CN101587948B - Preparation method for LiTiO/C compound electrode material - Google Patents

Preparation method for LiTiO/C compound electrode material Download PDF

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CN101587948B
CN101587948B CN2009100437239A CN200910043723A CN101587948B CN 101587948 B CN101587948 B CN 101587948B CN 2009100437239 A CN2009100437239 A CN 2009100437239A CN 200910043723 A CN200910043723 A CN 200910043723A CN 101587948 B CN101587948 B CN 101587948B
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electrode material
preparation
combination electrode
under
temperature
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CN101587948A (en
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张治安
李劼
赖延清
高宏权
王姣丽
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YEXIANG JINGKE NEW ENERGY CO Ltd HUNAN
Central South University
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YEXIANG JINGKE NEW ENERGY CO Ltd HUNAN
Central South 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method for Li4Ti5O12/C compound electrode material, using a solidifying phase reacting method of low temperature presintering firstly and further high temperature roasting. The method comprises following steps: (1) preparing compound containing Ti and inorganic lithium salts in a certain ratio, mixing and performing ball grinding in an organic solvent medium;(2) in the air atmosphere, increasing temperature to 300-700 DEG C and after keeping the temperature for 2-8h, cooling the mixture to the constant temperature with the furnace to obtain the intermediate product; (3) mixing and performing ball grinding on the intermediate product and carbon source; under the protection of inert gas atmosphere, increasing temperature to 780-950 DEG C and keeping the temperature for 2-20h, then cooling the mixture with the furnace to obtain the Li4Ti5O12/C compound electrode material. The invention has low preparation cost and a characteristic easy to achieve scale production; the synthesized sample has a regular appearance and a stable structure, having high charging-discharging multiplying power and a great circulation performance, which can be used as the electrode material of super capacitor, lithium ion battery or super capacitor battery.

Description

A kind of Li 4Ti 5O 12The preparation method of/C combination electrode material
Technical field
The invention belongs to the new energy materials technical field, be specifically related to a kind of Li as lithium ion battery, ultracapacitor or super capacitance cell 4Ti 5O 12The preparation method of/C combination electrode material.
Background technology
The world today, petroleum resources are day by day nervous, and environmental pollution is on the rise, and forces various countries to strive to find the novel energy of sustainable development.Along with Aero-Space, defence and military, communications and transportation, electronic information and instrument and meter, especially practical application such as electric automobile is urgent day by day to the demand of high power density, wide temperature range energy storage system, is the focus that the environmental protection energy storage device of representative has become current concern with lithium ion battery, ultracapacitor or super capacitance cell.The performance of electrode material and preparation technology are determining the performance of energy storage device to a great extent, so the research of battery material is particularly important.
Spinel lithium titanate (Li 4Ti 5O 12) theoretical embedding lithium current potential is 1.55V (vs.Li +/ Li), theoretical specific capacity is 175mAh/g, is a kind of " zero strain " material, volume changes hardly in the charge and discharge process, has advantages such as charging and discharging capabilities is good, cycle performance is good, charging/discharging voltage platform stable.Simultaneously, abundant, the cheap and more easily preparation of titanium resource.These advantages make it become the electrode material that lithium ion battery, ultracapacitor or super capacitance cell have prospect, and huge researching value and commercial application prospect are arranged.
Lithium ion battery has advantages such as high-energy-density, high working voltage, memory-less effect, is expected to one of major impetus source that becomes by electric automobile.At present, though the graphite-like carbon negative pole material successfully is applied in the lithium ion battery, because the current potential of the current potential of carbon electrode and lithium metal is very approaching, easily the precipitating metal lithium forms dendrite, has potential safety hazard; Lithium ion embeds repeatedly and deviates from simultaneously, and material structure can be damaged and cause capacity attenuation.And with Li 4Ti 5O 12As the lithium ion battery of negative material, cycle life is up to 4000 times, obviously greater than graphite cathode; Fail safe is also good than lithium metal and carbon negative pole.Toshiba Corp announces that in 2007 exploitation is based on Li 4Ti 5O 12Lithium ion battery " SCiB ", be intended to be used for the hybrid power field.U.S. EnerDel company has also showed employing Li in the AABC-07 meeting 4Ti 5O 12The hybrid vehicle lithium ion battery.
