CN107342410A - A kind of aluminium boron modification manganate cathode material for lithium and preparation method thereof - Google Patents

A kind of aluminium boron modification manganate cathode material for lithium and preparation method thereof Download PDF

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CN107342410A
CN107342410A CN201710542670.XA CN201710542670A CN107342410A CN 107342410 A CN107342410 A CN 107342410A CN 201710542670 A CN201710542670 A CN 201710542670A CN 107342410 A CN107342410 A CN 107342410A
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lithium
ball
cathode material
manganate cathode
aluminium
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彭忠东
胡国荣
李莹
杜柯
曹雁冰
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Central South University
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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 a kind of aluminium boron modification manganate cathode material for lithium and preparation method thereof, the aluminium boron modification manganate cathode material for lithium, with LiMn2‑xAlxO4For core, with inorganic lithium boron oxide compound glass Li2O·2B2O3(LBO) it is clad, wherein, 0 ＜ x≤0.2；Its preparation method is that high temperature solid-state method prepares LiMn2‑xAlxO4, LiMn2‑xAlxO4The slurry being well mixed is made with the solution movement ball milling containing lithium source and boron source；After slurry is carried out into spray drying treatment, spherical precursor is obtained；Above-mentioned presoma is calcined, obtains modified lithium manganate cathode material；The modified lithium manganate cathode material of preparation have passed through doping and coat dual modified, can effectively suppress the dissolving of bivalent manganese in the electrolytic solution, significantly improve the high temperature cyclic performance of LiMn2O4, and preparation technology is simple to operate easily controllable, be adapted to industrialized production.

Description

A kind of aluminium boron modification manganate cathode material for lithium and preparation method thereof
Technical field
The present invention relates to a kind of LiMn2O4 class positive electrode, more particularly to a kind of aluminium boron modification manganate cathode material for lithium, tool Body is related to one kind with LiMn2-xAlxO4For core, Li2O·2B2O3(LBO) it is the aluminium boron modification manganate cathode material for lithium of shell, belongs to lithium Ion battery positive electrode preparation field.
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.To mangaic acid Lithium material carries out element doping, can improve the chemical property of lithium manganate battery material to a certain extent.Report at present The method of doped chemical mainly has solid phase method and liquid phase method in lithium manganate material, such as Chinese invention patent application (publication No. CN 102195042 A) a kind of high performance lithium ion battery anode material LiMn2O4 and preparation method thereof is disclosed, it uses solid phase Method, it will be calcined after the compound ball milling of lithium source, manganese source and doped metallic elements, be cooled to after room temperature ball milling again, finally High performance lithium ion battery anode material LiMn2O4 is obtained through high temperature sintering, broken, classification, high temperature solid-state is respectively adopted in the technique Method and liquid phase method, the lithium manganate particle prepared by solid phase method is uneven, and pattern is irregular, and product capacity decay is fast.Chinese invention Patent application (A of publication No. CN 105244492) discloses a kind of boracic lithium ion anode material and preparation method thereof, will be compound Oxide particle adds in the salting liquid of boracic and forms paste mixture, adds containing at least one of doped metallic elements M salting liquids are reacted, and clad is formed on composite oxide particle surface, stirring and drying, heat treatment, obtains final product.Liquid LiMn2O4 prepared by phase method has more consistent particle size distribution, but liquid phase method is often required to using expensive reaction reagent, needed Drying time that will be longer and adjoint complicated course of reaction, therefore liquid phase production technology condition is difficult to control, production cost It is higher, it is not suitable for industrial production.
The content of the invention
The defects of existing for prior art, there is special core shell structure it is an object of the invention to provide one kind and include aluminium Boron adulterates phase, chemical property, high temperature cyclic performance and the excellent modified lithium manganate cathode material of structural stability.
Another object of the present invention is to provide a kind of lithium manganate cathode for preparing aluminium boron modification simple to operate, inexpensive The method of material.
In order to realize above-mentioned technical purpose, the invention provides a kind of aluminium boron modification manganate cathode material for lithium, material tool There is core shell structure；Core is by LiMn2-xAlxO4Form, shell is by Li2O·2B2O3Form；Wherein, 0 ＜ x≤0.2.
The aluminium boron modification manganate cathode material for lithium of the present invention has carried out aluminium doping simultaneously to existing manganate cathode material for lithium It with Surface coating boric acid lithium layer, can effectively suppress the dissolving of bivalent manganese in the electrolytic solution, improve the structural stability of material, show Write the high temperature cyclic performance for improving LiMn2O4.
Preferable scheme, LiMn2-xAlxO4In 0.05≤x≤0.15.The aluminium element content of doping in preferable scope, The electric property of positive electrode is more excellent.
