CN108110236A - A kind of sodium-ion battery positive material and preparation method thereof - Google Patents

A kind of sodium-ion battery positive material and preparation method thereof Download PDF

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Publication number
CN108110236A
CN108110236A CN201711340890.0A CN201711340890A CN108110236A CN 108110236 A CN108110236 A CN 108110236A CN 201711340890 A CN201711340890 A CN 201711340890A CN 108110236 A CN108110236 A CN 108110236A
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CN
China
Prior art keywords
sodium
ion battery
powder mixture
precursor powder
calcining
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Pending
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CN201711340890.0A
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Chinese (zh)
Inventor
刘国强
于晗
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Northeastern University China
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Northeastern University China
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Priority to CN201711340890.0A priority Critical patent/CN108110236A/en
Publication of CN108110236A publication Critical patent/CN108110236A/en
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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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese 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
    • H01M4/36—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
    • 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 positive electrodes of sodium-ion battery and preparation method thereof, belong to field of new energy technologies.A kind of sodium-ion battery positive material, it is characterised in that：The positive electrode is with Na2/3Fe1/3Co1/6Mn1/2O2Chemical formula compound, is made as follows：By chemical formula Na2/3Fe1/3Co1/6Mn1/2O2The ratio between atomicity of middle Na, Fe, Co, Mn mixes sodium carbonate, ferrous oxalate, cobalt acetate, manganese carbonate, grinds at least 40min under room temperature, obtains precursor powder mixture；By precursor powder mixture under air atmosphere, 800 DEG C~850 DEG C calcining 8h~10h, grinding, both.Sodium-ion battery positive material Na of the present invention2/3Fe1/3Co1/ 6Mn1/2O2Material, its preparation method is simple, gained Na2/3Fe1/ 3Co1/6Mn1/2O2The charging and discharging curve of material is smooth, does not undergo phase transition, good cycle.

