CN105244503A - Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material - Google Patents

Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material Download PDF

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Publication number
CN105244503A
CN105244503A CN201510773577.0A CN201510773577A CN105244503A CN 105244503 A CN105244503 A CN 105244503A CN 201510773577 A CN201510773577 A CN 201510773577A CN 105244503 A CN105244503 A CN 105244503A
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China
Prior art keywords
graphene
electrode material
sodium
ion battery
raw materials
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CN201510773577.0A
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Chinese (zh)
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曹余良
方永进
艾新平
杨汉西
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Wuhan University WHU
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Wuhan University WHU
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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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 invention discloses a method for preparing a graphene-grading-modification spherical sodium-ion battery electrode material. The method includes the steps that reaction raw materials and graphene oxide are mixed, and graded-graphene-modified microspheres (three-dimensional graphene supporting and material surface graphene wrapping) are obtained through spraying drying and high-temperature roasting. The microspheres serve as the sodium-ion battery electrode material and show quite excellent electrochemical performance. According to the method, the synthesis cycle is short, the raw materials are low in price, the technology is simple, control is easy, and remarkable practical value and good application prospects are achieved.

Description

A kind of preparation method of spherical sodium ion battery electrode material of classification graphene modified
Technical field
The present invention relates to a kind of preparation method of spherical sodium ion battery electrode material of classification graphene modified, belong to energy and material and technical field.
Background technology
Sodium-ion battery, owing to having with low cost, the feature such as environmental friendliness, aboundresources, becomes the study hotspot in extensive energy storage field gradually.In recent years, many research of storage sodium electrode material, has shown certain storage sodium capacity and cycle performance.Carrying out conductive carbon to electrode material coated, is a kind of effective ways improving battery performance.Graphene has the conductivity of superelevation, above the modification being widely used in battery material.Meanwhile, improve the size of electrode material, effectively can improve the volumetric specific energy of electrode material.
The present invention, by spray-dired method, by high-temperature process, obtains the sphere material of the graphene modified of classification.The method both can well improve the conductivity of material, greatly improved the chemical property of material, also improved the tap density of material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of sodium-ion battery positive material of graphene modified, and the method greatly improves the chemical property of material, also improves the tap density of material.
Technical solution of the present invention is:
Sodium ion battery electrode material is vanadium phosphate sodium or titanium phosphate sodium, and its reaction raw materials is corresponding phosphorus source, vanadium source, sodium source or phosphorus source, titanium source, sodium source; With reaction raw materials and graphene oxide mixing, the quality of graphene oxide is the 5%-50% of resulting materials, spherical forerunner is formed by spraying dry, then high-temperature calcination 6 ~ 12 hours, realize the crystallization of electrode material and the reduction of graphene oxide, thus obtain the spherical sodium ion battery electrode material of classification graphene modified.
The electrode material of conventional method and Graphene compound gained, just simple physics compound.And in this method thus obtained microsphere, Graphene plays three-dimensional supporting role and forms three-dimensional conductive network, material surface is by graphene coated simultaneously.The support of the graphene conductive network of this classification be connected, electronics transmission in the electrodes will be improved greatly, improves the chemical property of material greatly.As Fig. 4, gained vanadium phosphate sodium can show close to theoretical specific capacity; Fig. 7, the titanium phosphate sodium grapheme material of gained shows the superior chemical property surmounting current all titanium phosphate sodium.
The key point of technical solution of the present invention is: the classification being realized Graphene by spray-dired method is modified, and forms three-dimensional conductive network, has both improve the chemical property of material, and also improved the tap density of material.
Described graphene oxide is oneself synthesis or business purchase.
Described reaction raw materials mixes with graphene oxide, refers to and is dissolved in a solvent by reaction raw materials, then add the dispersion liquid of graphene oxide; Or directly reaction raw materials is dissolved in the dispersion liquid of Graphene.The dispersant or the binding agent that add other is not needed in mixed process.
Described spraying dry, inlet temperature is 80 ~ 300 DEG C.
Described high-temperature calcination, temperature can realize the crystallization of electrode material and the reduction of graphene oxide, and for vanadium phosphate sodium or titanium phosphate sodium, calcining heat is 600 ~ 1000 DEG C.Use atmosphere can be one or more of argon gas, nitrogen, hydrogen etc.
