CN101442125A - Titanate radical manganese lithium/carbon composite anode material for chargeable lithium battery and preparation method thereof - Google Patents

Titanate radical manganese lithium/carbon composite anode material for chargeable lithium battery and preparation method thereof Download PDF

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CN101442125A
CN101442125A CNA2008100723857A CN200810072385A CN101442125A CN 101442125 A CN101442125 A CN 101442125A CN A2008100723857 A CNA2008100723857 A CN A2008100723857A CN 200810072385 A CN200810072385 A CN 200810072385A CN 101442125 A CN101442125 A CN 101442125A
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lithium
manganese
anode material
carbon composite
preparation
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杨勇
李益孝
何冠男
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Xiamen University
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Xiamen University
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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 relates to a manganese lithium titanate/carbon composite anode material for a rechargeable lithium battery and a preparation method thereof, and relates to an anode material. The invention provides a manganese lithium titanate/carbon composite anode material with good electrochemical activity for the rechargeable lithium battery and a preparation method thereof. The composite anode material is Li[2-x]MnTiO4/C, wherein x is more than 0 and less than 1, titanate accounts for 98 to 85 percent, and composite carbon accounts for 2 to 15 percent. The preparation method comprises: mixing at least one among manganese salts such as manganous acetate, manganous carbonate and mangauous oxalate and at least one among titanium compounds such as n-butyl titanate and titanium dioxide in a water-alcohol system, drying the mixture after heating reaction, and performing heat treatment to obtain manganese metatitanic acid; mixing the manganese metatitanic acid and at least one among lithium compounds such as lithium acetate, lithium carbonate and lithium hydroxide, adding sugar into the mixture, and performing ball grinding and heat treatment to obtain a Li2MnTiO4/C composite material; and heating the Li2MnTiO4/C composite material, and performing chemical lithium removal, water washing and drying to obtain a product.

Description

Chargeable lithium battery manganese titanate lithium/carbon composite anode material and preparation method thereof
Technical field
The present invention relates to a kind of positive electrode, especially relate to manganese titanate lithium/carbon (Li that a kind of chargeable lithium battery is used 2-xMnTiO 4/ C, 0＜x＜1) composite positive pole and preparation method thereof.
Background technology
Chargeable lithium battery (as lithium ion battery etc.) through 10 years of development, has been widely used in various portable type electronic products, and promises to be the energy storage device of electric motor car and hybrid vehicle.The positive electrode of present commercial lithium ion battery is with oxide anode material especially stratiform LiCoO 2Material is main.LiCoO 2Shortcoming such as there is resource-constrained in positive electrode, cost an arm and a leg and environment is unfriendly.And nearly all oxide anode material all is strong oxidizer when Charging state, directly contacts with the organic electrolyte of present use to have serious potential safety hazard.Therefore, the chargeable lithium battery positive electrode of seeking cheapness, safety, environmental friendliness and having a high-energy-density becomes one of the research focus in chargeable lithium battery field.2003, Litty Sebastian and J.Gopalakrishnan were at article " Li 2MTiO 4(M=Mn, Fe, Co, Ni): New cation-disordered rocksalt oxidesexhibiting oxidative deintercalation of lithium:Synthesis of an ordered Li 2NiTiO 4" in just related to lithium battery titanate positive electrode (Journal of Solid State Chemistry, 172 (2003) 171-177).People such as M.K ü zma have reported the chemical property " Li of iron titanate lithium and manganese titanate lithium in the 14th international lithium battery meeting (Tianjin) (International Meeting of Lithium Batteries, 2008, Tianjin, China, abstract 325) 2FeTiO 4And Li 2MnTiO 4As a New Potential Li-battery Cathode Materials ", though they adopt the sol-gal process of modification, prepared Li 2MnTiO 4Material is not the pure phase material, contains 30% MnO dephasign nearly, has influenced the chemical property (even if at 60 ℃, its capacity also only is 100mAh/g) of this material.
The titanate aboundresources, environmental friendliness has inherent thermal stability and security performance, is a kind of very promising chargeable lithium battery positive electrode.
