CN102368556A - Preparation method of wide potential window negative electrode material of lithium ion battery - Google Patents

Preparation method of wide potential window negative electrode material of lithium ion battery Download PDF

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CN102368556A
CN102368556A CN2011103291715A CN201110329171A CN102368556A CN 102368556 A CN102368556 A CN 102368556A CN 2011103291715 A CN2011103291715 A CN 2011103291715A CN 201110329171 A CN201110329171 A CN 201110329171A CN 102368556 A CN102368556 A CN 102368556A
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lithium
ion battery
lithium ion
potential window
preparation
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伊廷锋
谢颖
朱彦荣
诸荣孙
周安娜
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention which provides a preparation method of a wide potential window negative electrode material of a lithium ion battery belongs to the technical field of lithium ion batteries. The preparation method of the invention comprises the following steps: 1, mixing a lanthanum source, TiO2 with different crystal forms, and a lithium source, and grinding for 6-12h in a ball mill to obtain a mixture; and 2, putting the mixture in a muffle furnace, reacting for 12-24h at 800-950DEG C, and naturally cooling to room temperature to obtain the wide potential window negative material Li4La5-xLaxO12of the lithium ion battery, wherein x is 0.05 or 0.1. The negative electrode material prepared in the invention has a wide potential window, a good reversible capacity, an excellent rate performance and a stable cycle life, so the material which has a high practical use value allows practical requirements of various applications of the lithium ion battery to be effectively satisfied. In addition, the method of the invention has the characteristics of simplified preparation technology, high controllable reappearance, low production cost and the like.

