CN109346717A - A kind of self-supporting NaxMnO2Array sodium-ion battery positive material and preparation method thereof - Google Patents

A kind of self-supporting NaxMnO2Array sodium-ion battery positive material and preparation method thereof Download PDF

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Publication number
CN109346717A
CN109346717A CN201811056777.4A CN201811056777A CN109346717A CN 109346717 A CN109346717 A CN 109346717A CN 201811056777 A CN201811056777 A CN 201811056777A CN 109346717 A CN109346717 A CN 109346717A
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mno
sodium
array
ion battery
battery positive
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CN109346717B (en
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高林
陈思
杨学林
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China Three Gorges University CTGU
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of Na of self-supportingxMnO2The preparation method of (0 < x≤1) array.NaxMnO2Nanometer sheet width is 1~2 μm, and with a thickness of 4~8 μm, unit area active matter quality is about 1.0~1.5mgcm on nickel screen‑2.The NaxMnO2Sodium ion battery electrode material is using two oxalic acid hydrates, potassium permanganate as presoma, the Mn that calcines in air after ultrasonic treatment2O3Nano-array.Na in order to obtainxMnO2Array, by Mn obtained above2O3Array, which is placed in the sodium hydroxide of high concentration, carries out hydro-thermal reaction, and then annealing obtains Na in airxMnO2Array.With NaxMnO2The sodium-ion battery that positive electrode is assembled into has excellent high rate performance and cycle performance, has 82mAh g under 6C current density‑1Specific capacity, circulation 500 times after its capacity retention ratio be 87.8%.By NaxMnO2The sodium ion half-cell stable cycle performance that positive plate is assembled into, has potential application in sodium-ion battery.

