CN106299339A - A kind of preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium - Google Patents

A kind of preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium Download PDF

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CN106299339A
CN106299339A CN201610851546.7A CN201610851546A CN106299339A CN 106299339 A CN106299339 A CN 106299339A CN 201610851546 A CN201610851546 A CN 201610851546A CN 106299339 A CN106299339 A CN 106299339A
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lithium
manganate
mixed liquor
hours
stirring
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刘向峰
张继成
张恒
胡中波
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University of Chinese Academy of Sciences
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University of Chinese Academy of Sciences
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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
    • H01M4/48—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Abstract

The invention discloses the preparation method of a kind of lithium ion conductor coating spinelle manganate cathode material for lithium, use hydro-thermal method cladding and direct paddling process to be coated with two kinds of methods；Lithium ion conductor (lithium zirconate, lithium titanate, Lithium metasilicate) clad and principal phase spinel lithium manganese oxide anode material concurrently form during lithiation, to improve the bond strength between clad and principal phase spinel lithium manganese oxide anode material, and coating thickness is uniform, the high rate performance of lithium ion battery and cyclical stability obtain and significantly improve, especially long-range cyclical stability and high rate capability.The present invention can improve the high rate performance of spinel lithium manganese oxide anode material, stable circulation performance and high-temperature behavior；Synthesis technique is simple, and production efficiency is high, suitable for scale production；Have reactant needed raw material be easy to get, nontoxic, with low cost, production process has the advantages such as yield is big, result is reproducible without special protection, easy control of reaction conditions, obtained product.

Description

A kind of preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium
Technical field
The invention belongs to spinel lithium manganese oxide anode material technical field, particularly relate to a kind of lithium ion conductor cladding point brilliant The preparation method of stone manganate cathode material for lithium.
Background technology
Spinel lithium manganese oxide anode material is owing to having excellent energy density and prominent high voltage window in recent years Receive much attention.Particularly needing urgent Development of EV instantly, spinel lithium manganate is excellent owing to having Different security performance and good price advantage obtain important one seat in the development field of electrokinetic cell.But, At present spinel lithium manganese oxide anode material can not fully meet the demand of electric automobile, technical barrier therein mainly have with Under several: 1) cyclical stability of spinel lithium manganese oxide anode material is bad；2) spinel lithium manganese oxide anode material is high temperatures Can be poor；3) metal ion of spinel lithium manganese oxide anode material is soluble；4) spinel lithium manganese oxide anode material and electrolyte Side reaction material surface is passivated, cause high rate performance poor.Therefore, how to improve spinel lithium manganese oxide anode material, Can have long circulating stability, high rate capability and good high-temperature behavior, be spinel lithium manganese oxide anode material neck One significant challenge in territory.
The main method improving spinel lithium manganese oxide anode material performance at present has Surface coating (that is: at its Surface coating One layer of oxide or other inert material), element doping (such as metallic elements such as Al, Zr).These methods to a certain extent may be used To improve multiplying power and cyclical stability, but overall performance promotes the most highly satisfactory.And these traditional oxides Covering material is poor because of lithium ion conductive, can affect the high rate capability of material.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of lithium ion conductor coating spinelle manganate cathode material for lithium, Aim to solve the problem that the method improving spinel lithium manganese oxide anode material performance at present exists oxide covering material because of lithium ion conducting Property is poor so that the problem that the high rate capability of material is poor.The present invention synchronizes lithiumation and obtains the coating spinelle of lithium ion conductor The clad structure of LiMn2O4, advantage is as follows: 1 lithium ion conductor cladding improves interface and leads lithium, and 2 synchronize lithiumation contributes to strengthening Bond strength between clad and principal phase, 3 reduce heat treatment step uses one-step method Technology for Heating Processing (asynchronous lithiumation method Cladding uses two-step thermal treatment process)
The present invention is achieved in that the preparation method of a kind of lithium ion conductor coating spinelle manganate cathode material for lithium, described The preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium uses hydro-thermal method cladding and direct paddling process to be coated with two The method of kind；
The spinel lithium manganate presoma obtained is dispersed in dehydrated alcohol by described hydro-thermal method cladding, stirring ultrasonic disperse, According to the molar ratio of Zr, Ti or Si Mn=α 100, add the Zr (OC that mass percent concentration is 10%wt4H9)4 、Ti (OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, then will Mixed liquor proceeds to heat treatment in the teflon-lined water heating kettle being thoroughly dried, after natural cooling, centrifuge washing, will be centrifugal The drying precipitate that washing obtains, obtains oxide ZrO2 、TiO2Or SiO2The spinel lithium manganate presoma of cladding；
The spinel lithium manganate presoma obtained is dispersed in dehydrated alcohol by described direct paddling process cladding, stirs after adding ammonia Mixing and ultrasonic disperse, according to the molar ratio of Zr, Ti or Si:Mn=α: 100, adding mass percent concentration is the Zr of 10%wt (OC4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, is mixed Close liquid, then this mixed liquor is stirred, the completely rear centrifuge washing of question response, the drying precipitate that centrifuge washing is obtained, obtain Oxide ZrO2 、TiO2Or SiO2The spinel lithium manganate presoma of cladding.