Ultracapacitor then is another high power energy storage device that is rapidly developed, and have strong, the advantage such as have extended cycle life of power density height, large current density ability, but energy density is lower.Typical ultracapacitor is that two electrodes are in the middle of active carbon (AC) electrode symmetric form capacitor that barrier film in addition constitutes.Asymmetric ultracapacitor then is a kind of novel energy-storing device between symmetry ultracapacitor and secondary cell that new development is got up, and compares with traditional charcoal/charcoal symmetry ultracapacitor, has more high-energy-density; Compare with battery, have more high power density and more long-life.(US 6252762, Journal of the Electrochemical Society, 2001,148 (8): the Li of A930～A939) for TelcordiaTechnologies 4Ti 5O 12Material constitutes Li 4Ti 5O 12The asymmetric ultracapacitor of/AC, energy density reaches tens Wh/kg, far above the energy density (5～10Wh/kg) of traditional symmetric form charcoal/charcoal super capacitor.On this basis, Deng Z H etc. (Journalof Power Sources, 2009,187:635～639) has studied with Li 4Ti 5O 12Be negative pole, constitute (LiMn 2O 4+ AC)/Li 4Ti 5O 12Super capacitance cell.
At present, the synthetic method of spinel lithium titanate is many, and high-temperature solid phase reaction method is arranged usually, molten salt growth method, sol-gel process etc.
High temperature solid-state is synthetic to be preparation Li 4Ti 5O 12Main method, usually by TiO 2With Li 2CO 3Or lithium salts such as lithium hydroxide makes through the high temperature solid-state method one-step calcination, and reaction temperature is generally 800～1000 ℃, reaction time 12～24h.This technology is fairly simple, has the large-scale production advantage.Yet these high-temperature solid phase reaction method shortcomings are that the reaction time is long, the energy consumption height; Simultaneously, because the reaction temperature height, temperature retention time is long, and inorganic lithium salt volatilizees easily, therefore in order to obtain the Li of desirable metering ratio 4Ti 5O 12, often need lithium excessive about 8% in the reaction raw materials.(the process engineering journal, 2005,5 (2): 170～174) by nLi: nTi=0.84 (mol ratio) accurately takes by weighing Li to people such as Yang Jianwen 2CO 3And TiO 2And be scattered in the ethanol, with three-head grinding machine continuously grinding 2h, remove ethanol, contain in the corundum boat, place in the tube furnace.In air, with Pt-Rh thermocouple measurement temperature, employing AI Artificial intelligence industry regulator control programming rate (5 ℃/min), temperature is kept 24h after reaching 950 ℃, slowly is cooled to below 100 ℃, uses three-head grinding machine continuously grinding 2h (in the air) again, 250 ℃ of oven dry make Li 4Ti 5O 12High temperature length consuming time, the energy consumption height, relatively poor with the product cycle performance that this technology makes.
Patent (ZL 200610109497.6) then adopts molten salt growth method, 500～1200 ℃ of reaction temperatures, reaction time 6～16h, cool to room temperature then with the furnace, after the taking-up of the product after the solid phase reaction, wash with distilled water, remove remaining low temperature melting salt, put in 80～100 ℃ the vacuum drying chamber and dry by the fire 24h, obtain the spinel lithium titanate material of particle diameter 50nm～100 μ m.
(Journal of Power Sources such as M Venkateswarlu, 2005,146:204～208) by Li: Ti=4: 5 atomic ratio mixes normal propyl alcohol titanium and lithium acetate in the 75ml ethanolic solution, stir 10min under the room temperature after solution become white by yellow.Solution is increased to 80 ℃, continues to stir the formation gel.At 60～70 ℃ of stable heating 20h, obtain Li 4Ti 5O 12Precursor powder, organic principle, wherein Li are removed in calcining under 800 ℃ of Oxygen Flow states 4Ti 5O 12Mean particle size is 39nm.But sol-gel process needs expensive organic alkoxide as reactant, and complex process, and is restive, therefore is difficult to realize that large-scale industrial production satisfies the wilderness demand of new energy field.
