CN101699641B - Composite cathode material for high-capacity lithium ion battery and preparation method thereof - Google Patents
Composite cathode material for high-capacity lithium ion battery and preparation method thereof Download PDFInfo
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- CN101699641B CN101699641B CN2009103088155A CN200910308815A CN101699641B CN 101699641 B CN101699641 B CN 101699641B CN 2009103088155 A CN2009103088155 A CN 2009103088155A CN 200910308815 A CN200910308815 A CN 200910308815A CN 101699641 B CN101699641 B CN 101699641B
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- lithium ion
- citrate
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Abstract
The invention discloses a composite cathode material for high-capacity lithium ion battery and a preparation method thereof; the material is alpha-Fe2O3/Fe3O4 composite cathode material, the synthesizing technology of the material comprises the following steps: carrying out ball milling process on ironic citrate or ferric ammonium citrate for 3 hours to be prepared into coarse powder, thermally treating ironic citrate or ferric ammonium citrate powder in the air within the temperature range of 600-900 DEG C for 0.5-48 hours, and then milling and screening after cooling to obtain powder with the grain size less than 38 micrometers that is the alpha-Fe2O3/Fe3O4 composite cathode material. The material has high specific capacity, good conductive capability, long cycle life, simple manufacture method, low cost, environment friendliness and good industrialization foreground.
Description
Technical field
The present invention relates to the negative electrode for lithium ion battery Material Field, particularly high-capacity lithium ion cell α-Fe
2O
3/ Fe
3O
4Composite negative pole material and preparation method thereof.
Background technology
Lithium ion battery is one of the hottest energy storage device of research at present, be widely used in all kinds of light-type electronic equipments, along with the day by day raising of people to the secondary power supply performance requirement, lithium ion battery is also brought in constant renewal in the replacement, yet, the overall price/performance ratio of lithium ion battery but improves very little, becomes the main bottleneck of present lithium ion battery development.As one of critical material of lithium ion battery, the cost performance of negative material is one of key factor that influences battery performance, and the negative material of exploring novel high performance-price ratio is a research focus in lithium ion battery field all the time.High power capacity negative materials such as various materials such as hard charcoal, tinbase compound, antimony based compound and nano-silicon all become research object.Hard charcoal class material does not have voltage platform, and not only price is high for tinbase compound, antimony based compound and nano-silicon, and bulk effect is remarkable, causes material cycle life can't satisfy practicality.Seek negative material cheap, high power capacity and become one of present problem demanding prompt solution.
Ferriferous oxide has aboundresources, cheap and advantages of environment protection, is used widely in fields such as gas sensitive, coating and microwave absorbing materials.It is lithium ion battery negative material that Poizot in 2000 etc. attempt first with FeO, and set up FeO the doff lithium model (Poizot.P, Laruelle.S, Grugeon S.Nature, 2000,407:496).Afterwards, more and more many electrochemical research personnel begin to pay close attention to the ferriferous oxide negative material, study at present more ferriferous oxide and mainly concentrate on α-Fe
2O
3With Fe
3O
4Larcher D had studied micron order and nanometer alpha-Fe in 2003
2O
3The doff lithium performance (Larcher D, Masquelier C, Bonnin D, et al.J Electrochem Soc, 2003,150:A133), P.L.Taberna is at column copper metal end face electrodeposition of Fe
3O
4, find that this material has good cyclical stability and high rate capability ((P.L.Taberna, S.Mitra, P.Poizot, P.Simon, J.M.Tarascon, Nat.Mat.2006,5:567)) as lithium ion battery negative material.Domestic researcher such as units such as Shanghai university of communications also prepares the α-Fe of " petal " shape by hydro-thermal technology
2O
3, its first reversible capacity near 1000mAh/g.From above-mentioned bibliographical information, can find α-Fe
2O
3Specific capacity higher, but ubiquity enclosed pasture efficient problem on the low side first, this commercial application to materials is totally unfavorable.Inverse spinel structure Fe
3O
4Although first the enclosed pasture efficient higher, specific capacity is lower than α-Fe
2O
3If can make α-Fe by suitable building-up process
2O
3/ Fe
3O
4Composite then is expected to learn from other's strong points to offset one's weaknesses, and prepares the better iron-based negative material of combination property, promotes the development of high-capacity lithium ion cell.
