CN103413933A - Positive electrode material for honeycomb lithium ion battery and preparation method of positive electrode material - Google Patents

Positive electrode material for honeycomb lithium ion battery and preparation method of positive electrode material Download PDF

Info

Publication number
CN103413933A
CN103413933A CN2013103940809A CN201310394080A CN103413933A CN 103413933 A CN103413933 A CN 103413933A CN 2013103940809 A CN2013103940809 A CN 2013103940809A CN 201310394080 A CN201310394080 A CN 201310394080A CN 103413933 A CN103413933 A CN 103413933A
Authority
CN
China
Prior art keywords
lithium
preparation
positive electrode
electrode material
ion batteries
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013103940809A
Other languages
Chinese (zh)
Other versions
CN103413933B (en
Inventor
沈建兴
张克昌
张加艳
魏长宝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN201310394080.9A priority Critical patent/CN103413933B/en
Publication of CN103413933A publication Critical patent/CN103413933A/en
Application granted granted Critical
Publication of CN103413933B publication Critical patent/CN103413933B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a positive electrode material for a battery, and particularly relates to a positive electrode material for a honeycomb lithium ion battery and a preparation method of the positive electrode material. The positive electrode material for the honeycomb lithium ion battery is characterized in that a honeycomb microscopic structure is formed by a modified lithium manganate positive electrode material, so that the internal structure of the active material is stable, structural deformation does not occur easily, and the contact area of the active material and electrolyte is increased, thereby improving the electrochemical performance of the material. The positive electrode material for the honeycomb lithium ion battery prepared by the invention has good cycle performance and electrochemical stability and meets the requirement of easiness in preparation.

