CN107026266B - A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material - Google Patents

A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material Download PDF

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Publication number
CN107026266B
CN107026266B CN201710413609.5A CN201710413609A CN107026266B CN 107026266 B CN107026266 B CN 107026266B CN 201710413609 A CN201710413609 A CN 201710413609A CN 107026266 B CN107026266 B CN 107026266B
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cnts
parts
weight
negative pole
lithium ion
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CN107026266A (en
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罗大为
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Shenzhen Polytechnic
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material includes the following steps: step 1: weighing 0.05 ~ 0.2 parts by weight CNTs, is dissolved in ethylene glycol, ultrasonic oscillation 1h is completely dispersed；Step 2: 0.3 ~ 0.5 parts by weight FeCl is added3·6H2O, 8 ~ 9 parts by weight potassium acetates and 1.5 ~ 3 parts by weight polyethylene glycol, magnetic agitation 30min；Step 3: being transferred in polytetrafluoroethyllining lining, isothermal holding is cooled to room temperature, is washed with deionized three times, and vacuum drying obtains black powder；Step 4: 3 ~ 5 parts by weight polyethylene glycol are weighed, are mixed with black powder, are fitted into planetary ball mill, ball milling 4h；Step 5: the mixture that step 4 is obtained is placed in crucible, under high-purity argon gas protection, is warming up between 550 ~ 650 DEG C with 10 DEG C/min speed, is kept the temperature 6h, slow cooling to room temperature.The anode material capacity height and good cycle that the present invention obtains have potential application foreground in the fields such as portable electronic device and electric car.

