CN103956482B - A kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material - Google Patents

A kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material Download PDF

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CN103956482B
CN103956482B CN201410124126.XA CN201410124126A CN103956482B CN 103956482 B CN103956482 B CN 103956482B CN 201410124126 A CN201410124126 A CN 201410124126A CN 103956482 B CN103956482 B CN 103956482B
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foam
lithium ion
ion battery
ferroferric oxide
electrode material
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CN103956482A (en
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穆道斌
吴锋
黄荣
吴伯荣
陈实
赵菲菲
侯雄雄
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Beijing Institute of Technology BIT
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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
    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • 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 present invention relates to a kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material, belong to chemical industry electrode material manufacturing process technology field.Its preparation process: adopt gelatin as carbon source and carrier, by itself and source of iron Homogeneous phase mixing; By mixed solution evaporate to dryness under condition of heating and stirring, further vacuumize; Mixture is put into tube furnace calcine under an inert atmosphere, obtain calcined product; Calcined product grinding is obtained metal oxide/carbon composite.Safety non-toxic of the present invention, method is simple, and preparation parameter is controlled, and products therefrom has foam-like porous structures, constant current charge-discharge test is carried out to lithium-ion button battery prepared by this material, does it show high charging and discharging capacity and good cycle performance: 0.2C(200mA? g -1) circulation 50 weeks under condition, does capacity remain on 700-900mAh? g -1.