Description

A kind of cellular anode material for lithium-ion batteries and preparation method thereof
(1) technical field
The present invention relates to a kind of anode material for lithium-ion batteries, particularly a kind of cellular anode material for lithium-ion batteries and preparation method thereof.
(2) background technology
LiMn2O4 is one of more promising lithium ion anode material, compares traditional positive electrodes such as cobalt acid lithium, and LiMn2O4 has aboundresources, environmental friendliness, easily reclaims and the advantage such as security performance is good.Become one of lithium ion battery positive electrode of greatest concern.But the capacity attenuation when manganate cathode material for lithium recycles is very fast, more obvious when high magnification and high temperature charge and discharge cycles, affected the extensive use of LiMn2O4.
(3) summary of the invention
The present invention is in order to make up the deficiencies in the prior art, and it is cellular that a kind of microstructure is provided, and cycle performance and electrochemical stability are good, simple cellular anode material for lithium-ion batteries of preparation and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of cellular anode material for lithium-ion batteries, its special character is: the raw material by following parts by weight is made: LiMn2O4 70-90 part, titanium colloidal sol 10-30 part.
The preparation method of cellular anode material for lithium-ion batteries of the present invention, comprise the following steps: at first titanium colloidal sol is joined in dispersant, magnetic agitation 10-60min, then add LiMn2O4, continue to stir 10-60min, obtain modified lithium manganate cathode material through heat treatment.
The preparation method of cellular anode material for lithium-ion batteries of the present invention, dispersant is water, ethanol, acetone and other dispersants, dispersant is satisfied to be distributed in LiMn2O4 titanium colloidal sol and volatile reagent.
The preparation method of cellular anode material for lithium-ion batteries of the present invention, the LiMn2O4 preparation process is: lithium carbonate and manganese dioxide were joined in ball grinder in 1: 4 in molar ratio, ball milling 6-10h, be transferred to sintering in Muffle furnace by the ball milling product and obtain the pure phase LiMn2O4.
The preparation method of cellular anode material for lithium-ion batteries of the present invention, the preparation process of titanium colloidal sol is: the 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then add the 8ml glacial acetic acid solution, magnetic agitation, obtain titanium colloidal sol.
The invention has the beneficial effects as follows: cellular anode material for lithium-ion batteries prepared by the present invention, cycle performance and electrochemical stability are good, and meet the simple requirement of preparation.
(4) accompanying drawing explanation
Accompanying drawing 1 is the XRD figure of LiMn2O4, modified lithium manganate;
Accompanying drawing 2 is the SEM figure of modified lithium manganate;
Accompanying drawing 3 is the first charge-discharge curve of modified lithium manganate 0.5C multiplying power;
Accompanying drawing 4 is front 100 the cycle performance curves of modified lithium manganate.
(5) embodiment
Embodiment 1:
Lithium carbonate and manganese dioxide were joined in ball grinder in 1: 4 in molar ratio, with 250r/min ball milling 6-10h.The ball milling product is transferred in Muffle furnace and heat-treats: first with 3 ℃/min, be warming up to 500 ℃ and be incubated 3h, then be warming up to 780 ℃ and be incubated 10h with 3 ℃/min, with the cooling pure phase LiMn2O4 (LiMn that obtains of stove 2O 4).
The 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, and magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then adds the 8ml glacial acetic acid solution, and magnetic agitation, obtain titanium colloidal sol.
Accurately take 0.296g titanium colloidal sol, it is joined in the 15ml absolute ethyl alcohol, magnetic agitation 10min, then by 2.66g LiMn 2O 4Add and stir 1h, it is mixed.It is transferred in 70 ℃ of thermostatic drying chambers ethanol is volatilized fully, then, be placed in Muffle furnace and heat-treat, be warming up to 600 ℃ with 3 ℃/min, insulation 30min, with the cooling modified lithium manganate sample that obtains of stove.By the modified lithium manganate cathode material for preparing and acetylene black and PVDF in mass ratio after the accurate weighing of ratio of 85:10:5 by the abundant ground and mixed of agate mortar, be dissolved in magnetic agitation 4h in the 0.8ml METHYLPYRROLIDONE, product is coated on aluminium foil to dry 5 h in 120 ℃ of thermostatic drying chambers.The above-mentioned sample prepared is cut into to the disk that diameter is 15 mm, take metal lithium sheet as to electrode, Celgard 2320 polypropylene screens are barrier film, and electrolyte is for containing 1 molL -1LiPF 6Ethylene carbonate (EC) and the mixed liquor (volume ratio of EC and DEC is 1: 1) of diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into the CR2016 button cell, carry out the charge-discharge test of modified lithium manganate battery.
Embodiment 2:
The preparation of pure phase LiMn2O4 is identical with embodiment 1.
The 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, and magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then adds the 8ml glacial acetic acid solution, and magnetic agitation, obtain titanium colloidal sol.
Accurately take 0.664g titanium colloidal sol, it is joined in the 15ml absolute ethyl alcohol, magnetic agitation 10min, then by 2.60g LiMn 2O 4Join in ethanol and stir 1h, it is mixed.It is transferred in 70 ℃ of thermostatic drying chambers and makes the ethanol volatilization fully, then, be placed in Muffle furnace and heat-treat, be warming up to 600 ℃ with 3 ℃/min, insulation 30min, with the cooling modified lithium manganate sample that obtains of stove.By the modified lithium manganate cathode material for preparing and acetylene black and PVDF in mass ratio after the accurate weighing of ratio of 85:10:5 by the abundant ground and mixed of agate mortar, be dissolved in magnetic agitation 3h in the 0.8ml METHYLPYRROLIDONE, product is coated on aluminium foil, dry 5 h in 120 ℃ of thermostatic drying chambers, the above-mentioned sample prepared is cut into to the disk that diameter is 15 mm, take metal lithium sheet as to electrode, and Celgard 2320 polypropylene screens are barrier film, and electrolyte is for containing 1 molL -1LiPF 6Ethylene carbonate (EC) and the mixed liquor (volume ratio of EC and DEC is 1: 1) of diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into the CR2016 button cell, carry out the charge-discharge test of modified lithium manganate battery.
Embodiment 3:
The preparation of pure phase LiMn2O4 is identical with embodiment 1.
The 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, and magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then adds the 8ml glacial acetic acid solution, and magnetic agitation, obtain titanium colloidal sol.
