiform lithium-rich manganese base material, a part of shape At Spinel Mn-based material, reach the compatibility of nanoscale phase and phase.Also, traditional lithium-rich manganese base material charges in first lap When due to lithium ion from stratiform manganous acid lithium Li2MnO3 abjection cause oxygen to escape, this be also restrict lithium-rich manganese base material it is extensive Using the main reason for.Material of the invention is when first lap charges, due to multiphase is heterogeneous, stratiform manganous acid lithium Li2MnO3 takes off the effect after lithium due to around Spinel, and combining oxygen atom makes structure to layer structure LiNi0.5Mn0.5O2 transformation avoids oxygen evolution, solves and restricts the root problem that lithium-rich manganese base material enters market.It should Preparation process is without modified work high, the good cycling stability composite spinelle that obtains specific discharge capacity such as being doped, coat The lithium-rich manganese base material of phase.Preparation process of the present invention is simple, easily controllable, good product consistency, is suitble to extensive raw It produces.

Detailed description of the invention

Fig. 1 is prepared by the lithium-rich manganese-based anode material of composite spinelle phase prepared by the embodiment of the present invention 1 and comparative example 1 The mutually lithium-rich manganese-based X-ray diffraction comparison diagram of the coating spinelle for preparing of not compound lithium-rich manganese-based and comparative example 2;

Fig. 2 is the charging and discharging curve of the lithium-rich manganese-based anode material of composite spinelle phase prepared by the embodiment of the present invention 1 Figure;

Fig. 3 is the embodiment of the present invention 1,2,3 and lithium-rich manganese-based anode material charge and discharge specific volume prepared by comparative example 2,3,4 Measure comparison diagram;

Fig. 4 is the charge and discharge of the lithium-rich manganese-based anode material without compound phase prepared by 1 sol-gal process of comparative example of the invention Electric curve graph;

Fig. 5 is the lithium-rich manganese-based anode material of coating spinelle phase prepared by 2 hydrothermal synthesis method of comparative example of the invention Charging and discharging curve figure;

Fig. 6 is that the lithium-rich manganese-based anode material of composite spinelle phase prepared by the embodiment of the present invention 1 and comparative example 1,2 are made The cycle performance comparison diagram of standby positive electrode charge and discharge in the case where multiplying power is 0.1C.

Specific embodiment

A specific embodiment of the invention is further described below in conjunction with attached drawing.

Embodiment 1

Prepare sample 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05LiN0.5Mn1.5O4.Stoichiometrically It is dissolved in deionized water than weighing nickel sulfate and manganese sulfate, forms the solution A that manganese ion concentration is 0.77mol/L;It is added six Methenamine obtains mixed solution B, and the molar ratio of nickel sulfate and hexa is 0.15;It is anti-that solution B is transferred to high pressure It answers in kettle, hydro-thermal 12h at 160 DEG C.After fully reacting will precipitating using deionized water filtration washing for several times, dry presoma C; After presoma C is ground several minutes using agate mortar, it is placed in corundum boat, is added in air with the heating rate of 5 DEG C/min Heat is heated to 600 DEG C, calcining at constant temperature 5h to 350 DEG C, calcining at constant temperature 3h, after be cooled to room temperature with the rate of temperature fall of 5 DEG C/min, 1.25 times of lithium hydroxide is added, is ground using agate mortar, obtains precursor B;Precursor B is placed in corundum boat, in sky 700 DEG C, calcining at constant temperature 5h are heated to the heating rate of 5 DEG C/min in gas, is heated to 850 DEG C, calcining at constant temperature 10h, using Ma Nao mortar grinder finally obtains the lithium-rich manganese-based anode material 0.4Li2MnO3 of composite spinelle phase 0.35LiNi0.5Mn0.5O2·0.05LiMn2O4.Thus obtained microsphere shape lithium-rich manganese base material diameter is 10 microns, by size 20- 50 nanometers of particle composition.Its X-ray diffraction (XRD) is shown in Fig. 1, and charging and discharging curve figure is shown in that Fig. 2, charge-discharge performance figure are shown in figure 3, positive electrode cycle performance of charge and discharge in the case where multiplying power is 0.1C is shown in Fig. 6.

Embodiment 2

Prepare sample 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05Li0.5Mn1.5O4.Stoichiometrically It weighs nickel sulfate and manganese sulfate is dissolved in deionized water, form the solution A that manganese ion concentration is 0.77mol/L;Urea is added Mixed solution B, the molar ratio of nickel sulfate and urea are 0.15;Subsequent step finally obtains composite spinelle phase with embodiment 1 Lithium-rich manganese-based anode material 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05LiMn2O4.Thus obtained microsphere shape richness lithium Mn-based material diameter is 20 microns, is made of 30-50 nanometers of particle of size.Its charging and discharging curve figure is shown in Fig. 3.