Description

A kind of preparation method of lithium ion battery negative material of broad potential window
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of preparation method of lithium ion battery negative material of broad potential window.
Background technology
Along with the development of various electronic equipments and electric automobile, hybrid vehicle,, the lithium ion battery of energy has higher requirement to being provided for it.The capacity density and the energy density of lithium ion battery are higher, are acknowledged as electrokinetic cell the most likely.The commercial li-ion cell negative electrode material adopts various embedding lithium carbon/graphite materials mostly at present, and still, the embedding lithium current potential (0 ~ 0.26 V) of material with carbon element is very approaching with the sedimentation potential of lithium metal; When over-charging of battery; Lithium metal may be separated out and forms Li dendrite in carbon electrodes, and the dendrite further growth then maybe diaphragm; Cause both positive and negative polarity to join, thereby cause short circuit; In addition, material with carbon element also exist first charge-discharge efficiency low, with electrolyte have an effect, exist shortcomings such as tangible voltage delay phenomenon, preparation method's more complicated.Compare with the carbon negative pole, though the alloy type negative material generally has higher specific capacity, the embedding repeatedly of lithium ion is taken off and is caused alloy type electrode change in volume in charge and discharge process bigger, and efflorescence was lost efficacy gradually, thereby cycle performance is relatively poor.Therefore, searching can replace material with carbon element and current potential than carbon electrode slightly just, cheap and easy to get, safe and reliable novel negative material is the emphasis of present lithium ion battery negative research.
Spinel type lithium titanate Li 4Ti 5O 12Be a kind of " zero strain " material, embed at lithium ion that crystal structure can keep the stability of height in the process of deviating from, and make it have good cycle performance and discharge voltage stably.And have higher relatively electrode voltage (1.55 V), in whole discharge process, separating out of lithium metal can not occur, improved the fail safe that electrode material uses greatly.But Li 4Ti 5O 12Maximum deficiency is that its electronic conductance and ionic conductance are lower, and capacity attenuation is fast when high current charge-discharge, high rate performance is relatively poor, and reversible capacity far can not reach required target call.Therefore, improve high rate performance through doping and become Li 4Ti 5O 12The key of practicalization.At present, improve Li 4Ti 5O 12The approach of performance mainly contains three aspects: prepare nanometer particle size material, preparation porous structure material and improve its electronic conductivity.Preceding two kinds of methods have that process is complicated and changeable, energy consumption is excessive, the more high shortcoming of cost, are unfavorable for realizing large-scale industrial production.Therefore, improve Li through mixing 4Ti 5O 12Chemical property have very application prospects.Document (Jian Gao et al. is arranged Journal of The Electrochemical Society, 2010,157 (2): K39-K42; Jian Gao et al. Ionics, 2009,15 (5): 597 – 601.) and report: utilize the La Li doped 4Ti 5O 12, improve its chemical property, but the synthetic method that adopts being a sol-gal process, the raw material of employing are TiCl 4, LaCl 3, its voltage range that discharges and recharges is 1-3 V, synthetic method and route more complicated, and cost is high.Consider that electrokinetic cell abuse or overdischarge behavior occur through regular meeting, research Li 4Ti 5O 12It is particularly important that fail safe during the negative material overdischarge seems, i.e. the broad potential window performance.
Summary of the invention
The present invention is directed to the problem that prior art exists, a kind of preparation method of lithium ion battery negative material of broad potential window is provided.
Preparation method's concrete steps of the lithium ion battery negative material of a kind of broad potential window provided by the present invention are following:
(1) with the TiO of lanthanum source, different crystal forms 2Mix with the lithium source,, make it to mix and obtain mixture, the TiO of said lithium source, different crystal forms at grinding in ball grinder 6-12 hour 2With the metallic atom mol ratio in niobium source be (3.5 ~ 5): (5- x): x, wherein x=0.05,0.1;
(2) step (1) gained mixture is put into Muffle furnace, reacted 12-24 hour down, naturally cool to room temperature subsequently, promptly make a kind of lithium ion battery negative material Li of broad potential window at 800-950 ℃ 4La 5- x La x O 12( x=0.05,0.1).
Described lanthanum source is a kind of in lanthanum sesquioxide, lanthanum nitrate, the lanthanum acetate.
Described lithium source is a kind of in lithium carbonate, lithium acetate, lithium nitrate, the lithium hydroxide.
The TiO of described different crystal forms 2A kind of in Detitanium-ore-type, rutile-type, brookite type, the amorphous type.
The chemical formula of the lithium ion battery negative material of a kind of broad potential window that the present invention is prepared is: Li 4Ti 5- x La x O 12, wherein x=0.05,0.1, this negative material has the particle diameter of 1-2 μ m and very high wide current potential chemical property, can be used for high performance lithium ionic cell cathode material.
Characteristics of the present invention are:
(1) simplified Li 4Ti 5- x La x O 12Preparation process, controllability is good, reappearance is high, does not use chelating agent, has practiced thrift production cost.
(2) utilize the synthetic material granule uniformity of this method, good dispersion, degree of crystallinity height, and, also can obtain the material of different-grain diameter through the conditioned reaction temperature and time.
(3) resulting material has considerable broad potential window reversible capacity, the high rate performance of excellence and stable cycle life among the present invention; Make this material have very high actual use value, can effectively satisfy the actual requirement of the various application of lithium ion battery.