Summary of the invention
The objective of the invention is to shortcoming, the chargeable lithium battery manganese titanate lithium/carbon composite anode material and preparation method thereof that provides a kind of preparation to have good electrochemical activity at titanate positive electrode poorly conductive.
Chargeable lithium battery of the present invention is Li with manganese titanate lithium/carbon composite anode material 2-xMnTiO 4/ C, 0＜x＜1, by mass percentage, the content of titanate is 98%～85%, the content of compound carbon be 2%～15%.
Described chargeable lithium battery comes down to a kind of compound system of non-whole metering ratio with manganese titanate lithium/carbon composite anode material.
Chargeable lithium battery of the present invention may further comprise the steps with the preparation method of manganese titanate lithium/carbon composite anode material:
1) at least a with at least a and titanium compounds such as tetrabutyl titanate, titanium dioxide in the manganese salt such as manganese acetate, manganese carbonate and manganese oxalate, by stoichiometric proportion, in water-ethanol system, mix, transfer to the open containers oven dry after in closed system, adding thermal response, heat treatment in protective atmospheres such as nitrogen or argon gas obtains metatitanic acid manganese;
2) at least a with in prepared metatitanic acid manganese and the lithium compounds such as lithium acetate, lithium carbonate and lithium hydroxide; mix by stoichiometric proportion, add at least a in the carbohydrates such as sucrose, glucose, ball milling; mix back heat treatment under nitrogen or argon shield, get Li 2MnTiO 4/ C composite material;
3) with prepared Li 2MnTiO 4/ C composite material heats in air, carries out chemistry and takes off lithium, through washing, oven dry, obtains manganese titanate lithium/carbon composite anode material Li again 2-xMnTiO 4/ C target product, 0＜x＜1.
In step 1), in molar ratio, manganese salt and titanium compound satisfy amount of substance than being Mn: Ti=1: 1; Described water-ethanol system should satisfy: in molar ratio, and water: Ti 〉=4: 1; By volume, water: ethanol≤1: 5, water comprise the crystallization water from reactant feed; The described temperature that adds thermal response can be 30～180 ℃, is preferably 120～150 ℃; The temperature of described oven dry can be 80～150 ℃, is preferably 100～120 ℃; Described heat treatment temperature can be 300～800 ℃, is preferably 400～600 ℃.
In step 2) in, the time of described ball milling is preferably 2～5h; Press mass ratio, metatitanic acid manganese: sugar=1:(0.2～1.0), be preferably metatitanic acid manganese: sugar=1:(0.35～0.75); Heat treated temperature can be 800～1100 ℃, is preferably 900～1000 ℃.
In step 3), the temperature of described heating is preferably 150～200 ℃, and the time of heating is preferably 5～24h, and the temperature of oven dry is preferably 100～150 ℃.
Described manganese titanate lithium/carbon composite anode material can be used for the positive pole of chargeable lithium battery, and described manganese titanate lithium/carbon composite anode material can be used for lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium and three fluorocarbons semi-annular jade pendants acid lithium (LiPF 6, LiClO 4, LiAsF 6And CF 3SO 3Li) be electrolytical chargeable lithium battery.
Adopt manganese titanate lithium/carbon composite material of the present invention to prepare manganese titanate lithium/carbon composite electrode and can adopt coating method, its concrete steps be by quality than composite material: acetylene black: binding agent=80: 10: 10, with composite material, acetylene black and binding agent ball milling mixing, be coated on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa.With above-mentioned manganese titanate lithium/carbon composite electrode is positive pole, and lithium metal is a negative pole, and Cellgard 2400 is a barrier film, 1molL -1LiPF 6EC/DMC solution be electrolyte, be assembled into the CR2025 button cell, on LAND battery test system (Jin Nuo Electronics Co., Ltd. in Wuhan provides), carry out the constant current charge-discharge performance test.Voltage range: 2～4.8V.