Embodiment 3

Prepare sample 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05Li0.5Mn1.5O4.Stoichiometrically It weighs nickel sulfate and manganese sulfate is dissolved in deionized water, form the solution A that manganese ion concentration is 0.77mol/L;Carbonic acid is added Hydrogen ammonium obtains mixed solution B, and the molar ratio of nickel sulfate and ammonium hydrogen carbonate is 0.15;Subsequent step finally obtains compound with embodiment 1 The lithium-rich manganese-based anode material 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05LiMn2O4 of Spinel.Gained is micro- Spherical lithium-rich manganese base material diameter is 30 microns, is made of 50-100 nanometers of particle of size.Its charge-discharge performance figure is shown in Fig. 3.

Comparative example 1

Sol-gal process prepares 0.4Li2MnO30.4LiNi0.5Mn0.5O2.Lithium hydroxide is stoichiometrically weighed, Nickel sulfate, cobaltous sulfate and manganese sulfate are dissolved in deionized water, and constant temperature stirs 30min at 60 DEG C, and forming manganese ion concentration is The solution A of 0.134mol/L;Solution is warming up to 120 DEG C with the heating rate of 5 DEG C/min, citric acid, which is added, to be made to dissolve, and is added Citric acid amount is the sum of added metal ion, and return stirring 90min evaporates solvent afterwards and obtains precursor A;Presoma is set In corundum boat, be heated to 450 DEG C, calcining at constant temperature 3h in air with the heating rate of 5 DEG C/min, after with the liter of 5 DEG C/min Warm rate is heated to 850 DEG C, calcining at constant temperature 12h, after be cooled to room temperature to obtain the lithium-rich manganese base material without Spinel 0.4Li2MnO3·0.4LiNi0.5Mn0.5O2.Its X-ray diffraction (XRD) is shown in Fig. 1, and charging and discharging curve figure is shown in Fig. 4, Multiplying power is that the cycle performance of charge and discharge under 0.1C is shown in Fig. 6.

Comparative example 2

Hydrothermal synthesis method prepares 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05LiNi0.5Mn1.5O4.By reality It applies 1 method of example and obtains presoma C;Presoma C is mixed with 1.25 times of lithium hydroxide, after being ground several minutes using agate mortar, is set In corundum boat, divide double sintering in air, centre is without milled processed, respectively in 450 DEG C of burnings 5h, 850 DEG C of burning 12h, Obtain the lithium-rich manganese-based anode material 0.4Li2MnO30.35LiNi0.5Mn0.5O2 of layer structure.Then take 0.05gPVP molten In 10ml deionized water, the above-mentioned product ultrasonic disperse of 1g is added, stirs 2h.5% manganese sulfate is added, stirring flashes to underflow, 90 DEG C of vacuum drying.Burn the lithium-rich manganese base material 0.4Li2MnO3 that 5h obtains coating spinelle phase for 750 DEG C in air 0.35LiNi0.5Mn0.5O2·0.05LiMn2O4.Its X-ray diffraction (XRD) is shown in Fig. 1, and charging and discharging curve figure is shown in Fig. 5, In the case where multiplying power is 0.1C, the cycle performance of charge and discharge is shown in Fig. 6.

Comparative example 3

Hydrothermal synthesis method prepares 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05LiNi0.5Mn1.5O4.By reality It applies 2 method of example and obtains presoma C;Subsequent step is shown in Fig. 3 with comparative example 2, charge-discharge performance figure.

Comparative example 4

Hydrothermal synthesis method prepares 0.4Li2MnO30.35LiNi0.5Mn0.5O20.05LiNi0.5Mn1.5O4.By reality It applies 3 method of example and obtains presoma C;, subsequent step is shown in Fig. 3 with comparative example 2, charge-discharge performance figure.