Yet, because Li 4Ti 5O 12The intrinsic electronic conductivity of material is lower by (about 10 -13S/cm), the Li of above-mentioned technology preparation 4Ti 5O 12Capacity attenuation is fast when high current charge-discharge, high rate performance is poor, has limited the application under the high current charge-discharge condition, and therefore improving its high rate performance becomes Li 4Ti 5O 12The key of practicalization.
Part Study person then be chosen in Li 4Ti 5O 12Material surface coated with conductive agent (mainly being carbon), the structure conductive network increases the electron conduction ability between the particle, improves electronic conductivity, improves the high current charge-discharge multiplying power property then.
Patent (CN 101378119A) adopts solid phase reaction that lithium salts and titanium dioxide are mixed, and makes lithium titanate at 750～1000 ℃ of roasting 8～20h.Then, the lithium titanate that utilizes the dipping steam seasoning will be coated with carbon source material places tube furnace, under inert gas shielding, at 750～1000 ℃ of roasting 0.5～5h, obtains the charcoal coating type lithium titanate.Coat charcoal behind the synthetic lithium titanate, the charcoal that is difficult to the processability homogeneous coats Li 4Ti 5O 12Electrode material; Twice high-temperature process length consuming time has also consumed big energy simultaneously.
Yu Haiying (SCI, 2007,28 (8): 1556～1560),, join Li with hard carbon material coalescence benzene (PAS) 2CO 3And TiO 2Mixture in, pour an amount of ethanol into, stir, dipping 12h places ball grinder with batch mixing, put into diameter and be 10 and the agate ball of 6mm some, at room temperature ball milling 3h takes out batch mixing and also places 80 ℃ baking oven, removes ethanol, siccative is placed quartz boat, at N 2In tube furnace, calcine under the gas shiled.After cooling, with product ball milling 30min again, make doped lithium titanate, high rate performance is improved.Yet said method adopts the charcoal source that adds in reaction raw materials, exists reaction to generate dephasign not exclusively, easily, causes problems such as capacity is not high, cycle performance difference.
(Journal of the Electrochemical Society, 2007,154 (7): 692-697) adopt thermal evaporation to decompose, be that the charcoal source is at Li with the toluene vapours to Cheng L etc. 4Ti 5O 12The surface coats balanced graphitized carbon, has improved Li 4Ti 5O 12Conductivity.But toluene is noxious substance, and its steam and air can form explosive mixture, meets naked light, high thermoae easy firing blast, causes operational danger and highly difficult.
Summary of the invention
At Li 4Ti 5O 12The problem of the electronic conductivity difference of material own the objective of the invention is to propose a kind of Li 4Ti 5O 12The preparation method of/C combination electrode can prepare the good Li of high-rate charge-discharge capability 4Ti 5O 12/ C combination electrode material improves the electron conduction ability of material.The present invention has that preparation cost is cheap, technology is simple, power consumption is few, the characteristics of accomplishing scale production easily.
The objective of the invention is to realize in the following manner.
A kind of Li 4Ti 5O 12The preparation method of/C combination electrode material may further comprise the steps:
(1) will contain Ti compound and inorganic lithium salt, ball milling mixes 2～6h in organic solvent medium, and vacuumize obtains presoma;
(2) under the air atmosphere, precursor is warming up to 300～700 ℃ of insulation 2～8h after, be cooled to room temperature obtain in the middle of the phase product;
(3) charcoal source and middle product are mutually carried out ball milling in organic solvent medium and mix 2～6h, under the inertia protective atmosphere, be warming up to 780 ℃～950 ℃ insulation 2～20h then, cooling promptly makes Li then 4Ti 5O 12/ C combination electrode material.
Described (2) are warming up to 400～650 ℃ of better heat preservation with precursor in the step.
Described (3) are warming up to 800 ℃～900 ℃ better heat preservation in the step.
The charcoal source is one or more in glucose, sucrose, starch, phenolic resins, epoxy resin, the polyacrylonitrile.
The content of C in combination electrode material is: 1～10wt%; Be preferably 1.5～5wt%.
The inertia protective atmosphere is one or more in nitrogen, argon gas, the hydrogen.
Organic solvent medium is one or more in acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, the absolute ethyl alcohol.
