CN105280899A - Method for preparing carbon-coated sodium ferric phosphate material - Google Patents

Method for preparing carbon-coated sodium ferric phosphate material Download PDF

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Publication number
CN105280899A
CN105280899A CN201510605542.6A CN201510605542A CN105280899A CN 105280899 A CN105280899 A CN 105280899A CN 201510605542 A CN201510605542 A CN 201510605542A CN 105280899 A CN105280899 A CN 105280899A
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China
Prior art keywords
nafepo
carbon
phosphoric acid
coated
beaker
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张佳峰
刘益
张宝
明磊
王小玮
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Central South University
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Central South 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
    • H01M4/58—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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a method for preparing a carbon-coated sodium ferric phosphate material. The method comprises the following steps: putting Fe(NO3)3.9H2O and NaH2PO4.2H2O in a beaker in proportion; then adding glucose and citric acid; then adding ethylene glycol and mixing uniformly; putting the mixture in a water bath kettle at 60-90 DEG C, and stirring; stopping stirring after gel formation, putting the gel in a baking oven for drying; after the drying is finished, grinding the material; and calcining the ground material in argon gas to obtain the carbon-coated sodium ferric phosphate material. The method is simple in reaction process and convenient for industrial control; and the prepared carbon-coated sodium ferric phosphate material is stable in structure, and has higher high rate cycle performance.