Accurately take 1.09g titanium colloidal sol, it is joined in the 15ml absolute ethyl alcohol, magnetic agitation 10min, then by 2.54g LiMn 2O 4Join in ethanol and stir 1h, it is mixed.It is transferred in 70 ℃ of thermostatic drying chambers and makes the ethanol volatilization fully, then, be placed in Muffle furnace and heat-treat, be warming up to 600 ℃ with 3 ℃/min, insulation 30min, with the cooling modified lithium manganate sample that obtains of stove.
By the modified lithium manganate cathode material for preparing and acetylene black and PVDF in mass ratio after the accurate weighing of ratio of 85:10:5 by the abundant ground and mixed of agate mortar, be dissolved in magnetic agitation 3h in the 0.6ml METHYLPYRROLIDONE, product is coated on aluminium foil, dry 5 h in 120 ℃ of thermostatic drying chambers, the above-mentioned sample prepared is cut into to the disk that diameter is 15 mm, take metal lithium sheet as to electrode, and Celgard 2320 polypropylene screens are barrier film, and electrolyte is for containing 1 molL -1LiPF 6Ethylene carbonate (EC) and the mixed liquor (volume ratio of EC and DEC is 1: 1) of diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into the CR2016 button cell, carry out the charge-discharge test of modified lithium manganate battery.
Embodiment 4:
The preparation of pure phase LiMn2O4 is identical with embodiment 1.
The 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, and magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then adds the 8ml glacial acetic acid solution, and magnetic agitation, obtain titanium colloidal sol.
Accurately take 0.664g titanium colloidal sol, it is joined in 15ml ethanol, magnetic agitation 10min, then by 2.60g LiMn 2O 4Join in ethanol and stir 60min, it is mixed.It is transferred in 65 ℃ of thermostatic drying chambers and makes the ethanol volatilization fully, then, be placed in Muffle furnace and heat-treat, be warming up to 500 ℃ with 3 ℃/min, insulation 30min.With the cooling modified lithium manganate sample that obtains of stove.
By the modified lithium manganate cathode material for preparing and acetylene black and PVDF in mass ratio after the accurate weighing of ratio of 85:10:5 by the abundant ground and mixed of agate mortar, be dissolved in magnetic agitation 3h in the 0.6ml METHYLPYRROLIDONE, product is coated on aluminium foil, dry 5 h in 120 ℃ of thermostatic drying chambers, the above-mentioned sample prepared is cut into to the disk that diameter is 15 mm, take metal lithium sheet as to electrode, and Celgard 2320 polypropylene screens are barrier film, and electrolyte is for containing 1 molL -1LiPF 6Ethylene carbonate (EC) and the mixed liquor (volume ratio of EC and DEC is 1: 1) of diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into the CR2016 button cell, carry out the charge-discharge test of modified lithium manganate battery.
Embodiment 5:
The preparation of pure phase LiMn2O4 is identical with embodiment 1.
The 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, and magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then adds the 8ml glacial acetic acid solution, and magnetic agitation, obtain titanium colloidal sol.
Accurately take 0.664g titanium colloidal sol, it is joined in 15ml ethanol, magnetic agitation 60min, then by 2.60g LiMn 2O 4Join in ethanol and stir 10min, it is mixed.It is transferred in 75 ℃ of thermostatic drying chambers and makes the ethanol volatilization fully, then, be placed in Muffle furnace and heat-treat, be warming up to 600 ℃ with 3 ℃/min, insulation 30min.With the cooling modified lithium manganate sample that obtains of stove.
By the modified lithium manganate cathode material for preparing and acetylene black and PVDF in mass ratio after the accurate weighing of ratio of 85:10:5 by the abundant ground and mixed of agate mortar, be dissolved in magnetic agitation 3h in the 0.6ml METHYLPYRROLIDONE, product is coated on aluminium foil, dry 5 h in 120 ℃ of thermostatic drying chambers, the above-mentioned sample prepared is cut into to the disk that diameter is 15 mm, take metal lithium sheet as to electrode, and Celgard 2320 polypropylene screens are barrier film, and electrolyte is for containing 1 molL -1LiPF 6Ethylene carbonate (EC) and the mixed liquor (volume ratio of EC and DEC is 1: 1) of diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into the CR2016 button cell, carry out the charge-discharge test of modified lithium manganate battery.
Embodiment 6:
The preparation of pure phase LiMn2O4 is identical with embodiment 1.
The 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, and magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then adds the 8ml glacial acetic acid solution, and magnetic agitation, obtain titanium colloidal sol.
Accurately take 0.664g titanium colloidal sol, it is joined in 15ml ethanol, magnetic agitation 30min, then by 2.60g LiMn 2O 4Join in ethanol and stir 30min, it is mixed.It is transferred in 70 ℃ of thermostatic drying chambers and makes the ethanol volatilization fully, then, be placed in Muffle furnace and heat-treat, be warming up to 700 ℃ with 3 ℃/min, insulation 30min.With the cooling modified lithium manganate sample that obtains of stove.
By the modified lithium manganate cathode material for preparing and acetylene black and PVDF in mass ratio after the accurate weighing of ratio of 85:10:5 by the abundant ground and mixed of agate mortar, be dissolved in magnetic agitation 3h in the 0.6ml METHYLPYRROLIDONE, product is coated on aluminium foil, dry 5 h in 120 ℃ of thermostatic drying chambers, the above-mentioned sample prepared is cut into to the disk that diameter is 15 mm, take metal lithium sheet as to electrode, and Celgard 2320 polypropylene screens are barrier film, and electrolyte is for containing 1 molL -1LiPF 6Ethylene carbonate (EC) and the mixed liquor (volume ratio of EC and DEC is 1: 1) of diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into the CR2016 button cell, carry out the charge-discharge test of modified lithium manganate battery.
Embodiment 7:
Above-described embodiment gained modified lithium manganate sample, carry out XRD, SEM and electrochemical property test, and wherein the characteristic peak by sample after accompanying drawing 1 modification as can be known obviously moves to left, and illustrates that the titanium ion in titanium colloidal sol has replaced the manganese ion in the pure phase LiMn2O4.By sample after accompanying drawing 2 modification as can be known, form a kind of cellular microstructure, made the active material internal structure more stable, be difficult for the recurring structure distortion, and increased the contact area of active material and electrolyte, thereby improved the chemical property of material.By accompanying drawing 3, can be found out, the first discharge specific capacity of the sol-gel modified manganate cathode material for lithium of titanium is up to 130mAhg -1, show higher specific discharge capacity, and the charging/discharging voltage platform is more stable.By accompanying drawing 4, can be found out, after 100 circulations of former manganate cathode material for lithium, capability retention is 87%, and the capability retention after 100 circulations of modified lithium manganate cathode material is 92%, obviously increases, and still have more stable charging/discharging voltage platform after 100 circulations.