(4) the present invention has made full use of the rare earth resources (reserves rank first in the world) of China's abundant and nontoxic titanium ore resource is developed lithium ion battery, has reduced the actual cost of lithium ion battery from the source of manufactured materials, is particularly suitable for large-scale industrialization production.
Description of drawings
Fig. 1 is gained Li in the embodiment of the invention 1 4Ti 5- x La x O 12( x=0.05,0.1) XRD figure.
Fig. 2 is the SEM figure of gained Li4Ti5-xLaxO12 (x=0.05) in the embodiment of the invention 1.
Fig. 3 is gained Li in the embodiment of the invention 1 4Ti 5- x La x O 12( x=0.1) SEM figure.
Fig. 4 is gained Li in the embodiment of the invention 1 4Ti 5- x La x O 12( x=0.05,0.1) discharge curve first.
Fig. 5 is gained Li in the embodiment of the invention 1 4Ti 5- x Nb x O 12( x=0.05,0.1) cycle performance curve.
Embodiment
Embodiment 1: with 0.22 mol lithium carbonate, 0.495 mol TiO 2(Detitanium-ore-type), 0.005 mol lanthanum nitrate mix, and put into ball mill ball milling 8 h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 24 h down at 850 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.95La 0.05O 12The X-ray powder diffraction analysis shows the Li of gained 4Ti 4.95La 0.05O 12The small amount of impurities peak is arranged, and degree of crystallinity is high.The even particle size of learning products therefrom from scanning electron microscope analysis is consistent, and particle diameter is 1-2 μ m.The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5 V, carry out charge and discharge cycles, Li 4Ti 4.95La 0.05O 12Discharge capacity is 243.9 mAhg first -1, discharge capacity is respectively 213.6 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating still reaches 206.6 mAhg -1, Li 4Ti 4.95La 0.05O 12Shown excellent broad potential window high rate performance.
Embodiment 2: with 0.23mol lithium carbonate, 0.49 mol TiO 2(Detitanium-ore-type), 0.01 mol lanthanum nitrate mix, and put into ball mill ball milling 6h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 18h down at 850 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.9La 0.1O 12The X-ray powder diffraction analysis shows the Li of gained 4Ti 4.9La 0.1O 12Contain a small amount of Li 3xLa 2/3 xTiO 3Impurity.The even particle size of learning products therefrom from scanning electron microscope analysis is consistent, and particle diameter is 1-2 μ m.The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5V, carry out charge and discharge cycles, Li 4Ti 4.9La 0.1O 12Discharge capacity is 235.1 mAhg first -1, discharge capacity is respectively 205.6 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating is respectively 196.6 mAhg -1Li 4Ti 4.9La 0.1O 12Shown excellent broad potential window high rate performance.
Embodiment 3: with 0.4 mol lithium acetate, 0.495 mol TiO 2(amorphous type), 0.0025 mol lanthanum sesquioxide mix, and put into ball mill ball milling 12h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 12h down at 950 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.95La 0.05O 12The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5V, carry out charge and discharge cycles, Li 4Ti 4.95La 0.05O 12Discharge capacity is respectively 240.1mAhg first -1, discharge capacity is 211.3 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating is respectively 201.8 mAhg -1, Li 4Ti 4.95La 0.05O 12Shown excellent broad potential window high rate performance.
Embodiment 4: with 0.42 mol lithium hydroxide, 0.49 mol TiO 2(brookite type), 0.005 mol lanthanum sesquioxide mix, and put into ball mill ball milling 24h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 20h down at 900 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.9La 0.1O 12The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5V, carry out charge and discharge cycles, Li 4Ti 4.9La 0.1O 12Discharge capacity is 229.1mAhg first -1, discharge capacity is 201.7 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating is 190.2mAhg -1Li 4Ti 4.9La 0.1O 12Shown excellent broad potential window high rate performance.
Embodiment 5: with 0.5 mol lithium nitrate, 0.495 mol TiO 2(amorphous type), 0.005mol lanthanum acetate mix, and put into ball mill ball milling 6h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 16h down at 800 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.95La 0.05O 12The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5V, carry out charge and discharge cycles, Li 4Ti 4.95La 0.05O 12Discharge capacity is respectively 239.2 mAhg first -1, discharge capacity is 208.4 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating is respectively 199.9 mAhg -1, Li 4Ti 4.95La 0.05O 12Shown excellent broad potential window high rate performance.
Embodiment 6: with 0.35 mol lithium nitrate, 0.495 mol TiO 2(Detitanium-ore-type), 0.005mol lanthanum acetate mix, and put into ball mill ball milling 10h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 18h down at 800 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.95La 0.05O 12The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5 V, carry out charge and discharge cycles, Li 4Ti 4.95La 0.05O 12Discharge capacity is 217.7 mAhg first -1, discharge capacity is respectively 196 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating is 188.1 mAhg -1, Li 4Ti 4.95La 0.05O 12Shown excellent broad potential window high rate performance.
Embodiment 7: with 0.39 mol lithium acetate, 0.495 mol TiO 2(Detitanium-ore-type), 0.005 lanthanum nitrate mix, and put into ball mill ball milling 10h then, make it to mix, and the mixture that then will finally form is put into Muffle furnace, react 16h down at 850 ℃, naturally cool to room temperature then, promptly get Li 4Ti 4.95La 0.05O 12The product of gained as electrode material, is assembled into experiment buckle type lithium-ion battery, with 1 in being full of the glove box of argon gas CMultiplying power between 0-2.5V, carry out charge and discharge cycles, Li 4Ti 4.95La 0.05O 12Discharge capacity is 226.8 mAhg first -1, discharge capacity is 208.1 mAhg for the second time -1, the reversible capacity after 100 weeks of circulating is respectively 195.9 mAhg -1, Li 4Ti 4.95La 0.05O 12Shown excellent broad potential window high rate performance.