More preferably scheme, the Li2O·2B2O3Quality account for LiMn2-xAlxO4The 1%~5% of quality.
Present invention also offers a kind of preparation method of aluminium boron modification manganate cathode material for lithium, this method includes following step Suddenly：
1) by lithium source, manganese source and silicon source ball milling mixing it is uniform after, one section of roasting is first carried out at 350~650 DEG C, then 650 ~1000 DEG C of progress two-stage calcinations, produce LiMn2-xAlxO4；
2) by LiMn2-xAlxO4With the solution ball milling mixing containing lithium source and boron source, slurry is obtained；
3) slurry obtains ball material by spray drying；
4) the ball material is placed at a temperature of 450~500 DEG C and be calcined, produced.
Preferable scheme, the ball milling in step 1) realize that the abrading-ball used uses for zirconia ball by planetary ball mill Dispersant include acetone, absolute ethyl alcohol, at least one of water, drum's speed of rotation is 200~250r/min, Ball-milling Time 2 ~3h.
Preferable scheme, the roasting process in step 1), heating rate are not more than 12 DEG C/min, and the time of one section of roasting is 3~15h, the time of two-stage calcination is 3~24h.Heating rate is more preferably 1~3 DEG C/min, and heating rate is too fast to be caused instead Impurity not exclusively should be produced, cause material electrochemical performance to decline.
Preferable scheme, the temperature of one section of roasting is 400~600 DEG C, and roasting time is 4~8h.
Preferable scheme, the temperature of two-stage calcination is 700~900 DEG C, and roasting time is 10~16h, and roasting time is long Material primary particle overgrowth can be caused to cause chemical property to decline.
Preferable scheme, the ball milling in step 2) realize that the abrading-ball used is zirconium oxide by vertical type superfine agitator mill Ball, for the dispersant used for water, drum's speed of rotation is 350~400r/min, and Ball-milling Time is 1.5~2h.
More preferably scheme, the lithium source include at least one of lithium nitrate, lithium carbonate, lithium acetate, lithium hydroxide；It is optimal Elect lithium carbonate as.
More preferably scheme, the manganese source are included in manganese dioxide, mangano-manganic oxide, manganese carbonate, manganese nitrate, manganese acetate extremely Few one kind；Most preferably manganese dioxide and/or mangano-manganic oxide.
More preferably scheme, the boron source include boron oxide and/or boric acid.
More preferably scheme, source of aluminium include aluminum oxide, aluminium hydroxide, aluminium carbonate, aluminum nitrate, aluminum acetate, isopropyl acetone At least one of aluminium.Most preferably aluminium hydroxide.
The lithium source of the present invention, manganese source, the amount ratio of boron source and silicon source, according to above-mentioned aluminium boron modification manganate cathode material for lithium Nucleocapsid molecular formula and nucleocapsid mass ratio are measured, and this is the category that this technology personnel are readily appreciated that.
More preferably scheme, the condition of the spray drying：200~400 DEG C of feedstock inlet temperature, ball material outlet temperature 60 ~150 DEG C, the particle diameter of ball material is 10~20 microns.Feedstock inlet temperature is most preferably 280~320 DEG C, ball material outlet temperature 80 ~120 DEG C, the particle diameter of ball material is 13~17 microns.
More preferably scheme, the roasting process of step 4), heating rate are no more than 12 DEG C/min, roasting time 0.2 ~12h.Heating rate is more preferably 1~3 DEG C/min.Roasting time is preferably 4~8h.
Preferable scheme, the mol ratio of the Mn in Li and manganese source in step 1) in lithium source is 1.02~1.10, to make up The volatilization of lithium at high temperature.
Compared with prior art, the beneficial effect that technical scheme is brought：
1) aluminium boron modification manganate cathode material for lithium of the invention is with LiMn2-xAlxO4For core, using LBO as clad, wherein, 0 ＜ x≤0.2, it have passed through doping and coat dual modified, restrained effectively the dissolving of bivalent manganese in the electrolytic solution, composite Structural stability improved, significantly improve the high temperature cyclic performance of LiMn2O4.
2) can be made using spray drying pelletizing technology in aluminium boron modification manganate cathode material for lithium preparation process of the invention The spheric granules of standby pattern rule, epigranular, can be avoided using expensive reaction reagent, and use the cheap materials such as lithium carbonate Material is sprayed, and the cost of material is reduced while material morphology rule is ensured.
3) preparation technology of aluminium boron modification manganate cathode material for lithium of the invention is simple to operate easily controllable, and cost is cheap easily In accomplishing scale production.
