CN103208624A - Preparation method of Fe3O4@C nano composite lithium battery negative electrode materials of monodisperse core-shell structure - Google Patents
Preparation method of Fe3O4@C nano composite lithium battery negative electrode materials of monodisperse core-shell structure Download PDFInfo
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- CN103208624A CN103208624A CN2013101009812A CN201310100981A CN103208624A CN 103208624 A CN103208624 A CN 103208624A CN 2013101009812 A CN2013101009812 A CN 2013101009812A CN 201310100981 A CN201310100981 A CN 201310100981A CN 103208624 A CN103208624 A CN 103208624A
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Abstract
The invention belongs to the technical field of nano materials and particularly relates to a preparation method of Fe3O4@C nano composite lithium battery negative electrode materials of monodisperse core-shell structure. Firstly, by means of high-temperature hydrolysis, anhydrous FeCl3 is used as raw materials to synthesize uniform-size and good-dispersibility Fe2O3 nano particles. Then, in isopropanol-water mixed system, the Fe2O3 nano particles are subjected to PAA (polyacrylic acid) coating, calcined under argon shield, and the Fe3O4@C nano composite materials of the monodisperse core-shell structure are obtained. The obtained Fe3O4@C nano composite materials are good in dispersibility, uniform in carbon coating, stable in structure, higher in capacity, better in cycling stability and longer in service life by adopting unique PAA coating method.
Description
Technical field
The invention belongs to nano composite material and applied technical field thereof, be specifically related to a kind of single diffuse nuclei shell structure Fe
3O
4The preparation method of the nano combined lithium cell cathode material of @C.
Background technology
Along with the development of electric automobile and hybrid vehicle, need lithium ion battery to have more high power capacity and better multiplying power discharging property, but present lithium ion battery can't reach these requirements fully.With regard to lithium ion battery negative material, there are problems such as specific capacity is low, security performance is not good enough in present business-like material with carbon element, and (theoretical capacity only is 372 mAh g
-1), can not satisfy the demand of height ratio capacity cell negative electrode material of new generation.Therefore, but how using the compound of low-voltage embedding lithium to substitute used material with carbon element at present, is a very important problem with energy density and the security performance that improves lithium ion battery.
Transition metal oxide has than higher theoretical capacity, and reaction mechanism is a kind of switching mechanism of novelty, is hopeful the negative material for high performance lithium ion battery.(list of references: P. Poizot, S. Laruelle, S. Grugeon, et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries.
Nature 2000,
407, 496-499; S. Mitra, P. Poizot, A. Finke, et al. Growth and Electrochemical Characterization versus Lithium of Fe
3O
4Electrodes Made by Electrodeposition.
Adv. Funct. Mater. 2006,
16, 2281-2287.) Fe wherein
3O
4Owing to have high theoretical capacity, low price, high stability, characteristics such as environmentally friendly, so it has attracted everybody extensive concern as potential lithium ion battery anode material.But Fe
3O
4The cycle performance of lithium ion battery negative material is relatively poor, and electrode can not keep well consistent with initial condition after charge and discharge cycles repeatedly.Nano-sized materials can be slowed down at Li
+Take off the STRESS VARIATION in the embedding process, work as Fe
3O
4When particle is nanoscale, it also is nano-scale between particle voids, the embedding that can be lithium ion provides good nanochannel and embedding lithium position, have big embedding lithium capacity and good embedding lithium performance, nanometer can also more effectively be slowed down change in volume and the reunion pulverizing problem that brings in charge and discharge process in addition, reaches the purpose of improving cycle performance.In addition transition metal oxide being carried out surface modification also is to improve the effective means of material property.Particularly carbon coats Fe
3O
4Nano particle is than pure Fe
3O
4Nano particle has better circulation and high-rate discharge ability.Thereby strengthen multiplying power discharging property because carbon coating layer can obviously improve the electron conduction of electrode material, and the SEI that carbon material surface forms is relatively stable, so the carbon coating is widely used in the negative material.As Fe
3O
4Multiple nanostructures such as @C nanosphere, nanometer rods, spindle-type nano particle all are synthesized.But, the Fe that existing synthetic method obtains
3O
4The @C nano particle is much all to be state of aggregation, dispersed relatively poor.This has just reduced the raising of nanometer to battery performance to a great extent, can not embody the characteristic of nano-electrode material fully, is the key that addresses these problems so how to realize the controlledly synthesis of dispersed nano electrode material.
