CN104393260A - Preparation method of silicate coated material rich in lithium and manganese - Google Patents

Preparation method of silicate coated material rich in lithium and manganese Download PDF

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CN104393260A
CN104393260A CN201410539093.5A CN201410539093A CN104393260A CN 104393260 A CN104393260 A CN 104393260A CN 201410539093 A CN201410539093 A CN 201410539093A CN 104393260 A CN104393260 A CN 104393260A
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lithium manganese
rich lithium
preparation
coated
manganese
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徐士民
李宏斌
马毅
宋静静
徐一丹
都云
刘志坚
陈俊桦
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XI'AN ZHONGKE NEW ENERGY SCIENCE & TECHNOLOGY Co Ltd
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XI'AN ZHONGKE NEW ENERGY SCIENCE & TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a preparation method of a silicate coated material rich in lithium and manganese. The preparation method of the silicate coated material rich in lithium and manganese comprises the following steps: preparing a precursor of a positive material rich in lithium and manganese, calcining the precursor of the positive material rich in lithium and manganese in a muffle furnace to prepare the positive material rich in lithium and manganese, adding the positive material rich in lithium and manganese into ethyl orthosilicate, a lithium salt and a water and alcohol solution of soluble salts of other metals, carrying out reflux stirring, evaporating the solution, and calcining the obtained solid under the protection of vacuum or inert gas to prepare the orthosilicate coated positive material rich in lithium and manganese. The preparation method has the advantages of simplicity, easy implementation, low requirement on devices, no pollution in the reaction process, and good industrial application prospect.

Description

The preparation method of the coated rich lithium manganese material of a kind of silicate
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method of lithium ion secondary battery anode material.
Background technology
Smart mobile phone, panel computer, electric automobile (EV) and energy storage growth propose requirements at the higher level to lithium secondary battery.
Rich lithium manganese material has higher reversible capacity (250-320mAh/g) and excellent chemical property.Cause the common concern of scientist.
The people such as Numata took the lead in 1997 reporting the rich lithium manganese material of layed solid-solution, and structure is Li 2mnO 3liCoO 2.And new solid solution structure Li is proposed the earliest 2aO 3liBO 2design electrode material.
The general molecular formula of rich lithium manganese anode material can be expressed as: xLi 2mnO 3(1-x) LiMO 2(M=Ni, Co, Mn ..., 0≤x≤1), be by Li 2mnO 3and LiMO 2composite solid solution (Debasish Mohanty, Sergiy Kalnaus, Roberta A.Meisner, et al., the Structural transformation of a lithium-richLi formed 1.2co 0.1mn 0.55ni 0.15o 2cathode during high voltage cycling resolved by situ X-raydiffraction, Journal of Power Sources, 2013,229,239-248).Wherein Li 2mnO 3li [Li can be rewritten as 1/3mn 2/3] O 2, structure belongs to monoclinic system, and space group is the transition metal layer atom site that C2/m, part Li atom occupies it, and lithium atom and manganese atom are alternately arranged, the superlattice structure that two kinds of atomic buildings are certain.LiMO 2(M=Ni, Co, Mn) also belongs to layer structure, belongs to hexagonal crystal system.Via Li 2mnO 3and LiMO 2combination has the stratiform α-NaFeO that space group is R-3m 2type layer structure, belongs to hexagonal crystal system.
Due to rich lithium manganese xLi 2mnO 3(l-x) LiMO 2employ a large amount of Mn elements in material, make it cheap, fail safe is good, environmentally friendly, and this material also has excellent electrochemical properties simultaneously, as wide charging/discharging voltage and height ratio capacity high, and progressively become the desirable positive electrode of lithium ion battery.Although the rich lithium manganese material of stratiform, as the extremely promising positive electrode of one, has the performance of a series of excellence, also has certain defect simultaneously.As large irreversible and poor high rate performance.Irreversible capacity loss in cyclic process is (Wu Y, Murugan A V, Manthiram A., Surfacemodification of high capacity layered Li Li between 40 ~ 100mAh/g usually 0.2mn 0.54ni 0.13co 0.13o 2cathodes by AlPO 4, Journal of the Electrochemical Society, 2008,155, A635-A641).Due to component Li 2mnO 3electronic conductivity lower by (10 -6-10 -3s/cm), the high rate performance of this material is made to reduce.