Description

A kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material
Technical field
The present invention relates to a kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material, belong to chemical industry electrode material manufacturing process technology field.
Background technology
Lithium ion battery, since nineteen ninety realizes commercialization, has just been widely used in the fields such as digital camera, mobile phone, notebook computer and Portable Measurement Instrument.In recent years, along with extensively popularizing of electric bicycle, the commercialized development of a new generation's pure electric automobile (EV), hybrid vehicle (HEV), the demand of high-capacity secondary battery is also increased day by day, in addition the needs of environmental protection, research and development high-energy-density, long circulation life and free of contamination " green battery " are all being devoted in countries in the world.Relative to other secondary cells such as traditional lead-acid battery, Ni-MH battery and Ni-Cr batteries, lithium ion battery relies on the excellent properties such as its specific energy is high, operating voltage is high, have extended cycle life, self discharge is little, memory-less effect just progressively to dominate the market, be called as and 20th century dominated power supply, become the study hotspot of countries in the world in the recent decade.
In the research of lithium ion battery negative material, traditional carbonaceous negative material is mainly graphite and carbosphere, its earliest to study by people and shiploads of merchandise.Material with carbon element has the features such as good charge-discharge characteristic, the insertion reaction of high reversible, Thermodynamically stable and compatibility of electrolyte be good, but its theoretical capacity is only 372mAh/g, show certain limitation relative to the pursuit of current people to cell high-capacity characteristic.In recent years, nano transition metal oxides (Fe 2o 3, Fe 3o 4, Co 3o 4, CuO and NiO etc.) become the study hotspot of Novel cathode material for lithium ion battery with its height ratio capacity and high rate capability.Wherein tri-iron tetroxide (Fe 3o 4) there is the high (928mAhg of theoretical capacity -1), Stability Analysis of Structures, cheap and advantages of environment protection, become very concerned lithium ion battery negative material.But, Fe 3o 4very large obstacle is still faced: first, Fe as lithium ion battery negative material 3o 4storage lithium belong to and transform class mechanism, namely store up after lithium and generate nanometer Fe and Li 2o particle (<5nm), nanometer Fe has very strong catalytic action, easily causes a large amount of irreversible side reaction, causes larger irreversible capacity first.Secondly, material structure of matter before and after storage lithium changes, and huge change in volume can make the SEI film of material surface be destroyed, and electrode material is exposed in the electrolytic solution and causes the consumption of active material, causing poor cyclical stability.At present, Fe is overcome 3o 4the main method of negative material shortcoming carries out compound by material nano or with carbon, and wherein carbon has high conductivity, good Li +the effects such as permeability and buffering volumetric expansion.
Summary of the invention
The object of the invention is to provide a kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material, to improve the chemical property of lithium ion battery tri-iron tetroxide negative material.
The object of the invention is to be achieved through the following technical solutions.
A kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material of the present invention, its concrete steps are as follows:
1) be that 1 ~ 10:90 is 60 ~ 80 DEG C of heating stirring and dissolving by gelatin and deionized water according to mass ratio;
2) molysite being dissolved in deionized water, being added to step 1) in the mixed solution that obtains, wherein the mass ratio of molysite and mixed solution is 1 ~ 2:5, continues to add thermal agitation until solution evaporate to dryness in 60 ~ 80 DEG C;
3) by step 2) obtained product moves in vacuum drying chamber dry, until product Self-expanding obtains foam-like presoma; Baking temperature is lower than the calcining heat of this product;
4) by step 3) the foam-like presoma that obtains pulverizes, and calcine under an inert atmosphere, calcination time is 2 ~ 4h; After reaction terminates, under inert atmosphere protection, be cooled to room temperature, obtain foam-like ferroferric oxide/carbon lithium ion battery negative material.
Above-mentioned steps 2) in molysite be one in ferric nitrate, iron chloride, ferric acetate, ferric acetyl acetonade.
Above-mentioned steps 4) in inert gas be argon gas or nitrogen, calcining heat is 400 ~ 600 DEG C, heating rate 1 ~ 10 DEG C/min.
Beneficial effect
1, the present invention selects gelatin as carbon source, and the composite material of obtained foam-like ferroferric oxide/carbon, utilizes the hole of foam-like composite structure prosperity and good conductivity, improve Fe 3o 4the cyclical stability of negative material and high rate performance.It shows high charging and discharging capacity and good cycle performance: 0.2C(200mAg -1) circulation 50 weeks under condition, capacity remains on 700-900mAhg -1.
2, safety non-toxic of the present invention, preparation is simple, preparation parameter controllability is strong, the ferroferric oxide/carbon composite material preparing gained has loose structure, wherein the introducing of carbon effectively increases the conductivity of composite material, simultaneously for the change in volume of material provides certain cushion space, this composite material shows higher specific capacity as lithium ion battery negative material, good cyclical stability and high rate performance.
Accompanying drawing explanation
Fig. 1 is the SEM shape appearance figure of foam-like ferroferric oxide/carbon negative material prepared by embodiment;
Fig. 2 is that foam-like ferroferric oxide/carbon negative material is at 200mAg -1specific capacity and coulombic efficiency change curve during lower discharge and recharge.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is elaborated
Embodiment 1
Prepare a method for lithium ion battery foam-like ferroferric oxide/carbon negative material, concrete steps are:
1) 10g gelatin and 90g deionized water are heated stirring and dissolving at 80 DEG C;
2), after 4.04g ferric nitrate being dissolved in 40ml deionized water, step 1 is measured) the mixed solution 20g that obtains, iron salt solutions is added step 1) gained mixed solution, continue to add thermal agitation until solution evaporate to dryness in 60 DEG C;
3) by step 2) obtained product moves in vacuum drying chamber in 80 DEG C of further dry 10h.
4) by step 3) drying object pulverizes; after move to tube furnace flat-temperature zone and calcine; pass into inert gas; heating reacts, reaction time 2h, reaction temperature 500 DEG C; reaction time 2h; after reaction terminates, under inert atmosphere protection, be cooled to room temperature, obtain foam-like ferroferric oxide/carbon lithium ion battery negative material.Its SEM pattern as shown in Figure 1.
Charging and discharging capacity and cycle performance test is carried out: ferroferric oxide/carbon negative material and conductive agent, binding agent are mixed and made into electrode slice as work electrode after the foam-like ferroferric oxide/carbon composite negative electrode material obtained is applied to lithium ion battery negative material, lithium metal is to electrode, the LiF of 1mol/L 6/ EC-DMC (volume ratio 1: 1) is electrolyte, in argon gas atmosphere glove box, be assembled into simulated battery.Carry out charge-discharge test to simulated battery, voltage range is 0.005 ~ 3V (vs.Li +/ Li), current density is 200mAg -1.
Test result: ferroferric oxide/carbon composite negative electrode material is at 200mAg -1during lower discharge and recharge, specific capacity and coulombic efficiency change curve are as shown in Figure 2, and (embedding lithium) specific capacity that it discharges first and charging (de-lithium) specific capacity are respectively 1312.5mAhg -1, 940.9mAhg -1, after circulating 50 weeks, its electric discharge (embedding lithium) specific capacity and charging (de-lithium) specific capacity are respectively 911.5mAhg -1, 900mAhg -1.
Embodiment 2
Prepare a method for lithium ion battery foam-like ferroferric oxide/carbon negative material, concrete steps are:
1) 10g gelatin and 90g deionized water are heated stirring and dissolving at 80 DEG C;
2) after 4.04g ferric nitrate being dissolved in 40ml deionized water, measure the mixed solution 20g that step 1) obtains, iron salt solutions is added step 1) gained mixed solution, continue to add thermal agitation until solution evaporate to dryness in 60 DEG C;
3) by step 2) obtained product moves in vacuum drying chamber in 80 DEG C of further dry 10h.
4) step 3) drying object is pulverized; after move to tube furnace flat-temperature zone and calcine; pass into inert gas; heating reacts, reaction time 2h, reaction temperature 400 DEG C; reaction time 2h; after reaction terminates, under inert atmosphere protection, be cooled to room temperature, obtain ferroferric oxide/carbon lithium ion battery negative material.
Charging and discharging capacity and cycle performance test is carried out: ferroferric oxide/carbon negative material and conductive agent, binding agent are mixed and made into electrode slice as work electrode after the foam-like ferroferric oxide/carbon composite negative electrode material obtained is applied to lithium ion battery negative material, lithium metal is to electrode, the LiF of 1mol/L 6/ EC-DMC (volume ratio 1: 1) is electrolyte, in argon gas atmosphere glove box, be assembled into simulated battery.Carry out charge-discharge test to simulated battery, voltage range is 0.005 ~ 3V (vs.Li +/ Li), current density is 200mAg -1.
Test result: ferroferric oxide/carbon composite negative electrode material is at 200mAg -1lower discharge and recharge, (embedding lithium) specific capacity that it discharges first and charging (de-lithium) specific capacity are respectively 1122.8mAhg -1, 797.2mAhg -1, after circulating 300 weeks, its electric discharge (embedding lithium) specific capacity and charging (de-lithium) specific capacity are respectively 729.4mAhg -1, 724.5mAhg -1.

