CN106252626A - The tool lithium titanate electrode material of nucleocapsid structure, preparation method and application - Google Patents

The tool lithium titanate electrode material of nucleocapsid structure, preparation method and application Download PDF

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CN106252626A
CN106252626A CN201610741881.1A CN201610741881A CN106252626A CN 106252626 A CN106252626 A CN 106252626A CN 201610741881 A CN201610741881 A CN 201610741881A CN 106252626 A CN106252626 A CN 106252626A
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lithium
acid
electrode material
lithium titanate
carbon
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CN106252626B (en
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王燕
吴英鹏
张帆
原东甲
李志�
赵晓锋
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Shenzhen Boleida New Energy Science & Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/485—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses and a kind of have the lithium titanate electrode material of nucleocapsid structure, preparation method and application, belong to lithium ion battery material and battery preparation technology field.In the present invention, lithium titanate electrode material is nucleocapsid structure, and its kernel is lithium titanate, is outwards followed successively by middle carbon-coating and lithium metaaluminate composite bed, the shell of the two constituent material along kernel.In the structure shown here, middle carbon-coating can intercept the electron transfer between lithium titanate and electrolyte, it is to avoid the two directly contacts, thus reduces the generation of side reaction, reduces battery flatulence amount, reduces its expansion rate.Meanwhile, the lithium metaaluminate material of electrode material surface cladding has the advantages that lithium ion conducting rate is high, it is possible to increase lithium titanate battery lithium ion transport speed under the conditions of big multiplying power, thus improves the high rate performance of battery.Further, because of under high temperature binding agent decompose and in lithium metaaluminate composite bed formed Nano/micron hole can absorb and store electrolyte, be conducive to raising electrode material cycle performance.

Description

The tool lithium titanate electrode material of nucleocapsid structure, preparation method and application
Technical field
The present invention relates to a kind of lithium titanate electrode material having nucleocapsid structure, also relate to the preparation side of this electrode material Method and application, belong to lithium ion battery material and battery preparation technology field.
Background technology
Lithium titanate (the Li of spinel structure4Ti5O12, LTO) as the negative material of lithium ion battery, bear with conventional graphite Pole material is compared has irreplaceable advantage: 1) intercalation potential high (about 1.55V, vsLi/Li+), will not in charge and discharge process Separating out Li dendrite, security performance is good, can eliminate the potential safety hazard of lithium ion battery from material；2) material knot in charge and discharge process There is any change in fruit, is a kind of " zero strain " material hardly, good cycle；3) lithium electron chemistry diffusion coefficient compares graphite High an order of magnitude, is suitable for fast charging and discharging；4) charging/discharging voltage is steady, and platform voltage capacity exceedes the 90% of total capacity.Titanium One of acid lithium titanate cathode material selection being the most increasingly becoming energy-storage system and hybrid-electric car.But, lithium titanate battery is universal The problem that there is flatulence, this seriously inhibits the popularization commercially of this battery.
For solving flatulence problem, the patent of invention of application number 201510715892.8 discloses a kind of with ionic liquid electrolysis Liquid substitutes tradition lithium hexafluoro phosphate (LiPF6) lithium titanate battery prepared by organic solvent electrolyte, fundamentally solve battery In charge and discharge process, rich lithium state lithium titanate (Li7Ti5O12) organic with alkylcarbonic acid esters under the catalytic action of lithium hexafluoro phosphate Solvent generation decarboxylation, decarbonylation base and the problem of dehydrogenation reaction aerogenesis, but its electrical conductivity is on the low side.Application number 201610070026.2 patent of invention disclose a kind of lithium titanate electrode material, by lithium titanate Surface coating Graphene and CNT, can be effectively improved the electric conductivity of lithium titanate electrode material, the problem improving battery flatulence, improves its circulation simultaneously Performance.But in charge and discharge process, lithium ion embedding go out speed relatively slow, battery high rate performance is deteriorated.