Containing the Ti compound is unformed TiO 2, rutile TiO 2, Detitanium-ore-type TiO 2, in the metatitanic acid one or more; Inorganic lithium salt be in lithium hydroxide, lithium acetate, lithium nitrate, lithium carbonate, the lithium chloride one or more; Contain that the Li/Ti atomic ratio is 4.0～4.4: 5 in Ti compound and the inorganic lithium salt.
Li prepared according to the methods of the invention 4Ti 5O 12/ C combination electrode material is grey to black powder, the gram volume 〉=145mAh/g of material when 0.2C discharges and recharges, the gram volume 〉=120mAh/g of material when 3C discharges and recharges; Capability retention 〉=90% of 100 of material circulations when 1C discharges and recharges.
The present invention adopts two steps calcining solid phase reaction process, promptly carries out low temperature presintering earlier, and the phase product carries out high-temperature calcination again in the middle of making, suppress the volatilization that high temperature descends lithium salts for a long time, first on the other hand low temperature presintering, back high temperature crystallization on the one hand, reduce reaction temperature, shorten the reaction time, energy savings.Simultaneously, in middle phase product, add the charcoal source, save reaction raw materials on the one hand, prepare the Li that conducts electricity very well 4Ti 5O 12/ C material effectively suppresses further growing up of crystallite dimension under the high temperature on the other hand, effectively improves high rate performance.
Adopt the prepared Li of preparation method provided by the invention 4Ti 5O 12/ C combination electrode material has high charge, and has good cycle performance.The present invention has that preparation cost is cheap, technology is simple, the reaction power consumption is few; the characteristics of accomplishing scale production easily; synthetic regular, the Stability Analysis of Structures of sample topography; has high charge; and cycle performance is good, can be used as the electrode material of ultracapacitor, lithium ion battery or super capacitance cell.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1, embodiment 2, embodiment 3;
Fig. 2 is the SEM figure of embodiment 1;
Fig. 3 is the SEM figure of embodiment 2;
Fig. 4 is the SEM figure of embodiment 3.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
Take by weighing 7.62g and analyze pure Li 2CO 3, then by Li: Ti=4.12: 5 take by weighing the 20.00g rutile TiO 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 650 ℃ of insulation 6h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 2wt% adds starch 0.46g respectively in the/C composite material, and ball milling mixing 2h in the anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N 2Be warming up to 800 ℃ of insulation 6h under the protective atmosphere, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Material property characterizes:
The crystal structure of Japan Rigaku 3014 type X-ray diffractometer analysis of material is with scanning electron microscopy (Japan, JSM-6360) pattern of observation material.With the C content in the leco CS-600 charcoal sulphur analyzer working sample.
Electrochemical property test:
Electrode slice is with assembling all prepares as follows to the lithium half-cell: with embodiment 1 prepared Li 4Ti 5O 12/ C combination electrode material, conductive black, binding agent evenly mix according to mass ratio at 8: 1: 1, drip an amount of solvent (NMP), after fully grinding slurry evenly is coated on the 10 μ m Copper Foil collectors, 120 ℃ of following vacuumize 12h strike out diameter and are the electrode thin slice about 0.8cm then.In being full of the glove box of argon gas work electrode, barrier film, metal lithium sheet be assembled into the lithium half-cell is carried out electrochemical property test, barrier film is Celgard 2400, and electrolyte is LiPF 6/ EC-DMC-EMC, wherein: DMC: EMC: EC=1: 1: 1 (W/W), LiPF 6Concentration 1.0M.
Take out the back and carry out the constant current charge and discharge with blue electricity (LAND) series battery test macro and test, the test voltage scope is 0.8～2.8V, with a certain multiplying power electric current constant-current discharge to 0.8V, again with same electric current constant current charge to 2.8V.
XRD detects and is spinelle Li 4Ti 5O 12Characteristic peak.The SEM of JSM-6360 sem observation particle size as can be known is more even, regular, and is spherical in shape or class is spherical.Using leco CS-600 charcoal sulphur analyzer to detect C content is 1.29%.
Press the Li of embodiment 1 method and proportioning preparation 4Ti 5O 12Gram volume is 156.4mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 146.5mAhg under the 0.5C charging and discharging currents -1, gram volume is 133mAh/g under the 3C charging and discharging currents.Capability retention 〉=94% of 100 of material circulations when 1C discharges and recharges.
