CN104078676A - Preparation method of sodium vanadyl phosphate/graphene composite material - Google Patents

Preparation method of sodium vanadyl phosphate/graphene composite material Download PDF

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CN104078676A
CN104078676A CN201410363701.1A CN201410363701A CN104078676A CN 104078676 A CN104078676 A CN 104078676A CN 201410363701 A CN201410363701 A CN 201410363701A CN 104078676 A CN104078676 A CN 104078676A
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sodium
phosphate
vanadyl phosphate
composite material
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CN104078676B (en
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刘伟良
周广盖
赵丹
任慢慢
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Qilu University of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/45Phosphates containing plural metal, or metal and ammonium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a sodium vanadyl phosphate/graphene composite material. The preparation method specifically comprises the steps as follows: a sodium salt, a vanadium salt, phosphate, an oxalic acid or a citric acid and water are stirred in a certain proportion at the temperature of 50-90 DEG C to form a homogeneous solution, the solution is dried at the temperature of 60-150 DEG C to form gel, then the gel is ground into powder after being pre-sintered at the temperature of 250-300 DEG C for 3-6 h, the powder is sintered at the temperature of 450-550 DEG C for 3-5 h, sodium vanadyl phosphate powder is obtained through grinding and composited with a graphene oxide, and the sodium vanadyl phosphate/graphene composite material is obtained under the action of microwaves finally. The preparation method is simple in process, short in flow, low in preparation cost and low in environmental pollution; the prepared sodium vanadyl phosphate/graphene composite material is uniform in particle, high in electronic conductivity and good in electrochemical sodium storage performance.

Description

A kind of preparation method of vanadyl phosphate sodium/graphene composite material
Technical field
The invention belongs to battery technology field, be specially the preparation method of sodium ion secondary battery positive electrode.
Background technology
Lithium ion battery is widely used in portable electric appts as digital camera, mobile phone, notebook computer etc. because of advantages such as energy density are high, specific capacity is large, quality is light.In recent years, because of fossil energy shortage and increasing environmental pollution, electric automobile is developed rapidly, and the demand of lithium ion battery also increases greatly.But the reserves of lithium are limited in the earth's crust, therefore need to develop new energy-storage system.
Sodium and lithium are all the first major element, have similar chemical property, and sodium reserves are on earth very abundant, are easy to obtain from seawater.Sodium-ion battery has the features such as cost is low, fail safe is high, is considered to substitute lithium ion battery and better selects as electrical source of power.Relatively less about the research of sodium-ion battery positive electrode, material can choice less, therefore positive electrode is the key of restriction sodium-ion battery development.F. Sauvage etc. has studied Na 1.5vOPO 4f 0.5as the electrochemical properties of sodium-ion battery positive electrode, at 3.6V and 4.0V(v.s. Na +/ Na) there are two platforms, there is the reversible capacity (Solid State Sciences, 2006,8 (10), 2046-2069) of 87mAh/g.Jun Liu etc. has studied Na 3v 2(PO 4) 3/ C nano wire, as sodium-ion battery positive electrode, has the reversible capacity (Nanoscale, 2014,6,5081-5086) of 101 mAh/g.
Vanadyl phosphate sodium (NaVOPO 4) during as sodium ion secondary battery positive electrode, the embedding/deintercalation of sodium ion depends on V 4+/ V 5+reduce right reversible conversion.The average voltage platform of material is at 3.6V(v.s. Na+/Na), theoretical capacity is 145 mAh/g.Due to the lower electronic conductivity of vanadyl phosphate sodium and charge/discharge capacity, therefore vanadyl phosphate sodium material is carried out to study on the modification.
Summary of the invention
The present invention seeks to utilize the fabulous electric conductivity of Graphene to improve the performance of vanadyl phosphate sodium as sodium-ion battery positive electrode.The method preparation process is simple, cost of material is cheap, and the vanadyl phosphate sodium material that the material of preparing is compared pure phase has higher conductivity and reversible capacity, and while discharging and recharging under the multiplying power of 1/15C, discharge capacity can reach 88.5mAh/g.
