CN107507976A - Composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron and preparation method thereof - Google Patents
Composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron and preparation method thereof Download PDFInfo
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- CN107507976A CN107507976A CN201710606178.4A CN201710606178A CN107507976A CN 107507976 A CN107507976 A CN 107507976A CN 201710606178 A CN201710606178 A CN 201710606178A CN 107507976 A CN107507976 A CN 107507976A
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron and preparation method thereof, the chemical formula of the composite mixed LiMn2O4 of the lithium aluminium boron is：Li1+xMn2‑xAlxO4·0.3xLiBO2, wherein, 0 ＜ x≤0.2.Pattern rule, the composite mixed manganate cathode material for lithium of the porous spherical lithium aluminium boron of uniform particle sizes is made by using the method for two-stage calcination after spraying pelletizing in the present invention.By introducing lithium, aluminium, boron these three elements in LiMn2O4 lattice, boron is with LiBO2Form forms Li with LiMn2O41+xMn2‑xAlxO4·0.3xLiBO2Solid solution, the dissolving of manganese in the electrolytic solution is restrained effectively, improve the intensity of Mn O keys so as to enhance the structural stability of material, significantly improve the high temperature cyclic performance of LiMn2O4.The preparation technology of material is simple to operate easily controllable, and cost is cheap to be easily achieved large-scale production.
Description
Technical field
The invention belongs to positive electrode preparation field, and in particular to a kind of composite mixed manganate cathode material for lithium of lithium aluminium boron
And preparation method thereof.
Background technology
Lithium ion battery is a kind of new energy battery succeeded in developing late 1980s to the beginning of the nineties, wide at present
It is general to be applied in day electronic product, and the first choice of electric automobile power battery.
The selection of positive electrode determines the performance of lithium ion battery, and lithium manganate having spinel structure is provided with its cheap, manganese
Source is abundant, safe, advantages of environment protection turn into power battery anode material first choice.But LiMn2O4 high temperature cyclic performance
With the poor industrialization that but greatly limit electrokinetic cell type LiMn2O4 of structural stability, there is an urgent need to be improved.
The A of publication number CN 102195042 Chinese patent literature discloses a kind of high performance lithium ion battery anode material
LiMn2O4 and preparation method thereof, it uses solid phase method, will be forged after the compound ball milling of lithium source, manganese source and doped metallic elements
Burn, be cooled to after room temperature ball milling again, most obtain high performance lithium ion battery anode material through high temperature sintering, broken, classification afterwards
LiMn2O4.
The A of publication number CN 105244492 Chinese patent literature discloses a kind of boracic lithium ion anode material and its system
Preparation Method, composite oxide particle is added in the salting liquid of boracic and forms paste mixture, added containing doping metals member
The M salting liquids of at least one of element are reacted, and clad is formed on composite oxide particle surface, stirring and drying, is heat-treated,
Obtain final product.
High temperature solid-state method and liquid phase method is respectively adopted in above-mentioned technique, and the lithium manganate particle prepared by solid phase method is uneven, shape
Looks are irregular, and product capacity decay is fast；LiMn2O4 prepared by liquid phase method has more consistent particle size distribution, but liquid phase method is normal
Often to use expensive reaction reagent, need longer drying time and with complicated course of reaction, therefore liquid phase method produces
Process conditions are difficult to control, and production cost is higher, are not suitable for industrial production.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron；It is intended to make
Obtain a kind of high temperature cyclic performance and the positive electrode of structural stability.
Another object of the present invention is to, there is provided a kind of composite mixed mangaic acid of lithium aluminium boron made from described preparation method
Lithium anode material.
The preparation method of the composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron, by chemical formula Li1+xMn2-xAlxO4·
0.3xLiBO2Stoichiometric proportion, lithium source, manganese source, silicon source and boron source are placed in medium, ball milling mixing, wherein, 0 ＜ x≤
0.2；
Material after ball milling is subjected to spray drying pelletizing, obtains compound green-ball；
By described compound green-ball after 350~650 DEG C of next section of roastings, then the two-stage calcination at 650~890 DEG C,
The composite mixed manganate cathode material for lithium of obtained described lithium aluminium boron.
