CN108288701A - A kind of sodium-ion battery anode composite diphase material - Google Patents

A kind of sodium-ion battery anode composite diphase material Download PDF

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CN108288701A
CN108288701A CN201810074725.3A CN201810074725A CN108288701A CN 108288701 A CN108288701 A CN 108288701A CN 201810074725 A CN201810074725 A CN 201810074725A CN 108288701 A CN108288701 A CN 108288701A
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sodium
nav
ion battery
ratio
battery anode
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CN108288701B (en
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赵萍
庄会峰
高敏
李卓辉
刘继发
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Qilu University of Technology
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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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 anode composite diphase material Na1.1V3O7.9/NaV6O15, which is to prepare persursor material VO using adjusting hydrothermal temperature2And mixed with NaOH according to certain proportioning, complex phase target material Na is made after Overheating Treatment1.1V3O7.9/NaV6O15, with excellent chemical property when the composite electrode material is as sodium-ion battery anode.

Description

A kind of sodium-ion battery anode composite diphase material
Technical field
The present invention relates to a kind of sodium-ion battery anode composite diphase material Na with good chemical property1.1V3O7.9/ NaV6O15, belong to sodium-ion battery positive material technical field.
Background technology
Sodium element is in same main group with elemental lithium, has similar physicochemical properties, while sodium element has the whole world Rich reserves, the advantages such as widely distributed, extraction is simple.Research conditions in recent years show that sodium-ion battery has and lithium ion The similar chemical property of battery, therefore, sodium-ion battery are also considered as having very much a kind of potential novel energy storage cell System carries out the research work of sodium-ion battery to maintaining the sustainable development of the energy to be extremely important.With lithium from Sub- battery is similar, major problem is that cell positive material still cannot be satisfied, high energy is powerful to be wanted sodium-ion battery at present It asks.At low cost, the vanadium sub-group compound material of height ratio capacity becomes the hot spot of research sodium-ion battery.Vanadic acid salt material has height Capacity, low cost, the advantages that being easily-synthesized, there is good application prospect in fields such as sodium-ion batteries.But vanadium system positive electrode follows Ring stability and high rate performance difference are the main problem faced at present.Na1.1V3O7.9Belong to monoclinic system, 21/m space groups Lamellar compound, Na+The octahedral interstices position of interlayer is occupied, the activation energy of the position is higher.Na1.1V3O7.9For Li/Na from Sub- secondary battery positive electrode material, by the way that oxidation occurs with ion, reduction reaction carries out the insertion and abjection of ion, has higher Specific capacity, current research are mainly nanosizing and structure composite by scantling to improve its cyclical stability. NaV6O15Belong to A2/m（12）Space group a=10.07, b=3.61, c=15.38, while possessing sodium ion migration can be provided Three-dimensional channel structure, by [the VO on total side6] octahedron formation zigzag chain, zigzag chain is made up of concurrent connection flat again Face.[VO5] quadrangular pyramid is arranged in face in a manner of a kind of distortion, with [VO6] octahedral layer forms channel design together, inside Lithium/sodium ion can then be filled.NaV6O15The chemical valence of middle v element is+4.83, close to its highest valence state（+5）.V4+/V5+ Mixed valence make it have very high electronic conductance and chemical reactivity.Targetedly electrode material pattern is modified and is mixed Miscellaneous is the effective means for being promoted specific capacity, cycle performance and high rate performance.The invention mainly relates to composite electrode material Na1.1V3O7.9/NaV6O15, show excellent chemical property when as sodium-ion battery anode.
Invention content
Mainly for the problem of vanadium system positive electrode stable circulation performance difference, the present invention adjusts hydrothermal temperature and prepares presoma VO2And mixed with NaOH according to certain proportioning, complex phase target material Na is made after Overheating Treatment1.1V3O7.9/NaV6O15, should With excellent chemical property when material is as sodium-ion battery anode.
Specific solution is：
（1）By a certain amount of V2O5（Molecular weight 181.88, analysis it is pure), oxalic acid, distilled water in mass ratio 1：1：30 ratio is matched It is poured into ptfe autoclave after stirring 2h at suspension and at 80 DEG C, fill volume control adjusts hydro-thermal temperature 80% 160 ~ 200 DEG C of degree is simultaneously kept the temperature for 24 hours, collects black-and-blue precipitation, required persursor material VO is obtained after washed drying2。
（2）It will（1）In a certain amount of persursor material VO2, NaOH, ethyl alcohol in mass ratio 1：0.16：100 ratio is made into Suspension stirs at 80 DEG C makes ethyl alcohol volatilization be evaporated, and finally collection powder calcines 8h at 450 DEG C and obtains target material Na1.1V3O7.9/NaV6O15。