Further, the spinel lithium manganate presoma 500mg obtained is dispersed in the anhydrous second of 10mL by described employing hydro-thermal method In alcohol, stirring also ultrasonic disperse 10 minutes, according to the molar ratio of Zr, Ti or Si Mn=α 100, add mass percent concentration Zr (OC for 10%wt4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring Uniformly, obtain mixed liquor, then this mixed liquor proceeded in the teflon-lined water heating kettle being thoroughly dried, 150～ Hydrothermal treatment consists 5～12 hours at 180 DEG C, after natural cooling, centrifuge washing, the precipitate obtained by centrifuge washing is dry at 80 DEG C Dry 12 hours, obtain oxide ZrO2、TiO2Or SiO2The spinel lithium manganate presoma of cladding.
Further, described direct paddling process cladding by the spinel lithium manganate presoma that obtains according to the mass ratio of 1:x Be dispersed in dehydrated alcohol, x 1, add stirring also ultrasonic disperse 10 minutes after 10 μ L ~ 1mL ammonia, according to Zr, Ti or Si:Mn= The molar ratio of α: 100, adds the Zr (OC that mass percent concentration is 10%wt4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Nothing Hydrous ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, then by this mixed liquor at 25 ~ 75 DEG C Stirring 24～72 hours under 300-700 rotating speed, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is at 80 DEG C Under be dried 12 hours, obtain oxide ZrO2、TiO2Or SiO2The spinel lithium manganate presoma of cladding.
Further, the preparation method bag of the lithium ion conductor coating spinelle manganate cathode material for lithium of described employing hydro-thermal method Include following steps:
Step one, by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2Slaine NiSO with nickel4、Ni (NO3)2Or NiCl2Or Ni (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 3:1, makes the total mol concentration of metal ion It is 1 ~ 3 mol/L, obtains metallic ion mixed liquor, or by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 1 ~ 3 mol/L, obtains metallic ion mixed liquor；Configuration molar concentration It is the K of 1 ~ 3 mol/L2C2O4 、Na2C2O4Or H2C2O4Or (NH4)2C2O4Or Na2CO3Or K2CO3Solution 50mL, under magnetic agitation Precipitant solution is joined in metallic ion mixed liquor, produce precipitate, after stirring 2 hours, centrifugation, spend respectively Ionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens and be dried 12 hours, obtain spinelle mangaic acid Lithium presoma；
Step 2, the spinel lithium manganate presoma 500mg obtained is dispersed in 10mL dehydrated alcohol, stirring ultrasonic disperse 10 Minute, according to the molar ratio of Zr, Ti or Si Mn=α 100, add the Zr (OC that mass percent concentration is 10%wt4H9)4 、 Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, then This mixed liquor is proceeded in the teflon-lined water heating kettle being thoroughly dried, hydrothermal treatment consists 5～12 at 150～180 DEG C Hour, after natural cooling, centrifuge washing, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains oxide ZrO2、TiO2Or SiO2The spinel lithium manganate presoma of cladding；
Step 3, according to the molar ratio of Li Mn=(x+ α)/100, wherein 20≤x≤100,0≤α≤15, by brilliant for the point of preparation Stone manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the liter of 3～5 DEG C/min Temperature speed, calcination processing 12～24 hours at 600～1000 DEG C, naturally cool to room temperature, room temperature be 15 DEG C to obtaining zirconic acid Lithium, lithium titanate or the lithium ion battery spinel lithium manganese oxide anode material of Lithium metasilicate cladding.
Further, the system of the lithium ion conductor coating spinelle manganate cathode material for lithium of described employing direct paddling process cladding Preparation Method comprises the following steps:
Step one, by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2Slaine NiSO with nickel4、Ni (NO3)2Or NiCl2Or Ni (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 3:1, makes the total mol concentration of metal ion It is 1 ~ 3 mol/L, obtains metallic ion mixed liquor, or by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 1 ~ 3 mol/L, obtains metallic ion mixed liquor.Configuration molar concentration It is the K of 1 ~ 3 mol/L2C2O4 、Na2C2O4Or H2C2O4Or (NH4)2C2O4Or Na2CO3Or K2CO3Solution 50mL, under magnetic agitation Precipitant solution is joined in metallic ion mixed liquor, produce precipitate, after stirring 2 hours, centrifugation, spend respectively Ionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens and be dried 12 hours, obtain spinelle mangaic acid Lithium presoma；
Step 2, is dispersed in the spinel lithium manganate presoma obtained in dehydrated alcohol according to the mass ratio of 1:x, x > 1, adds Enter stirring also ultrasonic disperse 10 minutes after 10 μ L ~ 1mL ammonia, according to the molar ratio of Zr, Ti or Si:Mn=α: 100, add matter Amount percent concentration is the Zr (OC of 10%wt4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤ 35, dispersed with stirring is uniform, obtains mixed liquor, then mixed liquor stirs at 25 ~ 75 DEG C 24～72 little under 300-700 rotating speed Time, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains oxide ZrO2 、TiO2Or SiO2Coating spinelle manganate precursor for lithium；
Step 3, according to the molar ratio of Li Mn=(x+ α)/100, wherein 20≤x≤100,0≤α≤15, by brilliant for the point of preparation Stone manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the liter of 3～5 DEG C/min Temperature speed, calcination processing 12～24 hours at 600～1000 DEG C, naturally cool to room temperature, room temperature be 15 DEG C to obtaining zirconic acid Lithium, lithium titanate or the lithium ion battery spinel lithium manganese oxide anode material of Lithium metasilicate cladding.