The present invention can prepare pattern rule, even-grained porous spherical LiMn2O4 using spray drying pelletizing technology
Particle, avoid using expensive reaction reagent, and sprayed using cheap materials such as lithium carbonates, ensureing material morphology rule
The cost of material is reduced while then.Preparation technology is simple to operate easily controllable, and cost is cheap to be easily achieved large-scale production.
Therefore, the present invention is beneficial to the mass production of lithium manganate having spinel structure positive electrode and improves its performance.
Using spray drying pelletizing, then coordinate described two-stage calcination mechanism, help that the porous ball of pattern rule is made
Shape particle, epigranular, the good manganate cathode material for lithium of chemical property.
In the present invention, described lithium source is Li water soluble compound and/or oxide.
Preferably, described lithium source is at least one of lithium nitrate, lithium carbonate, lithium acetate and lithium hydroxide.
In the present invention, described manganese source is the oxide of manganese, salt etc..
Preferably, described manganese source be manganese dioxide, mangano-manganic oxide, manganese carbonate, manganese nitrate or manganese acetate in extremely
Few one kind.
Preferably, described boron source is boron oxide and/or boric acid.
Preferably, described silicon source is aluminium hydroxide.
In the present invention, by described chemical formula Li, Mn, B, Al stoichiometric proportion by described lithium source, manganese source, boron source,
Ball milling mixing of the silicon source in described medium.
Preferably, x is 0.02~0.2；More preferably 0.05~0.15；Still more preferably it is 0.05~0.1.
Preferably, the mol ratio that adds of lithium and manganese in manganese source exceeds theoretical stoichiometric ratio in lithium source.It can help to more
Mend the volatilization of lithium at high temperature.
Preferably, medium is at least one of acetone, deionized water, absolute ethyl alcohol.
Preferably, the solid mass ratio of the liquid of mechanical milling process is (8~10): 1,250~450r/min of rotating speed, Ball-milling Time are
2~20h.
Further preferably, it is 10: 1 that mechanical milling process, which chooses the solid mass ratio of liquid, rotating speed 300r/min, Ball-milling Time 4h.
Preferably, in spray drying balling process, 200~400 DEG C of inlet temperature, 60~150 DEG C of outlet temperature.
Further preferably, it is 300 DEG C to be spray-dried pelletizing inlet temperature, and outlet temperature is 100 DEG C.
Preferably, the particle diameter of compound green-ball is 10~20 microns made from spray drying pelletizing.
Further preferably, the average grain diameter for being spray-dried compound green-ball made from pelletizing is 15 μm.
Preferably, one section of roasting, the heating rate of two-stage calcination process are less than or equal to 12 DEG C/min；Preferably 2
~8 DEG C/min.
Heating rate is too fast to cause reaction not exclusively to produce impurity, cause material electrochemical performance to decline.Described
Heating rate under, help that the positive electrode that pure phase is high, electric property is excellent is made.
Preferably, the temperature of one section of roasting process is 600~650 DEG C.
Preferably, one section of roasting time is 3~20h；More preferably 3~15h；Still more preferably for 6~
10h。
Preferably, the heating rate of one section of roasting process is 2 DEG C/min, sintering temperature is 650 DEG C, and roasting time is
6h。
Preferably, the temperature of two-stage calcination process is 800~850 DEG C.
At a temperature of described bis sintering, the positive pole material of electrochemical performance can be made in the suitable two-stage calcination time
Material.Roasting time is long to cause material primary particle overgrowth to cause chemical property to decline.
Preferably, the roasting time of two-stage calcination process is 3~30h；More preferably 3~24h；It is further excellent
Elect 13~20h as.
