CN101409344A - Lithium ion battery cathode material and preparation method thereof - Google Patents

Lithium ion battery cathode material and preparation method thereof Download PDF

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Publication number
CN101409344A
CN101409344A CNA2008101437373A CN200810143737A CN101409344A CN 101409344 A CN101409344 A CN 101409344A CN A2008101437373 A CNA2008101437373 A CN A2008101437373A CN 200810143737 A CN200810143737 A CN 200810143737A CN 101409344 A CN101409344 A CN 101409344A
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lithium ion
ion battery
preparation
negative material
battery negative
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刘素琴
管海英
黄可龙
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Central South University
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Central South 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
    • 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 lithium ion battery cathode material and a preparation method thereof. The preparation method is characterized in that the lithium ion battery cathode is prepared by compounding transition metal oxide or silicon oxide and Li4Ti5O12 powder, the mass ratio of the Li4Ti5O12 to the transition metal oxide or the silicon oxide is (1.0-0.85):(0-0.15). The transition metal oxide or the silicon oxide is any one of Mn3O4, MnO2, Fe3O4, Co3O4, NiO, CoO, Co2O3, SnOx and SiOx, wherein, x is not less than 1 and not more than 2. The lithium ion battery cathode material has the advantages of high safety, high cyclical stability, high specific capacity and low discharge voltage.