Description

A kind of self-supporting NaxMnO2Array sodium-ion battery positive material and preparation method thereof
Technical field
The present invention relates to a kind of novel self-supporting nano-array sodium-ion battery material, in particular to a kind of laminated structures NaxMnO2The preparation method of nano-chip arrays material belongs to sodium-ion battery field.
Technical background
With the development of current energy storage device, lithium ion battery energy storage device starts to play in our daily life More and more important role.Current lithium ion battery is mainly applied to such as mobile phone, digital camera, notebook portable electronic Application in product, and in terms of Large-sized Communication transporting equipment such as electric vehicle still suffers from one of many difficulties, challenge therein It is cost problem.Since lithium resource reserves are limited on the earth, and lithium is the indispensable raw material of lithium ion battery, therefore cost is asked The main reason for topic is limiting lithium ion cell large-scale application.The reserves of sodium element on earth are studied far more than lithium Sodium-ion battery applies the cost problem for solving lithium ion battery to be of great significance.Recently, NaxMnO2(0 x≤1 <) is made Start to enter into the visual field of researcher, environment friend high with energy density for a kind of novel sodium-ion battery positive material The advantages of good and abundant raw materials, there are great potential using values.But the Na currently reportedxMnO2Material only limits to In dusty material, and correlative study is fairly limited, about NaxMnO2The correlative study of array material is rarely reported, therefore right NaxMnO2Sodium ion anode array material carries out further investigation and is of great significance.Invention is a kind of to prepare self-supporting NaxMnO2The method of nano-array, while this array material contacts closely with Ni substrate, being assembled into sodium-ion battery has Stable chemical property, there are great potential using values.
Summary of the invention
It is an object of the invention to using nickel foam as substrate, be burnt by ultrasound using two oxalic acid hydrates, potassium permanganate as raw material Knot process prepares Mn2O3Array, then by the NaOH of high concentration to Mn2O3Array carries out sodium ion processing and annealing Prepare NaxMnO2(0 x≤1 <) nano-chip arrays.Raw material according to the present invention is two oxalic acid hydrates, potassium permanganate, hydrogen-oxygen Change sodium.A certain amount of two oxalic acid hydrate is first weighed in material preparation process in beaker, and a certain amount of deionized water is added and holds Continuous stir to it is completely dissolved.Then it will be placed in ultrasound 10-30min in the above solution except the clean nickel foam of oxide layer, with After weigh a certain amount of potassium permanganate and be dissolved in deionized water, and it is quickly instilled in the oxalic acid solution equipped with nickel foam and continues to surpass Sound 30-40min becomes milky to solution.Then nickel foam is taken out and is quickly moved back for directly in air 300~400 DEG C after drying Fiery 2-5h obtains Mn2O3Array.By Mn2O3Array is placed in 1~3M NaOH solution hydro-thermal reaction 6- under the conditions of 80-150 DEG C 24h.The above nano-chip arrays are finally placed directly within 600~700 DEG C of annealing 2-10h in air, obtain NaxMnO2Nanometer sheet battle array Column.
The Ni-based Na of foam prepared by the present inventionxMnO2Nano-chip arrays sodium-ion battery positive material preparation method have with Lower feature:
(1) preparation cost of the present invention is cheap, and synthesis technology is simple, easily operated.
(2) Na that the present invention synthesizesxMnO2Adhesive ability of the array material on base material is good, places it in deionization Prolonged ultrasound is carried out in water to fall off almost without active material.
(3) Na being preparedxMnO2Nanometer sheet width is 1~2 μm, with a thickness of 4~8 μm, this NaxMnO2Nanometer sheet Array has layered multi-stage structure.
(4) Na of this nanoscale arrays structurexMnO2It is anti-that the phase transformation generated in its charge and discharge process can be effectively relieved It answers, so that NaxMnO2Sodium-ion battery positive material has stable electrochemistry cycle performance.
Detailed description of the invention
Fig. 1 is the SEM figure of sample prepared by embodiment 1.
Fig. 2 is the XRD diagram of sample prepared by embodiment 1.
Fig. 3 is the TEM figure of sample prepared by embodiment 1.
Fig. 4 is the corresponding cycle performance figure (a) of 1 sample of embodiment, high rate performance figure (b), charge-discharge performance figure (c) and follows Ring voltammogram (d).
Fig. 5 is the SEM figure of sample prepared by embodiment 2.
Fig. 6 is the charge-discharge performance figure of sample prepared by embodiment 2.
Specific embodiment
Embodiment 1
By nickel foam (2 × 4cm2) it is placed in the two oxalic acid hydrate (H that 100mL concentration is 0.5M2C2O4·2H2O ultrasonic in) 10min.Then the liquor potassic permanganate that 50mL concentration is 0.1M is slowly dropped into the above solution and 30min is sufficiently stirred.Finally Nickel foam is taken out and 350 DEG C of annealing 2h obtain Mn in air atmosphere2O3Nano-array.Wherein nickel foam is leaned to 60 ° of angles In water heating kettle.It is to dry after keeping 10h at 120 DEG C in 2M NaOH solution that array after reaction, which is placed in concentration, then will It is placed in air the 3h that anneals at 600 DEG C and obtains Na0.7MnO2Nano-chip arrays.Fig. 1 is the Na being prepared0.7MnO2Nanometer The SEM of chip arrays schemes, it can be seen that Na0.7MnO2(x=0.7) nanometer sheet is evenly distributed within sweep of the eye, the average width of nanometer sheet Degree is 1 μm.Fig. 2 is the Na being prepared0.7MnO2The XRD spectrum of nano-chip arrays.It can be seen that in addition to Ni characteristic peak it Outside, remaining XRD characteristic peak respectively with Na0.7MnO2(JCPDS No.27-0752) card is consistent.Fig. 3 is corresponding single Na0.7MnO2The TEM of nanometer sheet schemes, it can be seen that it is with apparent layered multi-stage structure.It assembles them into as half electricity of sodium ion Pond, in 0.5C (1C=125mA g-1) voltage window is 2.0~3.8V (vs Na/Na under multiplying power+) when initial specific capacities be up to 144.0mAh g-1.Still there is 114.1mAh g after 374 circle charge-discharge tests-1Specific capacity (Fig. 4 a), average coulombic Efficiency is up to 95.7%.To Na0.7MnO2Half-cell carries out high rate performance test, it is found that it still has height under 0.25C multiplying power Up to 155.4mAh g-1Specific capacity.Even if in the big multiplying power of 60C, Na0.7MnO2Half-cell still has 63.6mAh g-1Specific capacity (Fig. 4 b).According to Na0.7MnO2Half-cell is 0.1mV s sweeping speed-1When cyclic voltammogram can see it Without there are apparent redox peaks between 2.0~3.0V, main redox peaks are appeared between 3.0~3.8V. Average discharge volt is about 3.3V, illustrates that this nano array structure helps to inhibit Mn3+Reaction, be conducive to NaxMnO2Electricity The promotion of the electrochemical stability of pole provides new thinking to improve sodium-ion battery positive material chemical property.
Embodiment 2
By nickel foam (2 × 4cm2) it is placed in the two oxalic acid hydrate (H that 100mL concentration is 0.5M2C2O4·2H2O ultrasonic in) 10min.Then the liquor potassic permanganate that 50mL concentration is 0.1M is slowly dropped into the above solution and 30min is sufficiently stirred.Finally Nickel foam is taken out and 350 DEG C of annealing 2h obtain Mn in air atmosphere2O3Nano-array.Wherein nickel foam is leaned to 60 ° of angles In water heating kettle.It is to dry after keeping 10h at 80 DEG C in 2M NaOH solution that array after reaction, which is placed in concentration, then will It is placed in air the 3h that anneals at 600 DEG C and obtains Na0.7MnO2Nano-chip arrays.Fig. 5 is the SEM figure that array is prepared, It can be seen that this nanometer sheet is evenly distributed within sweep of the eye, nanometer sheet mean breadth is about 0.5 μm.It assembles them into as sodium Ion half-cell does not see apparent NaxMnO2Charging/discharging voltage platform (Fig. 6).This is because in NaOH treatment process The reason of hydrothermal temperature too low (80 DEG C).Typical case can be prepared in discovery after NaOH hydro-thermal process temperature is increased to 120 DEG C NaxMnO2Sodium-ion battery positive material illustrates the reaction temperature during sodium ion for synthesizing NaxMnO2Positive material Material has great influence.