In order to solve these problems above, improve xLi 2mnO 3(l-x) LiMO 2material first charge-discharge efficiency, improves its cyclical stability, and researcher proposes the method for various modification, as Surface coating, doping vario-property, acid treatment and circulation preliminary treatment etc.
Surface coating adopts liquid phase or solid phase method, rich lithium manganese material surface coating modification, improves the cycle performance of positive electrode, high rate performance, overcharging resisting performance and thermal stability etc. by the surface state changing electrode.Conventional coated material has Al 2o 3, ZnO, MnO 2, MgO, TiO 2, ZrO 2deng oxide, AlPO 4, CoPO 4, LiNiPO 4deng phosphate, Al (OH) 3hydroxide and material with carbon element.In addition, AlF 3, SrF 2also clad anode material is used to fluorides such as CaF.The coated shortcoming of fluoride is exactly that fluoride toxicity is comparatively large, and needs heat treatment under anhydrous nitrogen atmosphere, and process is more loaded down with trivial details.Except single-phase being coated with, the people such as Manthiram are to Li [Li 0.2mn 0.54ni 0.13co 0.13] O 2carry out double-contracting to cover.
In addition, patent is also had to metal oxide (oxide of manganese, the oxide of nickel, zinc oxide, cobalt/cobalt oxide) (application publication number CN102646830A), Al 3o 2(CN102916172A), ZrO 2(CN103094577A), rich lithium manganese material (application publication number: CN101859887A, CN103035906A) of metal fluoride (application publication number CN102496722A), nitride application publication number (application publication number CN103107330A) and Phosphate coating has carried out system research.
Doping can rock-steady structure, improves the first charge-discharge efficiency of material, cycle performance and high rate performance.Doped chemical conventional is at present Al, Zn, Zr, Co, Cr, Mg.Some rear-earth-doped (La are also there are now 3+and Ce 3+deng) appropriate cation doping can rock-steady structure, improves the first charge-discharge efficiency of material, cycle performance and high rate performance.
Due to SiO 4 4-polyanion Si-O key is very strong, can stop certain chemical erosion.Stop electrolyte and the reaction of rich lithium manganese material, reduce manganese ion stripping, thus increase reversible charge/discharge capacity and the cycle performance of rich lithium manganese material.
The people such as Z.X Yang are to LiCoO 2material adopts MnSiO 4coated, study its chemical property, find coated after, material also has 183.0mAhg afterwards circulation 20 times -1discharge capacity, exceed about 70mAhg than not coated -1, MnSiO simultaneously 4coatedly LiCoO can also be made equally 2more overcharging resisting (X Yang, W.S.Yang, D.G.Evans et al., Enhanced Overcharge Behavior and Thermal Stabilityof Commercial LiCoO2by Coating with a Novel Material., Electrochem.Commun., 2008,10,1136-1139).
Dongguan New Energy Technology Co adopts coated cobalt acid lithium (application publication number CN103199242A) of borosilicate.The structural formula of borosilicate is RO x-SiO 2-B 2o 3, 0<x≤3, the thickness of shell is 5-150nm, and the battery of coated preparation has more excellent cycle performance.
In addition, due to LiMSiO 4(M=Fe, Co, Mn etc.) material inherently can as a kind of positive electrode, and patent (CN101604745B, CN101635345B, CN101582495B, application publication number CN102088074A, CN102569788A) etc. reports using silicate as anode material for lithium-ion batteries.
But with the preparation method of the coated rich lithium manganese material of silicate, yet there are no report.