Summary of the invention
It is an object of the invention to provide a kind of lithium titanate electrode material having nucleocapsid structure, carry by improving its flatulence problem The high rate performance of high battery and cycle performance.
Meanwhile, the present invention also provides for the preparation method of a kind of lithium titanate electrode material.
Finally, the present invention reoffers the application in preparing lithium titanate battery of a kind of above-mentioned electrode material.
In order to realize object above, the technical solution adopted in the present invention is:
The lithium titanate electrode material of tool nucleocapsid structure, its kernel is lithium titanate, is outwards sequentially provided with middle carbon-coating along kernel With lithium metaaluminate composite bed, middle carbon-coating and the shell of lithium metaaluminate composite bed constituent material.Wherein, the size of kernel is 200 ～800nm, middle carbon-coating, the thickness of lithium metaaluminate composite bed are respectively 10～50nm.
The raw material of preparing of described lithium titanate electrode material includes:
Kernel: lithium titanate 500～1000g；
Shell: middle carbon-coating: organic carbon source 50～200g, dispersant 1～2g, CNT 1～2g, solvent 1000mL；
Lithium metaaluminate composite bed: lithium metaaluminate 50～200g, Kynoar 10～20g, N-Methyl pyrrolidone 1000mL。
The preparation process of described middle carbon-coating is: joined by lithium carbonate in the mixed liquor of middle carbon-coating raw material, after mixing In nitrogen atmosphere, sinter 2～10h at 200～400 DEG C, to obtain final product.Wherein, organic carbon source is in glucose, sucrose, citric acid One or more；Dispersant is selected from one or both in Polyethylene Glycol, 120,000 base sodium sulfonates；Solvent is selected from formic acid, second Acid, propanoic acid, butanoic acid, octanoic acid, adipic acid, ethanedioic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, neighbour One in phthalic acid, p-phthalic acid.Sinter forward and backward heating rate and rate of temperature fall is respectively 5～10 DEG C/min.
The preparation process of described lithium metaaluminate composite bed is: the lithium titanate being coated with middle carbon-coating is joined lithium metaaluminate In the mixed liquor of composite bed raw material, it is spray-dried after mixing, to obtain final product.Wherein, the technological parameter of spray drying is: inlet air temperatures 300～500 DEG C, feed rate 10～50mL/min, air mass flow 100～500L/h, leaving air temp 80～120 DEG C.
The preparation method of the lithium titanate electrode material of tool nucleocapsid structure, comprises the following steps:
1) organic carbon source, dispersant, CNT are mixed homogeneously with solvent, obtain mixed liquor A；
Lithium metaaluminate, Kynoar are mixed homogeneously with N-Methyl pyrrolidone, obtains mixed liquid B；
2) lithium titanate is joined in solution A, after mixing in nitrogen atmosphere, sinter 2～10h at 200～400 DEG C, obtain Metatitanic acid lithium/carbon composite material；
3) metatitanic acid lithium/carbon composite material is joined in solution B, be spray-dried after mixing, obtain lithium titanate/carbon/inclined aluminum Acid lithium composite material, namely lithium titanate electrode material.
Step 2) in sinter forward and backward heating rate and rate of temperature fall and be respectively 5～10 DEG C/min.
Step 3) in be spray-dried technological parameter be: inlet air temperatures 300～500 DEG C, feed rate 10～50mL/min, Air mass flow 100～500L/h, leaving air temp 80～120 DEG C.
The application in preparing lithium titanate battery of the above-mentioned lithium titanate electrode material.