Another object of the present invention is to provide a kind of and apply described lithium ion conductor coating spinelle lithium manganate cathode material The battery of ion conductor coating spinelle manganate cathode material for lithium prepared by the preparation method of material.
Another object of the present invention is to provide a kind of automobile applying described battery.
Another object of the present invention is to provide a kind of electric bicycle applying described battery.
Another object of the present invention is to provide a kind of unmanned aerial vehicle applying described battery.
The preparation method of the lithium ion conductor coating spinelle manganate cathode material for lithium that the present invention provides, lithium ion conductor The while that (lithium zirconate, lithium titanate, Lithium metasilicate) clad and principal phase spinel lithium manganese oxide anode material being during lithiation Formed, to improve the bond strength between clad and principal phase spinel lithium manganese oxide anode material, use synchronization lithiumation method to have Help the bond strength improving clad with body phase.And coating thickness is uniform, the high rate performance of lithium ion battery and circulation Stability obtains and significantly improves (such as Fig. 3-Fig. 5), especially long-range cyclical stability and high rate capability (such as Fig. 3-Fig. 5).This Invention can improve the high rate performance of spinel lithium manganese oxide anode material, stable circulation performance and high-temperature behavior；Synthesis technique letter Single, production efficiency height uses a step heat treatment i.e. to can get clad structure, saves the time.Suitable for scale production；Have anti- Answer thing needed raw material to be easy to get, nontoxic, with low cost, use a step heat treatment i.e. to can get clad structure, save the time；Produce Process is without special protection, easy control of reaction conditions, and liquid phase coating method has the advantage that yield is the most reproducible, obtained Product has the advantages such as yield is big, result is reproducible.
The preparation method of the present invention is the in-situ preparation method of " synchronization lithiumation ", i.e. clad and principal phase spinel lithium manganate Positive electrode concurrently forms during lithiation, and by feed change ratio, the most successfully will be coated on spinelle Manganate cathode material for lithium surface；Lithium ion has been prepared by simple co-precipitation, synchronization lithiumation and high temperature solid-phase sintering reaction The spinel lithium manganese oxide anode material of conductor (lithium zirconate, lithium titanate, Lithium metasilicate) uniformly cladding；Method synthesis technique is simple, raw Product efficiency is high, suitable for scale production.And the inventive method there is reactant required for raw material be easy to get, nontoxic, low cost Honest and clean, production process is without special protection, and easy control of reaction conditions, obtained product has that yield is big, result is reproducible Etc. advantage；The spinel lithium manganese oxide anode material that is coated with of lithium ion conductor (lithium zirconate, lithium titanate, Lithium metasilicate) of preparation, and The uncoated material having is compared, and is all greatly improved and changes in terms of the battery performances such as circulating battery stability and multiplying power Entering, high-temperature behavior also has clear improvement simultaneously.
Accompanying drawing explanation
Fig. 1 is the lithium ion conductor coating spinelle lithium manganate cathode of the employing hydro-thermal method cladding that the embodiment of the present invention provides The preparation method flow chart of material.
Fig. 2 is the lithium ion conductor coating spinelle LiMn2O4 using direct paddling process cladding that the embodiment of the present invention provides The preparation method flow chart of positive electrode.
Fig. 3 is that the spinel lithium manganese oxide anode material of the cladding lithium zirconate that the embodiment of the present invention provides is brilliant with uncoated point Stone manganate cathode material for lithium specific discharge capacity circulation comparison diagram under room temperature 1C electric current density.
Fig. 4 is that the spinel lithium manganese oxide anode material of the cladding lithium zirconate that the embodiment of the present invention provides is brilliant with uncoated point Stone manganate cathode material for lithium specific discharge capacity circulation comparison diagram under 55 DEG C of 1C electric current densities.
Fig. 5 is that the spinel lithium manganese oxide anode material of the cladding lithium zirconate that the embodiment of the present invention provides is brilliant with uncoated point Stone manganate cathode material for lithium high rate performance figure under different current density condition.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, to the present invention It is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to Limit the present invention.
