CN106450281A - Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping - Google Patents

Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping Download PDF

Info

Publication number
CN106450281A
CN106450281A CN201610990190.5A CN201610990190A CN106450281A CN 106450281 A CN106450281 A CN 106450281A CN 201610990190 A CN201610990190 A CN 201610990190A CN 106450281 A CN106450281 A CN 106450281A
Authority
CN
China
Prior art keywords
zinc
lithium
mixtures
fluorine
source
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.)
Pending
Application number
CN201610990190.5A
Other languages
Chinese (zh)
Inventor
李超
肖顺华
占涛涛
罗晓冬
林刚
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.)
Guilin University of Technology
Original Assignee
Guilin 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 Guilin University of Technology filed Critical Guilin University of Technology
Priority to CN201610990190.5A priority Critical patent/CN106450281A/en
Publication of CN106450281A publication Critical patent/CN106450281A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 discloses a method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping. The method includes (1), dissolving manganese sources and strong oxidizing agents in distilled water to obtain mixtures, transferring the mixtures into a reaction kettle after a period of time, arranging the reaction kettle in an oven and carrying out reaction to obtain MnO<2> powder; (2), grinding manganese dioxide, lithium sources, fluorine ion doping sources and zinc ion doping sources to obtain mixtures; (3), sintering the mixtures in a muffle furnace, cooling the mixtures with the furnace until the temperatures of the mixtures reach the room temperature, grinding and sintering the mixtures and naturally cooling the mixtures until the temperatures of the mixtures reach the room temperature so as to obtain LiZn<x>Mn<2-x>O<4-y>F<y>. The x is equal to 0.01-0.2, and the y is equal to 0.01-0.2. The method has the advantages that the method is low in cost and includes simple processes, the zinc-fluorine-composite-doped lithium manganate anode materials which have small grains and smooth surfaces without ridge spine, are excellent in crystallinity and are in regular and uniform shapes can be prepared by the aid of the method, and the electrochemical performance, including the cycle performance and the rate performance, of the lithium manganate anode materials can be greatly improved.