For realizing object of the present invention, provide following technical scheme:
A preparation method for vanadyl phosphate sodium/graphene composite material, is characterized in that, comprises the steps:
(1) sodium salt, vanadic salts, phosphate, oxalic acid or citric acid and deionized water are pressed to sodium: vanadium: phosphate radical: oxalic acid or citric acid: mol ratio 1:1:1:1 ~ 3:200 ~ 1000 of deionized water form uniform solution for 2 ~ 6 hours 50 ~ 90 DEG C of mechanical agitation, solution is obtained to gel after 60 ~ 150 DEG C of abundant being dried;
(2) by step (1) gained gel in air atmosphere, be warming up to 250 ~ 300 DEG C of presintering 3 ~ 6 hours with 3 ~ 10 DEG C/min of speed, naturally cool to room temperature, grind evenly, then,, in air atmosphere, be warming up to 450 ~ 550 DEG C of double sinterings 3 ~ 5 hours with 3 ~ 10 DEG C/min of speed, naturally cool to room temperature, after grinding evenly, obtain vanadyl phosphate sodium powder;
(3) step (2) gained vanadyl phosphate sodium powder is joined in a certain amount of deionized water, disperse 1 ~ 2 hour under ul-trasonic irradiation, obtaining concentration is the vanadyl phosphate sodium dispersion liquid of 2 ~ 10 mg/ml;
(4) a certain amount of graphene oxide is added in deionized water, under ul-trasonic irradiation, disperse 2 ~ 6 hours, forming concentration is the graphene oxide solution of 0.1 ~ 2 mg/ml, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 ~ 6 hours, freeze drying obtains pressed powder, and in described pressed powder, the content of graphene oxide is 5 ~ 10 wt%;
(5) step (4) gained pressed powder is well dispersed in to the dispersion liquid that forms stable uniform in a certain amount of 1-METHYLPYRROLIDONE, wherein, pressed powder concentration is 10 ~ 50 mg/ml, then under microwave action, react 2 ~ 3 minutes, after being fully dried, obtain described vanadyl phosphate sodium/graphene composite material at 60 ~ 150 DEG C of temperature.
Further, in described a kind of vanadyl phosphate sodium/Graphene sodium composite material, the content of Graphene is 2 ~ 4 wt%
Further, in described step, sodium salt is at least one in sodium carbonate, sodium acetate, sodium dihydrogen phosphate.
Further, in described step, vanadic salts is at least one in vanadic oxide, ammonium metavanadate, vanadium dioxide, vanadium trioxide.
Further, in described step, phosphate is at least one in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate.
Feature of the present invention is: preparation process is simple, flow process is short, production cost is low, and the pollution of environment is very little; Vanadyl phosphate sodium/graphene composite material of preparing, uniform particles, electronic conductivity is high, has good electrochemistry storage sodium performance.
Brief description of the drawings
Fig. 1 is the XRD figure of sample in embodiment 1;
Fig. 2 is the constant current charge-discharge figure of sample in embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Following examples are intended to illustrate the present invention instead of limitation of the invention further.
Embodiment 1:
(1) 1.5601 g bis-hypophosphite monohydrate sodium dihydrogens, 0.9094 g vanadic oxide, 1.8911 g oxalic acid and 100 g deionized waters are formed to uniform solution for 2 hours 50 DEG C of mechanical agitation, solution is dried and obtains gels at 80 DEG C;
(2) by step (1) gained gel in air atmosphere, be warming up to 300 DEG C of presintering 4 hours with 5 DEG C/min of speed, naturally cool to room temperature, grind evenly, then,, in air atmosphere, be warming up to 500 DEG C of double sinterings 4 hours with 5 DEG C/min of speed, naturally cool to room temperature, grind and obtain vanadyl phosphate sodium powder;
(3) 0.5 g vanadyl phosphate sodium powder is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 1 hour, obtain vanadyl phosphate sodium dispersion liquid;
(4) 0.025 g graphene oxide is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 2 hours, form graphene oxide solution, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 hours, freeze drying obtains pressed powder;
(5) step (4) gained pressed powder is dispersed in 20 ml 1-METHYLPYRROLIDONEs, under microwave action, reacts 2 minutes, at 60 DEG C of dry vanadyl phosphate sodium/graphene composite materials that obtain.