The graphene modified of described classification, refers to that having three-dimensional grapheme supports and while forming three-dimensional conductive network, can realize the graphene coated of material surface.As Fig. 1, the material obtained is the spherical structure of micron; Fig. 2, the Graphene of classification supports, and shows as spherical structure and runs through connection by graphene conductive network, and material surface is realize Graphene coated.
This method adopts spray-dired method, by high-temperature process, obtains the sphere material of the graphene modified of classification.The present invention compared with prior art, has the following advantages and beneficial effect:
1, by spraying dry, the classification that can realize Graphene is modified, and improves the conductivity of material, improves the chemical property of material greatly;
2, by spraying dry, the particle of large-size can be obtained, be conducive to the tap density improving electrode material;
3, containing sodium ion electrode material of the present invention, have good chemical property, fail safe is high, low price, and synthesis technique is simple, easy to control, can be applied to energy storage device, back-up source, redundant electrical power etc.;
4, synthesis cycle of the present invention is short, cheaper starting materials, technique simple, be easy to control, has significant practical value and good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of vanadium phosphate sodium material of the present invention.
Fig. 2 is the transmission electron microscope picture of vanadium phosphate sodium material of the present invention.
Fig. 3 is the X-ray diffraction of vanadium phosphate sodium material of the present invention.
Fig. 4, be the charging and discharging curve of vanadium phosphate sodium electrode of the present invention in electrolyte organic solvent, voltage range is 2-4V, and current density is 20mA/g.
Fig. 5 is the scanning electron microscope (SEM) photograph of titanium phosphate sodium material of the present invention.
Fig. 6 is the high-resolution-ration transmission electric-lens figure of titanium phosphate sodium material of the present invention.
Fig. 7, be the charging and discharging curve under the different current densities of titanium phosphate sodium electrode of the present invention in electrolyte organic solvent, voltage range is 1.4-3V.
Embodiment
Embodiment 1
With sodium carbonate, ammonium dihydrogen phosphate, vanadic oxide, oxalic acid for raw material, wherein, the mol ratio of sodium, vanadium, phosphorus is 3:2:3, and the mol ratio of oxalic acid, vanadium is 3:1, is added by material in appropriate water, heating for dissolving.In this solution, add appropriate graphene oxide water solution, stir one hour.Spray-dried, obtain spherical forerunner, predecessor is proceeded to tube furnace, in argon gas atmosphere, be warming up to 850 DEG C, constant temperature 8 hours, obtain vanadium phosphate sodium material.Be spherical structure through scanning electron microscope analysis (Fig. 1) this material, X-ray diffraction analysis (Fig. 2) determines that this material is pure phase Na 3v 2(PO 4) 3, space group is R-3c.Obtained by elemental analyser analysis, in material, the content of Graphene is 5.4%
According to Na 3v 2(PO 4) 3/ C, acetylene black, PVDF mass ratio are that 80:10:10 is prepared into electrode, be to electrode with sodium metal, 1mol/L vinyl carbonate/diethyl carbonate (volume ratio 1:1) is electrolyte, barrier film is cellgard2035, in glove box, be assembled into battery and charge-discharge test is carried out to it, voltage range is 2-4V, and current density is 20mA/g, and test result is as Fig. 4.Can find out, by constructing the microballoon Na of this classification graphene modified 3v 2(PO 4) 3material, the specific discharge capacity of this material is 115mAh/g, close Na 3v 2(PO 4) 3theoretical specific capacity (117mAh/g), shows fabulous electrochemical reversibility.
Embodiment 2
With ammonium dihydrogen phosphate, titanium dioxide, sodium carbonate for raw material, wherein, the mol ratio of sodium, vanadium, phosphorus is 1:2:3, by stock dispersion in water, adds appropriate graphene oxide.Spray-dried, obtain spherical forerunner, predecessor is proceeded to tube furnace, in nitrogen atmosphere, be warming up to 800 DEG C, constant temperature 12 hours, obtain titanium phosphate sodium material.Be spherical structure through scanning electron microscope analysis (Fig. 5) this material.High-resolution-ration transmission electric-lens (Fig. 6) can have the obvious graphene coated layer of one deck in display material surface.By thermogravimetric analysis, in this composite material, the content of Graphene is 6.8%.
According to NaTi 2(PO 4) 3/ C, acetylene black, PVDF mass ratio are that 80:10:10 is prepared into electrode, be to electrode with sodium metal, 1mol/L vinyl carbonate/diethyl carbonate (volume ratio 1:1) is electrolyte, barrier film is cellgard2035, in glove box, be assembled into battery and charge-discharge test is carried out to it, voltage range is 1.4-3V, and current density is 0.1C to 200C(1C=133mA/g), test result is as Fig. 7.Can find out, this material list reveals high high rate performance, under the current density of 200C superelevation, still has higher specific discharge capacity (38mAh/g), and so high high rate performance titanium phosphate sodium material is reported first.Therefore, by the titanium phosphate sodium material of the graphene modified of classification, extremely excellent chemical property can be shown.