Description

A kind of sodium-ion battery positive material and preparation method thereof
Technical field
The present invention relates to a kind of positive electrode Na of sodium-ion battery2/3Fe1/3Co1/6Mn1/2O2And preparation method thereof, belong to Field of new energy technologies.
Background technology
In recent years, for sodium-ion battery due to resourceful, lower-price characteristic, the research for being increasingly becoming energy storage field is hot Point.However, sodium ion has larger ionic radius, migration resistance is big in crystal, becomes the master for restricting storage sodium Materials Factor is wanted, so the high performance embedding sodium positive electrode of development is the key that improve sodium-ion battery energy density.
P2-Na2/3Ni1/3Mn2/3O2The average working voltage of material is high, about 3.7V, and theoretical capacity is about 170.7 mAh/ G, therefore with higher energy density, there are the potentiality as sodium-ion battery positive material.But P2-Na2/3Ni1/ 3Mn2/3O2There is multi-stage platform when below 4.0V carries out charge and discharge on charging and discharging curve in material, and explanation is undergone phase transition, although this When cycle performance it is fair, but repeated phase transformation, can undoubtedly generate residual stress, influence practical application.
The content of the invention
In order to improve the reversible capacity of sodium-ion battery, improve sodium-ion battery performance, present invention design is prepared for one kind New composition material Na2/3Fe1/3Co1/6Mn1/2O2.It is prepared by the method that the present invention substitutes Ni using doped element Fe and Co, design A kind of new composition material Na2/3Fe1/3Co1/6Mn1/2O2, stable charge and discharge can be carried out, present preferable cyclicity Energy.
A kind of sodium-ion battery positive material, the positive electrode are with Na2/3Fe1/3Co1/6Mn1/2O2Chemical formula chemical combination Object is made as follows：
By chemical formula Na2/3Fe1/3Co1/6Mn1/2O2The ratio between atomicity of middle Na, Fe, Co, Mn by sodium carbonate, ferrous oxalate, Cobalt acetate, manganese carbonate mix, and grind at least 40min under room temperature, obtain precursor powder mixture；By precursor powder mixture in Under air atmosphere, 800 DEG C~850 DEG C calcining 8h~10h, grinding, both.
Preferably, precursor powder mixture is placed in corundum crucible, and in Muffle furnace, lower 800 DEG C of air atmosphere ~850 DEG C of calcining 8h~10h, wherein, heating rate is 5 DEG C/min；It is cooled to room temperature after calcining with the speed of 2~3 DEG C/min, Finally obtain electrode material Na2/3Fe1/3Co1/6Mn1/2O2。
Institute Na of the present invention2/3Fe1/3Co1/6Mn1/2O2Positive electrode is the compound with layer structure.
It is a further object of the present invention to provide the preparation methods of above-mentioned sodium-ion battery positive material.
A kind of preparation method of sodium-ion battery positive material, specially：
It is in molar ratio 2 by by sodium carbonate, ferrous oxalate, cobalt acetate, manganese carbonate:2:1:3 mix, and are ground at least under room temperature 40min obtains precursor powder mixture；By precursor powder mixture under air atmosphere, 800 DEG C~850 DEG C calcining 8h~ 10h, grinding, both.
In all technical solutions of the present invention, it is preferably to which calcination condition is：The lower 800 DEG C of calcinings 8h of air atmosphere.
Beneficial effects of the present invention are：Sodium-ion battery positive material Na of the present invention2/3Fe1/3Co1/6Mn1/2O2Material Material, its preparation method is simple, gained Na2/3Fe1/3Co1/6Mn1/2O2The charging and discharging curve of material is smooth, does not undergo phase transition, Xun Huan Performance is good.
Description of the drawings
Fig. 1 is Na of the present invention2/3Fe1/3Co1/6Mn1/2O2XRD spectrum；
Fig. 2 is Na of the present invention2/3Fe1/3Co1/6Mn1/2O2First charge-discharge collection of illustrative plates；
Fig. 3 is Na of the present invention2/3Fe1/3Co1/6Mn1/2O2Cycle performance collection of illustrative plates；
Fig. 4 is Na of the present invention2/3Fe1/3Co1/6Mn1/2O2SEM spectrum.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with Any mode limits the present invention.
Test method described in following embodiments is conventional method unless otherwise specified；The reagent and material, such as Without specified otherwise, commercially obtain.
Embodiment 1
Sodium-ion battery anode electrode material Na2/3Fe1/3Co1/6Mn1/2O2Preparation method, include the following steps：
Step 1, Na is prepared2/3Fe1/3Co1/6Mn1/2O2Precursor：
(1) sodium carbonate 1.6667g, ferrous oxalate (II) dihydrate 2.8304g, cobalt acetate (II) tetrahydrate are weighed 1.9594g with manganese carbonate 2.7128g；
(2) above-mentioned raw materials in mortar are mixed, 40min is ground under room temperature；
(3) it is Na with the product obtained after mortar grinder 40min2/3Fe1/3Co1/6Mn1/2O2Precursor powder；
Step 2, Na is prepared2/3Fe1/3Co1/6Mn1/2O2Electrode material：
The precursor powder of gained in step 1 is put into corundum crucible and in Muffle furnace, at 800 DEG C under air atmosphere 8h is calcined, heating rate is 5 DEG C/min, is cooled to room temperature with the speed of 3 DEG C/min, finally obtains electrode material Na2/3Fe1/ 3Co1/6Mn1/2O2。
The present invention passes through Solid phase synthesis positive electrode Na2/3Fe1/3Co1/6Mn1/2O2, it is convenient that this method prepares material, side Method is simple to operation, and the material particle after roasting is uniform, and material structure form is good.Battery is subjected to charge-discharge test under 0.1C, Na2/3Fe1/3Co1/6Mn1/2O2Discharge capacity for the first time be up to 153.8mAh/g.