（3）By the target material Na prepared by a certain amount of above-mentioned (2)1.1V3O7.9/NaV6O15, acetylene black, Kynoar （PVDF）In mass ratio 8：1：1 ratio is fully ground mixing, and N-Methyl pyrrolidone solvent is added, glue is obtained after stirring evenly Watery precoating refines slurries.
（4）It will be above-mentioned（3）Prepared precoating refines slurries and is coated on aluminium foil, true through 130 DEG C dry 0.5h and 110 DEG C Sky dries 12h, is cut into the disk of diameter 12mm after natural cooling using sheet-punching machine, that is, sodium-ion battery anode electrode piece is made.
（5）According to anode cover-electrode slice-electrolyte-diaphragm-electrolyte-sodium piece-gasket-shrapnel-negative electrode casing sequence according to Secondary assembly recycles sealing machine by cell sealing, you can CR2032 type button half-cells are made.
（6）With CT-3008W-5V-10mA-S4 type charge and discharge instrument, charging/discharging voltage is 1.5 ~ 4.0V and 300mAg-1Electric current Charge-discharge test is carried out to battery under density.
The present invention remarkable advantage be：
（1）Utilize V2O5, oxalic acid, NaOH be initial feed, material is cheap and easy to get, reduces production cost.
（2）Composite electrode material Na1.1V3O7.9/NaV6O15It is simple to operation with production process, it can advise greatly Mould industrialized production.
（3）Composite electrode material Na1.1V3O7.9/NaV6O15When as sodium-ion battery positive material, volumetric properties follow Ring performance is better than single-phase Na1.1V3O7.9With single-phase NaV6O15。
Description of the drawings：
Fig. 1 is composite electrode material Na in the present invention1.1V3O7.9/NaV6O15X ray diffracting spectrum, represent NaV in figure6O15 Peak, represent Na1.1V3O7.9Peak, it is consistent with the standard spectrogram of the two.
Fig. 2 is composite electrode material Na in the embodiment of the present invention 21.1V3O7.9/NaV6O15When as sodium-ion battery anode In 300mAg-1Current density under electrochemistry cycle performance figure, wherein ordinate be specific capacity, abscissa is cycle-index.
Specific implementation method：
Embodiment 1：
（1）By a certain amount of V2O5（Molecular weight 181.88, analysis it is pure), oxalic acid, distilled water in mass ratio 1：1：30 ratio is matched It is poured into ptfe autoclave after stirring 2h at suspension and at 80 DEG C, fill volume control adjusts hydro-thermal temperature 80% 160 DEG C of degree is simultaneously kept the temperature for 24 hours, collects black-and-blue precipitation, required persursor material VO is obtained after washed drying2。
（2）It will（1）In a certain amount of persursor material VO2, NaOH, ethyl alcohol（Mass ratio 1：0.16：100）It is made into suspension Stirring makes ethyl alcohol volatilization be evaporated at 80 DEG C, and finally collection powder calcines 8h at 450 DEG C and obtains target material Na1.1V3O7.9/ NaV6O15。
Above-mentioned synthetic material is 1.5 ~ 4.0V and 300mAg in charging/discharging voltage-1Under current density, first discharge specific capacity For 70mAhg-1, the specific discharge capacity after recycling 100 times is 61mAhg-1, embody excellent cycle performance.
Embodiment 2：
（1）By a certain amount of V2O5（Molecular weight 181.88, analysis it is pure), oxalic acid, distilled water in mass ratio 1：1：30 ratio is matched It is poured into ptfe autoclave after stirring 2h at suspension and at 80 DEG C, fill volume control adjusts hydro-thermal temperature 80% 180 DEG C of degree is simultaneously kept the temperature for 24 hours, collects black-and-blue precipitation, required persursor material VO is obtained after washed drying2。
（2）It will（1）In a certain amount of persursor material VO2, NaOH, ethyl alcohol（Mass ratio 1：0.16：100）It is made into suspension Stirring makes ethyl alcohol volatilization be evaporated at 80 DEG C, and finally collection powder calcines 8h at 450 DEG C and obtains target material Na1.1V3O7.9/ NaV6O15。
Above-mentioned synthetic material is 1.5 ~ 4.0V and 300mAg in charging/discharging voltage-1Under current density, first discharge specific capacity For 97mAhg-1, the specific discharge capacity after recycling 1000 times is 107mAhg-1.Show excellent cycle performance with it is higher Specific capacity, chemical property are as shown in Figure 2.
Embodiment 3：
（1）By a certain amount of V2O5（Molecular weight 181.88, analysis it is pure), oxalic acid, distilled water in mass ratio 1：1：30 ratio is matched It is poured into ptfe autoclave after stirring 2h at suspension and at 80 DEG C, fill volume control adjusts hydro-thermal temperature 80% 200 DEG C of degree is simultaneously kept the temperature for 24 hours, collects black-and-blue precipitation, required persursor material VO is obtained after washed drying2。
（2）It will（1）In a certain amount of persursor material VO2, NaOH, ethyl alcohol（Mass ratio 1：0.16：100）It is made into suspension Stirring makes ethyl alcohol volatilization be evaporated at 80 DEG C, and finally collection powder calcines 8h at 450 DEG C and obtains target material Na1.1V3O7.9/ NaV6O15。
Above-mentioned synthetic material is 1.5 ~ 4.0V and 300mAg in charging/discharging voltage-1Under current density, first discharge specific capacity For 163mAhg-1, the specific discharge capacity after recycling 100 times is 104mAhg-1, embody higher specific capacity.

