CN107591542A - A kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material - Google Patents
A kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material Download PDFInfo
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- CN107591542A CN107591542A CN201710730628.0A CN201710730628A CN107591542A CN 107591542 A CN107591542 A CN 107591542A CN 201710730628 A CN201710730628 A CN 201710730628A CN 107591542 A CN107591542 A CN 107591542A
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Abstract
Present invention relates particularly to a kind of preparation method of iron cobalt compound base lithium air battery positive electrode material, mainly solves nano Co Fe present in existing preparation method2O4Easily occur in charge and discharge process because crystalline structure it is unordered caused by agglomeration so as to influenceing the technical problem of the performance of lithium-air battery.The preparation method of the present invention obtains iron cobalt gel-like suspension including (1)；(2) obtain crystalline structure stable iron cobalt compound (3) and iron cobalt compound and Ketjen black, binding agent are mixed with lithium air battery positive electrode material.Obtained iron cobalt nano-complex base lithium air battery positive electrode material can effectively improve lithium-air battery discharge capacity 2943mAh/g (electrode) first, reduce lithium-air battery discharge and recharge overpotential 0.95V；Because its crystallization degree is high, can effectively alleviate cobalt ferrite material conductivity it is poor, easily reunion, charge and discharge process Volume Changes the defects of, be a kind of very promising lithium-air battery air cathode catalyst material.
Description
Technical field
The invention belongs to the preparation method technical field of cell positive material, and in particular to a kind of iron cobalt nano-complex base
The preparation method of lithium air battery positive electrode material.
Background technology
As people are continuously increased to the demand of the energy, coal, oil, the continuous exhausted continuous evil with environment of natural gas
Change, people continue to increase to research and development of new sources of energy.Lithium-air battery is because the theory of its superelevation is than energy (11140Wh
kg-1) and the preferable theoretical specific capacity (3860mAhg of lithium metal-1) enjoy the concern of researcher.And the hair of lithium-air battery
Exhibition still suffers from many difficulties.Such as：Unstable, electrolyte unstable, battery the invertibity efficiency of electrode structure is low, with
And the energy transformation ratio of battery is low, kinetics is low etc..In consideration of it, find to the hydrogen reduction (ORR) in lithium-air battery and
The bifunctional catalyst that oxygen separates out (OER) reaction and has good catalytic effect seems very crucial.
Iron cobalt nano-complex (CoFe2O4) it is a kind of metal oxide of spinel structure, it is verified that it has
Good hydrogen reduction and oxygen separate out catalytic performance and aboundresources, low cost and other advantages.Report nano Co Fe at present2O4It is multiple
Compound has as the preparation method of lithium air battery positive electrode material catalyst：Hydro-thermal-in-situ compositing, thermal decomposition-liquid phase are from group
Dress method, hydro-thermal method, solvent-thermal method etc..These preparation methods all select nano Co Fe substantially2O4With graphene, CNT, carbon
Carbon materials such as black (XC-72) carries out compound.Although these methods can be by nano Co Fe2O4It is grown in nano carbon material well
Material, but the nano material prepared is without roasting, CoFe that several method obtains2O4Lattice structure is unordered, easy reunion, unordered
Serious Volume Changes can occur in charge and discharge process for the lattice structure of change, easily block the air duct of carbon material, these are all
The serious chemical property for influenceing its lithium-air battery；CoFe prepared by colloidal sol-template2O4Although nano material can be very
Uniformly by nano wire or bar-shaped CoFe2O4It is distributed in template, improves CoFe2O4Properties, but it was prepared
Journey, template selection and prepare complex, be unfavorable for nano Co Fe2O4Application in lithium-air battery.
The content of the invention
The invention aims to solve the preparation method of existing cobalt nano-complex base lithium air battery positive electrode material
Due to nano Co Fe be present2O4Easily occur in charge and discharge process because crystalline structure it is unordered caused by agglomeration so as to shadow
Ring the technical problem of the performance of lithium-air battery, there is provided a kind of preparation of iron cobalt nano-complex base lithium air battery positive electrode material
Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material, comprises the following steps：
(1) the Fe(NO3)39H2O aqueous solution and the cabaltous nitrate hexahydrate aqueous solution are mixed, and ammoniacal liquor is added dropwise, coagulated
Colloidal suspensions；(2) above-mentioned gel-like suspension is transferred in the hydrothermal reaction kettle of acid and alkali-resistance and chemically reacted, sunk
Starch；(3) sediment is washed to neutrality repeatedly, and be dried；(4) dried sediment is calcined, obtains CoFe2O4
Nano material；(5) Ketjen black, CoFe2O4Nano material, binding agent, which are fully ground, is made iron cobalt nano-complex base lithium sky
Gas cell positive material.
The concentration of the Fe(NO3)39H2O aqueous solution is 1mol/L in the step (1), it is ensured that nano Co Fe2O4Middle iron member
The dosage of element.
The concentration of the cabaltous nitrate hexahydrate aqueous solution is 0.5mol/L in the step (1), it is ensured that nano Co Fe2O4Middle cobalt
The dosage of element.