Further preferably, the heating rate of two-stage calcination process is 2 DEG C/min, and sintering temperature is 850 DEG C, and roasting time is
13h。
The invention also discloses a kind of composite mixed manganate cathode material for lithium of lithium aluminium boron made from described preparation method.
By described preparation method, in LiMn2O4 situ doped with lithium aluminium boron, help to be obviously improved the electrical property of positive electrode
Energy.
Preferably, the chemical formula of the composite mixed LiMn2O4 of the lithium aluminium boron is：Li1+xMn2-xAlxO4·
0.3xLiBO2；Wherein, 0 ＜ x≤0.2.
The lithium manganate material of described composite mixed lithium aluminium boron provided by the invention, is used as positive electrode, can go out
People expects the cycle performance and structural stability that ground improves manganate cathode material for lithium.
Found by studying, preferably, x is 0.05~0.15.Under the conditions of this is preferable, the electric property of positive electrode
It is more excellent.
Compared with prior art, beneficial effects of the present invention：
Pattern rule, the porous spherical of uniform particle sizes is made by using the method for two-stage calcination after spraying pelletizing in the present invention
The composite mixed manganate cathode material for lithium of lithium aluminium boron.By introducing lithium, aluminium, boron these three elements, aluminium member in LiMn2O4 lattice
Element substitution manganese element enters in the lattice of LiMn2O4, and boron is with LiBO2Form forms Li with LiMn2O41+xMn2-xAlxO4·
0.3xLiBO2Solid solution, the dissolving of manganese in the electrolytic solution is restrained effectively, improve the intensity of Mn-O keys so as to enhance material
The structural stability of material, the high temperature cyclic performance of LiMn2O4 are significantly improved.
Brief description of the drawings
Fig. 1 is the XRD of the composite mixed manganate cathode material for lithium of lithium aluminium boron in embodiment 1, it can be seen from the figure that product
Comply fully with LiMn2O4 standard card JCPDS：71-3120 (the hypomere spectral line in Fig. 1).
Fig. 2 is that the SEM of the manganate cathode material for lithium that lithium aluminium boron is composite mixed in embodiment 1 schemes, the lithium manganate material of gained
For the porous spherical particles that particle diameter is 15 μm；
Fig. 3 is high temperature (55 DEG C) cycle life figure of the manganate cathode material for lithium that lithium aluminium boron is composite mixed in embodiment 1；
Fig. 4 is high temperature (55 DEG C) cycle life figure undoped with modified manganate cathode material for lithium in comparative example 1；
Embodiment
With reference to specific embodiment, the present invention is further elaborated.
The spraying pelletizing process of following examples and comparative example is：
The inlet temperature of spray drying device is risen to 200~400 DEG C, deionized water regulation and control outlet temperature is passed through with peristaltic pump
Deionized water is changed to well mixed slurry, is spray-dried by degree after 60~150 DEG C.
Embodiment 1
A kind of composite mixed manganate cathode material for lithium of lithium aluminium boron, its preparation method are as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 2 DEG C/min,
850 DEG C of insulation 13h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2。
The charge-discharge performance test of all embodiment and comparative example products obtained therefroms is carried out in accordance with the following methods：
Obtained LiMn2O4, acetylene black, PVDF are well mixed with 8: 1: 1 mass ratio, are ground into uniformly after adding NMP
Slurry is dried in vacuo in phase at 120 DEG C coated on aluminium foil and places 12h, using metal lithium sheet as negative pole, 1MLiPF6For electrolyte
CR2025 button cells are made.Electro-chemical test voltage range is 3~4.3V, and the circle of 0.2C (1C=148mAh/g) circulations 2 is laggard
Row 1C is circulated, and carries out high temperature test, temperature is 55 DEG C of (NMP：METHYLPYRROLIDONE；PVDF：Gather inclined tetrafluoroethene).Such as
Shown in accompanying drawing 2, the lithium manganate material that embodiment 1 obtains is the porous spherical particles that average grain diameter is 15 μm.It is as shown in figure 3, real
It is 103mAh/g to apply the lithium manganate material first discharge specific capacity that example 1 obtains, and the capability retention after high temperature circulation 200 is enclosed is
95%.