Description

A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material
Technical field
The present invention relates to lithium ion battery negative material fields, and in particular to a kind of lithium ion battery CNTs/Fe2O3/ C is multiple Close the preparation method of negative electrode material.CNTs, that is, carbon nanotube, Fe2O3That is iron oxide, C, that is, carbon.
Background technique
Lithium ion battery is a kind of renewable green energy resource of environmentally friendly high-performance, as the performance of lithium ion battery mentions Height, just gradually substitutes traditional energy, and increasingly extensive is applied to portable electronic devices and the electricity such as mobile phone and tablet computer Electrical automobile.With the micromation and intelligence of electronic product, energy density and cycle performance to lithium battery propose higher want It asks.Currently, graphite carbon material be it is most common can commercialized lithium ion battery negative material, but graphite-based carbon cathode material Its very close theoretical capacity (372mAh/g), existing technology have nearly reached its limit, therefore, have had the specific capacity of material Necessity, which is found, a kind of can substitute graphite-based carbon negative electrode material, new type lithium ion with higher energy density and cycle performance Cell negative electrode material.
In recent years, various transition metal oxides, such as Fe2O3、Fe3O4、MnO2And Co3O4Deng with environmental-friendly, resource The abundant and advantages such as theoretical capacity height, have the further investigation in terms of being used for cathode of lithium battery.Wherein, Fe2O3Due to theory Capacity height (1007 mAhg-1) and it is cheap receive significant attention, but Fe2O3Volume in poorly conductive and charge and discharge process Expansion is big, causes capacity attenuation very fast, strongly limits the application of its industrialization.
In order to solve Fe2O3Cathode there are the problem of, some scholars are from Fe2O3It furthers investigate, such as adopts in the preparation of cathode The Fe with different crystal structure and particle shape is prepared with different synthetic methods2O3Particle.Some scholars are with Fe2O3For Foundational development goes out a series of composite materials, such as Fe2O3/ CNTs laminated film, Fe2O3/ graphene composite negative pole material etc. Deng.It makes a general survey of domestic and international patent and publishes academic paper it is found that current various Fe2O3The research of base cathode is that comparison is positive, living Jump, get a good chance of becoming cathode material for high capacity lithium ion battery of new generation.The present invention proposes a kind of completely new lithium-ion electric Pond CNTs/Fe2O3The preparation method of/C composite negative pole material is inhibited by introducing two kinds of substance of CNTs and C layer from both direction Fe2O3Volume expansion in charge and discharge process, and in view of CNTs and C layers of good electric conductivity, therefore can very good solution Fe2O3 The big problem of volume expansion in poorly conductive and charge and discharge process has both high power density and high-energy density to prepare Lithium ion battery negative material.
Summary of the invention
The technical problem to be solved in the present invention is that: there are energy density is not high and cyclicity for lithium cell cathode material at present The undesirable problem of energy, proposes a kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material improves electrode Cyclical stability, and prepare the lithium ion battery negative material of high-energy density and high stability, so improve power lithium from The overall performance of sub- battery.
In order to solve the above-mentioned technical problem, the present invention proposes a kind of following technical scheme: lithium ion battery CNTs/Fe2O3/C The preparation method of composite negative pole material, includes the following steps:
Step 1: the CNTs of 0.05 ~ 0.2 parts by weight is weighed, is dissolved in a certain amount of ethylene glycol, the dosage of ethylene glycol 100mL ethylene glycol is corresponded to according to the CNTs of every 0.05 ~ 0.2 g to determine, then ultrasonic oscillation 1h, until dividing completely It dissipates；
Step 2: sequentially adding the FeCl of 0.3 ~ 0.5 parts by weight3·6H2O, the potassium acetate of 8 ~ 9 parts by weight and The polyethylene glycol of 1.5 ~ 3 parts by weight, magnetic agitation 30min；
Step 3: solution described in step 2 being transferred in polytetrafluoroethyllining lining, isothermal holding is carried out, is subsequently cooled to room Temperature.Then it is washed with deionized three times, is then dried in vacuo, obtain black powder；
Step 4: weighing the polyethylene glycol of 3 ~ 5 parts by weight, mixed with the black powder that step 3 obtains, and be packed into star In formula ball mill, ball milling 4h；
Step 5: the mixture that step 4 is obtained is placed in crucible, then under high-purity argon gas protection, with 10 DEG C/min speed Degree is warming up between 550 ~ 650 DEG C, and keeps the temperature 6h, and then slow cooling to room temperature is to get to CNTs/Fe2O3/ C composite negative pole material Material.
