CN106252645A - A kind of sodium-ion battery high nickel content ternary material and preparation method thereof - Google Patents

A kind of sodium-ion battery high nickel content ternary material and preparation method thereof Download PDF

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Publication number
CN106252645A
CN106252645A CN201610614440.5A CN201610614440A CN106252645A CN 106252645 A CN106252645 A CN 106252645A CN 201610614440 A CN201610614440 A CN 201610614440A CN 106252645 A CN106252645 A CN 106252645A
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sodium
preparation
ternary material
ion battery
nickel content
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CN201610614440.5A
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赖超
王洪波
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Jiangsu Normal University
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Jiangsu Normal University
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 sodium-ion battery high nickel content ternary material and preparation method thereof.Its chemical general formula is NaNi0.5Mn0.5‑xTixO2(0 < x < 0.5), the content of its Ni is 50%, mol ratio；Concrete preparation method is by Na2CO3, NiO, TiO2, Mn2O3After being sufficiently mixed, roll in bulk, form through high-temperature calcination.Material used in the present invention is all commercially available gained, easy and simple to handle, production cost is low, stable electrochemical property, it is simple to large-scale industrial production.Especially, using one-step calcination method in the present invention, synthetic method is simple, can effectively improve structural purity and the structural stability of ternary material.

Description

A kind of sodium-ion battery high nickel content ternary material and preparation method thereof
Technical field
The present invention relates to sodium-ion battery field, particularly relate to a kind of sodium-ion battery high nickel content ternary material and Preparation method.
Background technology
At present, electrochmical power source is increasingly subject to people's attention.Compared with traditional lithium ion battery, sodium-ion battery because of It has that cost of material is low, fast charging and discharging, continue to use existing operation, the feature such as environmentally friendly, becomes focus of concern. In sodium-ion battery, positive electrode decides the main performance of battery.How to seek one can accommodate sodium ion embed/de- The positive electrode gone out, is to improve sodium-ion battery chemical property, security performance and the important research direction promoting it to develop.
In the positive electrode that can accommodate sodium ion intercalation/deintercalation, sodium-ion battery ternary material stratiform ternary gold Belong to oxide NaTMO2(TM=Ni, Co, Mn, Fe, Cr and other transition metal) due to embedding/de-ability of its high sodium ion, The advantages such as safety is good, with low cost, stable cycle performance, non-environmental-pollution are it is considered to be a kind of most have the new of application prospect Type positive electrode, enjoys researcher to pay close attention to.
In prior art, the method for modifying to ternary material mainly has doping and cladding, by adulterating or being coated with different Transition metal ions is blended in Ni layer, and the metal-oxide system forming a series of sodium binary, ternary and quaternary improves The electric conductivity of material and stability, thus improve the chemical property of battery.
Chinese patent CN105226268A is prepared for the sodium ion positive electrode of ternary layered structure by solid-phase synthesis, Na2/3Ni1/3TixMn2/3-xO2, wherein 0 < X < 2/3.By utilizing the cooperative effect of different metal ion so that sodium ion positive pole Material has higher cycle performance of battery relative to single stratiform transition metal oxide, when 0.1C discharge and recharge, and electric discharge ratio Capacity > 120mAhg-1, capability retention is 90%.But the Ni's in the sodium ion positive electrode of its ternary layered structure prepared Content is only 20%(mol ratio).It is known that the existence of Ni is favorably improved the reversible embedding sodium capacity of material, but too much Ni2+ Again can because of with Na+Inconsistent phenomenon is occurred to cause the cycle performance of material to be deteriorated.So in sodium-ion battery ternary material, How to guarantee the structural stability of ternary material while improving Ni content, being one has a technical difficult problem to be solved.
Summary of the invention
It is an object of the invention to provide a kind of sodium-ion battery high nickel content ternary material and preparation method thereof.By this The tertiary cathode material Stability Analysis of Structures that preparation method is produced, simple to operate.The present invention is by with Ti4+Replace the Mn of part4+ And the content improving Ni forms a kind of novel ternary material.The Ti of doping4+Na can be effectively improved+Diffusion rate, thus subtract Irreversible capacity loss, and the raising of Ni content less contributes to increasing the reversible embedding sodium capacity of material.Electricity at 2.0-4.0V In nip, Ni2+Participate in chemical reaction and form Ni4+So that it is discharge platform extends, and provides extra electric discharge for ternary material Specific capacity.And other metal ions M n4+And Ti4+It is not involved in chemical reaction, so that it is guaranteed that the structure of prepared ternary material is steady Qualitative.The raising of Ni content and Ni2+Appraise at the current rate so that first week discharge capacity, the coulombic efficiency in first week and the cycle performance of material Significantly improve.Under the electric current density of 0.2C, the specific discharge capacity in its first week > 130mAhg-1, after circulating 50 weeks, its capacity Conservation rate is more than 90%.
A kind of sodium-ion battery high nickel content ternary material that the present invention provides, its chemical general formula is NaNi0.5Mn0.5- xTixO2(0 < x < 0.5), the content of its Ni is 50%(mol ratio).Described ternary composite cathode material specifically prepare be by Na2CO3, NiO, TiO2, Mn2O3After being sufficiently mixed, roll in bulk, form through high-temperature calcination.