Summary of the invention
The purpose of this invention is to provide a kind of single diffuse nuclei shell structure Fe
3O
4The preparation method of @C nano composite lithium ion cell negative material, the Fe that uses this method to prepare
3O
4@C nano composite lithium ion cell negative material has characteristics such as good dispersion, specific capacity are big, good cycle, long service life.
The single diffuse nuclei shell structure of the present invention Fe
3O
4The preparation method of the nano combined lithium cell cathode material of @C comprises the steps:
(1) the accurate a certain amount of anhydrous ferric trichloride of weighing, being mixed with concentration is 2 * 10
-2The M liquor ferri trichloridi.
(2) liquor ferri trichloridi that a certain amount of step (1) is obtained joins in the round-bottomed flask that has a condenser pipe, then flask is placed 100
oIn the C oil bath, under magnetic agitation, react 70 ~ 80 h, after reaction is finished firing equipment is turned off, be stirred to solution always and be cooled to room temperature.
(3) mixed solution that step (2) is obtained carries out centrifugation, and the gained solid alternately washs for several times with deionized water and absolute ethyl alcohol again, is deposited in 50
oDry 8 ~ 10 h in the C baking oven, namely get dry Fe
3O
2Nano particle.
(4) Fe that 5 ~ 8 mg steps (3) are obtained
3O
2Nano particle and 10 ~ 15mL deionized water add in the 100 mL flasks, ultrasonic dispersion 10 ~ 20 min.
(5) ammoniacal liquor of 50 ~ 100 μ L, the 0.2 g/mL polyacrylic acid aqueous solution and 75 ~ 150 μ L, 2 mol/L is successively added in the solution that step (4) obtains ultrasonic dispersion 10 ~ 30 min.
(6) under magnetic agitation 90 ~ 120 mL isopropyl alcohols slowly are added dropwise in the solution that step (5) obtains, carry out centrifugation after dropwising, gained is deposited in 50
oDry 12 ~ 20 h in the C baking oven.
(7) solid that step (6) is obtained places tube furnace, 400 ~ 500
o Calcine 3 ~ 5 h under the C argon shield, obtain nucleocapsid structure Fe
3O
4The @C nano composite material.
The present invention has following advantage:
1. the present invention is owing to adopting distinctive PAA method for coating, in water-isopropyl alcohol mixed system, to Fe
2O
3Nano particle carries out PAA and coats, and has guaranteed the dispersiveness of nano particle greatly.
2. the nucleocapsid structure Fe that obtains of the present invention
3O
4The @C nano composite material has super good dispersiveness, and carbon-coating coats evenly Stability Analysis of Structures.
3. use single diffuse nuclei shell structure Fe of the inventive method preparation
3O
4@C nano composite lithium ion cell negative material has characteristics such as capacity is big, good cycle, long service life.
Description of drawings
Fig. 1, the nucleocapsid structure Fe for preparing for the present invention
3O
2The transmission electron microscope picture of nano particle;
Fig. 2, the nucleocapsid structure Fe for preparing for the present invention
3O
2The sem photograph of nano particle;
Fig. 3, the single diffuse nuclei shell structure Fe for preparing for the present invention
3O
4The transmission electron microscope picture of @C nano particle, illustration are single Fe
3O
4The local transmission electron microscope picture that amplifies of @C nano particle;
Fig. 4, the single diffuse nuclei shell structure Fe for preparing for the present invention
3O
4The sem photograph of @C nano particle;
Fig. 5, the single diffuse nuclei shell structure Fe for preparing for the present invention
3O
4The @C nano particle charge and discharge curve first;
Fig. 6, the single diffuse nuclei shell structure Fe for preparing for the present invention
3O
4The charge and discharge cycles curve of @C nano particle.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, embodiment only is used for explanation the present invention and is not used in restriction protection scope of the present invention.