Six hydrations that the Fe(NO3)39H2O aqueous solution that concentration is 1mol/L in the step (1) is 0.5mol/L with concentration
The volume ratio of cobalt nitrate aqueous solution is 1:1, it is ensured that nanometer ensures the nano Co Fe prepared2O4In.
The dosage of ammoniacal liquor is the Fe(NO3)39H2O aqueous solution that concentration is 1mol/L in the step (1) and concentration is
The 1/100-1000 of 0.5mol/L cabaltous nitrate hexahydrate aqueous solution total amount, ensures that course of reaction is steady, obtains hydrogen-oxygen
Compound is co-precipitated presoma.
The hydrothermal reaction kettle of acid and alkali-resistance is the hydrothermal reaction kettle for being lined with polytetrafluoroethyllining lining in the step (2), is avoided
Corrosion in course of reaction to vessel such as reactors.
The temperature to be chemically reacted in the step (2) in hydrothermal reaction kettle is 140-200 DEG C, and the reaction time is
10-20 hours, preferably 180 DEG C, the crystallization process of vectolite can be improved, the progress that can react fully for 15 hours, avoided
Waste.
Sediment is washed to neutrality, deionized water repeatedly with deionized water in the step (3) washs repeatedly, can remove
The interference of ammoniacal liquor.
Calcining heat is 350-750 DEG C in the step (4), preferably 650 DEG C, is become with the rise cobalt ferrite crystal formation of temperature
In perfect, the nano material obtained by 650 DEG C is not in agglomeration.
Ketjen black, CoFe in the step (5)2O4Nano material, the mass ratio of binding agent are 6-8：3-1：1, preferably 7：2：
1, Ketjen black can be utilized to improve the electric conductivity of lithium air battery positive electrode, there is provided the deintercalation duct of lithium ion, the presence of Ketjen black
Can alleviate during Lithium-ion embeding and deintercalation because of Volume Changes and caused by battery polarization.
The present invention uses above technical scheme, compared with background technology, has the advantages that：
1st, the present invention, which obtains lithium air battery positive electrode material, can effectively improve lithium-air battery discharge capacity first
2943mAh/g (electrode), reduce lithium-air battery discharge and recharge overpotential 0.95V；
2nd, by the present invention in that preparing the cobalt ferrite material of spinel structure with gel precipitation, obtained product crystallizes
Degree is high, uses it for lithium-air battery air cathode, shows good first discharge specific capacity, can effectively alleviate ferrous acid
The defects of cobalt material conductivity is poor, easily reunite, charge and discharge process Volume Changes, is a kind of very promising lithium-air battery air
Anode catalytic agent material.
Embodiment
Embodiment 1
A kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material in the present embodiment, including it is following
Step：
(1) by the Fe(NO3)39H2O aqueous solution and concentration that concentration is 1mol/L be 5mol/L cabaltous nitrate hexahydrate it is water-soluble
Liquid is 1 according to volume ratio:1 ratio mixes, and ammoniacal liquor is added dropwise, and the dosage of ammoniacal liquor is the nine hydration nitre that concentration is 1mol/L
Sour water solution and concentration are the 1/100 of 0.5mol/L cabaltous nitrate hexahydrate aqueous solution total amount, obtain gel-like suspension；
(2) above-mentioned gel-like suspension is transferred in the hydrothermal reaction kettle for being lined with polytetrafluoroethyllining lining, it is anti-at a temperature of 140 DEG C
Answer 20 hours, obtain sediment；(3) sediment is washed to neutrality repeatedly with deionized water, and be dried；(4) by drying
Sediment afterwards is calcined at a temperature of 350 DEG C, obtains CoFe2O4Nano material；(5) Ketjen black, CoFe2O4Nano material,
Binding agent is according to 6：3：1 mass ratio, which is fully ground, is made iron cobalt nano-complex base lithium air battery positive electrode material.
Embodiment 2
A kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material in the present embodiment, including it is following
Step：
(1) the cabaltous nitrate hexahydrate water for being 0.5mol/L by the Fe(NO3)39H2O aqueous solution and concentration that concentration is 1mol/L
Solution is 1 according to volume ratio:1 ratio mixes, and ammoniacal liquor is added dropwise, and the dosage of ammoniacal liquor is nine hydrations that concentration is 1mol/L
Iron nitrate aqueous solution and concentration are the 1/1000 of 0.5mol/L cabaltous nitrate hexahydrate aqueous solution total amount, obtain gel suspension
Liquid；(2) above-mentioned gel-like suspension is transferred in the hydrothermal reaction kettle for being lined with polytetrafluoroethyllining lining, in 200 DEG C of temperature
Lower reaction 10 hours, obtains sediment；(3) sediment is washed to neutrality repeatedly with deionized water, and be dried；(4) will
Dried sediment is calcined at a temperature of 750 DEG C, obtains CoFe2O4Nano material；(5) Ketjen black, CoFe2O4Nanometer
Material, binding agent are according to 8：1：1 mass ratio, which is fully ground, is made iron cobalt nano-complex base lithium air battery positive electrode material.