The preparation method of a kind of sodium-ion battery high nickel content ternary material that the present invention provides comprises the steps:
1) by metering (sodium atom, nickle atom, manganese atom, the atomic molar ratio of titanium atom) by Na2CO3, NiO, TiO2, Mn2O3 Joining and carry out ball milling in ball mill, solid phase is sufficiently mixed uniformly.
2) transfer the sample into and Muffle furnace is calcined at 900 DEG C 15h.
4) sample after calcining is before temperature is cooled to 200 DEG C, transfers in hothouse.
5) then sieve by 200-400 mesh sieve.
In above-mentioned preparation method, described ternary precursor Na2CO3, NiO, Mn2O3, TiO2By commercially available acquisition.
Above-mentioned hybrid mode is mixing oxides method.Described calcination is for once to calcine.The atmosphere of calcination is air.
The present invention compared with prior art, has the following characteristics that the tertiary cathode material Stability Analysis of Structures produced, operation Simply.The i.e. present invention is by with Ti4+Replace the Mn of part4+And the content improving Ni forms a kind of novel ternary material Material.The Ti of doping4+Na can be effectively improved+Diffusion rate, thus reduce irreversible capacity loss, and the raising of Ni content helps In the reversible embedding sodium capacity increasing material.In the voltage range of 2.0-4.0V, Ni2+Participate in chemical reaction and form Ni4+So that it is Discharge platform extends, and provides extra specific discharge capacity for ternary material.And other metal ions M n4+And Ti4+It is not involved in Chemical reaction, so that it is guaranteed that the structural stability of prepared ternary material.The raising of Ni content and Ni2+Appraise at the current rate so that material First week discharge capacity, the coulombic efficiency in first week and cycle performance significantly improve.Under the electric current density of 0.2C, putting of its first week Electricity specific capacity > 130mAhg-1, after circulating 50 weeks, its capability retention is more than 90%.Material used in the present invention is equal It is commercially available gained, easy and simple to handle, production cost is low, stable electrochemical property, it is simple to large-scale industrial production.Especially, Using one-step calcination method in the present invention, synthetic method is simple, can effectively improve structural purity and the knot of ternary material Structure stability.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the high nickel content sodium ion trielement composite material prepared by the present invention.
Fig. 2 is the charging and discharging curve of battery of the present invention, and reversible capacity reaches 138mAh/g, and first all coulombic efficiency can reach 96%。
Fig. 3 is the long circulating curve of battery of the present invention, circulates 50 weeks under the electric current density of 0.2C, and its capability retention exists More than 90%.
Fig. 4 is the charging and discharging curve of full battery, at 0.1C(10mA/g) electric current density under, reversible capacity remains able to reach 106mAh/g。
Detailed description of the invention:
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Weigh commercially available (analytical pure) 4.36gNa respectively2CO3, 2.99gNiO, 1.89gMn2O3, 1.28gTiO2Transfer to In 250mL agate jar (QM-3SP2, Nanjing Nanda Instrument Co., Ltd.), it is then attached to 300 revs/min of balls in ball mill Mill 2h, so that it is sufficiently mixed uniformly.
With crucible, mixed sample transferred in Muffle furnace 900 DEG C of calcining 15h (under air atmosphere).Then in temperature Transferring the sample into continuation natural cooling in hothouse before being cooled to 200 DEG C, then sieving by 200 mesh sieve, it is made i.e. to obtain Standby ternary material.
As it is shown in figure 1, prepared high nickel content sodium ion trielement composite material, its XRD spectra and result of calculation phase one Causing, its crystal diffraction peak shows its higher structural purity.
By the ternary material of preparation, superconduction white carbon black and binding agent (PVDF) according to the ratio of 8:1:1 join N-methyl- In 2-Pyrrolidone (NMP) dispersant, after being sufficiently mixed, the slurry of gained is coated on Al paper tinsel, then Al paper tinsel is placed on very In empty drying baker, 120 DEG C are dried.Sample load capacity on Al paper tinsel is about 4.5mg/cm.Metallic sodium is as negative pole.Electrolyte is The NaClO of 1.0moldm-14Solution (the fluoro carbonic acid (FEC) of 5%w is as additive), flux is propylene carbonic acid (PC).Glass Fiber membrane is as barrier film.The half-cell filled and full battery are carried out discharge and recharge research, charging/discharging voltage at ambient temperature Scope is: 1.5V-4.0V.
Shown in Fig. 2 is the charging and discharging curve of battery, and reversible capacity can reach 138mAh/g, first week coulombic efficiency up to To 96%.
Shown in Fig. 3 is the long circulating curve of battery, circulates 50 weeks under the electric current density of 0.2C, and its capability retention exists More than 90%.
Embodiment 2
The ternary material of preparation, superconduction white carbon black are joined N-methyl-2-pyrrole with binding agent (PVDF) according to the ratio of 8:1:1 In pyrrolidone (NMP) dispersant, after being sufficiently mixed, the slurry of gained is coated on Al paper tinsel, then Al paper tinsel is placed on vacuum and does In dry case, 120 DEG C are dried.Sample load capacity on Al paper tinsel is about 4.5mg/cm.Using hard carbon as negative pole, active material on positive pole With the ratio of hard carbon: 1.75:1 on negative pole.Electrolyte is the NaClO of 1.0moldm-14Solution (the fluoro carbonic acid (FEC) of 5%wt As additive), flux is propylene carbonic acid (PC).Glass fiber membrane is as barrier film.The half-cell filled and full battery are existed Carrying out discharge and recharge research under room temperature condition, charging/discharging voltage scope is: 1.5V-4.0V.
Shown in Fig. 4 is the charging and discharging curve of full battery, at 0.1C(10mA/g) electric current density under, reversible capacity is still 106mAh/g can be reached.