Description

A kind of method preparing the coated phosphoric acid ferrisodium material of carbon
Technical field
The present invention relates to a kind of method preparing cell positive material, be specifically related to a kind of method preparing the coated phosphoric acid ferrisodium material of carbon.
Background technology
From the nineties in 20th century, lithium ion battery, because having the advantages such as high-energy-density, quality be light, is widely used in the electronic installations such as mobile device.But there is the defects such as price is high, reserves are limited in lithium ion battery.Sodium-ion battery is lithium ion battery comparatively, and its cost of material is lower than lithium ion battery, and cell potential is higher than corresponding lithium ion battery current potential, and security performance is good.
At present, relevant phosphoric acid ferrisodium material yet there are no relevant report.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of method preparing the coated phosphoric acid ferrisodium material of carbon.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method preparing the coated phosphoric acid ferrisodium material of carbon, and concrete steps are as follows:
1) by Fe (NO 3) 39H 20, NaH 2pO 42H 2o is according to chemical formula NaFePO 4, the ratio being 1:1:1 in the mol ratio of Na:Fe:P puts into beaker;
2) in above-mentioned beaker, glucose is added, NaFePO 4be 3 ~ 4:1 with the mass ratio of glucose;
Wherein, NaFePO 4quality be in theory generate quality come, its quality calculates according to following chemical equation:
Fe(NO 3) 3·9H 20+NaH 2PO 4·2H 2O+1/6C 6H 12O 6·H 2O→NaFePO 4+3NO+CO 2+79/6H 2O；
3) in above-mentioned beaker, citric acid is added, NaFePO 4be 1 ~ 2:1 with the mass ratio of citric acid;
Wherein, NaFePO 4quality be in theory generate quality come, its quality calculates according to following chemical equation:
Fe(NO 3) 3·9H 20+NaH 2PO 4·2H 2O+1/6C 6H 12O 6·H 2O→NaFePO 4+3NO+CO 2+79/6H 2O；
4) in above-mentioned beaker, add ethylene glycol to mix;
5) above-mentioned beaker is put into the water-bath of 60 ~ 90 DEG C, and stir;
6) take out beaker after forming gel, put into baking oven and dry;
7), after oven dry terminates, material is taken out and grinds;
8) material after grinding is calcined in an inert atmosphere, the temperature of calcining is 550 ~ 650 DEG C, the time of calcining is 6 ~ 10h, because having neither part nor lot in glucose that step (2) the reacts pyrogenetic decomposition at inert atmosphere, make part carbon be retained in material of main part, obtain the phosphoric acid ferrisodium material that carbon is coated.
Further, step 4) in, ethylene glycol addition and Fe (NO 3) 39H 20, NaH 2pO 42H 2o, glucose, citric acid total weight ratio are 1 ~ 3:1.
Further, step 5) in, the speed of stirring is the preferred 200r/min of 150-250r/min(), the time of stirring is 5 ~ 10h.
Further, step 6) in, the temperature of baking oven is set to 85-95 DEG C (preferably 90 DEG C), and the time of oven dry is the preferred 24h of 22-25h().
The present invention is by Fe (NO 3) 39H 20, NaH 2pO 42H 2o puts into beaker in proportion, is carbon source with glucose, take citric acid as gel, sinters after sol-gel, oven dry, the phosphoric acid ferrisodium material that obtained carbon is coated.
The coated phosphoric acid ferrisodium material of the carbon that the present invention obtains can reach 41.8mAhg at the 1C gram volume that discharges first -1, after 50 circulations, capability retention is 93.5%.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the coated phosphoric acid ferrisodium material of carbon prepared by embodiment 1;
Fig. 2 is the 1C first charge-discharge curve chart of the coated phosphoric acid ferrisodium material of carbon prepared by embodiment 1;
Fig. 3 is 1C discharge capacity and the capability retention scatter diagram of the coated phosphoric acid ferrisodium material of carbon prepared by embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
embodiment 1
By 0.1molFe (NO 3) 39H 20,0.1molNaH 2pO 42H 2o, 5.0g glucose, 12.5g citric acid, above-mentioned substance is put into beaker, add 76mL ethylene glycol as dispersant, under the bath temperature of 70 DEG C, stir 8h with the mixing speed of 200r/min and form gel, then dry 24h at the baking oven of 90 DEG C, grind after material is taken out, after grinding terminates, material is calcined 8h in 600 DEG C of argon gas, obtains the NaFePO that carbon is coated 4material.
The NaFePO that carbon obtained by the present embodiment is coated 4as shown in Figure 1, known as shown in Figure 1, material crystalline degree is high, and crystal formation is complete for the XRD figure of material.
Battery is assembled: by the NaFePO of preparation 4material, acetylene black and PVDF take with certain mass ratio (8:1:1), put into mortar, add appropriate NMP and grind, on aluminium foil, positive plate is made after mixing, in vacuum glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO 4/ EC:PC(1:1) be electrolyte, be assembled into the button cell of CR2025.
By battery in 2V ~ 4.5V voltage range, survey its charge/discharge capacity, it is 41.8mAhg at the 1C gram volume that discharges first -1(see figure 2).Circulate after 50 times under the multiplying power of 1C, capability retention is that 93.5%(is shown in Fig. 3).
embodiment 2
By 0.1molFe (NO 3) 39H 20,0.1molNaH 2pO 42H 2o, 4.5g glucose, 8.7g citric acid, above-mentioned substance is put into beaker, add 50mL ethylene glycol as dispersant, under the bath temperature of 60 DEG C, stir 10h with the mixing speed of 200r/min and form gel, then dry 24h at the baking oven of 90 DEG C, grind after material is taken out, after grinding terminates, material is calcined 6h in 550 DEG C of argon gas, obtains the NaFePO that carbon is coated 4material.
Battery is assembled: by NaFePO coated for the carbon of preparation 4material, acetylene black and PVDF take with certain mass ratio (8:1:1), put into mortar, add appropriate NMP and grind, on aluminium foil, positive plate is made after mixing, in vacuum glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO 4/ EC:PC(1:1) be electrolyte, be assembled into the button cell of CR2025.
By battery in 2V ~ 4.5V voltage range, survey its charge/discharge capacity, it is 35.6mAhg at the 1C gram volume that discharges first -1.Circulate after 50 times under the multiplying power of 1C, capability retention is 91.5%.
embodiment 3
By 0.1molFe (NO 3) 39H 20,0.1molNaH 2pO 42H 2o, 5.8g glucose, 17.4g citric acid, above-mentioned substance is put into beaker, add 100mL ethylene glycol as dispersant, under the bath temperature of 90 DEG C, stir 5h with the mixing speed of 200r/min and form gel, then dry 24h at the baking oven of 90 DEG C, grind after material is taken out, after grinding terminates, material is calcined 10h in 650 DEG C of argon gas, obtains the NaFePO that carbon is coated 4material.
Battery is assembled: by NaFePO coated for the carbon of preparation 4material, acetylene black and PVDF take with certain mass ratio (8:1:1), put into mortar, add appropriate NMP and grind, on aluminium foil, positive plate is made after mixing, in vacuum glove box with sodium metal sheet for negative pole, with WhatmanGF/D glass fibre for barrier film, 1mol/LNaClO 4/ EC:PC(1:1) be electrolyte, be assembled into the button cell of CR2025.
By battery in 2V ~ 4.5V voltage range, survey its charge/discharge capacity, it is 39.5mAhg at the 1C gram volume that discharges first -1.Circulate after 50 times under the multiplying power of 1C, capability retention is 92%.