Beneficial effects of the present invention:
In the present invention, lithium titanate electrode material (namely lithium titanate/carbon/lithium metaaluminate composite) is in nucleocapsid structure, in it Core is lithium titanate, is outwards followed successively by middle carbon-coating and lithium metaaluminate composite bed, middle carbon-coating and lithium metaaluminate composite bed along kernel The shell of constituent material.In the structure shown here, middle carbon-coating can intercept the electron transfer between lithium titanate and electrolyte, it is to avoid the two Directly contact, thus reduce the generation of side reaction, reduce battery flatulence amount, reduce its expansion rate.Further, cladding carbon-coating have with The characteristics such as compatibility of electrolyte is high.Meanwhile, it is high that the lithium metaaluminate material that electrode material surface is coated with has lithium ion conducting rate Feature, it is possible to increase lithium titanate battery lithium ion transport speed under the conditions of big multiplying power, thus improve the high rate performance of battery. Further, because of under high temperature binding agent decompose and in lithium metaaluminate composite bed formed Nano/micron hole can absorb and store Electrolyte, is conducive to improving the cycle performance of electrode material.
Accompanying drawing explanation
Fig. 1 is the SEM figure of lithium titanate electrode material in embodiment 1；
Fig. 2 is the charging and discharging curve figure of button cell in embodiment 1.
Detailed description of the invention
The present invention is only described in further detail by following embodiment, but does not constitute any limitation of the invention.
Embodiment 1
The lithium titanate electrode material of tool nucleocapsid structure, its kernel is lithium titanate, is outwards sequentially provided with middle carbon-coating along kernel With lithium metaaluminate composite bed, middle carbon-coating and the shell of lithium metaaluminate composite bed constituent material.Wherein, the size of kernel is 500nm, the thickness of middle carbon-coating is 30nm, and the thickness of lithium metaaluminate composite bed is 30nm.
The preparation process of lithium titanate electrode material is:
1) carbon-coating raw material mixed liquor, the preparation of lithium metaaluminate composite bed raw material mixed liquor in the middle of:
100g glucose, 2g Polyethylene Glycol, 2g CNT are mixed homogeneously with 1000mL formic acid, obtains mixed liquor A, be Middle carbon-coating raw material mixed liquor；
100g lithium metaaluminate, 15g Kynoar are mixed homogeneously with 1000mL N-Methyl pyrrolidone, obtains mixed liquor B, is lithium metaaluminate composite bed raw material mixed liquor；
2) 800g lithium titanate (purchased from Tianjin Bei Terui New Energy Technology Co., Ltd., model: LTO-1) is joined mixing In liquid A, under 30rpm rotating speed stir 2h, after be transferred in tube furnace, rise to 300 with the heating rate of 8 DEG C/min under nitrogen atmosphere DEG C, after insulation 6h, then it is down to room temperature with the rate of temperature fall of 8 DEG C/min, obtains metatitanic acid lithium/carbon composite material；
3) metatitanic acid lithium/carbon composite material is joined in solution B, high speed dispersion 2h under 3500rpm rotating speed, it is spray-dried (technological parameter: inlet air temperatures 400 DEG C, feed rate 30mL/min, air mass flow 300L/h, leaving air temp 100 DEG C), obtains titanium Acid lithium/carbon/lithium metaaluminate composite, namely the lithium titanate electrode material of tool nucleocapsid structure.
Lithium titanate button cell, takes the lithium titanate electrode material of the above-mentioned preparation of 9g, 0.5g conductive agent SP, 0.5g polyvinylidene fluoride Alkene (binding agent) is mixed homogeneously with 220mL N-Methyl pyrrolidone, and film makes diaphragm on Copper Foil, with lithium sheet as negative pole, Celegard 2400 is barrier film, 1mol/L LiPF6/ EC+DMC (volume ratio 1:1) is electrolyte (EC i.e. ethylene carbonate, DMC I.e. diethyl carbonate), it is below in the glove box of 0.1ppm assembling button cell at oxygen and water content.
Lithium titanate soft-package battery (5Ah), with the lithium titanate electrode material of above-mentioned preparation as negative material, LiNi1/3Co1/ 3Mn1/3O2Ternary material is positive electrode, and celegard 2400 is barrier film, 1.3mol/L LiPF6/ EC+DEC (volume ratio 1:1) Prepare for electrolyte.