Description

A kind of lithium ion battery cathode material and its preparation method
Technical field
Invention relates to the electrode material of lithium ion battery, is specifically related to a kind of negative material and this preparation methods of lithium ion battery.
Background technology
Chemical power source is the device that a kind of energy stores and transforms, and it plays an important role to the extensive utilization that realizes regenerative resource (as wind energy, solar energy, tidal energy), the energy crisis that solves human society.Along with the progress of electronics, mechanics of communication, the kind and the use amount of mobile communication, portable electronics, electric tool etc. constantly increase, and these are all had higher requirement to battery industry; On the other hand, in order fundamentally to solve the tail gas pollution of automobile, the electric automobile of development zero discharge has been the task of top priority.And the key of the alternative fuel-engined vehicle of electric automobile is the high-energy-density research and development of battery system cheaply.In addition, battery also plays an important role in Aeronautics and Astronautics, navigation, artificial satellite and military domain of communication equipment.
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 known as the leading power supply of 21 century.In order to better meet the demand for development of electrokinetic cell, high-performance, the research of novel positive and negative electrode material cheaply are the keys of lithium secondary battery development.
Present commercial lithium rechargeable battery all adopts carbon material as negative material, but there is following problem in this material: one is easily to have Li dendrite to separate out when overcharging, and causes battery short circuit easily; The 2nd, easily form solid electrolyte interface (SEI) film and cause first charge-discharge efficiency lower, irreversible capacity is higher first; The 3rd, because the platform voltage lower (0.1V vs.Li) of material with carbon element easily causes electrolyte decomposition etc.And has the Li of spinel structure 4Ti 5O 12All have remarkable advantages above-mentioned aspect several: cubical expansivity has only 1%, and this " zero strain " characteristic makes them after up to a hundred times circulations, and capacity does not have significant change; The relative lithium metal of discharge voltage plateau high and steady (1.55V vs.Li), under this voltage, electrolyte can not take place to decompose and not have Li dendrite and produce; This material also has the characteristic of anti-high power charging-discharging etc. simultaneously.
At present, to spinelle Li 4Ti 5O 12Research mainly concentrate on the following aspects: (1) is to the finishing of electrode material.Mainly comprise with precious metals ag or its oxide 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.
With Ag or C electrode is carried out finishing, Ag does not participate in electrode reaction, is dispersed in Li 4Ti 5O 12Between particle, strengthened Li 4Ti 5O 12Contacting between particle and collector, thereby improved Li 4Ti 5O 12High rate performance; Coat C or C introduces Li mutually as second 4Ti 5O 12Matrix, C play good bridging action, help the diffusion of lithium ion.
Luo Baisen (Robertson) has studied the doping of metallic elements such as Fe, Ni, Cr, finds that element doping can reduce the slotting lithium current potential of material to a certain extent.The U.S. looks into Cray (Thackeray) research group and has reported that the Mg doping can significantly improve Li subsequently 4Ti 5O 12Electronic conductivity.This (Jumas) group of the Yuma of France finds that the doping of Mn, V, Fe has reduced the specific capacity of material.Temperature million silver hairs of Shanghai silicate research institute show the raising that is beneficial to the material cyclical stability that is doped with of Al.
Above-mentioned research is to improving Li 4Ti 5O 12Thereby the conductivity of negative material improves its high rate performance has played some positive roles.But Li 4Ti 5O 12During as lithium ion battery negative material, its theoretical specific capacity 175mAh/g compares as material with carbon element, metal oxide etc. with other, and is lower.This has also limited the actual specific capacity of this material, thereby has restricted Li 4Ti 5O 12The extensive use of material.Secondly, higher slotting lithium current potential (1.55V vs.Li) makes by the energy content of battery density of this material assembling not high.Therefore, the lithium ion battery cathode material and its preparation method of seeking high security, high stability, height ratio capacity, high-energy-density is the focus of present material, chemistry and energy field research.
Summary of the invention
Technical problem to be solved by this invention is: at the deficiencies in the prior art, a kind of lithium ion battery cathode material and its preparation method is proposed, with obtain to have high security, the composite negative pole material of high cyclical stability, height ratio capacity and low discharge voltage.
Technical solution of the present invention is as follows:
A kind of lithium ion battery negative material is characterized in that, by transition metal oxide or Si oxide and Li 4Ti 5O 12Powder constituent, described Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (1.0～0.85): (0～0.15).
Described transition metal oxide or Si oxide are Mn 3O 4, MnO 2, Fe 3O 4, Co 3O 4, NiO, CoO, Co 2O 3, SnO xAnd SiO xIn any, 1≤x≤2 wherein.
Described Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (0.97～0.88): (0.03～0.12).
A kind of preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
Press Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (1.0～0.85): (0～0.15) takes by weighing raw material, and raw material is ground for the first time, and dry ball milling is compound again after mixing; Combination product is taken out, carry out the grinding second time again and promptly obtain described lithium ion battery negative material.
Described Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (0.97～0.88): (0.03～0.12).
Described transition metal oxide or silicon oxide powder are Mn 3O 4, MnO 2, Fe 3O 4, Co 3O 4, NiO, CoO, Co 2O 3, SnO xAnd SiO xIn the powder any, wherein 1≤x≤2.
The described first time and grinding are for the second time carried out in agate mortar.