Lithium ion conductor (lithium zirconate, lithium titanate, Lithium metasilicate) has good heat stability and higher lithium ion transport Performance, if being coated on positive electrode surface, not only can prevent directly contacting and causing of electrolyte and positive electrode surface Decomposition reaction and the dissolving of metal ion, also will be conducive to the transmission of lithium ion such that it is able to lithium ion battery is greatly improved Cyclical stability, high rate performance and high-temperature behavior.
Below in conjunction with the accompanying drawings the application principle of the present invention is explained in detail.
The preparation method of the lithium ion conductor coating spinelle manganate cathode material for lithium of the embodiment of the present invention uses hydro-thermal method Cladding and direct paddling process are coated with two kinds of methods.
As it is shown in figure 1, use hydro-thermal method to comprise the following steps:
S101: by the slaine MnSO of manganese4(Mn (NO3)2Or MnCl2Or Mn (CH3COO)2) and the slaine NiSO of nickel4(Ni (NO3)2Or NiCl2Or Ni (CH3COO)2) be dissolved in 50mL water according to the molar ratio of 3:1, make the total mol concentration of metal ion It is 1 ~ 3 mol/L, obtains metallic ion mixed liquor, or by the slaine MnSO of manganese4(Mn (NO3)2Or MnCl2Or Mn (CH3COO)2) be dissolved in 50mL water according to the molar ratio of 1 ~ 3 mol/L, obtain metallic ion mixed liquor.Configuration mole is dense Degree is the K of 1 ~ 3 mol/L2C2O4 (Na2C2O4Or H2C2O4Or (NH4)2C2O4Or Na2CO3Or K2CO3) solution 50mL, magnetic force stirs Mix and lower above-mentioned precipitant solution is joined in above-mentioned metallic ion mixed liquor, produce precipitate, after stir 2 hours, be centrifuged Separate, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens and be dried 12 hours, Obtain spinel lithium manganate presoma；
S102: the spinel lithium manganate presoma 500mg obtained is dispersed in 10mL dehydrated alcohol, stirring ultrasonic disperse 10 points Clock, according to the molar ratio of Zr (Ti or Si) Mn=α 100, adds the Zr (OC that mass percent concentration is 10%wt4H9)4 (Ti(OC4H9)4Or Si (OC2H5)4) ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, so After this mixed liquor proceeded in the teflon-lined water heating kettle being thoroughly dried, at 150～180 DEG C hydrothermal treatment consists 5～ 12 hours, after natural cooling, centrifuge washing, the precipitate obtained by centrifuge washing was dried 12 hours at 80 DEG C, obtains corresponding Oxide coating spinelle manganate precursor for lithium；
S103: according to the molar ratio of Li Mn=(x+ α)/100, wherein 20≤x≤100,0≤α≤15, by the spinelle of preparation Manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the intensification of 3～5 DEG C/min Speed, calcination processing 12～24 hours at 600～1000 DEG C, naturally cool to room temperature, room temperature be 15 DEG C corresponding to obtaining Lithium ion conductor (lithium zirconate, lithium titanate, Lithium metasilicate) coated lithium ion battery spinel lithium manganese oxide anode material.
As in figure 2 it is shown, use direct paddling process to be coated with, comprise the following steps:
S201: by the slaine MnSO of manganese4(Mn (NO3)2Or MnCl2Or Mn (CH3COO)2) and the slaine NiSO of nickel4(Ni (NO3)2Or NiCl2Or Ni (CH3COO)2) be dissolved in 50mL water according to the molar ratio of 3:1, make the total mol concentration of metal ion It is 1 ~ 3 mol/L, obtains metallic ion mixed liquor, or by the slaine MnSO of manganese4(Mn (NO3)2Or MnCl2Or Mn (CH3COO)2) be dissolved in 50mL water according to the molar ratio of 1 ~ 3 mol/L, obtain metallic ion mixed liquor.Configuration mole is dense Degree is the K of 1 ~ 3 mol/L2C2O4 (Na2C2O4Or H2C2O4Or (NH4)2C2O4Or Na2CO3Or K2CO3) solution 50mL, magnetic force stirs Mix and lower above-mentioned precipitant solution is joined in above-mentioned metallic ion mixed liquor, produce precipitate, after stir 2 hours, be centrifuged Separate, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens and be dried 12 hours, Obtain spinel lithium manganate presoma；
S202: the spinel lithium manganate presoma obtained is dispersed in dehydrated alcohol (x > 1) according to the mass ratio of 1:x, adds Enter stirring also ultrasonic disperse 10 minutes after 10 μ L ~ 1mL ammonia, according to Zr (Ti or Si): the molar ratio of Mn=α: 100, add matter Amount percent concentration is the Zr (OC of 10%wt4H9)4 (Ti(OC4H9)4Or Si (OC2H5)4) ethanol solution, wherein 0.2≤α ≤ 35, dispersed with stirring is uniform, obtains mixed liquor, and then this mixed liquor stirs under 300-700 rotating speed at 25 ~ 75 DEG C 24～72 Hour, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains oxide ZrO2 (TiO2Or SiO2) coating spinelle manganate precursor for lithium；
S203: according to the molar ratio of Li Mn=(x+ α)/100, wherein 20≤x≤100,0≤α≤15, by the spinelle of preparation Manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the intensification of 3～5 DEG C/min Speed, calcination processing 12～24 hours at 600～1000 DEG C, naturally cool to room temperature, room temperature be 15 DEG C corresponding to obtaining Lithium ion conductor (lithium zirconate, lithium titanate, Lithium metasilicate) coated lithium ion battery spinel lithium manganese oxide anode material.