Embodiment 2
The lithium titanate electrode material of tool nucleocapsid structure, its kernel is lithium titanate, is outwards sequentially provided with middle carbon-coating along kernel With lithium metaaluminate composite bed, middle carbon-coating and the shell of lithium metaaluminate composite bed constituent material.Wherein, the size of kernel is 200nm, the thickness of middle carbon-coating is 10nm, and the thickness of lithium metaaluminate composite bed is 10nm.
The preparation process of lithium titanate electrode material is:
1) carbon-coating raw material mixed liquor, the preparation of lithium metaaluminate composite bed raw material mixed liquor in the middle of:
50g sucrose, 1g dodecyl sodium sulfate, 1g CNT are mixed homogeneously with 1000mL acetic acid, obtain mixed liquor A, It is middle carbon-coating raw material mixed liquor；
50g lithium metaaluminate, 10g Kynoar are mixed homogeneously with 1000mL N-Methyl pyrrolidone, obtain mixed liquid B, It is lithium metaaluminate composite bed raw material mixed liquor；
2) 500g lithium titanate (purchased from Tianjin Bei Terui New Energy Technology Co., Ltd., model: LTO-1) is joined mixing In liquid A, under 30rpm rotating speed stir 2h, after be transferred in tube furnace, rise to 200 with the heating rate of 5 DEG C/min under nitrogen atmosphere DEG C, after insulation 10h, then it is down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains metatitanic acid lithium/carbon composite material；
3) metatitanic acid lithium/carbon composite material is joined in solution B, high speed dispersion 2h under 4500rpm rotating speed, it is spray-dried (technological parameter: inlet air temperatures 300 DEG C, feed rate 10mL/min, air mass flow 100L/h, leaving air temp 80 DEG C), obtains titanium Acid lithium/carbon/lithium metaaluminate composite, namely the lithium titanate electrode material of tool nucleocapsid structure.
The preparation of lithium titanate button cell and soft-package battery is all with embodiment 1.
Embodiment 3
The lithium titanate electrode material of tool nucleocapsid structure, its kernel is lithium titanate, is outwards sequentially provided with middle carbon-coating along kernel With lithium metaaluminate composite bed, middle carbon-coating and the shell of lithium metaaluminate composite bed constituent material.Wherein, the size of kernel is 500nm, the thickness of middle carbon-coating is 50nm, and the thickness of lithium metaaluminate composite bed is 50nm.
The preparation process of lithium titanate electrode material is:
1) carbon-coating raw material mixed liquor, the preparation of lithium metaaluminate composite bed raw material mixed liquor in the middle of:
200g citric acid, 2g dodecyl sodium sulfate, 2g CNT are mixed homogeneously with 1000mL benzoic acid, obtains mixing Liquid A, is middle carbon-coating raw material mixed liquor；
200g lithium metaaluminate, 20g Kynoar are mixed homogeneously with 1000mL N-Methyl pyrrolidone, obtains mixed liquor B, is lithium metaaluminate composite bed raw material mixed liquor；
2) 1000g lithium titanate (purchased from Tianjin Bei Terui New Energy Technology Co., Ltd., model: LTO-1) is joined mixed Close in liquid A, under 35rpm rotating speed, stir 2h, after be transferred in tube furnace, rise to the heating rate of 10 DEG C/min under nitrogen atmosphere 400 DEG C, after insulation 2h, then it is down to room temperature with the rate of temperature fall of 10 DEG C/min, obtains metatitanic acid lithium/carbon composite material；
3) metatitanic acid lithium/carbon composite material is joined in solution B, high speed dispersion 2h under 4000rpm rotating speed, it is spray-dried (technological parameter: inlet air temperatures 500 DEG C, feed rate 50mL/min, air mass flow 500L/h, leaving air temp 120 DEG C), obtains titanium Acid lithium/carbon/lithium metaaluminate composite, namely the lithium titanate electrode material of tool nucleocapsid structure.
The preparation of lithium titanate button cell and soft-package battery is all with embodiment 1.