Claims (2)

1. preparing presoma VO by adjusting hydrothermal temperature using hydro-thermal method2It is characterized in that, by a certain amount of V2O5（Molecular weight 181.88, analysis it is pure), oxalic acid, distilled water in mass ratio 1：1：30 ratio is made into suspension and is fallen after stirring 2h at 80 DEG C Enter in ptfe autoclave, fill volume control adjusts 160 ~ 200 DEG C of hydrothermal temperature and keep the temperature for 24 hours, collect blue 80% Black precipitate obtains required persursor material VO after washed drying2。
2. utilizing persursor material VO2Through being simply thermally treated resulting in complex phase target material Na after being mixed with NaOH1.1V3O7.9/ NaV6O15, which is characterized in that by a certain amount of presoma VO in above-mentioned 12, NaOH, ethyl alcohol in mass ratio 1：0.16：100 ratio Example, which is made into suspension and is stirred at 80 DEG C, makes ethyl alcohol volatilization be evaporated, and finally collection powder calcines 8h at 450 DEG C and obtains complex phase electricity Pole material Na1.1V3O7.9/NaV6O15。
CN201810074725.3A 2018-01-25 2018-01-25 Sodium ion battery positive electrode complex phase material Active CN108288701B (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN109626425A (en) * 2019-02-25 2019-04-16 上海海事大学 A kind of nanometer of threadiness Na1.1V3O7.9Material, preparation method and the usage
CN110467221A (en) * 2019-09-17 2019-11-19 安徽建筑大学 A kind of NaV6O15The preparation method of film and NaV obtained6O15Film
CN110729474A (en) * 2019-10-24 2020-01-24 成都先进金属材料产业技术研究院有限公司 NaV preparation by using failure vanadium battery electrolyte6O15Method for preparing sodium ion battery electrode material
CN111153436A (en) * 2019-12-31 2020-05-15 中国地质大学（武汉） Self-assembly NaV6O15Nanosheet microsphere and preparation method and application thereof
CN114956171A (en) * 2021-02-24 2022-08-30 陕西则明未来科技有限公司 Preparation and application of sodium-vanadium-oxygen heterojunction material

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626425A (en) * 2019-02-25 2019-04-16 上海海事大学 A kind of nanometer of threadiness Na1.1V3O7.9Material, preparation method and the usage
CN109626425B (en) * 2019-02-25 2021-02-02 上海海事大学 Nano linear Na1.1V3O7.9Material, method for the production thereof and use thereof
CN110467221A (en) * 2019-09-17 2019-11-19 安徽建筑大学 A kind of NaV6O15The preparation method of film and NaV obtained6O15Film
CN110729474A (en) * 2019-10-24 2020-01-24 成都先进金属材料产业技术研究院有限公司 NaV preparation by using failure vanadium battery electrolyte6O15Method for preparing sodium ion battery electrode material
CN111153436A (en) * 2019-12-31 2020-05-15 中国地质大学（武汉） Self-assembly NaV6O15Nanosheet microsphere and preparation method and application thereof
CN114956171A (en) * 2021-02-24 2022-08-30 陕西则明未来科技有限公司 Preparation and application of sodium-vanadium-oxygen heterojunction material

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