Summary of the invention
Technical problem to be solved of the present invention provides a kind of high-capacity lithium ion cell α-Fe
2O
3/ Fe
3O
4Composite negative pole material.This material specific capacity height, conduct electricity very well, have extended cycle life and manufacture method is simple, cost is low.
For achieving the above object, technical scheme of the present invention is:
A kind of preparation method of composite cathode material for high-capacity lithium ion battery is characterized in that, commercially available ironic citrate is made the ironic citrate meal; Or commercially available ferric citrate ball milling made the ferric citrate meal, and the particle size range of described ironic citrate meal is 75 ± 5 microns, the particle size range of described ferric citrate meal is 150 ± 5 microns; The described ironic citrate meal of heat treatment or ferric citrate meal in 600 degrees centigrade ~ 900 degree celsius temperature scopes in air, the thermal decomposition original position by citrate obtains α-Fe
2O
3/ Fe
3O
4Composite is with gained α-Fe
2O
3/ Fe
3O
4Composite cools down is by grinding, sieving, and obtains particle size less than 38 microns powder, is the high-capacity lithium ion cell negative material.
Described heat treatment period is 0.5 ~ 48h.
The gained particle is the octahedral bodily form, and its average particle size range is between 0.3 ~ 4 micron.
α-Fe in the described composite cathode material for high-capacity lithium ion battery
2O
3Mass percent between 20 ~ 45%.
The specification of the used sieve of target product is 400 mesh standard sieves.
A kind of composite cathode material for high-capacity lithium ion battery is characterized in that, this material adopts the preparation method of following composite cathode material for high-capacity lithium ion battery to make: commercially available ironic citrate is made the ironic citrate meal; Or commercially available ferric citrate ball milling made the ferric citrate meal, and the particle size range of described ironic citrate meal is 75 ± 5 microns, the particle size range of described ferric citrate meal is 150 ± 5 microns; Described ironic citrate meal of heat treatment or ferric citrate meal in 600 degrees centigrade ~ 900 degree celsius temperature scopes in air, cooling is after grind, sieve, obtain particle size less than 38 microns powder, be composite cathode material for high-capacity lithium ion battery.
Technical conceive of the present invention is at α-Fe
2O
3In compound Fe
3O
4, in conjunction with α-Fe
2O
3With Fe
3O
4Advantage, thereby obtain the higher lithium ion battery negative material of cost performance, promote the development of high-capacity lithium ion cell.The present invention prepares α-Fe take ironic citrate or ferric citrate as raw material by the Thermal Decomposition Mechanism original position of citrate
2O
3/ Fe
3O
4Composite negative pole material, and with it as cathode material for high capacity lithium ion battery.Wherein, the know-why of used synthesis technique comprises: the pyrolysis mechanism of ironic citrate and ferric citrate, ferriferous oxide phase-change mechanism.With gained α-Fe
2O
3/ Fe
3O
4Composite is used for cathode material for high capacity lithium ion battery, has fully utilized Fe
3O
4Good and the α-Fe of electric conductivity
2O
3The characteristic that embedding lithium capacity is higher makes it to become and is easy to practical compound electrode material.
The beneficial effect that the present invention had:
Gained α-Fe of the present invention
2O
3/ Fe
3O
4Composite negative pole material is octahedra shape (Fig. 1), illustrates that composite is with Fe
3O
4Monocrystalline is skeleton, and α-Fe
2O
3Then be attached to Fe
3O
4Single-crystal surface is also combined closely with it.With single-phase α-Fe
2O
3Compare α-Fe
2O
3/ Fe
3O
4The electric conductivity of composite negative pole material improves 5 orders of magnitude, with lithium ion battery with traditional positive electrode LiCoO
2Electric conductivity similar, meet the requirement of lithium ion battery electrode material electric conductivity.