Below in conjunction with specific embodiment, the application principle of the present invention is further described.
Embodiment 1:
(1) by the slaine MnSO of manganese4Slaine NiSO with nickel4It is dissolved in 50mL water according to the molar ratio of 3:1, makes metal The total mol concentration of ion is 1 mol/L, obtains metallic ion mixed liquor.Configuration molar concentration is the K of 1 mol/L2C2O4Molten Liquid 50mL, joins in above-mentioned metallic ion mixed liquor by above-mentioned precipitant solution under magnetic agitation, produces precipitate, stirring After 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens It is dried 12 hours, obtains spinel lithium manganate presoma；
(2) the spinel lithium manganate presoma that above-mentioned steps (1) obtains is dispersed in dehydrated alcohol according to the mass ratio of 1:10 In, add stirring also ultrasonic disperse 10 minutes after 1mL ammonia, according to the molar ratio of Zr:Mn=0.5:100, add percent mass Specific concentration is the Zr (OC of 10%wt4H9)4Ethanol solution, dispersed with stirring is uniform, obtains mixed liquor, is then existed by this mixed liquor Stirring 24 hours under 300 rotating speeds at 75 DEG C, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is at 80 DEG C It is dried 12 hours, obtains the coating spinelle manganate precursor for lithium of oxide zirconium dioxide；
(3) according to the molar ratio of Li Mn=(50+1)/100, wherein 20≤x≤100,0≤α≤15, by the spinelle of preparation Manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the intensification speed of 3 DEG C/min Rate, calcination processing 12 hours at 600 DEG C, naturally cool to room temperature, room temperature be 15 DEG C to obtaining corresponding lithium ion conductor zirconium Acid lithium coated lithium ion battery spinel lithium manganese oxide anode material.
Embodiment 2:
(1) by the slaine MnSO of manganese4Slaine NiSO with nickel4It is dissolved in 50mL water according to the molar ratio of 3:1, makes metal The total mol concentration of ion is 2 mol/L, obtains metallic ion mixed liquor.Configuration molar concentration is the K of 2 mol/L2C2O4Molten Liquid 50mL, joins in above-mentioned metallic ion mixed liquor by above-mentioned precipitant solution under magnetic agitation, produces precipitate, stirring After 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens It is dried 12 hours, obtains spinel lithium manganate presoma；
(2) the spinel lithium manganate presoma that above-mentioned steps (1) obtains is dispersed in dehydrated alcohol according to the mass ratio of 1:20 In, add stirring also ultrasonic disperse 10 minutes after 1mL ammonia, according to the molar ratio of Ti:Mn=0.6:100, add percent mass Specific concentration is the Ti (OC of 10%wt4H9)4Ethanol solution, dispersed with stirring is uniform, obtains mixed liquor, is then existed by this mixed liquor Stirring 24 hours under 300 rotating speeds at 55 DEG C, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is at 80 DEG C It is dried 12 hours, obtains the coating spinelle manganate precursor for lithium of oxide titanium dioxide；
(3) according to the molar ratio of Li Mn=(66+5)/100, by spinel lithium manganate presoma and the lithium salts LiOH of preparation H2O or Li2CO3Grinding and mix, be placed in Muffle furnace, with the heating rate of 3 DEG C/min, at 600 DEG C, calcination processing 12 is little Time, naturally cool to room temperature, room temperature be 15 DEG C to obtaining corresponding lithium ion conductor lithium titanate coated lithium ion battery spinelle Manganate cathode material for lithium.
Embodiment 3:
(1) by the slaine Mn (NO of manganese3)2Slaine Ni (NO with nickel3)2It is dissolved in 50mL water according to the molar ratio of 3:1, The total mol concentration making metal ion is 1.5 mol/L, obtains metallic ion mixed liquor.Configuration molar concentration is 1.5 mol/ The Na of L2C2O4Solution 50mL, joins in above-mentioned metallic ion mixed liquor by above-mentioned precipitant solution under magnetic agitation, produces Precipitate, after stirring 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, precipitate is put It is dried 12 hours in 80 DEG C of baking ovens, obtains spinel lithium manganate presoma；
(2) the spinel lithium manganate presoma that above-mentioned steps (1) obtains is dispersed in dehydrated alcohol according to the mass ratio of 1:15 In, add stirring also ultrasonic disperse 10 minutes after 1mL ammonia, according to the molar ratio of Si:Mn=0.2:100, add percent mass Specific concentration is the Si (OC of 10%wt2H5)4Ethanol solution, dispersed with stirring is uniform, obtains mixed liquor, is then existed by this mixed liquor Stirring 24 hours under 300 rotating speeds at 55 DEG C, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is at 80 DEG C It is dried 12 hours, obtains the coating spinelle manganate precursor for lithium of oxides silicon dioxide；
(3) according to the molar ratio of Li Mn=(66+2.5)/100, by spinel lithium manganate presoma and the lithium salts of preparation LiOH·H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the heating rate of 3 DEG C/min, calcination processing at 700 DEG C 12 hours, naturally cool to room temperature, room temperature be 15 DEG C to obtain corresponding lithium ion conductor Lithium metasilicate coated lithium ion battery point Spar manganate cathode material for lithium.