The present invention adopts three-step approach, and system metatitanic acid manganese is made the manganese titanate lithium/carbon composite material more earlier, takes off the technical scheme that lithium obtains target product through chemistry at last.System metatitanic acid manganese can guarantee titanium earlier, the even mixing of manganese, thereby the purity of manganese titanate lithium phase in the assurance composite material.Sugar is heated through molten condition, helps its even dispersion.The resulting carbon of sugar charcoalization can prevent intergranular sintering of titanate and reunion on the one hand, makes material granule tiny, shortens the transmission path of electrochemical process lithium ion, helps realizing good high rate performance; On the other hand, the carbon good electrical conductivity can be improved intergranular contact electricity and lead whole electronic conductance with material, also helps realizing good high rate performance; Take off lithium through chemistry, the chemical property of material is further activated and improve.
Be with the prior art difference, the present invention divides synthetic manganese titanate lithium/carbon composite material of three steps, make metatitanic acid manganese earlier, realize the even mixing of titanium and manganese, prepare the manganese titanate lithium/carbon composite material again, carbon has influence on the diffusion between titanium and manganese and influences the purity mutually of end product when having avoided original position bag carbon; Sugar with cheapness is the carbon raw material, realizes that by chemical method the original position carbonization is compound, and technology is simple, processing ease; At last, take off the chemical property that lithium activated and improved material through chemistry.Therefore composite material of the present invention has high cost performance and market potential preferably.The original position carbon complex method that the present invention adopts, prepared composite material has better electrochemical performance.With carbon containing 10%Li 2-xMnTiO 4/ C, the x=0.7 material is an example, at 30mAg -1Reversible capability of charging and discharging reaches 200mAhg under the current density -1
Description of drawings
Fig. 1 is MnTiO 3The x-ray diffraction pattern of material sample.In Fig. 1, heat treatment temperature: a, 800 ℃ (embodiment 1); B, 500 ℃ (embodiment 3); C, 400 ℃ (embodiment 5).Abscissa be 2 θ/°, θ is the angle of diffraction, ordinate is diffracted intensity Intensity (a.u.).
Fig. 2 is Li 2MnTiO 4The x-ray diffraction pattern of/C composite sample.In Fig. 2, phosphorus content: a, 2% (embodiment 1); B, 10% (embodiment 8); C, 15% (embodiment 4).Abscissa be 2 θ/°, θ is the angle of diffraction, ordinate is diffracted intensity Intensity (a.u.).
Fig. 3 is Li 2-xMnTiO 4/ C, the x-ray diffraction pattern of 0＜x＜1 composite sample.In Fig. 3, a, x=0.6 (embodiment 2); B, x=0.7 (embodiment 8); C, x=0.75 (embodiment 7).Abscissa be 2 θ/°, θ is the angle of diffraction, ordinate is diffracted intensity Intensity (a.u.).
Fig. 4 is the charging and discharging curve of battery among the embodiment 1.In Fig. 4, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Fig. 5 is the charging and discharging curve of battery among the embodiment 2.In Fig. 5, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Fig. 6 is the charging and discharging curve of battery among the embodiment 3.In Fig. 6, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Fig. 7 is the charging and discharging curve of battery among the embodiment 4.In Fig. 7, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Fig. 8 is the charging and discharging curve of battery among the embodiment 5.In Fig. 8, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Fig. 9 is the charging and discharging curve of battery among the embodiment 6.In Fig. 9, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Figure 10 is the charging and discharging curve of battery among the embodiment 7.In Figure 10, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Figure 11 is the charging and discharging curve of battery among the embodiment 8.In Figure 11, abscissa is discharge capacity Capacity/mAhg -1, ordinate is voltage Voltage/V, current density is 30mAg -1
Figure 12 is the cycle performance of battery among the embodiment 8.In Figure 12, abscissa is period Cycle number, and ordinate is discharge capacity Capacity/mAhg -1Charging/discharging voltage is 2.0～4.8V, and current density is 30mAg -1■ is charging charge, ● be discharge discharge.
