CN101630735A - Method for modifying spinel lithium titanate Li4Ti5O12, anode material for lithium-ion batteries - Google Patents

Method for modifying spinel lithium titanate Li4Ti5O12, anode material for lithium-ion batteries Download PDF

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Publication number
CN101630735A
CN101630735A CN200910086283A CN200910086283A CN101630735A CN 101630735 A CN101630735 A CN 101630735A CN 200910086283 A CN200910086283 A CN 200910086283A CN 200910086283 A CN200910086283 A CN 200910086283A CN 101630735 A CN101630735 A CN 101630735A
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lithium
anode material
inert gas
lithium ion
reaction vessel
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康晓红
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Beijing Jiaotong University
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Beijing Jiaotong 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a method for modifying an anode material for lithium-ion batteries, comprising the following steps: placing an anode material Li4Ti5O12 needing to be modified into a reaction vessel, then loading the reaction vessel into a reaction furnace according to the procedures, pumping inert gas Ar, heating the reaction furnace to the working temperature of 25-200 DEG C and maintaining for 10-20h, pumping fluorides (such as F2, NF3, ClF3 and the like) for fluoration for 2-20min, stopping pumping the fluorides, cutting off the power source of a heating device, after the fluorated products are cooled to the room temperature, stopping pumping the inert gas Ar and taking out the fluorated material, namely the fluorated anode material for the lithium-ion batteries. Through chemical reaction, the fluorion is introduced onto the surface of the existing anode material Li4Ti5O12 for the lithium-ion battery, thus finishing modification of the anode material and endowing the battery with good kinetics performance, good cycle performance and high-rate charge-discharge capacity, therefore, the performances of the lithium-ion battery with the material as the anode material are improved.