Specific embodiment
Embodiment 1:
Accurately take by weighing anhydrous ferric trichloride 0.3245 g, (concentration is about 2 * 10 to be mixed with 100 mL solution
-2M).The 100 mL liquor ferri trichloridis that prepare are joined in the round-bottomed bottle that has a condenser pipe, then round-bottomed bottle is placed 100
oIn the C oil bath, reaction 72 h under the magnetic agitation, after reaction is finished firing equipment is turned off, be stirred to solution always and be cooled to room temperature, then with reactant liquor centrifugation (6000 rpm, 10 min), with the alternately washing of deionized water and absolute ethyl alcohol, ultrasonic, and centrifugal (6000 rpm, 10 min), super work is three times repeatedly, and precipitation places 50
oIn the C baking oven oven dry 8 h, both dry Fe
3O
2Nano particle.
The Fe that 5 mg have been prepared
3O
2Nano particle and 10 mL deionized waters add in the 100 mL flasks, behind ultrasonic dispersion 10 min, successively add the ammoniacal liquor of 50 μ L, the 0.2 g/mL PAA aqueous solution and 75 μ L, 2 mol/L, ultrasonic dispersion 10 min.Under magnetic agitation 90 mL isopropyl alcohols slowly are added dropwise to reactant liquor subsequently, dropwise centrifugation, gained is deposited in 50
oBehind oven dry 12 h, 400 ° of C calcine 3 h under argon shield again, obtain single diffuse nuclei shell structure Fe under the C
3O
4The @C nano composite material.
Embodiment 2:
Accurately take by weighing anhydrous ferric trichloride 0.649 g, be mixed with 200 mL solution.The 200 mL liquor ferri trichloridis that prepare are joined in the round-bottomed bottle that has a condenser pipe, then round-bottomed bottle is placed 100
oIn the C oil bath, reaction 80 h under the magnetic agitation, after reaction is finished firing equipment is turned off, be stirred to solution always and be cooled to room temperature, then with reactant liquor centrifugation (7000 rpm, 6 min), with the alternately washing of deionized water and absolute ethyl alcohol, ultrasonic, and centrifugal (7000 rpm, 6 min), super work is three times repeatedly, and precipitation places 50
oIn the C baking oven oven dry 10 h, both dry Fe
3O
2Nano particle.
The Fe that 8 mg have been prepared
3O
2Nano particle and 15 mL deionized waters add in the 100 mL flasks, behind ultrasonic dispersion 20 min, successively add the ammoniacal liquor of 100 μ L, the 0.2 g/mL PAA aqueous solution and 150 μ L, 2 mol/L, ultrasonic dispersion 30 min.Under magnetic agitation 120 mL isopropyl alcohols slowly are added dropwise to reactant liquor subsequently, dropwise centrifugation, gained is deposited in 50
oBehind oven dry 20 h, 500 ° of C calcine 4 h under argon shield again, obtain single diffuse nuclei shell structure Fe under the C
3O
4The @C nano composite material.
Embodiment 3:
Accurately take by weighing anhydrous ferric trichloride 0.9735 g, be mixed with 300 mL solution.The 300 mL liquor ferri trichloridis that prepare are joined in the round-bottomed bottle that has a condenser pipe, then round-bottomed bottle is placed 100
oIn the C oil bath, reaction 75 h under the magnetic agitation, after reaction is finished firing equipment is turned off, be stirred to solution always and be cooled to room temperature, then with reactant liquor centrifugation (6000 rpm, 6 min), with the alternately washing of deionized water and absolute ethyl alcohol, ultrasonic, and centrifugal (6000 rpm, 6 min), super work is three times repeatedly, and precipitation places 50
oIn the C baking oven oven dry 8 h, both dry Fe
3O
2Nano particle.