Claims (4)

1. a sodium-ion battery high nickel content ternary material, it is characterised in that its chemical general formula is NaNi0.5Mn0.5-xTixO2 (0 < x < 0.5), the content of its Ni is 50%, mol ratio；Concrete preparation method is by Na2CO3, NiO, TiO2, Mn2O3It is sufficiently mixed After, roll in bulk, form through high-temperature calcination.
2. the preparation method of high nickel content ternary material of the sodium-ion battery described in claim 1, it is characterised in that include as Lower step:
1) pressing sodium atom, nickle atom, manganese atom, the atomic molar of titanium atom is than metering, by Na2CO3, NiO, Mn2O3, TiO2Add Entering in ball mill, solid phase is sufficiently mixed uniformly；
2) sample well-mixed in step 1) is transferred to calcine at 900 DEG C in Muffle furnace 15h；
4) sample after calcining is before temperature is cooled to 200 DEG C, transfers to natural cooling in hothouse；
5) then sieve by 200-400 mesh sieve.
3. according to the preparation method described in claim 2, it is characterised in that described calcination is for once to calcine；The atmosphere of calcination is Air.
4. according to the preparation method described in claim 2, it is characterised in that ball milling condition is: ball milling speed be 100-600 turn/ Point；Ball-milling Time is 0.5-12h.
CN201610614440.5A 2016-08-01 2016-08-01 A kind of sodium-ion battery high nickel content ternary material and preparation method thereof Pending CN106252645A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673075A (en) * 2017-01-03 2017-05-17 中国科学院化学研究所 Modified O3 type layered cathode material of sodium-ion battery, and preparation method and application thereof
CN106853996A (en) * 2016-12-26 2017-06-16 武汉理工大学 A kind of method of the porous micro-nano structure material of the manganese sesquioxide managnic oxide for preparing morphology controllable
CN108899538A (en) * 2018-07-19 2018-11-27 东北大学秦皇岛分校 A kind of ternary sodium-ion battery positive material, preparation method and sodium-ion battery
CN115057485A (en) * 2022-06-17 2022-09-16 中国科学技术大学 Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101065867A (en) * 2004-11-26 2007-10-31 住友化学株式会社 Positive electrode active material for nonaqueous electrolyte secondary battery
CN104428253A (en) * 2012-07-10 2015-03-18 法拉典有限公司 Doped nickelate compounds
WO2016103649A1 (en) * 2014-12-23 2016-06-30 Sharp Kabushiki Kaisha Layered oxide materials for batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101065867A (en) * 2004-11-26 2007-10-31 住友化学株式会社 Positive electrode active material for nonaqueous electrolyte secondary battery
CN104428253A (en) * 2012-07-10 2015-03-18 法拉典有限公司 Doped nickelate compounds
WO2016103649A1 (en) * 2014-12-23 2016-06-30 Sharp Kabushiki Kaisha Layered oxide materials for batteries

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106853996A (en) * 2016-12-26 2017-06-16 武汉理工大学 A kind of method of the porous micro-nano structure material of the manganese sesquioxide managnic oxide for preparing morphology controllable
CN106853996B (en) * 2016-12-26 2019-05-24 武汉理工大学 A method of preparing the porous micro-nano structure material of manganese sesquioxide managnic oxide of morphology controllable
CN106673075A (en) * 2017-01-03 2017-05-17 中国科学院化学研究所 Modified O3 type layered cathode material of sodium-ion battery, and preparation method and application thereof
CN106673075B (en) * 2017-01-03 2019-05-21 中国科学院化学研究所 A kind of modified O3 type sodium-ion battery layered cathode material and its preparation method and application
CN108899538A (en) * 2018-07-19 2018-11-27 东北大学秦皇岛分校 A kind of ternary sodium-ion battery positive material, preparation method and sodium-ion battery
CN115057485A (en) * 2022-06-17 2022-09-16 中国科学技术大学 Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof

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Application publication date: 20161221