Description

Lithium ion battery negative material spinel type lithium titanate Li 4Ti 5O 12Method of modifying
Technical field
The present invention relates to the lithium ion battery negative material technical field, be specially a kind of lithium ion battery negative material Li 4Ti 5O 12Method of modifying, can significantly improve the large current density capacitance and the cyclicity of chargeable secondary lithium battery.
Background technology
Lithium rechargeable battery enjoys people to favor with excellent specific properties such as its high voltage, high power capacity, high cycle performance and high-energy-densities, is called as the leading power supply of 21 century.In order to better meet the growth requirement of electrokinetic cell, high-performance, the research of novel positive and negative electrode material cheaply are the keys of lithium rechargeable battery development.
The negative material of lithium ion battery at present adopts various embedding lithium material with carbon elements, but still there are some shortcomings in material with carbon element as ion cathode material lithium: first charge-discharge efficiency is low; Have an effect with electrolyte; There is tangible voltage delay phenomenon; Preparation method's more complicated of material with carbon element.Compare with the carbon negative pole in the lithium ion battery, though the alloy type negative material generally has higher specific capacity, the embedding repeatedly of lithium is taken off and is caused the change in volume of alloy type electrode in charge and discharge process bigger, and efflorescence was lost efficacy gradually, thereby cycle performance is relatively poor.Therefore, seek cheap easily preparation, good cycle, negative material safe and reliable and that have a good electric chemical property are research directions highly significant.
Spinel type lithium titanate (Li 4Ti 5O 12) have remarkable advantages as lithium ion battery negative material: be a kind of unstressed insertion material, recurring structure does not change in charge and discharge process, good cycle; Good charge and discharge platform is arranged; Theoretical specific capacity is 175mAh/g, and actual specific capacity can reach 165mAh/g, and concentrates on land regions; Do not react with electrolyte; Low price, preparation easily.
At present to spinel type lithium titanate (Li 4Ti 5O 12) main (1) finishing of research: comprise with precious metals ag or other oxides (Cu xO) and Li 4Ti 5O 12Carry out compound; Cracking contains that carbon polymer carries out to it that carbon coats or carbon is introduced mutually as second and improved its conductivity; (2) doping improves the electronic conductivity of material; (3) preparation nano particle Li 4Ti 5O 12, with diffusion length that shortens lithium particle and the contact area that increases active material and electrolyte.But from present achievement in research, all exist charge-discharge magnification low, can not adapt to the demand of great current power battery, while cyclicity and capacity be defectiveness also.
Summary of the invention
Technical problem to be solved by this invention is: at the deficiencies in the prior art, propose a kind of lithium ion battery negative material Li 4Ti 5O 12Method of modifying is to improve lithium ion battery negative material Li 4Ti 5O 12High-rate charge-discharge capability and cycle performance.
The technical scheme that technical solution problem of the present invention is adopted is:
To need modification negative material Li 4Ti 5O 12Put in the reaction vessel, the reacting furnace of again reaction vessel being packed into feeds inert gas Ar, is heated to 25-200 ℃ and keep 10-20h, feeds fluoride (F 2, NF 3, ClF 3Etc. fluorine-containing fluoride), fluoridize 2-20min, fluoridize and finish, stop fluoride and feed, cut off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, gained is the lithium ion battery negative material through fluorination treatment.
With prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent (PVDF), acetylene black and active material are evenly made slurry by certain mass than mixing the back high-speed stirred.Slurry is coated on (Copper Foil or nickel foam) on the collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.
Beneficial effect of the present invention is as follows:
The present invention proposes existing lithium ion battery negative material Li 4Ti 5O 12Carry out fluorinated surface and handle, by chemical reaction, at existing lithium ion battery negative material Li 4Ti 5O 12Fluorine ion is introduced on the surface, has finished the anticathode material modification, makes it have good battery power and learns performance, cycle performance and high power charging-discharging capacity, thereby improved with the lithium ion battery performance of this material as negative material.
Surface fluorination lithium ion battery negative material Li of the present invention 4Ti 5O 12Has bigger specific area, increased the contact area with conductive agent, electrolyte and collector, improved the conductive capability of electrode, made the electrochemical polarization of battery alleviate and reduce with the internal resistance dividing potential drop, help the battery high power charging-discharging, efficiently solve lithium ion battery and adopt Li 4Ti 5O 12The problem of cycle performance of battery and battery capacity difference under the high power charging-discharging condition that exists during as negative material.
Description of drawings
Fig. 1 primary sample and the 5C multiplying power constant current charge-discharge curve that utilizes the inventive method (embodiment 1) modification processing back sample;
Fig. 2 primary sample and the capacity, the efficiency curve that utilize the inventive method (embodiment 1) modification processing back sample.
Embodiment
Embodiment 1:
Select average grain diameter 2um Li for use 4Ti 5O 12, put in the reaction vessel, follow procedure feeds inert gas Ar with the reaction vessel reacting furnace of packing into again, is heated to 200 ℃ and keep 10h, feeds fluoride NF 32min stops fluoride and feeds, and cuts off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, with prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent PVDF, acetylene black and active material mix the back high-speed stirred by mass ratio and evenly make slurry at 2: 2: 6.Slurry is coated on the Copper Foil collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance have all had large increase (Fig. 1 and Fig. 2) under identical rate charge-discharge condition.
Comparative Examples 1
With untreated average grain diameter 2um Li 4Ti 5O 12, be used as lithium ion battery negative material.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance are all than embodiments of the invention 1 poor (referring to Fig. 1 and Fig. 2) under identical rate charge-discharge condition.
Embodiment 2:
Select average grain diameter 2um Li for use 4Ti 5O 12, put in the reaction vessel, follow procedure feeds inert gas Ar with the reaction vessel reacting furnace of packing into again, is heated to 100 ℃ and keep 12h, feeds fluoride NF 32min stops fluoride and feeds, and cuts off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, with prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent PVDF, acetylene black and active material mix the back high-speed stirred by mass ratio and evenly make slurry at 2: 2: 6.Slurry is coated on the Copper Foil collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance have all had large increase under identical rate charge-discharge condition.
Embodiment 3:
Select average grain diameter 2um Li for use 4Ti 5O 12, put in the reaction vessel, follow procedure feeds inert gas (Ar) with the reaction vessel reacting furnace of packing into again, is heated to 150 ℃ and keep 12h, feeds fluoride F 210min stops fluoride and feeds, and cuts off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, with prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent PVDF, acetylene black and active material mix the back high-speed stirred by mass ratio and evenly make slurry at 2: 2: 6.Slurry is coated on the Copper Foil collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance have all had large increase under identical rate charge-discharge condition.
Embodiment 4:
Select average grain diameter 2um Li for use 4Ti 5O 12, put in the reaction vessel, follow procedure feeds inert gas Ar with the reaction vessel reacting furnace of packing into again, is heated to 70 ℃ and keep 12h, feeds fluoride F 22min stops fluoride and feeds, and cuts off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, with prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent PVDF, acetylene black and active material mix the back high-speed stirred by mass ratio and evenly make slurry at 2: 2: 6.Slurry is coated on the Copper Foil collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance have all had large increase under identical rate charge-discharge condition.
Embodiment 5:
Select average grain diameter 2um Li for use 4Ti 5O 12, put in the reaction vessel, follow procedure feeds inert gas Ar with the reaction vessel reacting furnace of packing into again, is heated to 150 ℃ and keep 12h, feeds fluoride ClF 32min stops fluoride and feeds, and cuts off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, with prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent PVDF, acetylene black and active material mix the back high-speed stirred by mass ratio and evenly make slurry at 2: 2: 6.Slurry is coated on the Copper Foil collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance have all had large increase under identical rate charge-discharge condition.
Embodiment 6:
Select average grain diameter 2um Li for use 4Ti 5O 12, put in the reaction vessel, follow procedure feeds inert gas Ar with the reaction vessel reacting furnace of packing into again, is heated to 25 ℃ and keep 20h, feeds fluoride ClF 320min stops fluoride and feeds, and cuts off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, with prepared modification negative material Li 4Ti 5O 12As electrode active material, be solvent with N-first-2-Pyrrolidone, with binding agent PVDF, acetylene black and active material mix the back high-speed stirred by mass ratio and evenly make slurry at 2: 2: 6.Slurry is coated on the Copper Foil collector equably.With wet electrode in vacuum drying oven in 120 ℃ of dry 12h, make electrode slice.Show that by conventional lithium ion battery negative evaluation method testing result capacity and cycle performance have all had large increase under identical rate charge-discharge condition.