Claims (10)

1. a kind of lithium-rich manganese base material, it is characterised in that: the lithium-rich manganese base material is by layer structure and spinelle shape structure A kind of multiphase heterojunction structure constituted, molecular formula xLi2MnO3·(1-x)LiMO2·yLiNi0.5Mn1.5O4, wherein 0.3 < 1,0 < y < 0.1 of x <;M is one of iron, chromium, nickel, cobalt, magnesium, aluminium, zinc, copper or two kinds or more;
It is mutually chimeric by nano particle with lamination structure, spinel structure nano particle and layer structure and spinelle on its is microcosmic Nano particle composition micron ball, the size range of nano particle is 20-500 nanometers, and the diameter range of microballoon is 5-20 micro- Rice.
2. a kind of preparation method of lithium-rich manganese base material described in claim 1, it is characterised in that: include the following steps,
1) by soluble ferric iron salt, soluble chromic salts, soluble nickel salt, soluble cobalt, soluble magnesium salt, aluminum soluble salt can Soluble zinc salt, one or more of soluble copper salt is soluble in water, and soluble manganese salt is added and forms solution A;
2) it is added sedimentation agent in step 1) acquired solution A, stirring is to dissolving to obtain solution B;
3) the step 2) solution B is placed in reaction vessel, it is made to issue unboiled water thermal response at 150~200 DEG C, reaction terminates After be filtered, washed, dry to obtain presoma C;
4) in step 3) the presoma C, first time calcining at constant temperature after smashing, the first time calcination temperature is 300-700 DEG C, Calcination time is 2-10h;
Lithium compound is added in first time calcined product and is calcined to obtain the lithium-rich manganese base material for the second time;Second of calcining Temperature is 500-900 DEG C, calcination time 3-15h;The first time calcination temperature is lower than second of calcination temperature.
3. the preparation method of lithium-rich manganese base material as claimed in claim 2, it is characterised in that:
The step 4) is that the first time calcination process after presoma C is smashed is made of two steps, the first of presoma C after smashing Walking calcination temperature is 300-400 DEG C, calcination time 2-5h;Second step calcination temperature is greater than 400-600 DEG C, and calcination time is 2-10h;
Second of calcination process of the mixture after addition lithiumation object is made of two steps, first step calcination temperature is 500-800 DEG C, calcination time 3-10h;Second step calcination temperature is the calcination time 8-15h greater than 800-900 DEG C.
4. the preparation method of lithium-rich manganese base material as claimed in claim 2, it is characterised in that:
Step 1) the soluble ferric iron salt is one or more of ferric nitrate, ferric acetate, ferric sulfate, iron chloride;It is solvable Property chromic salts be one or more of chromic nitrate, chromium acetate, chromium sulfate, chromium chloride;Soluble nickel salt is nickel nitrate, acetic acid One or more of nickel, nickel sulfate, nickel chloride;Soluble cobalt is cobalt nitrate, in cobalt acetate, cobaltous sulfate, cobalt chloride One or more;Soluble magnesium salt is one or more of magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride;It can Dissolubility aluminium salt is one or more of alchlor, aluminum sulfate, aluminum nitrate, aluminium chloride;Soluble zinc salt be zinc nitrate, One or more of zinc acetate, zinc sulfate, zinc chloride;Soluble copper salt is copper nitrate, copper acetate, copper sulphate, chlorination One or more of copper;Soluble manganese salt be one or both of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride with On.
5. the preparation method of lithium-rich manganese base material as claimed in claim 2, it is characterised in that: the step 2) precipitating reagent is containing ammonium The alkalescent substance of root;Alkalescent substance containing ammonium root is hexa, hexamethylene diamine, ammonium hydrogen carbonate, in urea One or more.
6. the preparation method of lithium-rich manganese base material as claimed in claim 2, it is characterised in that: metal in the step 1) solution A The total concentration of ion is 0.2~1mol/L;Final concentration of 0.02~the 0.2mol/L for the sedimentation agent being added in step 2).
7. the preparation method of lithium-rich manganese base material as described in claim 2 or 6, it is characterised in that: in step 2) metal ion with The molar ratio of ammonium ion in precipitating reagent is 0.1~0.5.
8. the preparation method of lithium-rich manganese base material as claimed in claim 2, it is characterised in that: lithium compound described in step 4) is One or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride;The amount for the substance that the lithium compound is added is So that the mass ratio of the material of lithium and manganese element is 3:2-4:1.
9. the preparation method of lithium-rich manganese base material as claimed in claim 2, it is characterised in that: the step 3) hydro-thermal reaction when Between be 8-24 hours;The washing process is to be cleaned using water 2 times or more.
10. a kind of application of the lithium-rich manganese base material described in claim 1 as positive electrode active materials in lithium ion battery.
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CN102148372B (en) * 2011-03-08 2013-08-28 中信国安盟固利动力科技有限公司 Anode material of high-energy composite lithium-ion battery

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