Embodiment
Embodiment 1
With 4.9g Mn (Ac) 24H 2O and 6.8g Ti (OC 4H 9) 4Join in the 20ml ethanol, react 24h under 30 ℃ of conditions in sealed flask, transfer to 80 ℃ of oven dry in the evaporating dish, then transfer in the tube type resistance furnace, the following 800 ℃ of heat treatment 3h of nitrogen protection obtain MnTiO 3Material.With 2.27g MnTiO 3Material and 1.26g LiOHH 2O, reaching 0.3g sucrose is dispersant with 30ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace under the Ar protection, 1050 ℃ of heat treatment 3h naturally cool to room temperature, promptly obtain Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 180 ℃ of heating 10h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 120 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 98%, C accounts for 2%, x=0.7.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 2
With 9.8g Mn (Ac) 24H 2O and 3.2g TiO 2Join in the 40ml ethanol, react 12h under 70 ℃ of conditions in sealed flask, transfer to 120 ℃ of oven dry in the evaporating dish, then transfer in the tube type resistance furnace, the following 700 ℃ of heat treatment 3h of nitrogen protection obtain MnTiO 3Material.With 2.27g MnTiO 3Material and 1.26g LiOHH 2O, reaching 1.5g sucrose is dispersant with 20ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace under the N2 protection, 900 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 160 ℃ of heating 24h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 120 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 90%, C accounts for 10%, x=0.6.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 3
With 4.9g Mn (Ac) 24H 2O and 6.8g Ti (OC 4H 9) 4Join in the 20ml ethanol, react 24h under 150 ℃ of conditions in water heating kettle, transfer to 90 ℃ of oven dry in the evaporating dish, then transfer in the tube type resistance furnace, the following 500 ℃ of heat treatment 5h of nitrogen protection obtain MnTiO 3Material.With 2.27g MnTiO 3Material and 1.26g LiOHH 2O, reaching 1.5g sucrose is dispersant with 30ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace at N 2Under the protection, 900 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 180 ℃ of heating 10h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 120 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 90%, C accounts for 10%, x=0.7.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 4
With 4.9g Mn (Ac) 24H 2O and 6.8g Ti (OC 4H 9) 4Join in the 20ml ethanol, react 24h under 120 ℃ of conditions in water heating kettle, transfer to 120 ℃ of oven dry in the evaporating dish, then transfer in the tube type resistance furnace, the following 500 ℃ of heat treatment 5h of nitrogen protection obtain MnTiO 3Material.With 2.27g MnTiO 3Material and 1.26g LiOHH 2O, reaching 2.2g sucrose is dispersant with 30ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace at N 2Under the protection, 900 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 180 ℃ of heating 10h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 120 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 85%, C accounts for 15%, x=0.7.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 5
With 9.8g Mn (Ac) 24H 2O and 13.6g Ti (OC 4H 9) 4Join in the 40ml ethanol, react 24h under 180 ℃ of conditions in water heating kettle, transfer to 130 ℃ of oven dry in the evaporating dish, then transfer in the tube type resistance furnace, the following 400 ℃ of heat treatment 5h of nitrogen protection obtain MnTiO 3Material.With 4.54g MnTiO 3Material and 2.52g LiOHH 2O, reaching 3.0g sucrose is dispersant with 40ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace under the Ar protection, 900 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 180 ℃ of heating 10h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 150 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 90%, C accounts for 10%, x=0.7.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 6
With 4.9g Mn (Ac) 24H 2O and 6.8g Ti (OC 4H 9) 4Join in the 40ml ethanol, add 6ml H 2O reacts 24h under 70 ℃ of conditions in sealed flask, transfer to 80 ℃ of oven dry in the evaporating dish, then transfers in the tube type resistance furnace, and the following 600 ℃ of heat treatment 3h of nitrogen protection obtain MnTiO 3Material.With 2.27g MnTiO 3Material and 1.26g LiOHH 2O, reaching 1.5g sucrose is dispersant with 30ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace at N 2Under the protection, 900 ℃ of heat treatment 3h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 180 ℃ of heating 24h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 120 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 90%, C accounts for 10%, x=0.7.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 7