Embodiment 2
It is Li to prepare chemical general formula1.05Mn1.95Al0.05O4·0.015LiBO2Manganate cathode material for lithium, stoichiometrically
Than adding deionized water after weighing mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, ball
Mill rotating speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is sprayed
Pelletizing is dried, obtains compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of guarantors with 2 DEG C/min
Warm 6h, 850 DEG C of insulation 13h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed lithium manganate cathode of the lithium aluminium boron
Material Li1.05Mn1.95Al0.05O4·0.015LiBO2.The electrochemical test method of this product is same as Example 1, the head of material
Secondary specific discharge capacity is 105mAh/g, and capability retention is 93% after high temperature circulation 200 is enclosed.
Embodiment 3
It is Li to prepare chemical general formula1.15Mn1.85Al0.15O4·0.045LiBO2Manganate cathode material for lithium, stoichiometrically
Than adding deionized water after weighing mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, ball
Mill rotating speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is sprayed
Pelletizing is dried, obtains compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of guarantors with 2 DEG C/min
Warm 6h, 850 DEG C of insulation 13h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed lithium manganate cathode of the lithium aluminium boron
Material Li1.15Mn1.85Al0.15O4·0.045LiBO2.The electrochemical test method of this product is same as Example 1, the head of material
Secondary specific discharge capacity is 102mAh/g, and capability retention is 92% after high temperature circulation 200 is enclosed.
Embodiment 4
It is Li to prepare chemical general formula1.2Mn1.8Al0.2O4·0.06LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 2 DEG C/min,
850 DEG C of insulation 13h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.2Mn1.8Al0.2O4·0.06LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 99mAh/g, and capability retention is 91% after high temperature circulation 200 is enclosed.
Embodiment 5
It is Li to prepare chemical general formula1.02Mn1.98Al0.02O4·0.006LiBO2Manganate cathode material for lithium, stoichiometrically
Than adding deionized water after weighing mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, ball
Mill rotating speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is sprayed
Pelletizing is dried, obtains compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of guarantors with 2 DEG C/min
Warm 6h, 850 DEG C of insulation 13h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed lithium manganate cathode of the lithium aluminium boron
Material Li1.02Mn1.98Al0.02O4·0.006LiBO2.The electrochemical test method of this product is same as Example 1, the head of material
Secondary specific discharge capacity is 109mAh/g, and capability retention is 90% after high temperature circulation 200 is enclosed.
Embodiment 6
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 8 DEG C/min,
850 DEG C of insulation 13h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 101mAh/g, and capability retention is 94% after high temperature circulation 200 is enclosed.
Embodiment 7
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 2 DEG C/min,
850 DEG C of insulation 20h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 102mAh/g, and capability retention is 92% after high temperature circulation 200 is enclosed.
Embodiment 8
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball (10~20 microns)；Described compound green-ball is warming up to 650 DEG C of insulations with 2 DEG C/min
10h, 850 DEG C of insulation 15h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed lithium manganate cathode of the lithium aluminium boron
Material Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, and material is put first
Electric specific capacity is 103mAh/g, and capability retention is 91% after high temperature circulation 200 is enclosed.
Embodiment 9
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball (10~20 microns)；Described compound green-ball is warming up to 620 DEG C of insulation 6h with 2 DEG C/min,
800 DEG C of insulation 20h are continuously heating to, room temperature is naturally cooled to, obtains the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 102mAh/g, and capability retention is 91% after high temperature circulation 200 is enclosed.
Embodiment 10
The present embodiment inquires into the bis sintering time, specific as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 2 DEG C/min, is continuously heating to
850 DEG C of insulation 30h, naturally cool to room temperature, obtain the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 101mAh/g, and capability retention is 88% after high temperature circulation 200 is enclosed.
