CN104617285B - Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method - Google Patents

Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method Download PDF

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Publication number
CN104617285B
CN104617285B CN201410781410.4A CN201410781410A CN104617285B CN 104617285 B CN104617285 B CN 104617285B CN 201410781410 A CN201410781410 A CN 201410781410A CN 104617285 B CN104617285 B CN 104617285B
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ball
preparation
lithium
fuse salt
ion battery
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CN201410781410.4A
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CN104617285A (en
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唐致远
唐好庆
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Tianjin University
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Tianjin University
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • 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 relates to a lithium ion battery electrode material Li2ZnTi3O8 preparation method, and aims at the defects of high temperature, longer reaction time, high organic material cost, toxicity and the like of lithium zinc titanate material preparation method in the prior art. The technical scheme is as follows: titanium dioxide (TiO2), lithium carbonate (Li2CO3) and zinc acetate (Zn (CH3COO) 2.2H2O) and mixed molten salt sodium chloride (NaCl) and potassium chloride (KCl) are mixed and stirred, in the high temperature sintering process, reactant precursors can be sufficiently contacted and reacted in liquid environment facilitating molten salts, prepared nanoscale particular material is uniform in size and free of obvious agglomeration, accumulation holes are among particles, and the structural features is conducive to play the electrochemical properties of the material.