Brief description of the drawings
【Fig. 1】For the XRD of aluminium boron modification manganate cathode material for lithium in the embodiment of the present invention 1, it can be seen from the figure that product Comply fully with LiMn2O4 standard card JCPDS:71-3120.
【Fig. 2】Comparison diagram is circulated for the LiMn2O4 1C of the embodiment of the present invention 1 and comparative example 1；Wherein 1 is the mangaic acid of embodiment 1 Lithium discharge cycles, 2 be the LiMn2O4 discharge cycles of comparative example 1.
Embodiment
Present invention is further elaborated with reference to specific embodiment, rather than the claims in the present invention are protected Shield scope does further restriction.
In following examples and comparative example, LiMn2-xAlxO4Ball milling realized by planetary ball mill, the mill of use Ball is zirconia ball, and the dispersant used is absolute ethyl alcohol, drum's speed of rotation 220r/min, Ball-milling Time 2.5h.
In following examples and comparative example, the preparation process of slurry is realized using vertical type superfine agitator mill, is used Abrading-ball be zirconia ball, the dispersant used is water, drum's speed of rotation 380r/min, Ball-milling Time 1.5h.
The condition being spray-dried in following examples and comparative example：300 DEG C of feedstock inlet temperature, ball material outlet temperature 100 DEG C, the particle diameter of ball material is about 15 microns.
Roasting process heating rate is 3 DEG C/min in following examples and comparative example.
Embodiment 1
Prepare Surface coating 1%LBO LiMn1.98Al0.02O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Than weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 450 DEG C carry out one section roasting 5h, then 800 DEG C of progress two-stage calcination 10h, produce LiMn1.98Al0.02O4；By LiMn1.98Al0.02O4With lithium carbonate containing and the solution of boric acid Ball milling mixing, obtain slurry；The slurry obtains ball material by spray drying；Carried out at a temperature of the ball material is placed in into 480 DEG C 8h is calcined, is produced.
The charge-discharge performance test of all embodiment and comparative example products obtained therefroms is carried out in accordance with the following methods：
By obtained LiMn2O4, acetylene black, PVDF with 8:1:1 mass ratio is well mixed, and is 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).It is real It is 103.8mAh/g to apply the aluminium boron modification manganate cathode material for lithium first discharge specific capacity that example 1 obtains, after high temperature circulation 200 is enclosed Capability retention is 87%.
Embodiment 2
Prepare Surface coating 2%LBO LiMn1.95Al0.05O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Than weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 600 DEG C carry out one section roasting 4h, then 850 DEG C of progress two-stage calcination 14h, produce LiMn1.95Al0.05O4；By LiMn1.98Al0.02O4With lithium carbonate containing and the solution of boric acid Ball milling mixing, obtain slurry；The slurry obtains ball material by spray drying；Carried out at a temperature of the ball material is placed in into 480 DEG C 4h is calcined, is produced.The electrochemical test method of this product is same as Example 1, and the first discharge specific capacity of material is 103.2mAh/g, capability retention is 90% after high temperature circulation 200 is enclosed.
Embodiment 3
Prepare Surface coating 3%LBO LiMn1.9Al0.1O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, one section of roasting 7h is first carried out at 450 DEG C, then 750 DEG C carry out two-stage calcination 13h, produce LiMn1.9Al0.1O4；By LiMn1.9Al0.1O4Mixed with the solution ball milling of lithium carbonate containing and boric acid Close, obtain slurry；The slurry obtains ball material by spray drying；The ball material is placed at a temperature of 480 DEG C and is calcined 6h, produce.The electrochemical test method of this product is same as Example 1, as shown in Figure 2, the first discharge specific capacity of material For 102.5mAh/g, capability retention is 94% after high temperature circulation 200 is enclosed.
Embodiment 4
Prepare Surface coating 4%LBO LiMn1.85Al0.15O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Than weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 550 DEG C carry out one section roasting 6h, then 800 DEG C of progress two-stage calcination 12h, produce LiMn1.85Al0.15O4；By LiMn1.85Al0.15O4With lithium carbonate containing and the solution of boric acid Ball milling mixing, obtain slurry；The slurry obtains ball material by spray drying；Carried out at a temperature of the ball material is placed in into 480 DEG C 6h is calcined, is produced.The electrochemical test method of this product is same as Example 1, and the first discharge specific capacity of material is 101.6mAh/g, capability retention is 92% after high temperature circulation 200 is enclosed.