Description

Hydro-thermal has the manganese of excellent cycle and high rate performance with reference to zinc and the composite mixed preparation of fluorine The method of sour lithium anode material
Technical field
The present invention relates to a kind of hydro-thermal combine zinc and fluorine composite mixed synthesis excellent cycle and high rate performance LiMn2O4 just The method of pole material.
Background technology
Lithium ion battery has safety non-pollution, energy density is higher, battery operating voltage is high, have extended cycle life, certainly put The advantages such as electric rate is low, memory-less effect, therefore, lithium ion battery becomes the most promising secondary of nowadays power supply research field One of battery.The more anode material for lithium-ion batteries of research includes LiCoO at present2, spinel-type LiMn2O4、LiFePO4With LiNiO2Deng, wherein spinel lithium manganate have the advantages that to have a safety feature, low cost, environmental protection, discharge voltage high, but due to The change of crystalline phase in the dissolving in the electrolytic solution of Jahn-Teller effect, manganese, the decomposition of electrolyte, oxygen defect and charge and discharge process Change, its capacity attenuation is serious.
Currently for the capacity greater attenuation of spinel lithium manganate, research is concentrated mainly on three aspects：Doping, surface bag Cover, add surfactant and improve electrolyte system.Doping refer to introduce valence state and radius respectively with O2-Close anion And and Mn3+Close metal cation, typical anion has Cl-、F-、Br-, metal cation has Cu2+、Zn2+、Al3+、 Ni3+、Ti4+、Mg2+、Fe3+、Co3+Deng.After mixing F, due to F（Electronegativity value is 3.98）Electronegativity is more than O（Electronegativity value is 3.44）, the electron-withdrawing power of F is strong, the combination between therefore F and Mn more even closer than O and Mn it is suppressed that the dissolving of manganese, carry The high stable charge/discharge of material；But F-Doping larger when, due to Mn3+Increase, the first charge-discharge capacity of material Can there is certain increase therewith, and a reduction of the average valence with manganese, Jahn-Teller effect is more serious, the circulation of material Stability can reduce.Zn after Zn introducing2+Instead of the Li of part tetrahedron 8a position+, define inverse spinel structure, reduce Li in charge and discharge process+Deintercalation, thus causing Lattice Contraction and the impact expanding the structural deterioration bringing, improves material repeatedly Cycle performance.But due to also having part Zn2+Instead of Mn3+, the Mn that leads to3+Reduce, the first charge-discharge specific capacity meeting of material Decrease.
The present invention synthesizes nanometer acanthosphere shape MnO initially with hydro-thermal method2, and as template, research is combined by zinc, fluorine The manganate cathode material for lithium of doping synthesis electrochemical performance.
Content of the invention
The present invention seeks to stablizing the crystal structure of lithium manganate material, on the basis of suppression Jahn-Teller effect, system Standby go out capacity be not susceptible to the manganate cathode material for lithium decayed, high rate performance is excellent.
Concretely comprise the following steps：
（1）Stoichiometrically weigh 0.01 ~ 0.1mol strong oxidizer, 0.01 ~ 0.1mol manganese source, both be placed in beaker, It is subsequently adding the deionized water of 40 ~ 400 mL.With DF-101S type heat collecting type constant temperature blender with magnetic force at ambient temperature by strong oxygen Agent and manganese source are thoroughly mixed, and are then transferred to mixed liquor in the polytetrafluoroethyllining lining of 50 ~ 500 mL, then by poly- four Fluorothene liner is sealed in stainless steel cauldron, under the conditions of the temperature setting is as 100 ~ 180 DEG C, is incubated 5 ~ 24 hours, from So it is cooled to room temperature, filters, be dried 20 ~ 30 hours under the conditions of 60 ~ 120 DEG C, obtain manganese source presoma black powder.
（2）Weigh step according to mol ratio（1）Obtained manganese source presoma 0.001 ~ 0.1 mol, weighs lithium source 0.001- 0.1 mol, Fluorine source 0.0001 ~ 0.1 mol of doping and zinc source 0.0001 ~ 0.1 mol；Four are placed in beaker and add The dehydrated alcohol of 20-40mL, puts into after ultrasonic vibration 30-50 minute in baking oven and dries under conditions of 50 ~ 120 DEG C, Ran Houfen Do not grind 10 ~ 120 minutes in mortar.
（3）By step（2）Sample after the grinding of gained, is placed in 200 ~ 650 DEG C of presintering 2-10 hours in Muffle furnace, in advance After sintering, sample is ground and in Muffle furnace 650 ~ 850 DEG C calcine 10 ~ 30 hours, cool to room temperature with the furnace, obtain final product zinc The manganate cathode material for lithium LiZn composite mixed with fluorinexMn2-xO4-yFy, wherein：X=0.01 ~ 0.2, y=0.01 ~ 0.2.
Described strong oxidizer is one or more of potassium permanganate, hydrogen peroxide, sodium peroxydisulfate and Ammonium persulfate..
Described manganese source is one or more of Manganous sulfate monohydrate, manganese acetate and manganese carbonate.
Described lithium source is one or more of a hydronium(ion) lithium oxide, lithium acetate and lithium carbonate.
Described zinc ion doped source is one or more of zinc hydroxide, zinc oxide and zinc carbonate.
Described fluorine-ion-doped source is one of lithium fluoride or ammonium fluoride or two kinds.