The Fe that 6 mg have been prepared
3O
2Nano particle and 12 mL deionized waters add in the 100 mL flasks, behind ultrasonic dispersion 15 min, successively add the ammoniacal liquor of 80 μ L, the 0.2 g/mL PAA aqueous solution and 120 μ L, 2 mol/L, ultrasonic dispersion 25 min.Under magnetic agitation 100 mL isopropyl alcohols slowly are added dropwise to reactant liquor subsequently, dropwise centrifugation, gained is deposited in 50
oBehind oven dry 18 h, 450 ° of C calcine 3 h under argon shield again, obtain single diffuse nuclei shell structure Fe under the C
3O
4The @C nano composite material.
The described single diffuse nuclei shell structure Fe for preparing
3O
4The @C nano composite material is used for lithium ion battery.With synthetic single diffuse nuclei shell structure Fe
3O
4The @C nano composite material is active material, and acetylene black is conductive agent, and Kynoar (PVDF) is binding agent, and n-formyl sarcolysine base pyrrolidones (NMP) is solvent.The assembling process of battery is: with the accurate weighing of weight ratio that active material, conductive agent, Kynoar are pressed 70:20:10, put into agate mortar then and fully mix, grind evenly, add several NMP then, continue to be ground to even pulpous state.Slurry evenly is applied on the Copper Foil of weighing.Then in vacuum drying chamber in 120
oC vacuumize 12 h are to constant weight, and 30 MPa lower sheetings continue drying at least 2 h again, drop to take out after the room temperature to weigh.
We test the chemical property of synthetic material with the experiment half-cell, being assembled in anhydrous and oxygen-free, being filled with in the glove box of argon gas and finishing of simulated battery.Pole piece, battery case and the barrier film of oven dry are put into glove box.Be to electrode with metal lithium sheet, the Celgard240 polypropylene porous film is made barrier film, 1.0 mol/L LiPF
6EC-DMC (volume ratio 1:1) solution do electrolyte, be assembled into button CR2032 simulated battery, carry out charge-discharge test.
Experiment shows prepared single diffuse nuclei shell structure Fe
3O
4@C nano composite lithium ion cell negative material has very high specific capacity and better cycle performance.As illustrated in Figures 5 and 6, in 0.01-3.0 V voltage range, under 0.2 C multiplying power, discharge and recharge, its first discharge capacity be 1031 mA h g
-1, discharge capacity still has 544 mAh g after 100 circulations
-1
Claims (3)
1. single diffuse nuclei shell structure Fe
3O
4The preparation method of the nano combined lithium cell cathode material of @C is characterized in that concrete steps are as follows:
(1) the accurate a certain amount of anhydrous ferric trichloride of weighing, being mixed with concentration is 2 * 10
-2The M liquor ferri trichloridi;
(2) liquor ferri trichloridi that a certain amount of step (1) is obtained joins in the round-bottomed flask that has a condenser pipe, then flask is placed 100
oIn the C oil bath, under magnetic agitation, react 70 ~ 80 h, after reaction is finished firing equipment is turned off, be stirred to solution always and be cooled to room temperature;
(3) mixed solution that step (2) is obtained carries out centrifugation, and the gained solid alternately washs for several times with deionized water and absolute ethyl alcohol again, is deposited in 50
oDry 8 ~ 10 h in the C baking oven, namely get dry Fe
3O
2Nano particle;
(4) Fe that 5 ~ 8 mg steps (3) are obtained
3O
2Nano particle and 10 ~ 15mL deionized water add in the 100 mL flasks, ultrasonic dispersion 10 ~ 20 min;
(5) ammoniacal liquor of 50 ~ 100 μ L, the 0.2 g/mL polyacrylic acid aqueous solution and 75 ~ 150 μ L, 2 mol/L is successively added in the solution that step (4) obtains ultrasonic dispersion 10 ~ 30 min;
(6) under magnetic agitation 90 ~ 120 mL isopropyl alcohols slowly are added dropwise in the solution that step (5) obtains, carry out centrifugation after dropwising, gained is deposited in 50
oDry 12 ~ 20 h in the C baking oven;
(7) solid that step (6) is obtained places tube furnace, 400 ~ 500
oCalcine 3 ~ 5 h under the C argon shield, obtain nucleocapsid structure Fe
3O
4The @C nano composite material.