Embodiment 2
Take by weighing 7.62g and analyze pure Li 2CO 3, then by Li: Ti=4.12: 5 take by weighing the unformed TiO of 20.00g 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in isopropanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 650 ℃ of insulation 6h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 3wt% adds glucose 0.69g respectively in the/C composite material, and ball milling mixing 2h in the isopropanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N 2Be warming up to 800 ℃ of insulation 8h under the protective atmosphere, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
The material property sign is identical with embodiment 1 with electrochemical property test.
Press the Li of embodiment 2 methods and proportioning preparation 4Ti 5O 12Gram volume is 152.4mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 141.3mAhg under the 0.5C charging and discharging currents -1, gram volume is 129.4mAh/g under the 3C charging and discharging currents.Capability retention 〉=95% of 100 of material circulations when 1C discharges and recharges.
Embodiment 3
Take by weighing 7.62g and analyze pure Li 2CO 3, then by Li: Ti=4.12: 5 take by weighing 20.00g anatase TiO 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in isopropanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 680 ℃ of insulation 6h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 2wt% adds glucose 0.46g respectively in the/C composite material, and ball milling mixing 2h in the isopropanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 900 ℃ of insulation 6h under argon shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
The material property sign is identical with embodiment 1 with electrochemical property test.
Press the Li of embodiment 3 methods and proportioning preparation 4Ti 5O 12Gram volume is 157.4mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 145.2mAhg under the 0.5C charging and discharging currents -1, gram volume is 128.4mAh/g under the 3C charging and discharging currents.Capability retention 〉=92% of 100 of material circulations when 1C discharges and recharges.
Embodiment 4
Take by weighing 7.62g and analyze pure Li 2CO 3, then by Li: Ti=4.12: 5 take by weighing 20.00g anatase TiO 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 650 ℃ of insulation 2h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 5wt% adds phenolic resins 1.15g respectively in the/C composite material, and ball milling mixing 2h in the anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 850 ℃ of insulation 6h under argon shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 4 methods and proportioning preparation 4Ti 5O 12Gram volume is 150.6mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 142.2mAhg under the 0.5C charging and discharging currents -1, gram volume is 127.4mAh/g under the 3C charging and discharging currents.Capability retention 〉=95% of 100 of material circulations when 1C discharges and recharges.
Embodiment 5
Take by weighing 7.62g and analyze pure Li 2CO 3, then by Li: Ti=4.12: 5 take by weighing 20.00g anatase TiO 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 600 ℃ of insulation 6h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 3wt% adds starch 0.69g respectively in the/C composite material, and ball milling mixing 2h in the anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 850 ℃ of insulation 6h under argon shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 5 methods and proportioning preparation 4Ti 5O 12Gram volume is 156.7mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 139.2mAhg under the 0.5C charging and discharging currents -1, gram volume is 130.1mAh/g under the 3C charging and discharging currents.Capability retention 〉=94% of 100 of material circulations when 1C discharges and recharges.
Embodiment 6
Take by weighing 7.62g and analyze pure Li 2CO 3, then by Li: Ti=4.12: 5 take by weighing the unformed TiO of 20.00g 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 600 ℃ of insulation 8h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 5wt% adds starch 1.15g respectively in the/C composite material, and ball milling mixing 2h in the anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 900 ℃ of insulation 4h under nitrogen+hydrogen shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 6 methods and proportioning preparation 4Ti 5O 12Gram volume is 151.3mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 139.2mAhg under the 0.5C charging and discharging currents -1, gram volume is 128.1mAh/g under the 3C charging and discharging currents.Capability retention 〉=94% of 100 of material circulations when 1C discharges and recharges.
Embodiment 7
Take by weighing 7.77g and analyze pure Li 2CO 3, then by Li: Ti=4.2: 5 take by weighing the unformed TiO of 20.00g 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 600 ℃ of insulation 6h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 5wt% adds starch 1.15g respectively in the/C composite material, and ball milling mixing 2h in the anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 900 ℃ of insulation 4h under nitrogen+hydrogen shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 7 methods and proportioning preparation 4Ti 5O 12Gram volume is 151.3mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 139.2mAhg under the 0.5C charging and discharging currents -1, gram volume is 128.1mAh/g under the 3C charging and discharging currents.Capability retention 〉=94% of 100 of material circulations when 1C discharges and recharges.