Claims (6)

1. a preparation method for the spherical sodium ion battery electrode material of classification graphene modified, is characterized in that:
Sodium ion battery electrode material is vanadium phosphate sodium or titanium phosphate sodium, and its reaction raw materials is corresponding phosphorus source, vanadium source, sodium source or phosphorus source, titanium source, sodium source; With reaction raw materials and graphene oxide mixing, the quality of graphene oxide is the 5%-50% of resulting materials, spherical forerunner is formed by spraying dry, then high-temperature calcination 6 ~ 12 hours, realize the crystallization of electrode material and the reduction of graphene oxide, thus obtain the spherical sodium ion battery electrode material of classification graphene modified.
2. preparation method according to claim 1, is characterized in that, in the spherical sodium ion battery electrode material of gained classification graphene modified, Graphene plays three-dimensional supporting role and forms three-dimensional conductive network, and electrode material surface is by graphene coated simultaneously.
3. preparation method according to claim 1, is characterized in that, described reaction raw materials mixes with graphene oxide, refers to and is dissolved in a solvent by reaction raw materials, then add the dispersion liquid of graphene oxide; Or directly reaction raw materials is dissolved in the dispersion liquid of Graphene.
4. preparation method according to claim 1, is characterized in that, described spraying dry, and inlet temperature is 80 ~ 300 DEG C.
5. preparation method according to claim 1, is characterized in that, described high-temperature calcination, and temperature is 600 ~ 1000 DEG C.
6. preparation method according to claim 1, is characterized in that, described high-temperature calcination, use atmosphere be argon gas, nitrogen, hydrogen one or more.
CN201510773577.0A 2015-11-13 2015-11-13 Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material Pending CN105244503A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784696A (en) * 2016-12-26 2017-05-31 深圳市贝特瑞纳米科技有限公司 A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use
CN106803582A (en) * 2017-01-26 2017-06-06 长安大学 A kind of anode material of lithium-ion battery and preparation method thereof
CN107359340A (en) * 2017-07-19 2017-11-17 广东迈纳科技有限公司 A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support
CN109205585A (en) * 2017-07-04 2019-01-15 北京金羽新能科技有限公司 A kind of preparation method of titanium phosphate sodium material
CN109728273A (en) * 2018-12-17 2019-05-07 西安工业大学 The preparation method of anode material of lithium-ion battery titanium phosphate sodium double nano carbon
CN111933899A (en) * 2020-06-22 2020-11-13 武汉大学 Composite oxide electrode material and preparation method thereof

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CN102315423A (en) * 2010-07-08 2012-01-11 中国科学院宁波材料技术与工程研究所 Graphene/lithium iron phosphate compound anode material, preparation method thereof and lithium ion secondary battery
CN102623708A (en) * 2012-04-12 2012-08-01 上海智荣科技有限责任公司 Preparation method of lithium vanadium phosphate (Li3V2(PO4)3)/graphene composite material for positive electrode of lithium ion battery
CN103456954A (en) * 2013-09-06 2013-12-18 四川一美能源科技有限公司 Preparation method of active electrode material
CN103779564A (en) * 2014-01-26 2014-05-07 武汉理工大学 High-performance sodium vanadyl phosphate symmetrical sodium-ion battery material and preparation method and application thereof
CN104362309A (en) * 2014-09-22 2015-02-18 安徽工业大学 High-magnification sodium-ion battery composite cathode material and preparation method

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN102315423A (en) * 2010-07-08 2012-01-11 中国科学院宁波材料技术与工程研究所 Graphene/lithium iron phosphate compound anode material, preparation method thereof and lithium ion secondary battery
CN102623708A (en) * 2012-04-12 2012-08-01 上海智荣科技有限责任公司 Preparation method of lithium vanadium phosphate (Li3V2(PO4)3)/graphene composite material for positive electrode of lithium ion battery
CN103456954A (en) * 2013-09-06 2013-12-18 四川一美能源科技有限公司 Preparation method of active electrode material
CN103779564A (en) * 2014-01-26 2014-05-07 武汉理工大学 High-performance sodium vanadyl phosphate symmetrical sodium-ion battery material and preparation method and application thereof
CN104362309A (en) * 2014-09-22 2015-02-18 安徽工业大学 High-magnification sodium-ion battery composite cathode material and preparation method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784696A (en) * 2016-12-26 2017-05-31 深圳市贝特瑞纳米科技有限公司 A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use
CN106803582A (en) * 2017-01-26 2017-06-06 长安大学 A kind of anode material of lithium-ion battery and preparation method thereof
CN106803582B (en) * 2017-01-26 2019-06-14 长安大学 A kind of anode material of lithium-ion battery and preparation method thereof
CN109205585A (en) * 2017-07-04 2019-01-15 北京金羽新能科技有限公司 A kind of preparation method of titanium phosphate sodium material
CN107359340A (en) * 2017-07-19 2017-11-17 广东迈纳科技有限公司 A kind of preparation method of the compound micron ball of fluorophosphoric acid vanadyl sodium of three-dimensional grapheme network skeleton support
CN109728273A (en) * 2018-12-17 2019-05-07 西安工业大学 The preparation method of anode material of lithium-ion battery titanium phosphate sodium double nano carbon
CN111933899A (en) * 2020-06-22 2020-11-13 武汉大学 Composite oxide electrode material and preparation method thereof
CN111933899B (en) * 2020-06-22 2021-11-26 武汉大学 Composite oxide electrode material and preparation method thereof

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Application publication date: 20160113