Embodiment 5
Prepare Surface coating 5%LBO LiMn1.85Al0.15O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Than weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 550 DEG C carry out one section roasting 6h, then 800 DEG C of progress two-stage calcination 12h, produce LiMn1.85Al0.15O4；By LiMn1.85Al0.15O4With lithium carbonate containing and the solution of boric acid Ball milling mixing, obtain slurry；The slurry obtains ball material by spray drying；Carried out at a temperature of the ball material is placed in into 480 DEG C 6h is calcined, is produced.The electrochemical test method of this product is same as Example 1, and the first discharge specific capacity of material is 100.9mAh/g, capability retention is 91% after high temperature circulation 200 is enclosed.
Embodiment 6
Prepare Surface coating 3%LBO LiMn1.8Al0.2O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, one section of roasting 6h is first carried out at 550 DEG C, then 800 DEG C carry out two-stage calcination 12h, produce LiMn1.8Al0.2O4；By LiMn1.8Al0.2O4Mixed with the solution ball milling of lithium carbonate containing and boric acid Close, obtain slurry；The slurry obtains ball material by spray drying；The ball material is placed at a temperature of 480 DEG C and is calcined 6h, produce.The electrochemical test method of this product is same as Example 1, and the first discharge specific capacity of material is 100.4mAh/g, Capability retention is 89% after high temperature circulation 200 is enclosed.
Comparative example 1
It is LiMn to prepare chemical general formula2O4Manganate cathode material for lithium, stoichiometrically weigh lithium carbonate and four oxidation three After manganese ball milling mixing is uniform, one section of roasting 6h is first carried out at 550 DEG C, then two-stage calcination 12h is carried out at 800 DEG C, produces LiMn2O4。 The electrochemical test method of this product is same as Example 1, and as shown in Figure 2, the first discharge specific capacity of material is 115mAh/ G, capability retention is 77% after high temperature circulation 200 is enclosed.
Comparative example 2
Prepare Surface coating 3%LBO LiMn2O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically weigh carbon Sour lithium, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 550 DEG C carry out one section roasting 6h, then 800 DEG C progress Two-stage calcination 12h, produces LiMn2O4；By LiMn2O4With the solution ball milling mixing of lithium carbonate containing and boric acid, 480 are placed in after drying It is calcined, is produced at a temperature of DEG C.The electrochemical test method of this product is same as Example 1, the electric discharge specific volume first of material Measure as 112.5mAh/g, capability retention is 79% after high temperature circulation 200 is enclosed.
Comparative example 3
Prepare Surface coating 3%LBO LiMn2O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically weigh carbon Sour lithium, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 550 DEG C carry out one section roasting 6h, then 800 DEG C progress Two-stage calcination 8h, produces LiMn2O4；By LiMn2O4With the solution ball milling mixing of lithium carbonate containing and boric acid, slurry is obtained；The slurry Material obtains ball material by spray drying；Roasting 6h is carried out at a temperature of the ball material is placed in into 480 DEG C, is produced.The electrification of this product Method of testing is same as Example 1, and the first discharge specific capacity of material is 113mAh/g, and capacity is protected after high temperature circulation 200 is enclosed Holdup is 81%.
Comparative example 4
It is LiMn to prepare chemical general formula1.9Al0.1O4Modified lithium manganate cathode material, stoichiometrically weigh carbonic acid Lithium, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, first 350 DEG C carry out one section roasting 6h, then 800 DEG C carry out two Section roasting 12h, produces LiMn1.9Al0.1O4.The electrochemical test method of this product is same as Example 1, the electric discharge first of material Specific capacity is 111mAh/g, and capability retention is 79% after high temperature circulation 200 is enclosed.
Comparative example 5
Prepare Surface coating 3%LBO LiMn1.9Al0.1O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, one section of roasting 6h is first carried out at 550 DEG C, then 800 DEG C carry out two-stage calcination 12h, produce LiMn1.9Al0.1O4；By LiMn1.9Al0.1O4Mixed with the solution ball milling of lithium carbonate containing and boric acid Close, carry out roasting 6h at a temperature of 480 DEG C are placed in after drying, produce.The electrochemical test method of this product is same as Example 1, The first discharge specific capacity of material is 107.4mAh/g, and capability retention is 84% after high temperature circulation 200 is enclosed.
Comparative example 6
Prepare Surface coating 10%LBO LiMn1.9Al0.1O4Aluminium boron modification manganate cathode material for lithium, stoichiometrically Than weigh lithium carbonate, mangano-manganic oxide and aluminium hydroxide ball milling mixing it is uniform after, one section of roasting is first carried out at 550 DEG C, then 800 DEG C carry out two-stage calcination, produce LiMn1.9Al0.1O4；By LiMn1.9Al0.1O4With the solution ball milling mixing of lithium carbonate containing and boric acid, Obtain slurry；The slurry obtains ball material by spray drying；The ball material is placed at a temperature of 480 DEG C and is calcined, i.e., .The electrochemical test method of this product is same as Example 1, and the first discharge specific capacity of material is 99.8mAh/g, and high temperature follows Capability retention is 80% after ring 200 encloses.