2. according to single diffuse nuclei shell structure Fe of the described preparation method of claim 1 preparation
3O
4The nano combined lithium cell cathode material of @C.
3. according to the described single diffuse nuclei shell structure Fe of claim 2
3O
4The application of the nano combined lithium cell cathode material of @C in lithium battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514419A (en) * | 2015-12-28 | 2016-04-20 | 安泰科技股份有限公司 | Graphite carbon/ferroferric oxide composite and preparation method and application thereof |
| WO2018033165A1 (en) * | 2016-08-19 | 2018-02-22 | 上海迈景纳米科技有限公司 | Polymer-metal oxide complex, preparation method therefor, and applications |
| CN107845787A (en) * | 2017-09-28 | 2018-03-27 | 东北师范大学 | Pomegranate shape Fe3O4@N C lithium cell cathode material preparation methods |
| CN115084515A (en) * | 2021-03-11 | 2022-09-20 | 中国科学院上海硅酸盐研究所 | Inorganic oligomer lithium-containing composite metal oxide material, preparation method thereof and application thereof in lithium ion battery cathode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101699641A (en) * | 2009-10-26 | 2010-04-28 | 湖南大学 | Composite cathode material for high-capacity lithium ion battery and preparation method thereof |
-
2013
- 2013-03-27 CN CN2013101009812A patent/CN103208624A/en active Pending
Patent Citations (1)
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|---|---|---|---|---|
| CN101699641A (en) * | 2009-10-26 | 2010-04-28 | 湖南大学 | Composite cathode material for high-capacity lithium ion battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LU LI等: ""Selected-Control Synthesis of Monodisperse Fe3O4@C Core–Shell Spheres,Chains, and Rings as High-Performance Anode Materials for Lithium-Ion Batteries"", 《CHEM. EUR. J.》, vol. 18, no. 36, 26 July 2012 (2012-07-26), pages 11417 - 11422 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514419A (en) * | 2015-12-28 | 2016-04-20 | 安泰科技股份有限公司 | Graphite carbon/ferroferric oxide composite and preparation method and application thereof |
| CN105514419B (en) * | 2015-12-28 | 2019-01-25 | 安泰科技股份有限公司 | Graphitic carbon/ferriferrous oxide composite material and its preparation method and application |
| WO2018033165A1 (en) * | 2016-08-19 | 2018-02-22 | 上海迈景纳米科技有限公司 | Polymer-metal oxide complex, preparation method therefor, and applications |
| GB2568434A (en) * | 2016-08-19 | 2019-05-15 | Jiangsu Nanofe Biomedical Tech Co Ltd | Polymer-metal oxide complex, preparation method therefor, and applications |
| CN107845787A (en) * | 2017-09-28 | 2018-03-27 | 东北师范大学 | Pomegranate shape Fe3O4@N C lithium cell cathode material preparation methods |
| CN107845787B (en) * | 2017-09-28 | 2020-04-14 | 东北师范大学 | Pomegranate-shaped Fe3O4Preparation method of @ N-C lithium battery negative electrode material |
| CN115084515A (en) * | 2021-03-11 | 2022-09-20 | 中国科学院上海硅酸盐研究所 | Inorganic oligomer lithium-containing composite metal oxide material, preparation method thereof and application thereof in lithium ion battery cathode material |
| CN115084515B (en) * | 2021-03-11 | 2023-12-26 | 中国科学院上海硅酸盐研究所 | Inorganic oligomer lithium-containing compound metal oxide material, preparation method thereof and application thereof in lithium ion battery anode material |
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Application publication date: 20130717 |