Description

The preparation method of lithium ion battery negative material Li2ZnTi3O8
Technical field：
The present invention relates to a kind of preparation method of lithium ion battery negative material, that is, a kind of molte-salt synthesis synthesizing lithium ion is negative The method of pole material zinc titanate lithium.
Background technology：
The development of the electric automobile of the continuous development with consumption electronic product and zero-emission, wants to lithium ion battery Seek more and more higher, especially to discharge capacity and service life.Compared with traditional battery, lithium ion battery has voltage platform Height, specific capacity is high, has extended cycle life, and self discharge is low and the advantages of memory-less effect.At present, business-like lithium ion battery negative Material adopts graphite mostly, and it can lead to the growth of dendrite lithium thus piercing barrier film to cause safety problem.Therefore, searching is alternative Safety and high power capacity negative material become the emphasis of research.
Spinel type lithium titanate negative material has Stability Analysis of Structures, and in charge and discharge process, Volume Changes are little, cyclical stability Good the advantages of, but there is also obvious shortcoming is that electronic conductivity is low, limits its high rate capability.Zinc titanate lithium (Li2ZnTi3O8) there is the function of reversible embedding lithium ionic insertion/deinsertion, discharge capacity is high, and high rate capability is good, Stability Analysis of Structures, circulation Performance is good, and safety is nontoxic, and cost of material is cheaply it is considered to be substitute the preferable negative material of lithium titanate.
The synthetic method of the zinc titanate lithium inclusion sol-gal process of employing and high temperature solid-state method etc. at present.Sol-gal process closes Butyl titanate or isopropyl titanate is needed, cost of material is high and poisonous during one-tenth；During high temperature solid-state method preparation, method is simple, but institute The material secondary particle prepared is larger, has obvious agglomeration.Additionally, the material prepared by solid phase method its in high magnification Discharge capacity is relatively low, and cycle performance is poor, limits its application.
Content of the invention：
Present invention aims to current zinc titanate lithium material preparation method needs high temperature and longer reaction time And organic substance high cost and toxic the shortcomings of, synthesizing lithium ion negative material zinc titanate lithium is come using fuse salt method, gram Required hot environment such shortcoming during clothes synthesis.
Technical scheme is as follows：
(1) the weighing of raw material and fuse salt：Titanium dioxide (TiO2), lithium carbonate (Li2CO3), zinc acetate (Zn (CH3COO)2·2H2O), fuse salt compares 3 according to molfraction：1：1：(2 4) prepare, described fuse salt is sodium chloride (NaCl) Mixture with one of potassium chloride (KCl) or two kinds；
(2) titanium dioxide (TiO2), lithium carbonate (Li2CO3), zinc acetate (Zn (CH3COO)2·2H2O), fuse salt is put into In high-energy ball milling tank, weigh some and the agate ball of ratio is put in high-energy ball milling tank, add appropriate ball-milling additive, with 200 400r/min ball millings 4 hours；Described agate ball includes two kinds of models, i.e. the diameter big ball different with quality and bead；
(3) mixture after ball milling is dried 24 hours in 80 degrees Celsius of air dry ovens；
(4) by dry after mixture in agate mortar grind into powder；
(5) mixture of powders is put in Muffle furnace 800 degrees Celsius to calcine 3 hours；
(6) product after calcining is washed with deionized, centrifugation, dries and obtain final product.
Fuse salt is preferably the mixture of NaCl KCl, and the two mol ratio is 1:1.
Titanium dioxide (TiO2), lithium carbonate (Li2CO3), zinc acetate (Zn (CH3COO)2·2H2O), fuse salt according to mole Portion rate is any one of following three kinds：
3：1：1：2；3：1：1：3；3：1：1：4.
Ball-milling additive preferred alcohol, addition is：Ethanol is 30 with the mol ratio of titanium dioxide:1.
The present invention is with respect to the advantage of prior art：
It becomes molten condition at a certain temperature using mixed melting salt provides liquid environment for other substance reactions, from And reduce required hot environment during materials synthesis, just can prepare zinc titanate lithium using the less energy at short notice, from And save time and the energy；Sodium salt and Potash Resources enrich and cheap it is easy to recycling use.
Brief description：
Fig. 1 is the Li prepared by embodiment 22ZnTi3O8X-ray diffraction spectrogram, abscissa represents X-ray diffraction peak and goes out Existing angle, ordinate represents the intensity of diffraction maximum；Using Rigaku D/max- III A diffractometer, material is tested, radiation Source is Cu target, and 4 °/min of sweep speed, scanning angle scope 2 θ are 5～80 °；The XRD spectrum surveyed is carried out with standard card Contrast, the diffraction maximum in the detected main peak of discovery and all standard card corresponds, and does not have the peak of other impurities to occur, Illustrate by the Li prepared by molte-salt synthesis2ZnTi3O8For pure phase.
Fig. 2 is the Li prepared by embodiment 22ZnTi3O8Scanning electron microscope (SEM) photograph, multiplication factor be 50000；Permissible from figure It is clearly visible that prepared material granule size in 100nm, good dispersion degree, there is no the obvious agglomeration, Exist between grain and pile up hole, be conducive to improving chemical property.
Fig. 3 is the Li prepared by embodiment 22ZnTi3O8Transmission electron microscope picture, be clear that lattice spreads out from figure Penetrate striped, and there is no the lattice fringe of other impurities, illustrate that prepared material is pure phase.
Fig. 4 is the Li of the 2-in-1 one-tenth of embodiment2ZnTi3O8It is 2.0A g in current density-1When first lap and second circle discharge and recharge Curve.
Fig. 5 is the Li of the 2-in-1 one-tenth of embodiment2ZnTi3O8The cycle life figure under different multiplying.
Specific embodiment：
In order to clearly the present invention is described further, below specific embodiment is done further specifically to the present invention Bright.
Embodiment 1：
Titanium dioxide (TiO2), lithium carbonate (Li2CO3), zinc acetate (Zn (CH3COO)2·2H2O), fuse salt according to mole Portion rate 3：1：1：4 preparations, fuse salt is the mixture of NaCl KCl, and the two mol ratio is 1:1；
It is placed in high-energy ball milling tank (big ball 15, bead 30), adds ethanol, titanium dioxide with the mol ratio of ethanol is =1：30,400r/min ball millings 4 hours.Take out, dry 24 hours in 80 degrees Celsius of forced air dryings, after grinding in Muffle furnace Calcine 3 hours for 800 degrees Celsius, be washed with deionized after natural cooling 3 times, centrifugation, dry, grind, prepared lithium ion battery Negative material zinc titanate lithium.
By active material zinc titanate lithium, conductive agent (Super P), binding agent (PVDF) in mass ratio 80:10:10 mixing, It is coated in coating device and the thick thin slice of 16um is painted on copper sheet, be pressed into the circular electric pole piece of diameter 0.785cm after drying, with lithium piece be To electrode, the LiPF of 1mol/L6/(EC:DMC=1:1, volum) be electrolyte, PE/PP/PE three-layer composite microporous membrane be every Film, is assembled into button 2032 battery in the glove box full of argon gas.By the button cell assembling in 1.0A g-1And 2.0A g-1Carry out charge-discharge test, voltage range 0.05-3.0V, result is as shown in Figure 4 and Figure 5 under multiplying power.In 2.0A g-1Under multiplying power, First discharge specific capacity is 192.19mAh/g, and after 100 charge and discharge cycles, specific discharge capacity still reaches 126.04mAh/g, and circulates Functional, no substantially decay.
Embodiment 2：
Titanium dioxide (TiO2), lithium carbonate (Li2CO3), zinc acetate (Zn (CH3COO)2·2H2O), fuse salt according to mole Portion rate 3：1：1：3 preparations, other technological parameters are same as Example 1.
Embodiment 3：
Titanium dioxide (TiO2), lithium carbonate (Li2CO3), zinc acetate (Zn (CH3COO)2·2H2O), fuse salt according to mole Portion rate 3：1：1：2 preparations, other technological parameters are same as Example 1.

