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 PDFInfo
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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
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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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