Comparative example
The preparation process of metatitanic acid lithium/carbon composite material is:
1) 50g sucrose, 1g dodecyl sodium sulfate, 1g CNT are mixed homogeneously with 1000mL formic acid, obtain carbon source and mix Close liquid；
2) 500g lithium titanate (purchased from Tianjin Bei Terui New Energy Technology Co., Ltd., model: LTO-1) is joined carbon source In mixed liquor, under 35rpm rotating speed stir 2h, after be transferred in tube furnace, rise to the heating rate of 5 DEG C/min under nitrogen atmosphere 200 DEG C, after insulation 10h, then it is down to room temperature with the rate of temperature fall of 5 DEG C/min, obtains metatitanic acid lithium/carbon composite material.
The preparation of lithium titanate button cell and soft-package battery is all with embodiment 1.
Test example
1) SEM test
In Example 1, lithium titanate electrode material carries out SEM test, as it is shown in figure 1, electrode material granules to be class spherical, Little granule it is evenly distributed with between bulky grain.
2) button cell performance test
Lithium titanate button cell in embodiment 1～3 and comparative example is connected on blue electric tester, fills with the multiplying power of 0.1C Electric discharge, voltage range 1.0～2.8V, stop after circulating 3 weeks, charging and discharging curve is shown in that Fig. 2, test result see table 1.
3) soft-package battery performance test
Example 1～3 and comparative example in lithium titanate soft-package battery, charge with 0.1C multiplying power, constant-current charge to 3.2V, row Go out the gas produced in charging process, then with 0.1C multiplying power discharging to 1.0V, it is standby that 2 heel row of charge and discharge cycles go out gas.
Cycle performance is tested: takes above-mentioned soft-package battery respectively, tests its cycle performance under the conditions of 2.0C/2.0C multiplying power (1000 times, 1.5～2.8V), result see table 2.
High rate performance is tested: take above-mentioned soft-package battery respectively, at charging/discharging voltage 1.5～2.8V, temperature 25 ± 3 DEG C, with 0.3C multiplying power is charged, more respectively with 0.3C, 1.0C, 5.0C, 10.0C, 20.0C multiplying power discharging, test result see table 3.
Thickness measuring: the thickness d of battery before record circulation1；Under 60 DEG C, 1.5～2.8V voltage, fill with 1.0C multiplying power Electricity, 1.0C multiplying power discharging are circulated test, record the thickness d of battery after circulating 500 times2, calculate the thickness swelling of battery (d2-d1)/d1, result see table 4.
Table 1 embodiment and the Performance comparision of button cell in comparative example
As shown in Table 1, in embodiment 1～3 lithium titanate electrode material gram volume and first efficiency be substantially better than comparative example. Analysis reason is: the lithium metaaluminate material of electrode material surface cladding has the advantages that lithium ion transport speed is high, can improve and fill The transfer rate of lithium ion in discharge process, contributes to the performance of lithium titanate gram volume, thus the electric discharge improving composite is held Amount and first efficiency.
Table 2 embodiment compares with the cycle performance of soft-package battery in comparative example
Table 3 embodiment compares with the high rate performance of soft-package battery in comparative example
Table 4 embodiment compares with the thickness change of soft-package battery in comparative example
As shown in Table 2, in embodiment 1～3, the cycle performance of lithium titanate soft-package battery is substantially better than comparative example.Analyze reason For: the lithium titanate electrode material stable in properties in the electrolytic solution of tool nucleocapsid structure, the lithium metaaluminate of its outermost cladding can fill Discharge process provides sufficient lithium ion, and then improves the structural stability that battery circulates under the conditions of big multiplying power.
As shown in Table 3, in embodiment 1～3, the high rate performance of lithium titanate soft-package battery is substantially better than comparative example.Analyze reason For: in charge and discharge process, lithium metaaluminate composite bed can provide for the transmission of lithium ion and be flushed to, and accelerates the transfer of lithium ion, Thus improve the high rate performance of battery.