Claims (2)

1. lithium ion battery negative material Li2ZnTi3O8Preparation method it is characterised in that process is as follows：
(1) the weighing of raw material and fuse salt：Titanium dioxide, lithium carbonate, Zinc diacetate dihydrate, fuse salt are according to molfraction ratio 3：1：1：(2-4) prepare, described fuse salt is the mixture of sodium chloride and potassium chloride, the two mol ratio is 1:1；
(2) titanium dioxide, lithium carbonate, Zinc diacetate dihydrate, fuse salt are put in high-energy ball milling tank, weigh some and ratio The agate ball of example was put in high-energy ball milling tank, adds appropriate ball-milling additive, with 200-400r/min ball milling 4 hours；Described agate Ball includes two kinds of models, i.e. the diameter big ball different with quality and bead；Described ball-milling additive is ethanol, ethanol and titanium dioxide Mol ratio be 30:1；
(3) mixture after ball milling is dried 24 hours in 80 degrees Celsius of air dry ovens；
(4) by dry after mixture in agate mortar grind into powder；
(5) mixture of powders is put in Muffle furnace 800 degrees Celsius to calcine 3 hours；
(6) product after calcining is washed with deionized, centrifugation, dries and obtain final product.
2. lithium ion battery negative material Li according to claim 12ZnTi3O8Preparation method it is characterised in that two Titanium oxide, lithium carbonate, Zinc diacetate dihydrate, fuse salt are according to molfraction than for any one of following three kinds：3：1：1： 2；3：1：1：3；3：1：1：4.
CN201410781410.4A 2014-12-16 2014-12-16 Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method Expired - Fee Related CN104617285B (en)

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CN106410264B (en) * 2016-06-23 2018-09-04 河南大学 The molten salt preparation method of lithium ion battery negative material zinc titanate
CN106219602B (en) * 2016-08-13 2018-05-11 南阳师范学院 A kind of preparation method of lithium ionic cell cathode material lithium titanate zinc
CN107204422A (en) * 2017-06-13 2017-09-26 四川大学 A kind of preparation method of carbon/nickel ferrite based magnetic loaded nanometer composite fiber material
CN107394153A (en) * 2017-07-18 2017-11-24 福州大学 A kind of lithium ion battery negative material
CN110474036A (en) * 2019-08-29 2019-11-19 桑顿新能源科技(长沙)有限公司 Anode material of lithium battery and preparation method thereof, lithium battery anode, lithium battery and power supply unit

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CN101624212A (en) * 2008-07-10 2010-01-13 上海比亚迪有限公司 Preparation method for lithium titanate composite material
CN102315427A (en) * 2010-06-29 2012-01-11 比亚迪股份有限公司 Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery
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CN102315427A (en) * 2010-06-29 2012-01-11 比亚迪股份有限公司 Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery
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