Claims (2)

1. the preparation method of the lithium ion battery negative material of a broad potential window is characterized in that the concrete steps of this method are following:
(1) with the TiO of lanthanum source, different crystal forms 2Mix with the lithium source,, make it to mix and obtain mixture, the TiO of said lithium source, different crystal forms at grinding in ball grinder 6-12 hour 2With the metallic atom mol ratio in niobium source be (3.5 ~ 5): (5- x): x, wherein x=0.05,0.1;
(2) step (1) gained mixture is put into Muffle furnace, reacted 12-24 hour down, naturally cool to room temperature subsequently, promptly make a kind of lithium ion battery negative material Li of broad potential window at 800-950 ℃ 4Ti 5- x La x O 12, wherein x=0.05,0.1.
2. preparation method according to claim 1 is characterized in that said lanthanum source is a kind of in lanthanum sesquioxide, lanthanum nitrate, the lanthanum acetate, and described lithium source is a kind of in lithium carbonate, lithium acetate, lithium nitrate, the lithium hydroxide, the TiO of described different crystal forms 2A kind of in Detitanium-ore-type, rutile-type, brookite type, the amorphous type.
CN2011103291715A 2011-10-26 2011-10-26 Preparation method of wide potential window negative electrode material of lithium ion battery Pending CN102368556A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102637864A (en) * 2012-05-10 2012-08-15 山东大学 Lanthanum-doped lithium titanate cathode material and preparation method thereof
CN103985839A (en) * 2014-05-12 2014-08-13 黑龙江大学 Broad potential window negative electrode material, preparation method and applications thereof
CN104393271A (en) * 2014-09-30 2015-03-04 李宏斌 Preparation and application of carbon-coated nitrogenated rare-earth-doped lithium titanate
CN105789607A (en) * 2016-05-10 2016-07-20 内蒙古科技大学 Preparation method of lithium titanate anode material doped with rare earth
CN106219601A (en) * 2016-07-20 2016-12-14 陕西科技大学 A kind of hydro-thermal method prepares flower-shaped multilevel hierarchy NaLaTi2o6method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101764212A (en) * 2009-12-25 2010-06-30 深圳市天骄科技开发有限公司 Method for preparing spinelle lithium titanate for lithium ion battery negative electrode material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101764212A (en) * 2009-12-25 2010-06-30 深圳市天骄科技开发有限公司 Method for preparing spinelle lithium titanate for lithium ion battery negative electrode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102637864A (en) * 2012-05-10 2012-08-15 山东大学 Lanthanum-doped lithium titanate cathode material and preparation method thereof
CN103985839A (en) * 2014-05-12 2014-08-13 黑龙江大学 Broad potential window negative electrode material, preparation method and applications thereof
CN104393271A (en) * 2014-09-30 2015-03-04 李宏斌 Preparation and application of carbon-coated nitrogenated rare-earth-doped lithium titanate
CN105789607A (en) * 2016-05-10 2016-07-20 内蒙古科技大学 Preparation method of lithium titanate anode material doped with rare earth
CN106219601A (en) * 2016-07-20 2016-12-14 陕西科技大学 A kind of hydro-thermal method prepares flower-shaped multilevel hierarchy NaLaTi2o6method
CN106219601B (en) * 2016-07-20 2018-02-23 陕西科技大学 A kind of hydro-thermal method prepares flower-shaped multilevel hierarchy NaLaTi2O6Method

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Application publication date: 20120307