As shown in Table 4, in embodiment 1～3, the thickness change of lithium titanate soft-package battery is much smaller than comparative example.Analyze reason For: the surface coated middle carbon-coating of lithium titanate can intercept the electron transfer between lithium titanate and electrolyte, it is to avoid the two directly connects Touch, reduce the generation of side reaction, thus reduce the flatulence amount of battery, reduce its expansion rate.

Claims (8)

1. have a lithium titanate electrode material of nucleocapsid structure, it is characterised in that: the kernel of this electrode material is lithium titanate, along kernel to It is sequentially provided with outward middle carbon-coating and lithium metaaluminate composite bed, the shell of the two constituent material；It is as follows that it prepares raw material:
Kernel: lithium titanate 500～1000g；
Shell:
Middle carbon-coating: organic carbon source 50～200g, dispersant 1～2g, CNT 1～2g, solvent 1000mL；
Lithium metaaluminate composite bed: lithium metaaluminate 50～200g, Kynoar 10～20g, N-Methyl pyrrolidone 1000mL.
Electrode material the most according to claim 1, it is characterised in that: the size of described kernel is 200～800nm, middle Carbon-coating, the thickness of lithium metaaluminate composite bed are respectively 10～50nm.
Electrode material the most according to claim 1 and 2, it is characterised in that: the preparation process of described middle carbon-coating is: by carbon Acid lithium joins in the mixed liquor of middle carbon-coating raw material, after mixing in nitrogen atmosphere, sinter 2～10h at 200～400 DEG C, i.e. ?；Wherein, one or more in glucose, sucrose, citric acid of organic carbon source；Dispersant selected from Polyethylene Glycol, 12 One or both in ten thousand base sodium sulfonates；Solvent selected from formic acid, acetic acid, propanoic acid, butanoic acid, octanoic acid, adipic acid, ethanedioic acid, the third two One in acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, p-phthalic acid.
Electrode material the most according to claim 1 and 2, it is characterised in that: the preparation process of described lithium metaaluminate composite bed For: the lithium titanate being coated with middle carbon-coating is joined in the mixed liquor of lithium metaaluminate composite bed raw material, be spray-dried after mixing, Obtain.
Electrode material the most according to claim 4, it is characterised in that: the technological parameter of described spray drying is: enter pathogenic wind-warm Spend 300～500 DEG C, feed rate 10～50mL/min, air mass flow 100～500L/h, leaving air temp 80～120 DEG C.
6. the preparation method of electrode material as according to any one of Claims 1 to 5, it is characterised in that: comprise the following steps:
1) organic carbon source, dispersant, CNT are mixed homogeneously with solvent, obtain mixed liquor A；
Lithium metaaluminate, Kynoar are mixed homogeneously with N-Methyl pyrrolidone, obtains mixed liquid B；
2) lithium titanate is joined in solution A, after mixing in nitrogen atmosphere, sinter 2～10h at 200～400 DEG C, obtain metatitanic acid Lithium/carbon composite material；
3) metatitanic acid lithium/carbon composite material is joined in solution B, be spray-dried after mixing, obtain lithium titanate/carbon/lithium metaaluminate Composite, namely lithium titanate electrode material.
Preparation method the most according to claim 6, it is characterised in that: step 2) in sinter forward and backward heating rate and fall Temperature speed is respectively 5～10 DEG C/min.
8. electrode material application in preparing lithium titanate battery as according to any one of Claims 1 to 5.
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CN108281641A (en) * 2018-02-08 2018-07-13 天津普兰能源科技有限公司 A kind of the lithium titanate battery material and preparation method of dual cladding
CN115571908A (en) * 2022-10-18 2023-01-06 深圳电网智慧能源技术有限公司 Lithium titanate electrode material and application thereof in composite battery and standby power supply
JP7413482B2 (en) 2022-04-17 2024-01-15 ▲暉▼▲陽▼（▲貴▼州）新能源材料有限公司 Manufacturing method for lithium ion battery negative electrode material

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