The present invention relates to a kind of hydro-thermal combines two-step sintering and the composite mixed system improving LiMn2O4 chemical property of zinc, fluorine Preparation Method, prepares nanometer thorn spherical manganese dioxide using the simple hydro-thermal method of operation, adds lithium source the zinc that adulterates, fluorine element, Pass through again to control the temperature and time that sinters, prepare that degree of crystallinity is high, particle size is tiny, the regular homogeneous zinc of pattern, fluorine from The composite mixed positive electrode of son.By zinc, the composite mixed chemical property significantly improving material of fluorion so as to have Higher specific discharge capacity and good cycle performance and high rate performance.When voltage range is 3.0 ~ 4.4 V, LiZnxMn4-xO2- yFyMaterial under 0.2 C multiplying power first discharge specific capacity up to 117.63 mAh/g；After circulation 100 circle under 0.5 C multiplying power, put Electric specific capacity conservation rate is 92.94%, has excellent cyclical stability；In 5 C multiplying power, the specific discharge capacity of material up to To 104.02 mAh/g.Compared with single anion or cation doping mode, the present invention can significantly improve material Big multiplying power discharging property and cyclical stability.This preparation method does not need that too high cost, environmental pollution be few, chemical property relatively Well, the application prospect in electrical source of power field for the positive electrode of synthesis is very wide it is adaptable to produce in large quantity.
Brief description
Fig. 1 be embodiment obtain zinc, fluorine-ion-doped before and after manganate cathode material for lithium XRD figure.
Fig. 2 be embodiment obtain zinc, fluorine-ion-doped front manganate cathode material for lithium SEM figure.
Fig. 3 be embodiment obtain zinc, fluorine-ion-doped rear manganate cathode material for lithium SEM figure.
Fig. 4 be embodiment obtain zinc, fluorine-ion-doped before and after manganate cathode material for lithium EDS figure.
Fig. 5 be embodiment obtain zinc, fluorine-ion-doped before and after cyclicity under 0.5 C multiplying power for the manganate cathode material for lithium Can figure.
Fig. 6 be embodiment obtain zinc, fluorine-ion-doped before and after manganate cathode material for lithium circulate the under 0.5 C multiplying power Charging and discharging curve figure during 100 circle.
Fig. 7 be embodiment obtain zinc, fluorine-ion-doped before and after manganate cathode material for lithium high rate performance figure.
Fig. 8 be embodiment obtain zinc, fluorine-ion-doped before and after manganate cathode material for lithium AC impedance figure.
Fig. 9 be embodiment obtain zinc, fluorine-ion-doped before and after manganate cathode material for lithium sweep speed for 0.1 mV/s when Cyclic voltammogram.
Specific embodiment
Embodiment：
（1）0.03mol potassium permanganate and the mixing of 0.03mol Manganous sulfate monohydrate are dissolved in 150mL deionized water, use DF- It is thoroughly mixed under 101S type heat-collecting magnetic stirring device room temperature.Then mixed liquor is transferred to the politef of 200 mL In liner, then polytetrafluoroethyllining lining is sealed in stainless steel cauldron, when the temperature setting is as 120 DEG C, insulation 15 is little When, naturally cool to room temperature, filter, be dried 20 hours under the conditions of 90 DEG C, obtain black MnO2Powder.
（2）Weigh 0.0115 mol step（1）Gained MnO2Powder, by LiZn0.05Mn1.95O3.92F0.8Stoichiometric proportion Weigh 0.00286 mol lithium acetate, 0.000295 mol zinc hydroxide and 0.000472 mol lithium fluoride, mixture is placed in burning In cup, add the dehydrated alcohol of 30 mL, ultrasonic vibration 45 minutes in beaker, dry and then grind 30 points in agate mortar Clock.
(3) by step（2）Gains are put in Muffle furnace after grinding, and sinter 5 hours at 450 DEG C, and sintering completes laggard Row sufficiently grinds, and then sinters 18 hours at 800 DEG C, finally cools to room temperature with the furnace, obtain after hand-ground LiZn0.05Mn1.95O3.92F0.08Sample.
The synthesized circular pole piece of sample making, it is assembled into button cell.
Concrete operations are as follows：Weigh active material according to mass ratio:PVDF:Acetylene black=8: 1 :1 ratio, fills Divide mixing to mill, add appropriate NMP, make electrode slip, with spreader, slip is being uniformly coated on aluminium foil, in 120 DEG C vacuum drying oven is after 15 hours, is washed into the circular pole piece of diameter 15 mm, and the quality of each pole piece is in 1.6 mg. With metal lithium sheet as negative pole, Celgard2400 microporous polypropylene membrane is barrier film, and electrolyte used is the LiPF of l mol/L6/EC+ (volume ratio is l to DMC+EMC: l :L), it is less than in the glove box that 5%, oxygen forces down in 10 pp and is full of argon in relative humidity It is assembled into CR2016 type button cell in certain sequence, then standing, after 12 hours, can carry out charge-discharge test, AC impedance Test and cyclic voltammetry.Charging/discharging voltage scope is 3.0 ~ 4.4 V, and during test material cycle performance, charge-discharge magnification is 0.5 C, its first discharge specific capacity of the sample after doping reaches 117.75 mAh/g.After circulation 100 times, discharge capacity is 109.44 mAh/g, capability retention is 92.94%.
Wherein, undoped p obtain manganate cathode material for lithium be labeled as：LMO；Zinc that embodiment obtains, fluorine-ion-doped Manganate cathode material for lithium be labeled as：LMO-ZF； PVDF：Kynoar；NMP：METHYLPYRROLIDONE；EC：Carbonic acid Vinyl acetate；DMC：Dimethyl carbonate；EMC：Ethyl methyl carbonate.

