CN107069031A - The preparation method and applications of ferroso-ferric oxide carbon core shell nanoparticles in situ - Google Patents
The preparation method and applications of ferroso-ferric oxide carbon core shell nanoparticles in situ Download PDFInfo
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- CN107069031A CN107069031A CN201610977834.7A CN201610977834A CN107069031A CN 107069031 A CN107069031 A CN 107069031A CN 201610977834 A CN201610977834 A CN 201610977834A CN 107069031 A CN107069031 A CN 107069031A
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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
- H01M4/48—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
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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
- 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
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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
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Abstract
A kind of preparation method of ferroso-ferric oxide carbon core shell nanoparticles in situ, step is：The aqueous solution of certain density etal molysite and iminodiacetic acid is placed in reactor, reacted at a certain temperature certain time, generation presoma Fe IDA；It is placed in after washing, drying in the tube furnace of argon gas protection, annealing experiment is carried out at a certain temperature, negative material ferroso-ferric oxide carbon is obtained；Positive pole, negative pole, barrier film are placed in button cell, certain density lithium hexafluorophosphate solution is added as electrolyte, lithium ion battery is obtained after encapsulation.The present invention realizes carbon coating using the method for fabricated in situ, solves that preparation time length, cost are high, electronic conductivity is low, the low problem of composite porosity.The new type lithium ion battery charge-discharge performance that the present invention is assembled is excellent, and with preferable cyclical stability, application is wide.
Description
Technical field
The present invention relates to a kind of preparation method and applications of ferroso-ferric oxide in situ-carbon core shell nanoparticles, belong to electricity
Pond and electrochemical technology field.
Background technology
Electrode material is the core of lithium-ion battery system, and wherein negative material is even more to improve lithium ion battery energy and follow
The key factor in ring life-span.At present, commercially use negative material is mostly graphite cathode material.But such negative material
Actual discharge specific capacity is already close to its theoretical value, it is impossible to meet the demand of lithium ion battery of new generation.Substituted finding graphite
Cause and grind during thing, some transition metal oxides have that higher theoretical capacity, security be good because of it, cost is low
The extensive concern for the person of studying carefully.However, often electronic conductivity is relatively low for this kind of transition metal oxide material, and its charge and discharge process
Along with larger Volume Changes, therefore capacity attenuation is very fast, high rate performance is poor.Build the transition metal of nano-porous structure
Oxide/carbon composite can greatly improve its chemical property, overcome its latent defect.But, synthesis at present has
Porous transition metal oxides/carbon composite of multilevel hierarchy often uses the synthetic method of ex situ, i.e., synthesize first
Transition metal oxide, is subsequently added carbon source and is handled, obtain composite.Thus there is preparation time length, cost high, multiple
The low problem of porosity of condensation material and limit and commercially produce.
In the prior art, CN103241777A discloses a kind of carbon material, the preparation side of carbon-ferriferrous oxide composite material
Method, this method is using chliorinated polyvinyl chloride as synthesis carbon material or the carbon source material of carbon-iron compound composite, in iron chemical combination
Under the quick catalysis of thing, chliorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action during combustion reaction, synthesizes the oxygen of carbon-four
Change three iron composite materials or carbon material.Substantial amounts of hydrogen chloride is discharged in the patent during combustion reaction, and is used
Organic solvent tetrahydrofuran, but hydrogen chloride is extremely toxic substance, and tetrahydrofuran is low toxicity material, to behaviour in material preparation process
Make that personnel are healthy to cause high risks, severe contamination is caused to plant area's ambient air and soil, is unfavorable for environmental protection.
CN103117388A discloses carbon coated ferriferrous oxide and preparation method thereof and the application in lithium ion battery,
This method is by Fe2O3Under an ar atmosphere in carrying out Fe by acetylene gas under high temperature2O3Reduction and carbon coating, you can obtain carbon bag
Cover Fe3O4Composite.The material of carbon coating is synthesized using the method for two steps in the patent, complex steps, cost are high, are not suitable for
Large-scale industrial production.
The content of the invention
The purpose of the present invention is there is problem for above-mentioned there is provided a kind of ferroso-ferric oxide in situ-carbon core shell nanoparticles
Preparation method and applications, the preparation method synthesis step is simple, cost is low, do not contain noxious material, green ring in composition
Protect.
Technical scheme：
A kind of preparation method of ferroso-ferric oxide in situ-carbon core shell nanoparticles, is comprised the following steps that：
1) it is (1-3) by mol ratio:1 etal molysite and iminodiacetic acid is added in ultra-pure water, configures etal molysite
The concentration of the aqueous solution is 0.03-0.5mol/L, is being stirred continuously up to being completely dissolved, is obtaining mixed liquor, the etal molysite is
Iron ammonium sulfate or iron chloride；
2) above-mentioned mixed liquor is transferred in reactor, reactor is placed in air dry oven and protected at 140-180 DEG C
It is warm 6-18 hours, room temperature is then down to, presoma Fe-IDA is obtained, product is washed into drying for standby with water and ethanol respectively；
3) above-mentioned presoma Fe-IDA is placed in tube furnace, 400-600 DEG C is heated to 2-10 DEG C/min heating rates
And 1-5 hours are incubated, obtain the Fe of fabricated in situ3O4@C core shell nanoparticles.