Claims (6)

1. cellular anode material for lithium-ion batteries, it is characterized in that: the raw material by following parts by weight is made: LiMn2O4 70-90 part, titanium colloidal sol 10-30 part.
2. cellular anode material for lithium-ion batteries according to claim 1, it is characterized in that: the modified lithium manganate cathode material microstructure is cellular.
3. the preparation method of cellular anode material for lithium-ion batteries according to claim 1, it is characterized in that: comprise the following steps: at first titanium colloidal sol is joined in dispersant, magnetic agitation 10-60min, then add LiMn2O4, continue to stir 10-60min, obtain modified lithium manganate cathode material through heat treatment.
4. the preparation method of cellular anode material for lithium-ion batteries according to claim 3, it is characterized in that: dispersant is water, ethanol, acetone and other dispersants.
5. the preparation method of cellular anode material for lithium-ion batteries according to claim 3, it is characterized in that: the LiMn2O4 preparation process is: lithium carbonate and manganese dioxide were joined in ball grinder in 1: 4 in molar ratio, ball milling 6-10h, be transferred to sintering in Muffle furnace by the ball milling product and obtain the pure phase LiMn2O4.
6. the preparation method of cellular anode material for lithium-ion batteries according to claim 3, it is characterized in that: the preparation process of titanium colloidal sol is: the 2g polyvinylpyrrolidone is dissolved in the 40mL absolute ethyl alcohol, magnetic agitation adds the 8ml butyl titanate after dissolving fully, and then add the 8ml glacial acetic acid solution, magnetic agitation, obtain titanium colloidal sol.
CN201310394080.9A 2013-09-03 2013-09-03 A kind of cellular anode material for lithium-ion batteries and preparation method thereof Expired - Fee Related CN103413933B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310394080.9A CN103413933B (en) 2013-09-03 2013-09-03 A kind of cellular anode material for lithium-ion batteries and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310394080.9A CN103413933B (en) 2013-09-03 2013-09-03 A kind of cellular anode material for lithium-ion batteries and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103413933A true CN103413933A (en) 2013-11-27
CN103413933B CN103413933B (en) 2016-01-20