With 19.6g Mn (Ac) 24H 2O and 6.4g TiO 2Join in the 80ml ethanol, react 12h under 70 ℃ of conditions in sealed flask, transfer to 120 ℃ of oven dry in the evaporating dish, then transfer in the tube type resistance furnace, the following 800 ℃ of heat treatment 10h of nitrogen protection obtain MnTiO 3Material.With 3.02g MnTiO 3Material and 0.74g Li 2CO 3, reaching 2.0g sucrose is dispersant with 30ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace at N 2Under the protection, 900 ℃ of heat treatment 10h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 200 ℃ of heating 5h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 150 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 95%, C accounts for 5%, x=0.75.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 8
With 4.9g Mn (Ac) 24H 2O and 6.8g Ti (OC 4H 9) 4Join in the 40ml ethanol, add 2ml H 2O reacts 24h under 150 ℃ of conditions in water heating kettle, transfer to 90 ℃ of oven dry in the evaporating dish, then transfers in the tube type resistance furnace, and the following 400 ℃ of heat treatment 5h of nitrogen protection obtain MnTiO 3Material.With 2.27g MnTiO 3Material and 1.26g LiOHH 2O, reaching 1.5g sucrose is dispersant with 30ml acetone, ball milling 5h (rotational velocity 500r/min).After treating acetone volatilization, transfer in the porcelain boat in tube type resistance furnace at N 2Under the protection, 900 ℃ of heat treatment 3h naturally cool to room temperature, promptly obtain described Li 2MnTiO 4/ C composite material.With Li 2MnTiO 4/ C composite material is 180 ℃ of heating 10h in air, washing filtering repeatedly after the cooling, be neutrality to filtrate after, promptly obtain described Li in 150 ℃ of oven dry 2-xMnTiO 4/ C composite material.In this compound gross mass, Li 2-xMnTiO 4Account for 90%, C accounts for 10%, x=0.7.By quality than composite material: acetylene black: binding agent=80: 10: 10, be coated in behind the ball milling mixing on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa obtains chargeable lithium battery usefulness positive pole.
Embodiment 9
The MnTiO that embodiment 1～8 is prepared 3Material, Li 2MnTiO 4/ C composite material, and Li 2-xMnTiO 4/ C composite material carries out the powder x-ray diffraction experiment on Panalytical X ' the Pert type powder x-ray diffraction instrument that Dutch Philip company produces.Experiment condition is as follows: the copper target,
Figure A200810072385D0010170939QIETU
Tube voltage 40KV, tube current 30mA uses the step-scan mode, 0.0167 ° of step-length, per time in step 10s, sweep limits: 10～90 °.Experimental data is shown in figure～3.
Embodiment 10
With embodiment 1～8 prepared electrode is positive pole, and lithium metal is a negative pole, and Cellgard 2400 is a barrier film, 1molL -1LiPF 6EC/DMC solution be electrolyte, be assembled into the CR2025 button cell, on LAND battery test system (Jin Nuo Electronics Co., Ltd. in Wuhan provides), carry out the constant current charge-discharge performance test.Voltage range is 2～4.8V.Current density is 30mAg -1Test environment is 27 ℃ of constant temperature.Test result is shown in Fig. 3～12.

Claims (10)

1. chargeable lithium battery is characterized in that being Li with manganese titanate lithium/carbon composite anode material 2-xMnTiO 4/ C, 0＜x＜1, by mass percentage, the content of titanate is 98%～85%, the content of compound carbon be 2%～15%.
2. the chargeable lithium battery as claimed in claim 1 preparation method of manganese titanate lithium/carbon composite anode material is characterized in that may further comprise the steps:
1) at least a with at least a and titanium compounds such as tetrabutyl titanate, titanium dioxide in the manganese salt such as manganese acetate, manganese carbonate and manganese oxalate, by stoichiometric proportion, in water-ethanol system, mix, transfer to the open containers oven dry after in closed system, adding thermal response, heat treatment in protective atmospheres such as nitrogen or argon gas obtains metatitanic acid manganese;
2) at least a with in prepared metatitanic acid manganese and the lithium compounds such as lithium acetate, lithium carbonate and lithium hydroxide; mix by stoichiometric proportion, add at least a in the carbohydrates such as sucrose, glucose, ball milling; mix back heat treatment under nitrogen or argon shield, get Li 2MnTiO 4/ C composite material;
3) with prepared Li 2MnTiO 4/ C composite material heats in air, carries out chemistry and takes off lithium, through washing, oven dry, obtains manganese titanate lithium/carbon composite anode material Li again 2-xMnTiO 4/ C target product, 0＜x＜1.