Embodiment 4:
(1) by the slaine Mn (CH of manganese3COO)2It is dissolved in 50mL water according to the molar ratio of 3 mol/L, obtains metal ion Mixed solution.Configuration molar concentration is the Na of 3 mol/L2CO3Solution 50mL, adds above-mentioned precipitant solution under magnetic agitation In above-mentioned metallic ion mixed liquor, produce precipitate, after stir 2 hours, centrifugation, use deionized water and anhydrous respectively Ethanol purge precipitate 2 times, puts the precipitate in 80 DEG C of baking ovens and is dried 12 hours, obtain spinel lithium manganate presoma；
(2) being dispersed in 10mL dehydrated alcohol by the spinel lithium manganate presoma 500mg that above-mentioned steps (1) obtains, stirring is also Ultrasonic disperse 10 minutes, according to the molar ratio of Zr Mn=7 100, adds the Zr (OC that mass percent concentration is 10%wt4H9)4 Ethanol solution, dispersed with stirring is uniform, obtains mixed liquor, is then proceeded to by this mixed liquor in the politef being thoroughly dried In the water heating kettle of lining, hydrothermal treatment consists 5 hours at 180 DEG C, after natural cooling, centrifuge washing, the precipitation that centrifuge washing is obtained Thing is dried 12 hours at 80 DEG C, obtains the coating spinelle manganate precursor for lithium of oxide zirconium dioxide；
(3) according to the molar ratio of Li Mn=(50+2.5)/100, by spinel lithium manganate presoma and the lithium salts of preparation LiOH·H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the heating rate of 3 DEG C/min, calcination processing at 700 DEG C 12 hours, naturally cool to room temperature, room temperature be 15 DEG C to obtain corresponding lithium ion conductor lithium zirconate coated lithium ion battery point Spar manganate cathode material for lithium.
Embodiment 5:
(1) by the slaine Mn (NO of manganese3)2Slaine Ni (NO with nickel3)2It is dissolved in 50mL water according to the molar ratio of 3:1, The total mol concentration making metal ion is 3 mol/L, obtains metallic ion mixed liquor.Configuration molar concentration is 3 mol/L's Na2C2O4Solution 50mL, joins in above-mentioned metallic ion mixed liquor by above-mentioned precipitant solution under magnetic agitation, and it is heavy to produce Shallow lake thing, after stirring 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens are dried 12 hours, obtain spinel lithium manganate presoma；
(2) the spinel lithium manganate presoma that above-mentioned steps (1) obtains is dispersed in dehydrated alcohol according to the mass ratio of 1:25 In, add stirring also ultrasonic disperse 10 minutes after 40 μ L ammonia, according to the molar ratio of Zr:Mn=5:100, add percent mass Specific concentration is the Zr (OC of 10%wt4H9)4Ethanol solution, dispersed with stirring is uniform, obtains mixed liquor, is then existed by this mixed liquor Stirring 24 hours under 300 rotating speeds at 45 DEG C, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is at 80 DEG C It is dried 12 hours, obtains the spinel lithium manganate presoma of oxide zirconia-coated.
(3) the spinel lithium manganate forerunner according to the molar ratio of Li Mn=(70+5)/100 prepared by above-mentioned steps (2) Body and lithium salts LiOH H2O grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3～5 DEG C/min, calcines at 900 DEG C Process 15 hours, naturally cool to room temperature, obtain corresponding lithium ion conductor lithium zirconate coated lithium ion battery spinelle mangaic acid Lithium anode material.
Embodiment 6:
(1) by the slaine Mn (NO of manganese3)2Slaine Ni (NO with nickel3)2It is dissolved in 50mL water according to the molar ratio of 3:1, The total mol concentration making metal ion is 2.5 mol/L, obtains metallic ion mixed liquor.Configuration molar concentration is 2.5 mol/ The Na of L2C2O4Solution 50mL, joins in above-mentioned metallic ion mixed liquor by above-mentioned precipitant solution under magnetic agitation, produces Precipitate, after stirring 2 hours, centrifugation, respectively with deionized water and washes of absolute alcohol precipitate 2 times, precipitate is put It is dried 12 hours in 80 DEG C of baking ovens, obtains spinel lithium manganate presoma；
(2) the spinel lithium manganate presoma that above-mentioned steps (1) obtains is dispersed in dehydrated alcohol according to the mass ratio of 1:25 In, add stirring also ultrasonic disperse 10 minutes after 40 μ L ammonia, according to the molar ratio of Ti:Mn=5:100, add percent mass Specific concentration is the Ti (OC of 10%wt4H9)4Ethanol solution, dispersed with stirring is uniform, obtains mixed liquor, is then existed by this mixed liquor Stirring 24 hours under 300 rotating speeds at 45 DEG C, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is at 80 DEG C It is dried 12 hours, obtains the spinel lithium manganate presoma of oxide coated by titanium dioxide.