Summary of the invention
In order to improve rich lithium manganese material first charge-discharge efficiency, improve its cyclical stability, the present invention proposes the preparation method of the coated rich lithium manganese material of a kind of silicate, and propose the application in lithium ion secondary battery anode material of the coated rich lithium manganese material of silicate.
The present invention adopts following technical scheme:
A preparation method for the coated rich lithium manganese material of silicate, its special character is: comprise the following steps:
1) one or both in nickel salt, cobalt salt and lithium salts and manganese salt are made solution, heated solution jointly, then add citric acid, regulate solution ph with ammoniacal liquor, evaporating liquid, prepare rich lithium manganese anode material presoma;
2) rich lithium manganese anode material presoma is placed in stove to calcine, prepares rich lithium manganese anode material, rich lithium manganese anode material molecular formula is expressed as xLi 2mnO 3(1-x) LiMO 2, wherein M is one or more in Ni, Co and Mn, and x is the molar fraction in molecular formula, 0.1≤x≤0.9;
3) rich lithium manganese anode material is added in tetraethoxysilane, lithium salts and the water of other metal soluble-salts and the solution of alcohol; return stirring; then evaporate to dryness solution, calcines under vacuum or inert gas shielding, prepares the rich lithium manganese anode material that orthosilicate is coated.
Above-mentioned steps 1) in lithium salts, nickel salt, manganese salt and cobalt salt be respectively in the acetate of solubility, villaumite, nitrate and sulfate one or more.
Above-mentioned steps 1) in the temperature of heated solution be 40 ~ 95 DEG C, the retention time is at this temperature 0.5 ~ 9 hour; The scope of the pH value of the solution after regulating with ammoniacal liquor is 6 ~ 9; Heating-up temperature used during evaporating liquid is 40 ~ 95 DEG C.
Above-mentioned steps 2) in aerial calcining heat be 200 ~ 950 DEG C, calcination time is 0.5 ~ 9 hour.
Above-mentioned steps 3) in the temperature of return stirring be 40 ~ 95 DEG C, mixing time is 1 ~ 20 hour, and calcining heat is 200 ~ 950 DEG C, and the time of calcining is 0.5 ~ 9 hour.
Above-mentioned alcohol comprise in ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol and ethylene glycol one or more;
The volume ratio of described water and alcohol is 100 ~ 40:1 ~ 60.
Above-mentioned steps 3) in protective gas be one or more in nitrogen, helium and argon gas.
The coated quality of above-mentioned orthosilicate be the quality of rich lithium manganese anode material be 0.5 ~ 6%.
The invention has the beneficial effects as follows:
1, by preparation method of the present invention, a kind of new lithium ion secondary battery anode material is provided.
2, preparation method's preparation process of the present invention is simple, and equipment requirement is low, and course of reaction is pollution-free, and product uniformity is good, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 step 2) the 2% orthosilicate Li for preparing 2niSiO 4coated rich lithium manganese 0.5Li 2mnO 30.5LiNi 1/3mn 1/3co 1/3o 2the XRD spectra of positive electrode.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but the present invention is not limited thereto.
Embodiment raw materials, is analysis pure, content >=99.9%.
Embodiment 1
A preparation method for the coated rich lithium manganese material of silicate, comprises the following steps:
Step 1) preparation of rich lithium manganese anode material
By molecular formula 0.5Li 2mnO 30.5LiNi 1/3mn 1/3co 1/3o 2take lithium nitrate 10.86g (0.1575mol), nickel nitrate 4.83g (0.0166mol), cobalt nitrate 4.83g (0.0166mol), manganese acetate 16.37g (0.0668mol), preparing metal ion concentration and be the deionized water solution 500mL of 1.25mol/L, being placed in preheat temperature is in advance the thermostat water bath of 70 DEG C, under vigorous stirring, citric acid solution (preparation: 33.1g (0.1575mol) citric acid is dissolved in 500mL deionized water) is dropwise added in metal salt solution.Be about 7.5 by ammoniacal liquor adjust ph subsequently, at stirring and temperature is under 90 DEG C of conditions, solvent slowly boiled off, obtains green transparent colloidal sol.Then be positioned over more than 10h in 120 DEG C of air dry ovens, obtained xerogel rich lithium manganese anode material presoma.