Embodiment 3
A kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material in the present embodiment, including it is following
Step：
(1) the cabaltous nitrate hexahydrate water for being 0.5mol/L by the Fe(NO3)39H2O aqueous solution and concentration that concentration is 1mol/L
Solution is 1 according to volume ratio:1 ratio mixes, and ammoniacal liquor is added dropwise, and the dosage of ammoniacal liquor is nine hydrations that concentration is 1mol/L
Iron nitrate aqueous solution and concentration are the 1/500 of 0.5mol/L cabaltous nitrate hexahydrate aqueous solution total amount, obtain gel-like suspension；
(2) above-mentioned gel-like suspension is transferred in the hydrothermal reaction kettle for being lined with polytetrafluoroethyllining lining, it is anti-at a temperature of 180 DEG C
Answer 15 hours, obtain sediment；(3) sediment is washed to neutrality repeatedly with deionized water, and be dried；(4) by drying
Sediment afterwards is calcined at a temperature of 650 DEG C, obtains CoFe2O4Nano material；(5) Ketjen black, CoFe2O4Nano material,
Binding agent is according to 7：2：1 mass ratio, which is fully ground, is made iron cobalt nano-complex base lithium air battery positive electrode material.
Claims (10)
- A kind of 1. preparation method of iron cobalt compound base lithium air battery positive electrode material, it is characterised in that：Comprise the following steps：(1) the Fe(NO3)39H2O aqueous solution and the cabaltous nitrate hexahydrate aqueous solution are mixed, and ammoniacal liquor is added dropwise, obtain gel Suspension；(2) above-mentioned gel-like suspension is transferred in the hydrothermal reaction kettle of acid and alkali-resistance and chemically reacted, precipitated Thing；(3) sediment is washed to neutrality repeatedly, and be dried；(4) dried sediment is calcined, obtains CoFe2O4Receive Rice material；(5) Ketjen black, CoFe2O4Nano material, binding agent are sufficiently mixed grinding and iron cobalt nano-complex base lithium are made O for cathode of air battery material.
- 2. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 1, its It is characterised by：The concentration of the Fe(NO3)39H2O aqueous solution is 1mol/L in the step (1).
- 3. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 2, its It is characterised by：The concentration of the cabaltous nitrate hexahydrate aqueous solution is 0.5mol/L in the step (1).
- 4. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 3, its It is characterised by：Six water that the Fe(NO3)39H2O aqueous solution that concentration is 1mol/L in the step (1) is 0.5mol/L with concentration The volume ratio for closing cobalt nitrate aqueous solution is 1:1.
- 5. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 4, its It is characterised by：The dosage of ammoniacal liquor is the Fe(NO3)39H2O aqueous solution that concentration is 1mol/L in the step (1) and concentration is The 1/100-1000 of 0.5mol/L cabaltous nitrate hexahydrate aqueous solution total amount.
- 6. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 4, its It is characterised by：The hydrothermal reaction kettle of acid and alkali-resistance is the hydrothermal reaction kettle for being lined with polytetrafluoroethyllining lining in the step (2).
- 7. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 6, its It is characterised by：The temperature to be chemically reacted in the step (2) in hydrothermal reaction kettle is 140-200 DEG C, and the reaction time is 10-20 hours.
- 8. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 6, its It is characterised by：Sediment is washed to neutrality repeatedly with deionized water in the step (3).
- 9. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 6, its It is characterised by：Calcining heat is 350-750 DEG C in the step (4).
- 10. a kind of preparation method of iron cobalt nano-complex base lithium air battery positive electrode material according to claim 6, its It is characterised by：Ketjen black, CoFe in the step (5)2O4Nano material, the mass ratio of binding agent are 6-8：3-1：1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111834613A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
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|---|---|---|---|---|
| CN1657490A (en) * | 2005-02-07 | 2005-08-24 | 武汉理工大学 | Method for preparing cobalt ferrite by coprecipitation |
| CN102275999A (en) * | 2011-05-27 | 2011-12-14 | 山东大学 | Network cobalt ferrite for anode material for lithium ion battery and use thereof |
| CN104529424A (en) * | 2015-01-16 | 2015-04-22 | 安徽工业大学 | Composite permagnetferrite with functions of two-phase exchange coupling and keeping high coercive force |
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2017
- 2017-08-23 CN CN201710730628.0A patent/CN107591542A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657490A (en) * | 2005-02-07 | 2005-08-24 | 武汉理工大学 | Method for preparing cobalt ferrite by coprecipitation |
| CN102275999A (en) * | 2011-05-27 | 2011-12-14 | 山东大学 | Network cobalt ferrite for anode material for lithium ion battery and use thereof |
| CN104529424A (en) * | 2015-01-16 | 2015-04-22 | 安徽工业大学 | Composite permagnetferrite with functions of two-phase exchange coupling and keeping high coercive force |
Non-Patent Citations (1)
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| KATALIN SINKO，ET AL: "Liquid-phase syntheses of cobalt ferrite nanoparticles", 《JOURNAL OF NANOPARTICLE RESEARCH》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111834613A (en) * | 2019-04-23 | 2020-10-27 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
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Application publication date: 20180116 |