(3) the spinel lithium manganate forerunner according to the molar ratio of Li Mn=(67+5)/100 prepared by above-mentioned steps (2) Body and lithium salts LiOH H2O grinds and mixes, and is placed in Muffle furnace, with the heating rate of 3～5 DEG C/min, calcines at 900 DEG C Process 15 hours, naturally cool to room temperature, obtain corresponding lithium ion conductor lithium titanate coated lithium ion battery spinelle mangaic acid Lithium anode material.
Fig. 3 is that the spinel lithium manganese oxide anode material of the cladding lithium zirconate that the embodiment of the present invention provides is brilliant with uncoated point Stone manganate cathode material for lithium specific discharge capacity circulation comparison diagram under room temperature 1C electric current density.
Fig. 4 is that the spinel lithium manganese oxide anode material of the cladding lithium zirconate that the embodiment of the present invention provides is brilliant with uncoated point Stone manganate cathode material for lithium specific discharge capacity circulation comparison diagram under 55 DEG C of 1C electric current densities.
Fig. 5 is that the spinel lithium manganese oxide anode material of the cladding lithium zirconate that the embodiment of the present invention provides is brilliant with uncoated point Stone manganate cathode material for lithium high rate performance figure under different current density condition.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.

Claims (9)

1. the preparation method of a lithium ion conductor coating spinelle manganate cathode material for lithium, it is characterised in that described lithium ion The preparation method of conductor coating spinelle manganate cathode material for lithium uses hydro-thermal method cladding and direct paddling process to be coated with two kinds of methods；
The spinel lithium manganate presoma obtained is dispersed in dehydrated alcohol by described hydro-thermal method cladding, stirring ultrasonic disperse, According to the molar ratio of Zr, Ti or Si Mn=α 100, add the Zr (OC that mass percent concentration is 10%wt4H9)4 、Ti (OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, then will Mixed liquor proceeds to heat treatment in the teflon-lined water heating kettle being thoroughly dried, after natural cooling, centrifuge washing, will be centrifugal The drying precipitate that washing obtains, obtains oxide ZrO2 、TiO2Or SiO2The spinel lithium manganate presoma of cladding；
The spinel lithium manganate presoma obtained is dispersed in dehydrated alcohol by described direct paddling process cladding, stirs after adding ammonia Mixing and ultrasonic disperse, according to the molar ratio of Zr, Ti or Si:Mn=α: 100, adding mass percent concentration is the Zr of 10%wt (OC4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, is mixed Close liquid, then this mixed liquor is stirred, the completely rear centrifuge washing of question response, the drying precipitate that centrifuge washing is obtained, obtain Oxide ZrO2 、TiO2Or SiO2The spinel lithium manganate presoma of cladding.
2. the preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium as claimed in claim 1, its feature exists In, the spinel lithium manganate presoma 500mg obtained is dispersed in 10mL dehydrated alcohol by described employing hydro-thermal method, stirs and surpasses Sound disperses 10 minutes, and according to the molar ratio of Zr, Ti or Si Mn=α 100, adding mass percent concentration is the Zr of 10%wt (OC4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, is mixed Close liquid, then this mixed liquor is proceeded in the teflon-lined water heating kettle being thoroughly dried, hydro-thermal at 150～180 DEG C Process 5～12 hours, after natural cooling, centrifuge washing, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, To oxide ZrO2、TiO2Or SiO2The spinel lithium manganate presoma of cladding.
3. the preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium as claimed in claim 1, its feature exists In, the spinel lithium manganate presoma obtained is dispersed in anhydrous second according to the mass ratio of 1:x by described direct paddling process cladding In alcohol, x > 1, add after 10 μ L ~ 1mL ammonia stirring ultrasonic disperse 10 minutes, according to Zr, Ti or Si:Mn=α: 100 mole Ratio, adds the Zr (OC that mass percent concentration is 10%wt4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, Wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, then by this mixed liquor at 25 ~ 75 DEG C under 300-700 rotating speed Stirring 24～72 hours, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, Obtain oxide ZrO2、TiO2Or SiO2The spinel lithium manganate presoma of cladding.