Claims (2)

1. a modified method for lithium ion cell negative electrode material is characterized in that: will need modification negative material Li 4Ti 5O 12Put in the reaction vessel, the reacting furnace of again reaction vessel being packed into feeds inert gas Ar, be heated to 25-200 ℃, and keep 10-20h, and feed fluoride, fluoridize 2-20min, stopping fluoride feeding, cut off the heater power supply, treat the fluorinated product cool to room temperature after, stop inert gas Ar and feed, take out fluorinated material, gained is the lithium ion battery negative material through fluorination treatment.
2. according to the described a kind of modified method for lithium ion cell negative electrode material of claim 1, it is characterized in that described fluoride is F 2, NF 3Or ClF 3In a kind of.
CN200910086283A 2009-06-09 2009-06-09 Method for modifying spinel lithium titanate Li4Ti5O12, anode material for lithium-ion batteries Pending CN101630735A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120028108A1 (en) * 2010-07-29 2012-02-02 Hiroki Inagaki Active material for battery, nonaqueous electrolyte battery, battery pack, and vehicle
CN102779989A (en) * 2012-08-14 2012-11-14 天津巴莫科技股份有限公司 Method for preparing fluorine-doped spherical lithium titanate for lithium ion battery
CN102800862A (en) * 2012-07-30 2012-11-28 彩虹集团公司 Titanium composite material, preparation method thereof and method for preparing cathode using composite material
CN103782421A (en) * 2011-07-29 2014-05-07 学校法人同志社 Negative electrode material for lithium ion batteries containing surface-fluorinated b-type titanium oxide powder, method for producing same, and lithium ion battery using same
CN106935831A (en) * 2017-03-31 2017-07-07 深圳市国创新能源研究院 A kind of lithium titanate anode material for suppressing flatulence and its preparation method and application
CN108899512A (en) * 2018-07-03 2018-11-27 江苏乐能电池股份有限公司 A kind of preparation method of multi-element metal compound codope trielement composite material
CN113346132A (en) * 2021-05-24 2021-09-03 上海大学 Fluorinated polyethylene oxide solid electrolyte material and preparation method and application thereof
CN114824245A (en) * 2022-03-24 2022-07-29 湖北钛时代新能源有限公司 Preparation method of ultralow temperature battery

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120028108A1 (en) * 2010-07-29 2012-02-02 Hiroki Inagaki Active material for battery, nonaqueous electrolyte battery, battery pack, and vehicle
CN102347484A (en) * 2010-07-29 2012-02-08 株式会社东芝 Active material for battery, nonaqueous electrolyte battery, battery pack, and vehicle
US8691440B2 (en) * 2010-07-29 2014-04-08 Kabushiki Kaisha Toshiba Active material for battery, nonaqueous electrolyte battery, battery pack, and vehicle
CN103782421A (en) * 2011-07-29 2014-05-07 学校法人同志社 Negative electrode material for lithium ion batteries containing surface-fluorinated b-type titanium oxide powder, method for producing same, and lithium ion battery using same
CN102800862A (en) * 2012-07-30 2012-11-28 彩虹集团公司 Titanium composite material, preparation method thereof and method for preparing cathode using composite material
CN102779989A (en) * 2012-08-14 2012-11-14 天津巴莫科技股份有限公司 Method for preparing fluorine-doped spherical lithium titanate for lithium ion battery
CN106935831A (en) * 2017-03-31 2017-07-07 深圳市国创新能源研究院 A kind of lithium titanate anode material for suppressing flatulence and its preparation method and application
CN108899512A (en) * 2018-07-03 2018-11-27 江苏乐能电池股份有限公司 A kind of preparation method of multi-element metal compound codope trielement composite material
CN113346132A (en) * 2021-05-24 2021-09-03 上海大学 Fluorinated polyethylene oxide solid electrolyte material and preparation method and application thereof
CN113346132B (en) * 2021-05-24 2023-03-10 上海大学 Fluorinated polyethylene oxide solid electrolyte material and preparation method and application thereof
CN114824245A (en) * 2022-03-24 2022-07-29 湖北钛时代新能源有限公司 Preparation method of ultralow temperature battery

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