Claims (3)

1. prepare a method for lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material, it is characterized in that: concrete steps are as follows:
1) be that 1 ~ 10:90 is 60 ~ 80 DEG C of heating stirring and dissolving by gelatin and deionized water according to mass ratio;
2) molysite being dissolved in deionized water, being added to step 1) in the mixed solution that obtains, wherein the mass ratio of molysite and mixed solution is 1 ~ 2:5, continues to add thermal agitation until solution evaporate to dryness in 60 ~ 80 DEG C;
3) by step 2) obtained product moves in vacuum drying chamber dry, until product Self-expanding obtains foam-like presoma; Baking temperature is lower than the calcining heat of this product;
4) by step 3) the foam-like presoma that obtains pulverizes, and calcine under an inert gas, calcination time is 2 ~ 4h; After reaction terminates, under inert atmosphere protection, be cooled to room temperature, obtain foam-like ferroferric oxide/carbon lithium ion battery negative material.
2. a kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material as claimed in claim 1, is characterized in that: step 2) described in molysite be one in ferric nitrate, iron chloride, ferric acetate, ferric acetyl acetonade.
3. a kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material as claimed in claim 1, it is characterized in that: step 4) described in inert gas be argon gas or nitrogen, calcining heat is 400 ~ 600 DEG C, heating rate 1 ~ 10 DEG C/min.
CN201410124126.XA 2014-03-28 2014-03-28 A kind of method preparing lithium ion battery foam-like ferroferric oxide/carbon composite negative electrode material Expired - Fee Related CN103956482B (en)

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CN106229487A (en) * 2016-08-25 2016-12-14 北京化工大学 The method of lithium-sulfur cell charcoal/lithium sulfide composite positive pole prepared by a kind of carbon thermal reduction lithium sulfate
CN108306001B (en) * 2018-01-08 2021-04-16 北京科技大学 Lithium ion battery cathode material Fe3O4Preparation method of/N-C
CN109904413A (en) * 2019-01-23 2019-06-18 超威电源有限公司 A kind of preparation method of the lead carbon composite for lead carbon battery
KR102651786B1 (en) * 2019-02-13 2024-03-26 주식회사 엘지에너지솔루션 Cathode active material for lithium secondary battery
CN109841795A (en) * 2019-03-14 2019-06-04 电子科技大学 A kind of preparation method of negative electrode of lithium ion battery
CN110931751B (en) * 2019-12-06 2022-03-18 怀化学院 Carbon-ferroferric oxide composite material and preparation method and application thereof
CN111509188A (en) * 2020-04-30 2020-08-07 石家庄铁道大学 Anode material, anode, lithium ion battery and preparation method
CN112794360B (en) * 2020-12-31 2023-04-14 鸡西市唯大新材料科技有限公司 Preparation of nano SnO 2 Method for preparing/GC composite anode material

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