The xerogel of synthesis rich lithium manganese anode material presoma is placed in box type furnace at 450 DEG C of pre-burning 5h, then calcines 8h in 850 DEG C, obtain 0.5Li 2mnO 30.5LiNi 1/3mn 1/3co 1/3o 2.
Step 2) orthosilicate Li 2niSiO 4coated rich lithium manganese 0.5Li 2mnO 30.5LiNi 1/ 3mn 1/3co 1/3o 2the preparation of positive electrode
By molecular formula Li 2niSiO 4take the tetraethoxysilane of 0.101g, 0.067g LiNO 3with 0.141gNi (NO 3) 2.6H 2o is dissolved in the mixed solution of 10mL ethanol and 10mL water, 60 DEG C of return stirring 8h.Be 50:1 according to the mass ratio of lithium-rich manganese base material and silicate, add 4g lithium-rich manganese base material in 50 DEG C of magnetic agitation 1h, and in the lower evaporate to dryness of stirring.By dried sample grinding evenly, in 600 DEG C of roastings 5 hours, be cooled to room temperature and grind, obtaining 2% orthosilicate Li 2niSiO 4coated rich lithium manganese 0.5Li 2mnO 30.5LiNi 1/3mn 1/3co 1/3o 2positive electrode.
Embodiment 2
A preparation method for the coated rich lithium manganese material of silicate, comprises the following steps: the reaction environment of embodiment 2 and condition are with embodiment 1, and difference is, in step 1) in, prepare 0.5Li 2mnO 30.5LiMn 1/2ni 1/2o 2rich lithium manganese anode material.
Step 2) Li 2mnSiO 4coated rich lithium manganese 0.5Li 2mnO 30.5LiMn 1/2ni 1/2o 2the preparation of positive electrode
Take the tetraethoxysilane of 0.8333g (4mmol), 0.8162g (8mmol) CH 3cOOLi2H 2o and 1.0040g (4mmol) Mn (NO 3) 24H 2o is dissolved in the mixed solution of 15mL ethanol and 15mL water, 65 DEG C of return stirrings 8 hours.Add 22.0006g (205mmol) 0.5Li 2mnO 30.5LiMn 1/2ni 1/2o 2rich lithium manganese material, in 60 DEG C of magnetic agitation 2h, is got this suspension-turbid liquid and is placed in drying box 50 DEG C of dry 12h.By dried sample grinding evenly, in 700 DEG C of roastings 3 hours, be cooled to room temperature and grind, obtaining orthosilicate Li 2mnSiO 4coated rich lithium manganese 0.5Li 2mnO 30.5LiMn 1/2ni 1/2o 2positive electrode.
Embodiment 3
A preparation method for the coated rich lithium manganese material of silicate, comprises the following steps: the reaction environment of embodiment 3 and condition are with embodiment 1, and difference is, in step 1) in, prepare 0.4Li 2mnO 30.6LiNi 1/2mn 1/2o 2rich lithium manganese anode material.
Step 2) Li 2mgSiO 4coated rich lithium manganese 0.4Li 2mnO 30.6LiNi 1/2mn 1/2o 2the preparation of positive electrode
Take the tetraethoxysilane of 1.5000g (7.2mmol), 1.4691g (14.4mmol) CH 3cOOLi2H 2o and 1.4638g (7.2mmol) MgCl 26H 2o is dissolved in the mixed solution of 20mL ethanol and 20mL water, 80 DEG C of return stirrings 20 hours.Add 38.5481g (370mmol) 0.4Li 2mnO 30.6LiNi 1/2mn 1/2o 2rich lithium manganese material, in 70 DEG C of magnetic agitation 1h, is got this suspension-turbid liquid and is placed in drying box 60 DEG C of dry 12h.By dried sample grinding evenly, in 400 DEG C of roastings 5 hours, be cooled to room temperature and grind, obtaining orthosilicate Li 2mgSiO 4coated rich lithium manganese 0.4Li 2mnO 30.6LiNi 1/2mn 1/2o 2positive electrode.