Claims (10)

  1. A kind of 1. aluminium boron modification manganate cathode material for lithium, it is characterised in that：With core shell structure；Core is by LiMn2-xAlxO4Form, Shell is by Li2O·2B2O3Form；Wherein, 0 ＜ x≤0.2.
  2. 2. aluminium boron modification manganate cathode material for lithium according to claim 1, it is characterised in that：0.05≤x≤0.15.
  3. 3. aluminium boron modification manganate cathode material for lithium according to claim 1 or 2, it is characterised in that：The Li2O·2B2O3 Quality account for LiMn2-xAlxO4The 1%~5% of quality.
  4. 4. the preparation method of the aluminium boron modification manganate cathode material for lithium described in any one of claims 1 to 3, it is characterised in that：Bag Include following steps：
    1) by lithium source, manganese source and silicon source ball milling mixing it is uniform after, first carry out one section of roasting at 350~650 DEG C, then 650~ 1000 DEG C of progress two-stage calcinations, produce LiMn2-xAlxO4；
    2) by LiMn2-xAlxO4With the solution ball milling mixing containing lithium source and boron source, slurry is obtained；
    3) slurry obtains ball material by spray drying；
    4) the ball material is placed at a temperature of 450~500 DEG C and be calcined, produced.
  5. 5. the preparation method of aluminium boron modification manganate cathode material for lithium according to claim 4, it is characterised in that：In step 1) Ball milling realized by planetary ball mill, the abrading-ball used for zirconia ball, the dispersant of use include acetone, absolute ethyl alcohol, At least one of water, drum's speed of rotation are 200~250r/min, and Ball-milling Time is 2~3h.
  6. 6. the preparation method of aluminium boron modification manganate cathode material for lithium according to claim 4, it is characterised in that：In step 1) Roasting process, heating rate is not more than 12 DEG C/min, and time of one section of roasting be 3~15h, time of two-stage calcination is 3~ 24h。
  7. 7. the preparation method of aluminium boron modification manganate cathode material for lithium according to claim 4, it is characterised in that：In step 2) Ball milling realized by vertical type superfine agitator mill, the abrading-ball used for zirconia ball, the dispersant used for water, ball mill turn Speed is 350~400r/min, and Ball-milling Time is 1.5~2h.
  8. 8. the preparation method of the aluminium boron modification manganate cathode material for lithium according to any one of claim 4~7, its feature exist In：
    The lithium source includes at least one of lithium nitrate, lithium carbonate, lithium acetate, lithium hydroxide；
    The manganese source includes at least one of manganese dioxide, mangano-manganic oxide, manganese carbonate, manganese nitrate, manganese acetate；
    The boron source includes boron oxide and/or boric acid；
    Source of aluminium includes at least one of aluminum oxide, aluminium hydroxide, aluminium carbonate, aluminum nitrate, aluminum acetate, isopropyl acetone aluminium.
  9. 9. the preparation method of the aluminium boron modification manganate cathode material for lithium according to any one of claim 4~7, its feature exist In：The condition of the spray drying：200~400 DEG C of feedstock inlet temperature, 60~150 DEG C of ball material outlet temperature, the particle diameter of ball material For 10~20 microns.
  10. 10. the preparation method of the aluminium boron modification manganate cathode material for lithium according to any one of claim 4~7, its feature exist In：The roasting process of step 4), heating rate are that roasting time is 0.2~12h no more than 12 DEG C/min.
CN201710542670.XA 2017-07-05 2017-07-05 A kind of aluminium boron modification manganate cathode material for lithium and preparation method thereof Pending CN107342410A (en)

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CN109879309A (en) * 2019-03-14 2019-06-14 上海电气集团股份有限公司 A kind of preparation method of high-tap density lithium titanate material
CN116425204A (en) * 2023-04-28 2023-07-14 巴斯夫杉杉电池材料有限公司 Spinel type lithium manganate, preparation method thereof and lithium ion battery

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CN109879309A (en) * 2019-03-14 2019-06-14 上海电气集团股份有限公司 A kind of preparation method of high-tap density lithium titanate material
CN116425204A (en) * 2023-04-28 2023-07-14 巴斯夫杉杉电池材料有限公司 Spinel type lithium manganate, preparation method thereof and lithium ion battery
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Application publication date: 20171110