Embodiment 11
The present embodiment inquires into the one-stage sintering time, specific as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball；Described compound green-ball is warming up to 650 DEG C of insulation 20h with 2 DEG C/min, is continuously heating to
850 DEG C of insulation 20h, naturally cool to room temperature, obtain the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 100mAh/g, and capability retention is 87% after high temperature circulation 200 is enclosed.
Comparative example 1
This comparative example is inquired into and undopes and operated without mist projection granulating, specific as follows：
It is LiMn to prepare chemical general formula2O4Manganate cathode material for lithium, stoichiometrically weigh mangano-manganic oxide and lithium carbonate
Deionized water is added after mixing, the solid mass ratio of liquid is 10: 1, and rotational speed of ball-mill 300r/min, Ball-milling Time 4h, ball milling obtain
Well mixed slurry, 650 DEG C of insulation 6h are warming up to 2 DEG C/min after drying, are continuously heating to 850 DEG C of insulation 13h, nature
Room temperature is cooled to, is obtained undoped with modified manganate cathode material for lithium LiMn2O4.The electrochemical test method of this product and implementation
Example 1 is identical, and as shown in Figure 4, the first discharge specific capacity of material is 112mAh/g, capability retention after high temperature circulation 200 is enclosed
For 74%.
Comparative example 2
This comparative example is inquired into and undopes and carry out mist projection granulating operation, specific as follows：
It is LiMn to prepare chemical general formula2O4Manganate cathode material for lithium, stoichiometrically weigh mangano-manganic oxide and lithium carbonate
Deionized water is added after mixing, the solid mass ratio of liquid is 10: 1, and rotational speed of ball-mill 300r/min, Ball-milling Time 4h, ball milling obtain
Well mixed slurry；Well mixed slurry is subjected to spray drying pelletizing, obtains compound green-ball；By described compound
Green-ball is warming up to 650 DEG C of insulation 6h with 2 DEG C/min, is continuously heating to 850 DEG C of insulation 13h, naturally cools to room temperature, do not mixed
The manganate cathode material for lithium LiMn of miscellaneous modification2O4.The electrochemical test method of this product is same as Example 1, as shown in Figure 4,
The first discharge specific capacity of material is 111mAh/g, and capability retention is 78% after high temperature circulation 200 is enclosed.
Comparative example 3
This comparative example is inquired into and operated without mist projection granulating, specific as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry, 650 DEG C are warming up to 2 DEG C/min after drying
6h is incubated, 850 DEG C of insulation 13h is continuously heating to, naturally cools to room temperature, obtain the manganate cathode material for lithium of doping vario-property
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 101mAh/g, and capability retention is 82% after high temperature circulation 200 is enclosed.Compared to embodiment 1, this comparative example does not carry out institute
The spray drying treatment stated, the capability retention of obtained material have dropped nearly 10% compared with embodiment 1.
Comparative example 4
This comparative example is inquired into, and x is more than 0.2 case, specific as follows：
It is Li to prepare chemical general formula1.3Mn1.7Al0.3O4·0.09LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry, 650 DEG C are warming up to 2 DEG C/min after drying
6h is incubated, 850 DEG C of insulation 13h is continuously heating to, naturally cools to room temperature, obtain the manganate cathode material for lithium of doping vario-property
Li1.3Mn1.7Al0.3O4·0.09LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 95mAh/g, and capability retention is 73% after high temperature circulation 200 is enclosed.
Comparative example 5
This comparative example is inquired into, and in sintering process, the influence of heating rate is specific as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 20 DEG C/min, is continuously heating to
850 DEG C of insulation 13h, naturally cool to room temperature, obtain the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 80mAh/g, and capability retention is 65% after high temperature circulation 200 is enclosed.
Comparative example 6
This comparative example inquires into bis sintering temperature, specific as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball；Described compound green-ball is warming up to 650 DEG C of insulation 6h with 2 DEG C/min, is continuously heating to
900 DEG C of insulation 20h, naturally cool to room temperature, obtain the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 101mAh/g, and capability retention is 68% after high temperature circulation 200 is enclosed.