3. chargeable lithium battery as claimed in claim 2 is characterized in that in step 1) that with the preparation method of manganese titanate lithium/carbon composite anode material in molar ratio, manganese salt and titanium compound satisfy amount of substance than being Mn: Ti=1: 1.
4. the chargeable lithium battery as claimed in claim 2 preparation method of manganese titanate lithium/carbon composite anode material is characterized in that in step 1) described water-ethanol system should satisfy: in molar ratio, and water: Ti 〉=4: 1; By volume, water: ethanol≤1: 5, water comprise the crystallization water from reactant feed.
5. the chargeable lithium battery as claimed in claim 2 preparation method of manganese titanate lithium/carbon composite anode material, it is characterized in that in step 1), the described temperature that adds thermal response is 30～180 ℃, and the temperature of described oven dry is 80～150 ℃, and described heat treatment temperature is 300～800 ℃.
6. chargeable lithium battery as claimed in claim 2 is characterized in that in step 2 with the preparation method of manganese titanate lithium/carbon composite anode material) in, the time of described ball milling is 2～5h.
7. chargeable lithium battery as claimed in claim 2 is characterized in that in step 2 with the preparation method of manganese titanate lithium/carbon composite anode material) in, mass ratio pressed, metatitanic acid manganese: sugar=1: 0.2～1.0.
8. chargeable lithium battery as claimed in claim 2 is characterized in that in step 2 with the preparation method of manganese titanate lithium/carbon composite anode material) in, heat treated temperature is 800～1100 ℃.
9. chargeable lithium battery as claimed in claim 2 is characterized in that with the preparation method of manganese titanate lithium/carbon composite anode material the temperature of described heating is 150～200 ℃ in step 3), and the time of heating is 5～24h, and the temperature of oven dry is 100～150 ℃.
10. chargeable lithium battery as claimed in claim 1 is used to prepare manganese titanate lithium/carbon composite electrode with manganese titanate lithium/carbon composite anode material, the steps include:
By quality than composite material: acetylene black: binding agent=80: 10: 10, with composite material, acetylene black and binding agent ball milling mixing, be coated on the aluminium foil of handling, in 120 ℃ of oven dry, compression moulding under 20MPa must manganese titanate lithium/carbon composite electrode.
CNA2008100723857A 2008-12-15 2008-12-15 Titanate radical manganese lithium/carbon composite anode material for chargeable lithium battery and preparation method thereof Pending CN101442125A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102456882A (en) * 2010-10-29 2012-05-16 比亚迪股份有限公司 Lithium-ion battery cathode material and preparation method thereof
CN106910642A (en) * 2015-12-22 2017-06-30 比亚迪股份有限公司 A kind of ultracapacitor and preparation method thereof
CN107890880A (en) * 2017-11-30 2018-04-10 南昌航空大学 A kind of preparation method of Nano-size Porous Graphite phase carbon nitride/metatitanic acid manganese composite photo-catalyst

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102456882A (en) * 2010-10-29 2012-05-16 比亚迪股份有限公司 Lithium-ion battery cathode material and preparation method thereof
CN102456882B (en) * 2010-10-29 2014-10-08 比亚迪股份有限公司 Lithium-ion battery cathode material and preparation method thereof
CN106910642A (en) * 2015-12-22 2017-06-30 比亚迪股份有限公司 A kind of ultracapacitor and preparation method thereof
CN106910642B (en) * 2015-12-22 2019-06-07 比亚迪股份有限公司 A kind of supercapacitor and preparation method thereof
CN107890880A (en) * 2017-11-30 2018-04-10 南昌航空大学 A kind of preparation method of Nano-size Porous Graphite phase carbon nitride/metatitanic acid manganese composite photo-catalyst

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