Compare with the iron oxide negative material of other bibliographical information, it is exactly this α-Fe that the present invention has maximum advantage
2O
3/ Fe
3O
4Composite negative pole material is at (0.1mA/cm under low current density
2, 0.5 ~ 3V.Vs.Li+/Li) first enclosed pasture efficient can reach more than 89%, exceeds other bibliographical information with nearly 10 percentage point.In addition, this material is done cycle performance test under above-mentioned current density, and experience does not have the capacity attenuation sign after circulating for 30 times.It is the raising of enclosed pasture efficient and Fe first
3O
4Electric conductivity is well relevant.In addition, Fe in the composite
3O
4With α-Fe
2O
3In conjunction with closely and doff lithium asynchronous, volume buffer each other in the doff lithium process stop the electrode material powder of detached, thereby reversibility improves greatly.The present invention adopts common solid-phase pyrolysis, and from the technical process angle, this method is only through steps such as heat treatment, grindings, have simple to operate, synthesis cycle short, low power consumption and other advantages; Prepare the aspect from material and consider, all be difficult to control α-Fe with liquid phase method or mixing solid phase method
2O
3/ Fe
3O
4The ratio of two-phase in the composite negative pole material, and liquid phase method need add a large amount of alkaline matters, can produce contaminated wastewater.If select labile inorganic molysite such as Fe (NO in the solid-phase pyrolysis
3)
3, FeCl
3Deng, then can cause serious atmosphere pollution, and the solid-phase pyrolysis take organic molysite ironic citrate or ferric citrate as raw material, its waste gas only is CO
2, less pollution.This shows preparation α-Fe of the present invention
2O
3/ Fe
3O
4The method of composite negative pole material is conducive to environmental protection, and technology is very simple, cost is low, has good industrialization prospect.
Description of drawings
Fig. 1: gained α-Fe of the present invention
2O
3/ Fe
3O
4The SEM photo of composite negative pole material
Fig. 2: gained α-Fe of the present invention
2O
3/ Fe
3O
4The first charge-discharge curve of composite negative pole material (embodiment 2) under the 0.05C multiplying power.
Embodiment
Following examples are intended to illustrate the present invention rather than further restriction of the present invention.
Comparative example:
With commercially available α-Fe
2O
3Particle is crossed 400 mesh sieves after grinding 2h, with gained α-Fe
2O
3Powder is made electrode, as a comparison sample.
Embodiment 1:
Adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, with the commercially available ironic citrate particle ball milling 3h that contains the crystallization water.Accurately take by weighing 10g ironic citrate powder and be put in the crucible, in air atmosphere, in 700 degrees centigrade of heat treatment 12h, take out after the cooling naturally that grinding sieves makes α-Fe
2O
3/ Fe
3O
4Composite negative pole material.Wherein should note in the heat treatment process preventing dust, programming rate is 2 degrees centigrade/min, and the standard screen of crossing is 400 orders.
Embodiment 2:
Adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, with the commercially available ironic citrate particle ball milling 3h that contains the crystallization water.Accurately take by weighing 10g ironic citrate powder and be put in the crucible, in air atmosphere, in 650 degrees centigrade of heat treatment 12h, take out after the cooling naturally that grinding sieves makes α-Fe
2O
3/ Fe
3O
4Composite negative pole material.Wherein should note in the heat treatment process preventing dust, programming rate is 2 degrees centigrade/min, and the standard screen of crossing is 400 orders.
Embodiment 3:
Adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, with the commercially available ironic citrate particle ball milling 3h that contains the crystallization water.Accurately take by weighing 10g ironic citrate powder and be put in the crucible, in air atmosphere, in 700 degrees centigrade of heat treatment 2h, take out after the cooling naturally that grinding sieves makes α-Fe
2O
3/ Fe
3O
4Composite negative pole material.Wherein should note in the heat treatment process preventing dust, programming rate is 2 degrees centigrade/min, and the standard screen of crossing is 400 orders.
Embodiment 4:
Adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, with the commercially available ironic citrate particle ball milling 3h that contains the crystallization water.Accurately take by weighing 10g ironic citrate powder and be put in the crucible, in air atmosphere, in 750 degrees centigrade of heat treatment 2h, take out after the cooling naturally that grinding sieves makes α-Fe
2O
3/ Fe
3O
4Composite negative pole material.Wherein should note in the heat treatment process preventing dust, programming rate is 2 degrees centigrade/min, and the standard screen of crossing is 400 orders.
Embodiment 5:
Adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, with the commercially available ironic citrate particle ball milling 3h that contains the crystallization water.Accurately take by weighing 10g ironic citrate powder and be put in the crucible, in air atmosphere, in 600 degrees centigrade of heat treatment 15h, take out after the cooling naturally that grinding sieves makes α-Fe
2O
3/ Fe
3O
4Composite negative pole material.Wherein should note in the heat treatment process preventing dust, programming rate is 4 degrees centigrade/min, and the standard screen of crossing is 400 orders.