A kind of prepared Fe in situ3O4The application of@C core shell nanoparticles, for the preparation of button lithium ion battery, tool
Body step is as follows：
The button lithium ion battery includes positive pole, negative pole and electrolyte, and positive pole is used as using metal lithium sheet；By Fe3O4@C、
Acetylene black and Kynoar are 85 according to mass ratio:10:5 ratio is slurried, and is coated on copper foil, as negative after drying
Pole；Positive pole and negative pole and Glass Fiber barrier films are positioned in button cell, electrolyte is added, the electrolyte is
1mol/L lithium hexafluoro phosphate is dissolved in the in the mixed solvent of ethylene carbonate and methyl ethyl carbonate, above two mixed solvent
Volume ratio is 1:1, obtain lithium ion battery after encapsulation.
It is an advantage of the invention that：
1) in prior art CN103117388A, carbon coated ferriferrous oxide composite has been synthesized using two-step method, and
The in-situ synthetic method used in the inventive method, method is easy, and operating procedure is easy, thus prior art CN103117388A
The preparation cost of middle electrode material is higher than the preparation cost in the inventive method.
2) prior art CN103241777A has used organic solvent tetrahydrofuran during negative material is synthesized,
Substantial amounts of hydrogen chloride is discharged in combustion, and hydrogen chloride is extremely toxic substance, and tetrahydrofuran is low toxicity material, will be in material system
It is healthy to operating personnel during standby to cause high risks, severe contamination is caused to plant area's ambient air and soil, it is unfavorable
In environmental protection.Noxious material, more environmental protection are free of in the raw material of the present invention.
Brief description of the drawings
Fig. 1 is the XRD of ferroso-ferric oxide-carbon core shell nanoparticles prepared by embodiment 1.
Fig. 2 is the SEM figures of ferroso-ferric oxide-carbon core shell nanoparticles prepared by embodiment 2.
Fig. 3 is the CV figures of lithium ion battery in embodiment 1.
Embodiment
The present invention is described further with reference to embodiment.
Embodiment 1：
A kind of preparation method of ferroso-ferric oxide in situ-carbon core shell nanoparticles, step is as follows：
1) it is 2.2 by mol ratio:1 iron ammonium sulfate and iminodiacetic acid is added in ultra-pure water, configures ferrous sulfate
The concentration of aqueous ammonium is 0.05mol/L, is being stirred continuously up to being completely dissolved, is obtaining mixed liquor；
2) above-mentioned mixed liquor is transferred in reactor, reactor is placed in air dry oven and is incubated 12 at 160 DEG C
Hour, room temperature is then down to, presoma Fe-IDA is obtained, product is washed into drying for standby；
3) above-mentioned presoma Fe-IDA is placed in tube furnace, 500 DEG C and insulation 2 is heated to 2 DEG C/min heating rates
Hour, obtain ferroso-ferric oxide-carbon core shell nanoparticles.
Fig. 1 is the XRD of ferroso-ferric oxide-carbon core shell nanoparticles prepared by embodiment 1.Show in figure：It is attached at 25 DEG C
Near great Bao peaks can be attributed to C, and remaining diffraction maximum can be attributed to Fe3O4, illustrate successfully to be prepared for ferroso-ferric oxide-carbon
Composite.
The application of prepared ferroso-ferric oxide in situ-carbon core shell nanoparticles, for the preparation of button lithium ion battery,
Comprise the following steps that：
Described button lithium ion battery includes positive pole, negative pole and electrolyte, and metal lithium sheet aoxidizes three as positive pole by four
Iron-carbon, acetylene black and Kynoar are 85 according to mass ratio:10:5 ratio is slurried, in coating and copper foil, after drying
It is used as negative pole；Positive pole and negative pole, and barrier film are positioned in button cell, certain density lithium hexafluorophosphate solution is added and makees
For electrolyte, lithium ion battery is obtained after encapsulation.Positive pole and negative pole, and barrier film are positioned in button cell, 1mol/ is added
It is 1 that L lithium hexafluoro phosphate, which is dissolved in volume ratio,:1 ethylene carbonate and the mixed solvent of methyl ethyl carbonate are used as electrolyte, envelope
Lithium ion battery is obtained after dress.