The described first time and for the second time milling time be 0.5～1.0 hour.
The time of described dry ball milling is 0.5～10 hour.
Described dry ball milling carries out under 200～500 rev/mins condition.
The present invention adopts lithium ion battery negative material such as Mn such as transition metal oxide or Si oxide 3O 4, MnO 2, Fe 3O 4, Co 3O 4, NiO, CoO, Co 2O 3, SnO x(1≤x≤2), SiO x(1≤x≤2) etc. (hereinafter to be referred as oxide, and use symbol M xO yRepresent) and Li 4Ti 5O 12Compound, keep Li to reach 4Ti 5O 12In the time of superior cycle performance, can utilize the part capacity of other oxide-based negative materials again, or even two cooperative effect takes place between the class material, thereby obtains to have high security, the composite negative pole material of high cyclical stability, height ratio capacity and low discharge voltage.
Beneficial effect:
(1) with Li 4Ti 5O 12Cyclical stability and fail safe and M xO yThe height ratio capacity advantage combine, and be two kinds of material generation electrochemistry cooperative effects.By regulating the ratio of two kinds of negative materials in the composite material, obtain than single Li 4Ti 5O 12Or M xO yThe better composite material of performance.Material first discharge specific capacity after compound is all above single Li 4Ti 5O 12Or M xO yTheoretical specific capacity.As Li 4Ti 5O 12With CoO xAfter compound, the specific capacity of composite material is greater than the theoretical specific capacity 700mAh/g of CoO.The preferred material first discharge specific capacity reaches 1290mAh/g, and 50 times circulation back specific capacity is higher than 370mAh/g.The more important thing is that the discharge platform of combination product has dropped to 0.25V (vs Li).Well below Li 4Ti 5O 12Discharge platform (with respect to about lithium metal 1.5V)
(2) the new material preparation method that proposes of the present invention simple, be easy to suitability for industrialized production and control.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of the composite material that obtains.
Li before Fig. 2 (a) is compound 4Ti 5O 12The figure of charging and discharging curve 3 times; (b) for pressing the figure of charging and discharging curve 3 times of embodiment 1 prepared composite material;
Fig. 3 is for pressing the cycle performance curve chart of embodiment 1 prepared composite material.
Embodiment
With embodiment enforcement of the present invention is described with reference to the accompanying drawings.
What the present invention used is the ML7 type planetary ball mill that Nanjing University produces, and the equipment important technological parameters has:
(1) ball grinder: material is a stainless steel
(2) ball: material is a stainless steel
(3) rotating speed: 0～300 rev/min
Embodiment 1
Get Li at 9: 1 by mass ratio 4Ti 5O 12And Co 3O 4, be medium with the stainless steel ball, mechanical ball milling mixed in 10 hours, ball milling speed is 250 rev/mins, take out in agate mortar grind even must the invention composite material.
Fig. 1 is the transmission electron microscope picture of this composite material.From figure we as can be seen, the composite material that obtains is a shell nuclear formula structure.
With this composite material is positive active material, is negative electrode active material with the lithium sheet, and electrolyte is 1molL -1LiPF 6/ DEC+DC+EMC (volume ratio 1: 1: 1) is assembled into simulated battery.Take the battery of stating making and carry out electrochemical property test, Fig. 2 (a) is pure Li 4Ti 5O 12The figure of charging and discharging curve 3 times; Fig. 2 (b) is the figure of charging and discharging curve 3 times of composite material; The cycle performance curve chart of this composite material of Fig. 3.The result shows that the first discharge specific capacity of the negative material that this embodiment prepares is 1290mAh/g (by Fig. 2 b as can be known), and the specific capacity (as shown in Figure 3) of 371.9mAh/g is still arranged after 50 circulations.
Embodiment 2
Get Li at 9: 1 by mass ratio 4Ti 5O 12And Co 3O 4, be medium with the stainless steel ball, mechanical ball milling mixed in 5 hours, ball milling speed is 250 rev/mins, take out in agate mortar grind even must the invention composite material.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the first discharge specific capacity of the negative material that this embodiment prepares is 1090mAh/g, and the specific capacity of 251.4mAh/g is arranged after 50 circulations.
Embodiment 3
Get Li at 95: 5 by mass ratio 4Ti 5O 12And Co 3O 4, be medium with the stainless steel ball, mechanical ball milling mixed in 10 hours, ball milling speed is 250 rev/mins, take out in agate mortar grind even must the invention composite material.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the first discharge specific capacity of the negative material that this embodiment prepares is 752.3mAh/g, and the specific capacity of 221.2mAh/g is arranged after 50 circulations.
Embodiment 4
Get Li at 95: 5 by mass ratio 4Ti 5O 12And Co 3O 4, be medium with the stainless steel ball, mechanical ball milling mixed in 5 hours, ball milling speed is 250 rev/mins, take out in agate mortar grind even must the invention composite material.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the first discharge specific capacity of the negative material that this embodiment prepares is 732.1mAh/g, and the specific capacity of 187.4mAh/g is arranged after 50 circulations.
Embodiment 5
Get Li at 9: 1 by mass ratio 4Ti 5O 12And SiO, be medium with the stainless steel ball, mechanical ball milling mixed in 10 hours, ball milling speed is 250 rev/mins, take out in agate mortar grind even must the invention composite material.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the first discharge specific capacity of the negative material that this embodiment prepares is 750.4mAh/g, and the specific capacity of 295.2mAh/g is arranged after 50 circulations.
Embodiment 6
Get Li at 9: 1 by mass ratio 4Ti 5O 12And SiO, be medium with the stainless steel ball, mechanical ball milling mixed in 5 hours, ball milling speed is 250 rev/mins, take out in agate mortar grind even must the invention composite material.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the first discharge specific capacity of the negative material that this embodiment prepares is 729.1mAh/g, and the specific capacity of 267.4mAh/g is arranged after 50 circulations.