Compared with prior art, the present invention has following the utility model has the advantages that the present invention is with high theoretical capacity and relatively inexpensive Fe2O3To store up lithium active particle, there are two advantages by the CNTs of introducing, first is that the one-dimensional porous structure of CNTs is made full use of both to facilitate The advantages of insertion of lithium ion and moving out in charge and discharge process, and can constructing three-dimensional conductive network, leads so as to improve composite material Electrically, second is that using CNTs as Fe2O3The carrier of active particle can alleviate Fe from single direction2O3Active particle resets electric mistake Volume change in journey, so as to improve the cycle performance of composite material.In Fe2O3Active particle surface deposits C layers, and advantage exists In following two o'clock, first is that being C layers and CNTs by Fe2O3Active particle is mixed in centre, can be to Fe2O3Implement from both direction Double protections, further suppress volume change, to further improve cycle performance, second is that C layers can further improve composite wood The electric conductivity of material.Therefore, the present invention constructs CNTs/Fe by effectively introducing CNTs and C2O3/ C composite negative pole material, can have Effect solves Fe2O3Particle conductive is poor and charge and discharge process in there are problems that larger volume variation, to prepare high capacity The lithium ion battery negative material of high stability, and then improve the overall performance of power lithium-ion battery.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the composite negative pole material of embodiment 1.
Fig. 2 is the cycle performance figure of the composite negative pole material of embodiment 1.
Fig. 3 is the AC impedance figure of the composite negative pole material of embodiment 1.
Specific embodiment
The present invention proposes a kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material, wherein CNTs is Carbon nanotube, Fe2O3That is iron oxide, C, that is, carbon, the preparation method include the following steps:
Step 1: the CNTs of 0.05 ~ 0.2 parts by weight is weighed, is dissolved in a certain amount of ethylene glycol, the dosage of ethylene glycol 100mL ethylene glycol is corresponded to according to the CNTs of every 0.05 ~ 0.2 g to determine, then ultrasonic oscillation 1h, until dividing completely It dissipates；
Step 2: sequentially adding the FeCl of 0.3 ~ 0.5 parts by weight3·6H2O, the potassium acetate of 8 ~ 9 parts by weight and The polyethylene glycol of 1.5 ~ 3 parts by weight, magnetic agitation 30min；
Step 3: solution described in step 2 being transferred in polytetrafluoroethyllining lining, isothermal holding is carried out, is subsequently cooled to room Temperature.Then it is washed with deionized three times, is then dried in vacuo, obtain black powder；
Step 4: weighing the polyethylene glycol of 3 ~ 5 parts by weight, mixed with the black powder that step 3 obtains, and be packed into star In formula ball mill, ball milling 4h；
Step 5: the mixture that step 4 is obtained is placed in crucible, then under high-purity argon gas protection, with 10 DEG C/min speed Degree is warming up between 550 ~ 650 DEG C, and keeps the temperature 6h, and then slow cooling to room temperature is to get to CNTs/Fe2O3/ C composite negative pole material Material.
The embodiment of the present invention 1-6, various parameters are as shown in table 1 below.
Parameter in the different embodiments of table 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
CNTs / g 0.05 0.05 0.1 0.1 0.2 0.2
FeCl3·6H2Quality/g of O 0.3 0.4 0.4 0.5 0.5 0.3
Quality/g of potassium acetate 8 8.5 8.5 9 9 8
Quality/the g of (in step 2) polyethylene glycol 1.5 2.0 2.0 3.0 3.0 1.5
Quality/the g of (in step 3) polyethylene glycol 3 3 4.0 4 5 5
Temperature/DEG C 550 550 550 650 650 650
Circulation volume/mAhg for the first time-1 932.5 942.4 941.0 943.8 947.9 933.5
Reversible capacity/mAhg after 50 times-1 788.6 798.4 806.9 805.1 803.3 802.1
Present invention is generally directed to technological parameters to adjust, and be explained with embodiment 3.
Step 1: weighing 0.1 g CNTs, be dissolved in 100 mL ethylene glycol, then 1 h of ultrasonic oscillation, until dividing completely It dissipates.
Step 2: sequentially adding 0.4 g FeCl3·6H2O, 8.5 g potassium acetates and 2.0 g polyethylene glycol, magnetic agitation 30 min。
Step 3: and then the solution is transferred in polytetrafluoroethyllining lining, isothermal holding is carried out, room temperature is subsequently cooled to. Then it is washed with deionized three times, is then dried in vacuo, obtain black powder.
Step 4: weighing 4.0 g polyethylene glycol, mixed with the black powder that step 3 obtains, and be packed into planetary ball mill In, then the mixture through ball milling is placed in crucible by ball milling 4h, then under high-purity argon gas protection, with 10 DEG C/min speed Be warming up to 550 DEG C and keep the temperature 6h, then slow cooling to room temperature to get arrive CNTs/Fe2O3/ C composite negative pole material.
Electrochemical property test is carried out to obtained composite negative pole material, the results showed that, in 100 mAg-1Electric current it is close Under degree, discharge capacity is respectively 941.0 mAhg to composite material for the first time-1, 50 times circulation after discharge capacity can still maintain 806.9 mAh·g-1, capacity retention ratio 85.7%, with preferable chemical property.