Fig. 1 is the XRD collection of illustrative plates of the prepared vanadyl phosphate sodium/graphene composite material of the present embodiment.Vanadyl phosphate sodium/graphene composite material prepared the present embodiment is assembled into experiment button cell as positive electrode, test it and discharge and recharge chemical property, test result shows: material the 2nd time and 30 specific discharge capacities under the multiplying power of 1/15C are respectively 88.5 mAh/g and 79.7 mAh/g, and the capability retention after 30 circulations is 90%.The charging and discharging curve of material as shown in Figure 2.
Embodiment 2:
(1) 0.8203 g sodium acetate, 0.9094 g vanadic oxide, 1.3206 g diammonium hydrogen phosphates, 1.8911 g oxalic acid and 100 g deionized waters are formed to uniform solution for 2 hours 60 DEG C of mechanical agitation, solution is dried and obtains gels at 80 DEG C;
(2) by step (1) gained gel in air atmosphere, be warming up to 300 DEG C of presintering 4 hours with 5 DEG C/min of speed, naturally cool to room temperature, grind evenly, then,, in air atmosphere, be warming up to 500 DEG C of double sinterings 4 hours with 5 DEG C/min of speed, naturally cool to room temperature, grind and obtain vanadyl phosphate sodium powder;
(3) 1 g vanadyl phosphate sodium powder is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 2 hours, obtain vanadyl phosphate sodium dispersion liquid;
(4) 0.08 g graphene oxide is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 2 hours, form graphene oxide solution, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 hours, freeze drying obtains pressed powder;
(5) step (4) gained pressed powder is dispersed in 50 ml 1-METHYLPYRROLIDONEs, under microwave action, reacts 2 minutes, at 60 DEG C of dry vanadyl phosphate sodium/graphene composite materials that obtain.
Embodiment 3:
(1) 1.0599 sodium carbonate, 2.3396 g ammonium metavanadates, 2.6411 g diammonium hydrogen phosphates, 2.5215 g oxalic acid and 200g deionized water are formed to uniform solution for 4 hours 60 DEG C of mechanical agitation, solution is dried and obtains gels at 100 DEG C;
(2) by step (1) gained gel in air atmosphere, be warming up to 300 DEG C of presintering 4 hours with 10 DEG C/min of speed, naturally cool to room temperature, grind evenly, then,, in air atmosphere, be warming up to 550 DEG C of double sinterings 4 hours with 10 DEG C/min of speed, naturally cool to room temperature, grind and obtain vanadyl phosphate sodium powder;
(3) 1 g vanadyl phosphate sodium powder is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 1 hour, obtain vanadyl phosphate sodium dispersion liquid;
(4) 0.05 g graphene oxide is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 3 hours, form graphene oxide solution, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 hours, freeze drying obtains pressed powder;
(5) step (4) gained pressed powder is dispersed in 50 ml 1-METHYLPYRROLIDONEs, under microwave action, reacts 2 minutes, at 60 DEG C of dry vanadyl phosphate sodium/graphene composite materials that obtain.
Embodiment 4:
(1) 1.0599 sodium carbonate, 1.8188 g vanadic oxides, 2.6411 g diammonium hydrogen phosphates, 3.7821 g oxalic acid and 300g deionized water are formed to uniform solution for 4 hours 80 DEG C of mechanical agitation, solution is dried and obtains gels at 120 DEG C;
(2) by step (1) gained gel in air atmosphere, be warming up to 300 DEG C of presintering 4 hours with 3 DEG C/min of speed, naturally cool to room temperature, grind evenly, then, in air atmosphere, be warming up to 500 DEG C of double sinterings 4 hours with 3 DEG C/min of speed, grind and obtain vanadyl phosphate sodium powder;
(3) 2 g vanadyl phosphate sodium powder are added in 300 g deionized waters, under ul-trasonic irradiation, disperse 2 hours, obtain vanadyl phosphate sodium dispersion liquid;
(4) 0.15 g graphene oxide is added in 150 g deionized waters, under ul-trasonic irradiation, disperse 3 hours, form graphene oxide solution, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 hours, freeze drying obtains pressed powder;
(5) step (4) gained pressed powder is dispersed in 50 ml 1-METHYLPYRROLIDONEs, under microwave action, reacts 2 minutes, at 60 DEG C of dry vanadyl phosphate sodium/graphene composite materials that obtain.