Claims (9)

1. a kind of self-supporting NaxMnO2Array sodium-ion battery positive material, it is characterised in that: the NaxMnO2For nanometer sheet Structure, the nanometer sheet diameter are 1~2 μm, with a thickness of 4~8 μm, (0 x≤1 <).
2. self-supporting Na described in claim 1xMnO2Array sodium-ion battery positive material, it is characterised in that: NaxMnO2Array Material activity material mass is 1~2mg cm-2。
3. self-supporting Na described in claim 1xMnO2Array sodium-ion battery positive material, it is characterised in that: NaxMnO2Array The structure of material is Na0.7MnO2, crystal form is rhombic system P2-Na0.7MnO2。
4. the described in any item self-supporting Na of claim 1-3xMnO2The preparation method of array sodium-ion battery positive material, It is characterized in that:
(1) it two oxalic acid hydrates is weighed is dissolved in deionized water and form uniform solution, nickel screen or nickel foam are immersed ultrasound 10~20min；
(2) by KMnO4The solution in (1) is added in solution, takes out nickel screen or nickel foam from solution after ultrasonic 25-35min, to It makes annealing treatment in air atmosphere after drying and obtains presoma Mn2O3Nano-chip arrays；
(3) sodium hydroxide solution is transferred in water heating kettle liner, by Mn2O3Nano-chip arrays, which are placed in hydro-thermal liner, carries out water Thermal response takes out drying after natural cooling, and the above nano-array is finally placed directly within annealing under air atmosphere and is obtained NaxMnO2Positive electrode.
5. Na as claimed in claim 4xMnO2The preparation method of sodium-ion battery positive material, it is characterised in that: in step (1) Two oxalic acid hydrate (H2C2O4·2H2) and potassium permanganate (KMnO O4) molar ratio be 3.0~5.0:1.0~2.0.
6. Na as claimed in claim 4xMnO2The preparation method of sodium-ion battery positive material, it is characterised in that: in step (3) Hydrothermal temperature be 80-150 DEG C, the hydro-thermal reaction time be 6~for 24 hours.
7. Na as claimed in claim 4xMnO2The preparation method of sodium-ion battery positive material, it is characterised in that: in step (2) Annealing is in air with temperature for 300-400 DEG C, and anneal 2~5h.
8. Na as claimed in claim 4xMnO2The preparation method of sodium-ion battery positive material, it is characterised in that: in step (3) The molar concentration of sodium hydroxide solution is 1-3M, and annealing is in air with temperature for 600~700 DEG C, and anneal 2~10h.
9. the described in any item Na of claim 1-3xMnO2Array material can be applied to sodium-ion battery positive material.
CN201811056777.4A 2018-09-11 2018-09-11 Self-supporting NaxMnO2Array sodium-ion battery positive electrode material and preparation method thereof Active CN109346717B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111592045A (en) * 2020-05-11 2020-08-28 三峡大学 Potassium manganate potassium ion battery anode material
CN112299493A (en) * 2019-07-26 2021-02-02 南京理工大学 Ni-doped delta-MnO2Material preparation method and application thereof in potassium ion battery
CN112830521A (en) * 2019-11-22 2021-05-25 南京理工大学 F-doped P2-Na0.7MnO2Electrode material and preparation method thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102568855A (en) * 2012-03-12 2012-07-11 重庆大学 Carbon material-loading manganese dioxide nanowire array composite and method for producing same
CN107827165A (en) * 2017-10-20 2018-03-23 三峡大学 A kind of sodium cobalt/cobalt oxide sodium-ion battery positive material and preparation method thereof

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102568855A (en) * 2012-03-12 2012-07-11 重庆大学 Carbon material-loading manganese dioxide nanowire array composite and method for producing same
CN107827165A (en) * 2017-10-20 2018-03-23 三峡大学 A kind of sodium cobalt/cobalt oxide sodium-ion battery positive material and preparation method thereof

Non-Patent Citations (1)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112299493A (en) * 2019-07-26 2021-02-02 南京理工大学 Ni-doped delta-MnO2Material preparation method and application thereof in potassium ion battery
CN112299493B (en) * 2019-07-26 2023-03-31 南京理工大学 Ni-doped delta-MnO 2 Material preparation method and application thereof in potassium ion battery
CN112830521A (en) * 2019-11-22 2021-05-25 南京理工大学 F-doped P2-Na0.7MnO2Electrode material and preparation method thereof
CN112830521B (en) * 2019-11-22 2022-03-15 南京理工大学 F-doped P2-Na0.7MnO2Electrode material and preparation method thereof
CN111592045A (en) * 2020-05-11 2020-08-28 三峡大学 Potassium manganate potassium ion battery anode material
CN111592045B (en) * 2020-05-11 2022-09-16 三峡大学 Potassium manganate potassium ion battery anode material

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