Embodiment 6:
Adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, with the commercially available ferric citrate particle ball milling 3h that contains the crystallization water.Accurately take by weighing 10g ferric citrate powder and be put in the crucible, in air atmosphere, in 650 degrees centigrade of heat treatment 12h, take out after the cooling naturally that grinding sieves makes α-Fe
2O
3/ Fe
3O
4Composite negative pole material.Wherein should note in the heat treatment process preventing dust, programming rate is 2 degrees centigrade/min, and the standard screen of crossing is 400 orders.
The material of comparative example, above-mentioned 6 embodiment gained and pertinent literature report chemical property as shown in table 1.As shown in Table 1, with single-phase α-Fe
2O
3Negative material is compared, lithium ion battery of the present invention α-Fe
2O
3/ Fe
3O
4Composite negative pole material has better chemical property.
Table 1: the chemical property and the pertinent literature data of comparative example, embodiment 1 ~ 6 sample
Claims (4)
1. the preparation method of a composite cathode material for high-capacity lithium ion battery is characterized in that, commercially available ironic citrate is made the ironic citrate meal; Or commercially available ferric citrate ball milling made the ferric citrate meal.The particle size range of described ironic citrate meal is the 75+5 micron, and the particle size range of described ferric citrate meal is 150 ± 5 microns; The described ironic citrate meal of heat treatment or ferric citrate meal in 600 degrees centigrade～900 degree celsius temperature scopes in air, the thermal decomposition original position by citrate obtains α-Fe
2O
3/ Fe
3O
4Composite is with gained α-Fe
2O
3/ Fe
3O
4Composite cools down is by grinding, sieving, and obtains particle size less than 38 microns powder, is the high-capacity lithium ion cell negative material;
Described heat treatment period is 0.5～48h.
2. the preparation method of composite cathode material for high-capacity lithium ion battery according to claim 1 is characterized in that, the granularity of ironic citrate meal is 75 microns, and the granularity of ferric citrate meal is 150 microns.
3. the preparation method of composite cathode material for high-capacity lithium ion battery according to claim 1 is characterized in that, the gained particle is the octahedral bodily form, and its average particle size range is between 0.3～4 micron.
4. the preparation method of composite cathode material for high-capacity lithium ion battery according to claim 1 is characterized in that, α-Fe in the described composite cathode material for high-capacity lithium ion battery
2O
3Mass percent between 20～45%.
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| CN101699641B true CN101699641B (en) | 2011-12-14 |
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|---|---|---|---|---|
| CN103208624A (en) * | 2013-03-27 | 2013-07-17 | 东北师范大学 | Preparation method of Fe3O4@C nano composite lithium battery negative electrode materials of monodisperse core-shell structure |
| CN104118858B (en) * | 2013-04-26 | 2016-04-13 | 中国科学院大连化学物理研究所 | A kind of preparation method of hollow nano cages material |
| CN106816590B (en) * | 2017-01-17 | 2020-08-14 | 常州大学 | Preparation method of high-capacity lithium ion battery composite negative electrode material |
| CN113991098A (en) * | 2021-10-20 | 2022-01-28 | 景德镇陶瓷大学 | alpha-Fe2O3Dendritic single crystal material and preparation method of lithium battery electrode thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465127B1 (en) * | 1999-02-19 | 2002-10-15 | Samsung Sdi Co., Ltd. | Negative electrode for secondary battery including a metal oxide |
| CN101453017A (en) * | 2008-12-12 | 2009-06-10 | 中国科学院化学研究所 | Lithium cell negative pole material and preparation thereof |
-
2009
- 2009-10-26 CN CN2009103088155A patent/CN101699641B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465127B1 (en) * | 1999-02-19 | 2002-10-15 | Samsung Sdi Co., Ltd. | Negative electrode for secondary battery including a metal oxide |
| CN101453017A (en) * | 2008-12-12 | 2009-06-10 | 中国科学院化学研究所 | Lithium cell negative pole material and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| X.H.Liu et al.Exchange bias and phase transformation inα-Fe2O3/Fe3O4 nanocomposites.《Journal of Alloys and Compounds》.2008,第475卷正文第42页第2栏第2段-第44页第2栏第2段. * |
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