Embodiment 4
A preparation method for the coated rich lithium manganese material of silicate, comprises the following steps: the reaction environment of embodiment 4 and condition are with embodiment 1, and difference is, in step 1) in, prepare 0.3Li 2mnO 30.7LiNi 1/2mn 1/2o 2rich lithium manganese anode material.
Step 2) Li 2alSiO 4coated rich lithium manganese 0.3Li 2mnO 30.7LiNi 1/2mn 1/2o 2the preparation of positive electrode
Take the tetraethoxysilane of 0.8750g (4.2mmol), 0.8550g (8.4mmol) CH 3cOOLi2H 2o and 1.5756g (4.2mmol) Al (NO 3) 39H 2o is dissolved in the mixed solution of 10mL ethanol and 10mL water, 60 DEG C of return stirrings 12 hours.Add 21.436g (210mmol) 0.3Li 2mnO 30.7LiNi 1/2mn 1/2o 2rich lithium manganese material ultrasonic disperse 10min.60 DEG C of magnetic agitation 2h, get this suspension-turbid liquid and are placed in drying box 60 DEG C of dry 6h.By dried sample grinding evenly, in 800 DEG C of roastings 3 hours, be cooled to room temperature and grind, obtaining orthosilicate Li 2alSiO 4coated rich lithium manganese 0.3Li 2mnO 30.7LiNi 1/2mn 1/2o 2positive electrode.
Embodiment 5
A preparation method for the coated rich lithium manganese material of silicate, comprises the following steps: the reaction environment of embodiment 5 and condition are with embodiment 1, and difference is, in step 1) in, prepare 0.2Li 2mnO 30.8LiNi 1/2mn 1/2o 2rich lithium manganese anode material.
Step 2) Li 2znSiO 4coated rich lithium manganese 0.2Li 2mnO 30.8LiNi 1/2mn 1/2o 2the preparation of positive electrode
Take the tetraethoxysilane of 1.0417g (5mmol), 1.0202g (10mmol) CH 3cOOLi2H 2o and 0.28g (5mmol) ZnCl 2be dissolved in the mixed solution of 20mL ethanol and 20mL water, 60 DEG C of return stirrings 10 hours.Add 24.7268g (255mmol) 0.2Li 2mnO 30.8LiNi 1/2mn 1/2o 2rich lithium manganese material ultrasonic disperse 10min.60 DEG C of magnetic agitation 1h, get this suspension-turbid liquid and are placed in drying box 50 DEG C of dry 12h.By dried sample grinding evenly, in 600 DEG C of roastings 8 hours, be cooled to room temperature and grind, obtaining orthosilicate Li 2znSiO 4coated rich lithium manganese 0.2Li 2mnO 30.8LiNi 1/2mn 1/2o 2positive electrode.
Material property characterizes
1) crystal structure test is carried out on Japanese Shimadzu X-ray diffractometer XRD-7000, adopts copper target, sweep speed 2 °/minute, measuring accuracy ± 0.04 °, sweep limits 5 ~ 90 °.
Embodiment 1 step 2) the 2% orthosilicate Li for preparing 2niSiO 4coated rich lithium manganese 0.5Li 2mnO 30.5LiNi 1/3mn 1/3co 1/3o 2the XRD spectra of positive electrode is shown in Fig. 1.