Claims (10)

1, a kind of lithium ion battery negative material is characterized in that, by transition metal oxide or Si oxide and Li 4Ti 5O 12Powder constituent, described Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (1.0～0.85): (0～0.15).
2, lithium ion battery negative material according to claim 1 is characterized in that, described transition metal oxide or Si oxide are Mn 3O 4, MnO 2, Fe 3O 4, Co 3O 4, NiO, CoO, Co 2O 3, SnO xAnd SiO xIn any, 1≤x≤2 wherein.
3, lithium ion battery negative material according to claim 1 and 2 is characterized in that, described Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (0.97～0.88): (0.03～0.12).
4, a kind of preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
Press Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (1.0～0.85): (0～0.15) takes by weighing raw material, and raw material is ground for the first time, and dry ball milling is compound again after mixing; Combination product is taken out, carry out the grinding second time again and promptly obtain described lithium ion battery negative material.
5, the preparation method of lithium ion battery negative material according to claim 4 is characterized in that, described Li 4Ti 5O 12With the mass ratio of transition metal oxide or silicon oxide powder be (0.97～0.88): (0.03～0.12).
6, the preparation method of lithium ion battery negative material according to claim 4 is characterized in that, described transition metal oxide or silicon oxide powder are Mn 3O 4, MnO 2, Fe 3O 4, Co 3O 4, NiO, CoO, Co 2O 3, SnO xAnd SiO xIn the powder any, wherein 1≤x≤2.
7, the preparation method of lithium ion battery negative material according to claim 4 is characterized in that, the described first time and grinding are for the second time carried out in agate mortar.
8, the preparation method of lithium ion battery negative material according to claim 7 is characterized in that, the described first time and for the second time milling time be 0.5～1.0 hour.
According to the preparation method of each described lithium ion battery negative material of claim 4～8, it is characterized in that 9, the time of described dry ball milling is 0.5～10 hour.
10, the preparation method of lithium ion battery negative material according to claim 9 is characterized in that, described dry ball milling carries out under 200～500 rev/mins condition.
CNA2008101437373A 2008-11-27 2008-11-27 Lithium ion battery cathode material and preparation method thereof Pending CN101409344A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102280640A (en) * 2011-07-12 2011-12-14 南开大学 Novel anode material for lithium-ion secondary battery
CN103326013A (en) * 2012-03-23 2013-09-25 株式会社东芝 Nonaqueous electrolyte battery and battery pack
CN103730641A (en) * 2013-12-18 2014-04-16 广西科技大学 Carbon-sulfur composite anode material and preparation method thereof
CN104425807A (en) * 2013-08-26 2015-03-18 华为技术有限公司 Lithium ion battery anode material and preparation method thereof, lithium ion battery anode piece and lithium ion battery
CN104600289A (en) * 2014-12-30 2015-05-06 深圳市贝特瑞纳米科技有限公司 High-capacity lithium titanate-zinc ferrite composite anode material and preparation method thereof
CN106663795A (en) * 2014-08-25 2017-05-10 罗伯特·博世有限公司 Composite anode for a galvanic cell and a galvanic cell
CN109713254A (en) * 2018-12-05 2019-05-03 郑州中科新兴产业技术研究院 A kind of preparation method of metal conductive oxide powder composite titanic acid lithium material
CN109830677A (en) * 2018-12-29 2019-05-31 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, negative electrode tab, battery
CN109888249A (en) * 2019-03-28 2019-06-14 辽宁工程技术大学 Cobaltosic oxide and lithium titanate composite material and preparation method thereof, lithium ion battery

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102280640B (en) * 2011-07-12 2013-11-06 南开大学 Novel anode material for lithium-ion secondary battery
CN102280640A (en) * 2011-07-12 2011-12-14 南开大学 Novel anode material for lithium-ion secondary battery
CN103326013B (en) * 2012-03-23 2015-09-16 株式会社东芝 Nonaqueous electrolyte battery and battery pack
CN103326013A (en) * 2012-03-23 2013-09-25 株式会社东芝 Nonaqueous electrolyte battery and battery pack
CN104425807A (en) * 2013-08-26 2015-03-18 华为技术有限公司 Lithium ion battery anode material and preparation method thereof, lithium ion battery anode piece and lithium ion battery
CN103730641A (en) * 2013-12-18 2014-04-16 广西科技大学 Carbon-sulfur composite anode material and preparation method thereof
CN106663795A (en) * 2014-08-25 2017-05-10 罗伯特·博世有限公司 Composite anode for a galvanic cell and a galvanic cell
CN106663795B (en) * 2014-08-25 2020-05-05 罗伯特·博世有限公司 Composite anode for a galvanic cell and galvanic cell
US10665860B2 (en) 2014-08-25 2020-05-26 Robert Bosch Gmbh Composite anode for a galvanic cell and a galvanic cell
CN104600289A (en) * 2014-12-30 2015-05-06 深圳市贝特瑞纳米科技有限公司 High-capacity lithium titanate-zinc ferrite composite anode material and preparation method thereof
CN104600289B (en) * 2014-12-30 2017-12-12 深圳市贝特瑞新能源材料股份有限公司 Composite negative pole material of lithium titanate zinc ferrite a kind of of high power capacity and preparation method thereof
CN109713254A (en) * 2018-12-05 2019-05-03 郑州中科新兴产业技术研究院 A kind of preparation method of metal conductive oxide powder composite titanic acid lithium material
CN109713254B (en) * 2018-12-05 2021-03-02 郑州中科新兴产业技术研究院 Preparation method of metal oxide conductive powder composite lithium titanate material
CN109830677A (en) * 2018-12-29 2019-05-31 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, negative electrode tab, battery
CN109888249A (en) * 2019-03-28 2019-06-14 辽宁工程技术大学 Cobaltosic oxide and lithium titanate composite material and preparation method thereof, lithium ion battery

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