Fig. 3 schemes for the CV of lithium ion battery.Show in figure：0.64 and 0.49V two reduction in first week circulation figure
Peak can be attributed to Fe3O4It is converted into Fe0, meanwhile, it can be attributed to Fe in 1.87V oxidation reaction0It is converted into Fe3O4；With
In rear second week, circulation in the 3rd week, there is a certain degree of skew the position of oxidation peak and reduction peak, and peak intensity has to a certain degree
Decay.
Embodiment 2：
A kind of preparation method of ferroso-ferric oxide in situ-carbon core shell nanoparticles, step is as follows：
1) it is 2.5 by mol ratio:1 iron chloride and iminodiacetic acid is added in ultra-pure water, configures ferric chloride in aqueous solution
Concentration be 0.05mol/L, be stirred continuously until be completely dissolved, obtaining mixed liquor；
2) above-mentioned mixed liquor is transferred in reactor, it is small that reactor is placed in air dry oven into the insulation 6 at 180 DEG C
When, room temperature is then down to, presoma Fe-IDA is obtained, product is washed into drying for standby；
3) above-mentioned presoma Fe-IDA is placed in tube furnace, 500 DEG C and insulation 2 is heated to 2 DEG C/min heating rates
Hour, obtain ferroso-ferric oxide-carbon core shell nanoparticles.
Fig. 2 is the SEM figures of ferroso-ferric oxide-carbon core shell nanoparticles prepared by embodiment 2.Show in figure：Four oxidations three
The nanometer rods that iron-carbon composite is made up of countless tiny nano particles, wherein shell of each nano particle by carbon-coating
Constituted with the core of ferroso-ferric oxide.
Raw material and equipment used are obtained by known approach in above-described embodiment, and operating procedure used is this
What those skilled in the art can grasp.
Claims (2)
1. a kind of preparation method of ferroso-ferric oxide in situ-carbon core shell nanoparticles, it is characterised in that comprise the following steps that：
1) it is (1-3) by mol ratio:1 etal molysite and iminodiacetic acid is added in ultra-pure water, and configuration etal molysite is water-soluble
The concentration of liquid is 0.03-0.5mol/L, is being stirred continuously up to being completely dissolved, is obtaining mixed liquor, the etal molysite is sulfuric acid
Ferrous ammonium or iron chloride；
2) above-mentioned mixed liquor is transferred in reactor, reactor is placed in air dry oven and is incubated 6- at 140-180 DEG C
18 hours, room temperature is then down to, presoma Fe-IDA is obtained, product is washed into drying for standby with water and ethanol respectively；
3) above-mentioned presoma Fe-IDA is placed in tube furnace, is heated to 400-600 DEG C with 2-10 DEG C/min heating rates and protects
It is warm 1-5 hours, obtain ferroso-ferric oxide-carbon core shell nanoparticles of fabricated in situ.
2. the application of ferroso-ferric oxide in situ-carbon core shell nanoparticles prepared by a kind of claim 1, it is characterised in that be used for
The preparation of button lithium ion battery, is comprised the following steps that：
The button lithium ion battery includes positive pole, negative pole and electrolyte, and positive pole is used as using metal lithium sheet；By Fe3O4@C, acetylene
Black and Kynoar is 85 according to mass ratio:10:5 ratio is slurried, and is coated on copper foil, and negative pole is used as after drying；
Positive pole and negative pole and Glass Fiber barrier films are positioned in button cell, electrolyte is added, the electrolyte is 1mol/L
Lithium hexafluoro phosphate be dissolved in the in the mixed solvent of ethylene carbonate and methyl ethyl carbonate, the volume ratio of above two mixed solvent
For 1:1, obtain lithium ion battery after encapsulation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108311100A (en) * | 2018-01-22 | 2018-07-24 | 山西大学 | A kind of preparation method of magnetism carbon material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102790217A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof |
| CN103035907A (en) * | 2012-12-08 | 2013-04-10 | 浙江工业大学 | Carbon-coated hollow ferriferrous oxide and application thereof |
| CN104045116A (en) * | 2014-06-12 | 2014-09-17 | 江苏大学 | Preparation method of nano porous metal oxide/carbon lithium ion battery cathode material |
-
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- 2016-11-08 CN CN201610977834.7A patent/CN107069031A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102790217A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof |
| CN103035907A (en) * | 2012-12-08 | 2013-04-10 | 浙江工业大学 | Carbon-coated hollow ferriferrous oxide and application thereof |
| CN104045116A (en) * | 2014-06-12 | 2014-09-17 | 江苏大学 | Preparation method of nano porous metal oxide/carbon lithium ion battery cathode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108311100A (en) * | 2018-01-22 | 2018-07-24 | 山西大学 | A kind of preparation method of magnetism carbon material |
| CN108311100B (en) * | 2018-01-22 | 2020-11-06 | 山西大学 | Preparation method of magnetic carbon material |
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Application publication date: 20170818 |