Claims (4)

1. a kind of sodium-ion battery positive material, it is characterised in that：The positive electrode is with Na2/3Fe1/3Co1/6Mn1/2O2Change Formula compound, is made as follows：
By chemical formula Na2/3Fe1/3Co1/6Mn1/2O2The ratio between atomicity of middle Na, Fe, Co, Mn is by sodium carbonate, ferrous oxalate, acetic acid Cobalt, manganese carbonate mix, and grind at least 40min under room temperature, obtain precursor powder mixture；By precursor powder mixture in air Under atmosphere, 800 DEG C~850 DEG C calcining 8h~10h, grinding, both.
2. material according to claim 1, it is characterised in that：Precursor powder mixture is placed in corundum crucible, and In Muffle furnace, lower 800 DEG C~850 DEG C calcining 8h~10h of air atmosphere, wherein, heating rate is 5 DEG C/min；With 2 after calcining The speed of~3 DEG C/min is cooled to room temperature, and finally obtains electrode material Na2/3Fe1/3Co1/6Mn1/2O2。
3. material according to claim 1 or 2, it is characterised in that：The calcination condition is：Lower 800 DEG C of air atmosphere is forged Burn 8h.
4. the preparation method of sodium-ion battery positive material described in claim 1, it is characterised in that：By sodium carbonate, oxalic acid is sub- Iron, cobalt acetate, manganese carbonate are 2 in molar ratio:2:1:3 mix, and grind at least 40min under room temperature, obtain precursor powder mixture； By precursor powder mixture under air atmosphere, 800 DEG C~850 DEG C calcining 8h~10h, grinding, both.
CN201711340890.0A 2017-12-14 2017-12-14 A kind of sodium-ion battery positive material and preparation method thereof Pending CN108110236A (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101933179A (en) * 2008-02-04 2010-12-29 住友化学株式会社 Composite metal oxide and sodium rechargeable battery
CN101933180A (en) * 2008-02-04 2010-12-29 住友化学株式会社 Composite metal oxide and sodium rechargeable battery
CN101933181A (en) * 2008-02-04 2010-12-29 住友化学株式会社 Sodium rechargeable battery
CN103348511A (en) * 2011-02-15 2013-10-09 住友化学株式会社 Sodium secondary battery electrode and sodium secondary battery
CN103443973A (en) * 2011-03-24 2013-12-11 学校法人东京理科大学 Sodium secondary cell electrode and sodium secondary cell
CN105070902A (en) * 2015-07-17 2015-11-18 济南大学 Mixed transition metal based preparation method for cathode material of sodium secondary battery
CN105810932A (en) * 2016-04-28 2016-07-27 复旦大学 Layered cathode material for sodium-ion battery and preparation method of the layered cathode material for the sodium-ion battery
CN105932260A (en) * 2016-06-30 2016-09-07 中南大学 Sodium-ion battery oxide cathode material, and preparation method and application thereof
CN106340627A (en) * 2016-10-12 2017-01-18 苏州大学 Preparation method of sodium-ion battery anode material
CN106575744A (en) * 2014-08-08 2017-04-19 住友电气工业株式会社 Positive electrode for sodium ion secondary cell, and sodium ion secondary cell

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101933179A (en) * 2008-02-04 2010-12-29 住友化学株式会社 Composite metal oxide and sodium rechargeable battery
CN101933180A (en) * 2008-02-04 2010-12-29 住友化学株式会社 Composite metal oxide and sodium rechargeable battery
CN101933181A (en) * 2008-02-04 2010-12-29 住友化学株式会社 Sodium rechargeable battery
CN103348511A (en) * 2011-02-15 2013-10-09 住友化学株式会社 Sodium secondary battery electrode and sodium secondary battery
CN103443973A (en) * 2011-03-24 2013-12-11 学校法人东京理科大学 Sodium secondary cell electrode and sodium secondary cell
CN106575744A (en) * 2014-08-08 2017-04-19 住友电气工业株式会社 Positive electrode for sodium ion secondary cell, and sodium ion secondary cell
CN105070902A (en) * 2015-07-17 2015-11-18 济南大学 Mixed transition metal based preparation method for cathode material of sodium secondary battery
CN105810932A (en) * 2016-04-28 2016-07-27 复旦大学 Layered cathode material for sodium-ion battery and preparation method of the layered cathode material for the sodium-ion battery
CN105932260A (en) * 2016-06-30 2016-09-07 中南大学 Sodium-ion battery oxide cathode material, and preparation method and application thereof
CN106340627A (en) * 2016-10-12 2017-01-18 苏州大学 Preparation method of sodium-ion battery anode material

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