Claims (1)

1. a kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material, which is characterized in that including walking as follows It is rapid:
Step 1: weighing the CNTs of 0.05 ~ 0.2 parts by weight, be dissolved in a certain amount of ethylene glycol, the dosage of ethylene glycol will be by It corresponds to 100mL ethylene glycol according to the CNTs of every 0.05 ~ 0.2 g and determines, then ultrasonic oscillation 1h, until being completely dispersed；
Step 2: sequentially adding the FeCl of 0.3 ~ 0.5 parts by weight3·6H2O, the potassium acetate of 8 ~ 9 parts by weight and 1.5 ~ The polyethylene glycol of 3 parts by weight, magnetic agitation 30min；
Step 3: the resulting mixture of step 2 being transferred in polytetrafluoroethyllining lining, isothermal holding is carried out, is subsequently cooled to room Temperature is then washed with deionized three times, is then dried in vacuo, obtains black powder；
Step 4: weighing the polyethylene glycol of 3 ~ 5 parts by weight, mixed with the black powder that step 3 obtains, and be packed into planetary ball In grinding machine, ball milling 4h；
Step 5: the mixture that step 4 is obtained is placed in crucible, then under high-purity argon gas protection, with 10 DEG C/min speed liter Temperature keeps the temperature 6h between 550 ~ 650 DEG C, and then slow cooling to room temperature is to get arriving CNTs/Fe2O3/ C composite negative pole material.
CN201710413609.5A 2017-06-05 2017-06-05 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material Expired - Fee Related CN107026266B (en)

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CN108933253A (en) * 2018-09-17 2018-12-04 深圳职业技术学院 A kind of lithium ion battery Fe2O3The preparation method of/C negative electrode material
CN110350179B (en) * 2019-07-17 2021-04-02 中国科学院福建物质结构研究所 Fe2O3Nano carbon composite material and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593446A (en) * 2012-02-22 2012-07-18 清华大学 Method for preparing active electrode material of lithium ion battery
CN103022422A (en) * 2012-11-26 2013-04-03 同济大学 Preparation method of active carbon nanotube/ferric oxide lithium ion battery electrode material
CN103151495A (en) * 2013-03-20 2013-06-12 河南师范大学 Method for preparing hybrid negative electrode materials of lithium ion battery
CN103531789A (en) * 2012-12-27 2014-01-22 中国矿业大学 Iron oxide-carbon nanotube ternary composite material and preparation method thereof
CN104505498A (en) * 2014-12-12 2015-04-08 天津大学 Preparation method of ferric oxide/carbon nanotube lithium ion battery anode material
CN106129385A (en) * 2016-09-09 2016-11-16 深圳职业技术学院 A kind of lithium ion battery CA/Fe2o3the preparation method of/PPy composite negative pole material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102593446A (en) * 2012-02-22 2012-07-18 清华大学 Method for preparing active electrode material of lithium ion battery
CN103022422A (en) * 2012-11-26 2013-04-03 同济大学 Preparation method of active carbon nanotube/ferric oxide lithium ion battery electrode material
CN103531789A (en) * 2012-12-27 2014-01-22 中国矿业大学 Iron oxide-carbon nanotube ternary composite material and preparation method thereof
CN103151495A (en) * 2013-03-20 2013-06-12 河南师范大学 Method for preparing hybrid negative electrode materials of lithium ion battery
CN104505498A (en) * 2014-12-12 2015-04-08 天津大学 Preparation method of ferric oxide/carbon nanotube lithium ion battery anode material
CN106129385A (en) * 2016-09-09 2016-11-16 深圳职业技术学院 A kind of lithium ion battery CA/Fe2o3the preparation method of/PPy composite negative pole material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"3D α-Fe2O3/掺氮石墨烯/碳纳米管复合材料及其储锂性能";刘晓峰 等;《无机化学学报》;20140210;第30卷(第2期);第242-250页
"CNT@Fe3O4@C Coaxial Nanocables: One-Pot, Additive-Free Synthesis and Remarkable Lithium Storage Behavior";Jianli Cheng 等;《Chem. Eur. J.》;20130612;第19卷;第9866-9874页
"米粒状α－Fe2O3的制备与电化学性能研究";武永鑫 等;《安徽建筑大学学报》;20150815;第23卷(第4期);第36-41页

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