Comparative example 7
This comparative example inquires into one-stage sintering temperature, specific as follows：
It is Li to prepare chemical general formula1.1Mn1.9Al0.1O4·0.03LiBO2Manganate cathode material for lithium, stoichiometrically claim
Deionized water is added after taking mangano-manganic oxide, aluminium hydroxide, boron oxide, lithium carbonate mixing, the solid mass ratio of liquid is 10: 1, and ball milling turns
Speed is 300r/min, Ball-milling Time 4h, and ball milling obtains well mixed slurry；Well mixed slurry is spray-dried
Pelletizing, obtain compound green-ball；Described compound green-ball is warming up to 200 DEG C of insulation 6h with 2 DEG C/min, is continuously heating to
850 DEG C of insulation 20h, naturally cool to room temperature, obtain the composite mixed manganate cathode material for lithium of the lithium aluminium boron
Li1.1Mn1.9Al0.1O4·0.03LiBO2.The electrochemical test method of this product is same as Example 1, the ratio of electric discharge first of material
Capacity is 99mAh/g, and capability retention is 70% after high temperature circulation 200 is enclosed.
As can be seen from the above Examples and Comparative Examples, as long as causing various parameters in preparation process, such as doped chemical
The amount of material, heating rate etc. are prepared that modified lithium manganate cathode material will have excellent high temperature in prescribed limit
Cycle performance.
Claims (10)
1. the preparation method of the composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron, it is characterised in that by chemical formula Li1+ xMn2-xAlxO4·0.3xLiBO2Stoichiometric proportion, lithium source, manganese source, silicon source and boron source are placed in medium, ball milling mixing, its
In, 0 ＜ x≤0.2；
Material after ball milling is subjected to spray drying pelletizing, obtains compound green-ball；
By described compound green-ball after 350~650 DEG C of next section of roastings, then the two-stage calcination at 650~890 DEG C, it is made
The composite mixed manganate cathode material for lithium of described lithium aluminium boron.
2. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron as claimed in claim 1, it is characterised in that x
For 0.02~0.2；Preferably 0.05~0.15.
3. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron as claimed in claim 1, it is characterised in that be situated between
Matter is at least one of acetone, deionized water, absolute ethyl alcohol；
The solid mass ratio of the liquid of mechanical milling process is (8~10): 1,250~450r/min of rotating speed, and Ball-milling Time is 2~20h.
4. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron according to claim 1, it is characterised in that
It is spray-dried in balling process, 200~400 DEG C of inlet temperature, 60~150 DEG C of outlet temperature.
5. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron according to claim 1, it is characterised in that
One section of roasting, the heating rate of two-stage calcination process are less than or equal to 12 DEG C/min；Preferably 2~8 DEG C/min.
6. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron, its feature exist according to claim 1 or 5
In the temperature of one section of roasting process is 600~650 DEG C；One section of roasting time is 3~20h；Preferably 3~15h；It is further excellent
Elect 6~10h as.
7. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron according to claim 1, it is characterised in that
The temperature of two-stage calcination process is 800~850 DEG C.
8. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron according to claim 1 or 7, its feature exist
In the roasting time of two-stage calcination process is 3~30h；Preferably 3~24h；More preferably 13~20h.
9. the preparation method of the composite mixed manganate cathode material for lithium of lithium aluminium boron according to claim 1, it is characterised in that
Described lithium source is at least one of lithium nitrate, lithium carbonate, lithium acetate and lithium hydroxide；
Described manganese source is at least one of manganese dioxide, mangano-manganic oxide, manganese carbonate, manganese nitrate or manganese acetate；
Described boron source is boron oxide and/or boric acid；
Described silicon source is aluminium hydroxide.
10. the composite mixed manganate cathode material for lithium of a kind of lithium aluminium boron, it is characterised in that using any one of claim 1~9 institute
The preparation method stated is made.
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