Family

ID=49606930

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310394080.9A Expired - Fee Related CN103413933B (en) 2013-09-03 2013-09-03 A kind of cellular anode material for lithium-ion batteries and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103413933B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072068A (en) * 2019-12-24 2020-04-28 江苏强劲新能源科技有限公司 Preparation method of ion-doped spinel type lithium manganate positive electrode material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102738454A (en) * 2012-07-19 2012-10-17 北大先行科技产业有限公司 Surface coating material for cathode material of lithium ion battery and preparation method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102738454A (en) * 2012-07-19 2012-10-17 北大先行科技产业有限公司 Surface coating material for cathode material of lithium ion battery and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YU LIHONG ET AL: "Enhanced high-potential and elevated-temperature cycling stability of LiMn2O4 cathode by TiO2 modification for Li-ion battery", 《ELECTROCHIMICA ACTA》 *
陈影声: "静电纺丝法制备TiO2及其光催化行为的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑（月刊）》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072068A (en) * 2019-12-24 2020-04-28 江苏强劲新能源科技有限公司 Preparation method of ion-doped spinel type lithium manganate positive electrode material

Also Published As

Publication number Publication date
CN103413933B (en) 2016-01-20

Similar Documents

Publication Publication Date Title
CN104600282A (en) Surface modified lithium ion battery anode material and preparation method thereof
CN107403913A (en) A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof
CN104157844B (en) High-rate lithium-rich manganese-based anode material of a kind of nano-micro structure and preparation method thereof
CN103151528A (en) Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material
CN102315453A (en) Method for synthesizing lithium titanate electrode material
CN103474625A (en) Coating method for core-shell novel positive electrode material for lithium ion battery
CN105789606A (en) Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material
CN103682315B (en) The preparation method of high power capacity, extended-life lithium ion battery manganate cathode material for lithium
CN103390748B (en) A kind of preparation method of alumina-coated lithium cobaltate cathode material
CN103490059A (en) Preparation method of high-voltage nickel lithium manganate cathode material with porous morphology
CN103682415A (en) High-energy-density lithium ion battery and preparation technology thereof
CN105742601A (en) Method for in-situ synthesis of carbon coated-hydrated V3O7 nanobelt and lithium ion battery
CN108649186B (en) Preparation method and application of composite positive plate rich in lithium-rich manganese base
CN104966814A (en) High-security metallic lithium cathode and preparation method thereof
CN103280579A (en) High-performance lithium ion battery positive-electrode material lithium manganese iron phosphate and preparation method thereof
CN105958027B (en) A kind of manganese base composite positive pole and preparation method thereof
CN107768664A (en) A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof
CN102881882B (en) Preparation method and application of thin-wall capsule-shaped lithium titanate electrode material
CN104241628A (en) Method for preparing titanium-dioxide-modified ferric oxide microspheres as well as produced product and use of titanium-dioxide-modified ferric oxide microspheres
CN106252593A (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN105489882A (en) Positive pole piece, preparation method thereof and lithium ion battery
CN104112846A (en) High-capacity lithium-ion battery used for electric tool and preparation method thereof
CN109860543B (en) Method for preparing chromium-doped nickel-cobalt lithium aluminate gradient cathode material for lithium battery
CN107834054B (en) Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery
CN103151515B (en) A kind of preparation method of niobium cation doping lithium manganate composite anode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160120

Termination date: 20160903

CF01 Termination of patent right due to non-payment of annual fee