Embodiment 5:
(1) 0.8203 g sodium acetate, 0.9094 g vanadic oxide, 0.9797 g phosphoric acid, 3.8428 g citric acids and 100 g deionized waters are formed to uniform solution for 2 hours 60 DEG C of mechanical agitation, solution is dried and obtains gels at 120 DEG C;
(2) by step (1) gained gel in air atmosphere, be warming up to 270 DEG C of presintering 6 hours with 5 DEG C/min of speed, naturally cool to room temperature, grind evenly, then, in air atmosphere, be warming up to 450 DEG C of double sinterings 5 hours with 5 DEG C/min of speed, grind and obtain vanadyl phosphate sodium powder;
(3) 1 g vanadyl phosphate sodium powder is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 2 hours, obtain vanadyl phosphate sodium dispersion liquid;
(4) 0.1 g graphene oxide is added in 100 g deionized waters, under ul-trasonic irradiation, disperse 2 hours, form graphene oxide solution, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 hours, freeze drying obtains pressed powder;
(5) step (4) gained pressed powder is dispersed in 50 ml 1-METHYLPYRROLIDONEs, under microwave action, reacts 3 minutes, at 60 DEG C of dry vanadyl phosphate sodium/graphene composite materials that obtain.

Claims (3)

1. the preparation method of vanadyl phosphate sodium/graphene composite material and an application thereof, is characterized in that, comprises the steps:
(1) by sodium salt, vanadic salts, phosphate, oxalic acid or citric acid and deionized water are pressed sodium: vanadium: phosphate radical: oxalic acid or citric acid: mol ratio 1:1:1:1 ~ 3:200 ~ 1000 of deionized water form uniform solution for 2 ~ 6 hours 50 ~ 90 DEG C of mechanical agitation, solution is obtained to gel after 60 ~ 150 DEG C of abundant being dried, wherein, described sodium salt is sodium carbonate, sodium acetate, at least one in sodium dihydrogen phosphate, described vanadic salts is vanadic oxide, ammonium metavanadate, vanadium dioxide, at least one in vanadium trioxide, described phosphate is phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, at least one in sodium dihydrogen phosphate,
(2) by step (1) gained gel in air atmosphere, be warming up to 250 ~ 300 DEG C of presintering 3 ~ 6 hours with 3 ~ 10 DEG C/min of speed, naturally cool to room temperature, grind evenly, then,, in air atmosphere, be warming up to 450 ~ 550 DEG C of double sinterings 3 ~ 5 hours with 3 ~ 10 DEG C/min of speed, naturally cool to room temperature, grind the evenly rear vanadyl phosphate sodium powder that obtains;
(3) step (2) gained vanadyl phosphate sodium powder is joined in a certain amount of deionized water, disperse 1 ~ 2 hour under ul-trasonic irradiation, obtaining concentration is the vanadyl phosphate sodium dispersion liquid of 2 ~ 10 mg/ml;
(4) a certain amount of graphene oxide is added in deionized water, under ul-trasonic irradiation, disperse 2 ~ 6 hours, forming concentration is the graphene oxide solution of 0.1 ~ 2 mg/ml, then add step (3) gained vanadyl phosphate sodium dispersion liquid, mechanical agitation 3 ~ 6 hours, freeze drying obtains pressed powder, and in described pressed powder, the content of graphene oxide is 5 ~ 10 wt%;
(5) step (4) gained pressed powder is well dispersed in to the dispersion liquid that forms stable uniform in a certain amount of 1-METHYLPYRROLIDONE, wherein, pressed powder concentration is 10 ~ 50 mg/ml, then under microwave action, react 2 ~ 3 minutes, after being fully dried, obtain described vanadyl phosphate sodium/graphene composite material at 60 ~ 150 DEG C of temperature.