Claims (1)

1. a kind of hydro-thermal has the manganate cathode material for lithium of excellent cycle and high rate performance with reference to zinc and the composite mixed preparation of fluorine Method is it is characterised in that concretely comprise the following steps：
（1）Stoichiometrically weigh 0.01 ~ 0.1mol strong oxidizer, 0.01 ~ 0.1mol manganese source, both be placed in beaker, It is subsequently adding the deionized water of 40 ~ 400 mL；With DF-101S type heat collecting type constant temperature blender with magnetic force at ambient temperature by strong oxygen Agent and manganese source are thoroughly mixed, and are then transferred to mixed liquor in the polytetrafluoroethyllining lining of 50 ~ 500 mL, then by poly- four Fluorothene liner is sealed in stainless steel cauldron, under the conditions of the temperature setting is as 100 ~ 180 DEG C, is incubated 5 ~ 24 hours, from So it is cooled to room temperature, filters, be dried 20 ~ 30 hours under the conditions of 60 ~ 120 DEG C, obtain manganese source presoma black powder；
（2）Weigh step according to mol ratio（1）Obtained manganese source presoma 0.001 ~ 0.1 mol, weighs lithium source 0.001-0.1 Mol, Fluorine source 0.0001 ~ 0.1 mol of doping and zinc source 0.0001 ~ 0.1 mol；Four are placed in beaker and add 20- The dehydrated alcohol of 40mL, puts into after ultrasonic vibration 30-50 minute in baking oven and dries under conditions of 50 ~ 120 DEG C, then distinguish Mortar grinds 10 ~ 120 minutes；
（3）By step（2）Sample after the grinding of gained, is placed in 200 ~ 650 DEG C of presintering 2-10 hours, presintering in Muffle furnace Afterwards sample is ground and in Muffle furnace 650 ~ 850 DEG C calcine 10 ~ 30 hours, cool to room temperature with the furnace, obtain final product zinc and fluorine Composite mixed manganate cathode material for lithium LiZnxMn2-xO4-yFy, wherein：X=0.01 ~ 0.2, y=0.01 ~ 0.2；
Described strong oxidizer is one or more of potassium permanganate, hydrogen peroxide, sodium peroxydisulfate and Ammonium persulfate.；
Described manganese source is one or more of Manganous sulfate monohydrate, manganese acetate and manganese carbonate；
Described lithium source is one or more of a hydronium(ion) lithium oxide, lithium acetate and lithium carbonate；
Described zinc ion doped source is one or more of zinc hydroxide, zinc oxide and zinc carbonate；
Described fluorine-ion-doped source is one of lithium fluoride or ammonium fluoride or two kinds.
CN201610990190.5A 2016-11-10 2016-11-10 Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping Pending CN106450281A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610990190.5A CN106450281A (en) 2016-11-10 2016-11-10 Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610990190.5A CN106450281A (en) 2016-11-10 2016-11-10 Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping

Publications (1)

Publication Number Publication Date
CN106450281A true CN106450281A (en) 2017-02-22

Family

ID=58207452

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610990190.5A Pending CN106450281A (en) 2016-11-10 2016-11-10 Method for preparing lithium manganate anode materials with excellent cycle and rate performance by means of hydrothermal bonding zinc and fluorine composite doping

Country Status (1)

Country Link
CN (1) CN106450281A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103794775A (en) * 2014-01-24 2014-05-14 国家纳米科学中心 Preparation method of positive electrode material of iron-doped lithium manganate acid lithium ion battery
CN105161711A (en) * 2015-09-08 2015-12-16 国家纳米科学中心 Lithium manganate cathode material, preparation method and use
CN105304894A (en) * 2015-10-11 2016-02-03 桂林理工大学 Method for preparing high-performance lithium manganite positive electrode material by compound doping
CN105932244A (en) * 2016-05-21 2016-09-07 桂林理工大学 Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103794775A (en) * 2014-01-24 2014-05-14 国家纳米科学中心 Preparation method of positive electrode material of iron-doped lithium manganate acid lithium ion battery
CN105161711A (en) * 2015-09-08 2015-12-16 国家纳米科学中心 Lithium manganate cathode material, preparation method and use
CN105304894A (en) * 2015-10-11 2016-02-03 桂林理工大学 Method for preparing high-performance lithium manganite positive electrode material by compound doping
CN105932244A (en) * 2016-05-21 2016-09-07 桂林理工大学 Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method

Similar Documents

Publication Publication Date Title
CN102324511B (en) Preparation method for lithium ion battery composite cathode material
KR101670664B1 (en) Cathode active material coated with F-dopped lithium metal manganese oxide, lithium-ion secondary battery comprising the same and the prepration method thereof
CN105932244A (en) Method for preparing iron-fluorine composite doped lithium manganate positive electrode material by combination of hydrothermal method and two-step sintering method
CN105140492A (en) Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method
CN103904321B (en) The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4
CN101752562B (en) Compound doped 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
CN106602016A (en) Preparation method for ammonium fluoride modified nickel-cobalt-aluminum ternary positive electrode material
CN105185954A (en) LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof
CN105576231A (en) High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material
CN103390748B (en) A kind of preparation method of alumina-coated lithium cobaltate cathode material
CN104218233A (en) Composite lithium ion battery positive electrode material with high rate performance and preparation method of material
CN107302083A (en) A kind of solid reaction process preparation method of nickel lithium manganate cathode material
CN108091854A (en) A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof
CN112002879A (en) Zirconium tetrafluoride coated aluminum fluoride double-doped lithium manganate positive electrode material and preparation method thereof
CN106207158A (en) The preparation method of rich lithium manganate cathode material for lithium
CN103311540A (en) Lithium ion battery anode material and preparation method thereof
CN105098158A (en) Zirconium-doped lithium-rich cathode material of lithium ion battery and preparation method of zirconium-doped lithium-rich cathode material
CN103078098A (en) Preparation method of lithium-rich layered manganese-cobalt oxide composite positive electrode material
CN106784657A (en) A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material
CN108232186A (en) A kind of preparation method of single crystal grain and its application in the secondary battery
CN105185981B (en) A kind of LiNixMn2-xO4The preparation method of positive electrode
CN106654255A (en) Aluminum-doped and modified cathode material for high-capacity lithium ion batteries
CN106025199A (en) Preparation method of nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material
CN107170976A (en) A kind of preparation method of cobalt doped lithium titanate nano composite 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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170222

WD01 Invention patent application deemed withdrawn after publication