Claims (8)

1. a preparation method for the coated rich lithium manganese material of silicate, is characterized in that: comprise the following steps:
1) one or both in nickel salt, cobalt salt and lithium salts and manganese salt are made solution, heated solution jointly, then add citric acid, regulate solution ph with ammoniacal liquor, evaporating liquid, prepare rich lithium manganese anode material presoma;
2) rich lithium manganese anode material presoma is placed in stove to calcine, prepares rich lithium manganese anode material, rich lithium manganese anode material molecular formula is expressed as xLi 2mnO 3(1-x) LiMO 2, wherein M is one or more in Ni, Co and Mn, and x is the molar fraction in molecular formula, 0.1≤x≤0.9;
3) rich lithium manganese anode material is added in tetraethoxysilane, lithium salts and the water of other metal soluble-salts and the solution of alcohol; return stirring; then evaporate to dryness solution, calcines under vacuum or inert gas shielding, prepares the rich lithium manganese anode material that orthosilicate is coated.
2. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
Described step 1) in lithium salts, nickel salt, manganese salt and cobalt salt be respectively in the acetate of solubility, villaumite, nitrate and sulfate one or more.
3. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
Described step 1) in the temperature of heated solution be 40 ~ 95 DEG C, the retention time is at this temperature 0.5 ~ 9 hour; The scope of the pH value of the solution after regulating with ammoniacal liquor is 6 ~ 9; Heating-up temperature used during evaporating liquid is 40 ~ 95 DEG C.
4. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
Described step 2) in aerial calcining heat be 200 ~ 950 DEG C, calcination time is 0.5 ~ 9 hour.
5. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
Described step 3) in the temperature of return stirring be 40 ~ 95 DEG C, mixing time is 1 ~ 20 hour, and calcining heat is 200 ~ 950 DEG C, and the time of calcining is 0.5 ~ 9 hour.
6. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
Described alcohol comprise in ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol and ethylene glycol one or more;
The volume ratio of described water and alcohol is 100 ~ 40:1 ~ 60.
7. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
Described step 3) in protective gas be one or more in nitrogen, helium and argon gas.
8. the preparation method of the coated rich lithium manganese material of a kind of silicate according to claim 1, is characterized in that:
The coated quality of described orthosilicate be the quality of rich lithium manganese anode material be 0.5 ~ 6%.
CN201410539093.5A 2014-10-13 2014-10-13 Preparation method of silicate coated material rich in lithium and manganese Pending CN104393260A (en)

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CN106058203A (en) * 2016-07-31 2016-10-26 湖南桑顿新能源有限公司 Preparation method of double-covering lithium-enriched manganese-based material using zirconium phosphate as outer covering and calcium fluoride as inner covering
CN108199024A (en) * 2017-12-30 2018-06-22 国联汽车动力电池研究院有限责任公司 A kind of rich lithium material of surface recombination cladding and preparation method thereof
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CN114284472A (en) * 2021-12-23 2022-04-05 北京理工大学重庆创新中心 Single crystal lithium-rich material with superconducting modification layer and preparation method and application thereof
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CN109873129A (en) * 2017-12-04 2019-06-11 惠州比亚迪电池有限公司 Composite cathode active material and preparation method thereof and anode and battery
CN108199024A (en) * 2017-12-30 2018-06-22 国联汽车动力电池研究院有限责任公司 A kind of rich lithium material of surface recombination cladding and preparation method thereof
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CN111689525A (en) * 2020-05-27 2020-09-22 厦门厦钨新能源材料股份有限公司 Preparation method of orthosilicate-based anode material coated ternary material
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CN114284472A (en) * 2021-12-23 2022-04-05 北京理工大学重庆创新中心 Single crystal lithium-rich material with superconducting modification layer and preparation method and application thereof
CN114284472B (en) * 2021-12-23 2023-11-03 北京理工大学重庆创新中心 Monocrystalline lithium-rich material with superconductive modification layer, and preparation method and application thereof
CN115360343A (en) * 2022-10-04 2022-11-18 兰州理工大学 Preparation method of modified lithium-rich nickel lithium manganate system cathode material

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