2. a kind of preparation method of vanadyl phosphate sodium/graphene composite material according to claim 1, the content that it is characterized in that Graphene in described composite material is 2 ~ 4 wt%.
3. a kind of preparation method of vanadyl phosphate sodium/graphene composite material according to claim 1, it is characterized in that the described sodium salt of step (1) is at least one in sodium carbonate, sodium acetate, sodium dihydrogen phosphate, described vanadic salts is at least one in vanadic oxide, ammonium metavanadate, vanadium dioxide, vanadium trioxide, and described phosphate is at least one in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108002356A (en) * 2017-11-28 2018-05-08 华中农业大学 δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application
CN108598418A (en) * 2018-04-24 2018-09-28 齐鲁工业大学 A kind of unformed NaVOPO of anode material of lithium-ion battery4/ C and the preparation method and application thereof
CN109802112A (en) * 2019-01-04 2019-05-24 三峡大学 A kind of Na4VO(PO4)2The preparation method of/C sodium-ion battery positive material
RU2704186C1 (en) * 2018-10-12 2019-10-24 Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" METHOD OF PRODUCING CATHODE MATERIAL OF COMPOSITION Na3V2O2X(PO4)2F3-2X (where 0<X≤1) FOR Na-ION BATTERIES
KR20200138198A (en) 2019-02-28 2020-12-09 인터내셔날 애드밴스드 리서치 센터 폴 파우더 메탈러지 앤드 뉴 머테리얼스 (에이알씨아이) Microwave assisted sol-gel method for manufacturing in-situ carbon-coated electrode material and product thereof
CN113921779A (en) * 2021-09-08 2022-01-11 西北大学 NASICON type sodium fast ion conductor material, preparation method and application
CN116395654A (en) * 2023-03-01 2023-07-07 湖南顺华锂业有限公司 Preparation method and application of sodium vanadyl phosphate anode material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040262571A1 (en) * 2003-06-03 2004-12-30 Jeremy Barker Battery active materials and methods for synthesis
CN1723578A (en) * 2001-04-06 2006-01-18 威伦斯技术公司 Sodium ion batteries
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
WO2014102531A2 (en) * 2012-12-28 2014-07-03 Faradion Ltd Metal-containing compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1723578A (en) * 2001-04-06 2006-01-18 威伦斯技术公司 Sodium ion batteries
US20040262571A1 (en) * 2003-06-03 2004-12-30 Jeremy Barker Battery active materials and methods for synthesis
WO2014102531A2 (en) * 2012-12-28 2014-07-03 Faradion Ltd Metal-containing compounds
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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108002356A (en) * 2017-11-28 2018-05-08 华中农业大学 δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application
CN108598418A (en) * 2018-04-24 2018-09-28 齐鲁工业大学 A kind of unformed NaVOPO of anode material of lithium-ion battery4/ C and the preparation method and application thereof
CN108598418B (en) * 2018-04-24 2021-01-26 齐鲁工业大学 Amorphous NaVOPO (sodium VOPO) as negative electrode material of sodium ion battery4/C and preparation method and application thereof
RU2704186C1 (en) * 2018-10-12 2019-10-24 Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий" METHOD OF PRODUCING CATHODE MATERIAL OF COMPOSITION Na3V2O2X(PO4)2F3-2X (where 0<X≤1) FOR Na-ION BATTERIES
CN109802112A (en) * 2019-01-04 2019-05-24 三峡大学 A kind of Na4VO(PO4)2The preparation method of/C sodium-ion battery positive material
KR20200138198A (en) 2019-02-28 2020-12-09 인터내셔날 애드밴스드 리서치 센터 폴 파우더 메탈러지 앤드 뉴 머테리얼스 (에이알씨아이) Microwave assisted sol-gel method for manufacturing in-situ carbon-coated electrode material and product thereof
CN113921779A (en) * 2021-09-08 2022-01-11 西北大学 NASICON type sodium fast ion conductor material, preparation method and application
CN116395654A (en) * 2023-03-01 2023-07-07 湖南顺华锂业有限公司 Preparation method and application of sodium vanadyl phosphate anode material

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