Embodiment 8
Take by weighing 8.74g LiOHH 2O, then by Li: Ti=4.16: 5 take by weighing 20.00g rutile TiO 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in absolute ethyl alcohol and isopropyl alcohol (weight ratio 1: 1) medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 580 ℃ of insulation 3h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 3wt% adds starch 0.69g respectively in the/C composite material, and ball milling mixing 2h in absolute ethyl alcohol and isopropyl alcohol (weight ratio 1: the 1) medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 850 ℃ of insulation 6h under nitrogen+hydrogen shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 8 methods and proportioning preparation 4Ti 5O 12Gram volume is 157.6mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 141.2mAhg under the 0.5C charging and discharging currents -1, gram volume is 130.4mAh/g under the 3C charging and discharging currents.Capability retention 〉=91% of 100 of material circulations when 1C discharges and recharges.
Embodiment 9
Take by weighing 8.57g LiOHH 2O, then by Li: Ti=4.08: 5 take by weighing the unformed TiO of 20.00g 2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in absolute ethyl alcohol and isopropyl alcohol (weight ratio 1: 1) medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 600 ℃ of insulation 2h, cools to room temperature with the furnace and obtains middle phase product.
Press Li 4Ti 5O 12The target carbon content is that 6wt% adds sucrose 1.38g respectively in the/C composite material, and ball milling mixing 2h in absolute ethyl alcohol and isopropyl alcohol (weight ratio 1: the 1) medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back is warming up to 900 ℃ of insulation 5h under nitrogen+hydrogen shield atmosphere in atmosphere furnace, cool off with stove then.Products therefrom is Li 4Ti 5O 12/ C combination electrode material.
Electrochemical property test is identical with embodiment 1.
Press the Li of embodiment 9 methods and proportioning preparation 4Ti 5O 12Gram volume is 149.6mAh/g under the/C combination electrode material 0.2C charging and discharging currents, and gram volume is 138.7mAhg under the 0.5C charging and discharging currents -1, gram volume is 130.2mAh/g under the 3C charging and discharging currents.Capability retention 〉=95% of 100 of material circulations when 1C discharges and recharges.

Claims (9)

1. Li 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that, described preparation method may further comprise the steps:
(1) will contain Ti compound and inorganic lithium salt, ball milling mixes 2～6h in organic solvent medium, and vacuumize obtains presoma;
(2) under the air atmosphere, precursor is warming up to 300～700 ℃ of insulation 2～8h after, be cooled to room temperature obtain in the middle of the phase product;
(3) charcoal source and middle product are mutually carried out ball milling in organic solvent medium and mix 2～6h, vacuumize under the inertia protective atmosphere, is warming up to 780 ℃～950 ℃ insulation 2～20h then, and cooling promptly makes Li then 4Ti 5O 12/ C combination electrode material.
2. Li according to claim 1 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that: described (2) are warming up to 400～650 ℃ of insulations with precursor in the step.
3. Li according to claim 1 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that: described (3) are warming up to 800 ℃～900 ℃ insulations in the step.
4. Li according to claim 1 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that, described charcoal source is one or more in glucose, sucrose, starch, phenolic resins, epoxy resin, the polyacrylonitrile.
5. according to claim 1 or 4 described Li 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that: the content of C in combination electrode material is: 1～10wt%.
6. Li according to claim 5 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that, the content of C in combination electrode material is: 1.5～5wt%.
7. Li according to claim 1 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that, described inertia protective atmosphere is one or more in nitrogen, the argon gas.
8. Li according to claim 1 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that, described organic solvent medium is one or more in acetone, isopropyl alcohol, n-butanol, normal propyl alcohol, the absolute ethyl alcohol.
9. Li according to claim 1 4Ti 5O 12The preparation method of/C combination electrode material is characterized in that, the described Ti of containing compound is unformed TiO 2, rutile TiO 2, Detitanium-ore-type TiO 2, in the metatitanic acid one or more; Inorganic lithium salt be in lithium nitrate, lithium carbonate, the lithium chloride one or more; Contain that the Li/Ti atomic ratio is 4.0～4.4: 5 in Ti compound and the inorganic lithium salt.
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