4. the preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium as claimed in claim 1, its feature exists In, the preparation method of the lithium ion conductor coating spinelle manganate cathode material for lithium of described employing hydro-thermal method comprises the following steps:
Step one, by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2Slaine NiSO with nickel4、Ni (NO3)2Or NiCl2Or Ni (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 3:1, makes the total mol concentration of metal ion It is 1 ~ 3 mol/L, obtains metallic ion mixed liquor, or by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 1 ~ 3 mol/L, obtains metallic ion mixed liquor；Configuration molar concentration It is the K of 1 ~ 3 mol/L2C2O4 、Na2C2O4Or H2C2O4Or (NH4)2C2O4Or Na2CO3Or K2CO3Solution 50mL, under magnetic agitation Precipitant solution is joined in metallic ion mixed liquor, produce precipitate, after stirring 2 hours, centrifugation, spend respectively Ionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens and be dried 12 hours, obtain spinelle mangaic acid Lithium presoma；
Step 2, the spinel lithium manganate presoma 500mg obtained is dispersed in 10mL dehydrated alcohol, stirring ultrasonic disperse 10 Minute, according to the molar ratio of Zr, Ti or Si Mn=α 100, add the Zr (OC that mass percent concentration is 10%wt4H9)4 、 Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤35, dispersed with stirring is uniform, obtains mixed liquor, then This mixed liquor is proceeded in the teflon-lined water heating kettle being thoroughly dried, hydrothermal treatment consists 5～12 at 150～180 DEG C Hour, after natural cooling, centrifuge washing, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains oxide ZrO2、TiO2Or SiO2The spinel lithium manganate presoma of cladding；
Step 3, according to the molar ratio of Li Mn=(x+ α)/100, wherein 20≤x≤100,0≤α≤15, by brilliant for the point of preparation Stone manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the liter of 3～5 DEG C/min Temperature speed, calcination processing 12～24 hours at 600～1000 DEG C, naturally cool to room temperature, room temperature be 15 DEG C to obtaining zirconic acid Lithium, lithium titanate or the lithium ion battery spinel lithium manganese oxide anode material of Lithium metasilicate cladding.
5. the preparation method of lithium ion conductor coating spinelle manganate cathode material for lithium as claimed in claim 1, its feature exists Preparation method in the lithium ion conductor coating spinelle manganate cathode material for lithium of, described employing direct paddling process cladding include with Lower step:
Step one, by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2Slaine NiSO with nickel4、Ni (NO3)2Or NiCl2Or Ni (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 3:1, makes the total mol concentration of metal ion It is 1 ~ 3 mol/L, obtains metallic ion mixed liquor, or by the slaine MnSO of manganese4、Mn(NO3)2Or MnCl2Or Mn (CH3COO)2It is dissolved in 50mL water according to the molar ratio of 1 ~ 3 mol/L, obtains metallic ion mixed liquor；Configuration molar concentration It is the K of 1 ~ 3 mol/L2C2O4 、Na2C2O4Or H2C2O4Or (NH4)2C2O4Or Na2CO3Or K2CO3Solution 50mL, under magnetic agitation Precipitant solution is joined in metallic ion mixed liquor, produce precipitate, after stirring 2 hours, centrifugation, spend respectively Ionized water and washes of absolute alcohol precipitate 2 times, put the precipitate in 80 DEG C of baking ovens and be dried 12 hours, obtain spinelle mangaic acid Lithium presoma；
Step 2, is dispersed in the spinel lithium manganate presoma obtained in dehydrated alcohol according to the mass ratio of 1:x, x > 1, adds Enter stirring also ultrasonic disperse 10 minutes after 10 μ L ~ 1mL ammonia, according to the molar ratio of Zr, Ti or Si:Mn=α: 100, add matter Amount percent concentration is the Zr (OC of 10%wt4H9)4 、Ti(OC4H9)4Or Si (OC2H5)4Ethanol solution, wherein 0.2≤α≤ 35, dispersed with stirring is uniform, obtains mixed liquor, then mixed liquor stirs at 25 ~ 75 DEG C 24～72 little under 300-700 rotating speed Time, the completely rear centrifuge washing of question response, the precipitate obtained by centrifuge washing is dried 12 hours at 80 DEG C, obtains oxide ZrO2 、TiO2Or SiO2Coating spinelle manganate precursor for lithium；
Step 3, according to the molar ratio of Li Mn=(x+ α)/100, wherein 20≤x≤100,0≤α≤15, by brilliant for the point of preparation Stone manganate precursor for lithium and lithium salts LiOH H2O or Li2CO3Grind and mix, be placed in Muffle furnace, with the liter of 3～5 DEG C/min Temperature speed, calcination processing 12～24 hours at 600～1000 DEG C, naturally cool to room temperature, room temperature be 15 DEG C to obtaining zirconic acid Lithium, lithium titanate or the lithium ion battery spinel lithium manganese oxide anode material of Lithium metasilicate cladding.
6. apply the preparation of lithium ion conductor coating spinelle manganate cathode material for lithium described in claim 1-5 any one for one kind The battery of ion conductor coating spinelle manganate cathode material for lithium prepared by method.
7. the automobile applying battery described in claim 6.
8. the electric bicycle applying battery described in claim 6.
9. the unmanned aerial vehicle applying battery described in claim 6.
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