Claims (5)

1. prepare a method for the coated phosphoric acid ferrisodium material of carbon, it is characterized in that, concrete steps are as follows:
1) by Fe (NO 3) 39H 20, NaH 2pO 42H 2o is according to chemical formula NaFePO 4, the ratio being 1:1:1 in the mol ratio of Na:Fe:P puts into beaker;
2) in above-mentioned beaker, glucose is added, NaFePO 4be 3 ~ 4:1 with the mass ratio of glucose;
Wherein, NaFePO 4quality be in theory generate quality come, its quality calculates according to following chemical equation:
Fe(NO 3) 3·9H 20+NaH 2PO 4·2H 2O+1/6C 6H 12O 6·H 2O→NaFePO 4+3NO+CO 2+79/6H 2O；
3) in above-mentioned beaker, citric acid is added, NaFePO 4be 1 ~ 2:1 with the mass ratio of citric acid;
Wherein, NaFePO 4quality be in theory generate quality come, its quality calculates according to following chemical equation:
Fe(NO 3) 3·9H 20+NaH 2PO 4·2H 2O+1/6C 6H 12O 6·H 2O→NaFePO 4+3NO+CO 2+79/6H 2O；
4) in above-mentioned beaker, add ethylene glycol to mix;
5) above-mentioned beaker is put into the water-bath of 60 ~ 90 DEG C, and stir;
6) take out beaker after forming gel, put into baking oven and dry;
7), after oven dry terminates, material is taken out and grinds;
8) calcined in an inert atmosphere by the material after grinding, the temperature of calcining is 550 ~ 650 DEG C, and the time of calcining is 6 ~ 10h, obtains the phosphoric acid ferrisodium material that carbon is coated.
2. the method preparing the coated phosphoric acid ferrisodium material of carbon according to claim 1, is characterized in that, step 4) in, ethylene glycol addition and Fe (NO 3) 39H 20, NaH 2pO 42H 2o, glucose, citric acid total weight ratio are 1 ~ 3:1.
3. the method preparing the coated phosphoric acid ferrisodium material of carbon according to claim 1 and 2, is characterized in that, step 5) in, the speed of stirring is 150-250r/min, and the time of stirring is 5 ~ 10h.
4. the method preparing the coated phosphoric acid ferrisodium material of carbon according to claim 1 and 2, is characterized in that, step 6) in, the temperature of baking oven is set to 85-95 DEG C, and the time of oven dry is 22-25h.
5. the method preparing the coated phosphoric acid ferrisodium material of carbon according to claim 4, is characterized in that, step 6) in, the temperature of baking oven is set to 90 DEG C, and the time of oven dry is 24h.
CN201510605542.6A 2015-09-22 2015-09-22 Method for preparing carbon-coated sodium ferric phosphate material Pending CN105280899A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845974A (en) * 2016-06-06 2016-08-10 四川国润新材料有限公司 Preparation method for positive electrode material NaFePO4/C of sodium ion battery
CN106684435A (en) * 2016-12-27 2017-05-17 陕西科技大学 Preparation method for NaFePO4/C nanosheet
CN108615855A (en) * 2016-12-10 2018-10-02 中国科学院大连化学物理研究所 Titanium phosphate sodium material prepared by a kind of carbon coating and preparation and application
CN110957490A (en) * 2019-07-30 2020-04-03 哈尔滨工业大学 Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure
CN111362247A (en) * 2020-03-12 2020-07-03 东莞理工学院 Carbon-coated sodium super-ion conductor Na3Fe2(PO4)3/C composite material and preparation method and application thereof
CN113991089A (en) * 2021-11-11 2022-01-28 雅迪科技集团有限公司 Sodium ion battery and preparation method thereof
CN114050250A (en) * 2021-11-18 2022-02-15 中国科学技术大学 Carbon-coated sodium iron phosphate sodium ion battery positive electrode material, and preparation method and application thereof
CN114044504A (en) * 2021-11-11 2022-02-15 雅迪科技集团有限公司 Preparation method of sodium iron phosphate cathode material

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CN101593832A (en) * 2009-06-29 2009-12-02 南开大学 The process for preparing sol-gel of lithium ferrous phosphate as anode material of lithium ion battery
US20110008233A1 (en) * 2009-07-10 2011-01-13 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845974A (en) * 2016-06-06 2016-08-10 四川国润新材料有限公司 Preparation method for positive electrode material NaFePO4/C of sodium ion battery
CN108615855A (en) * 2016-12-10 2018-10-02 中国科学院大连化学物理研究所 Titanium phosphate sodium material prepared by a kind of carbon coating and preparation and application
CN106684435A (en) * 2016-12-27 2017-05-17 陕西科技大学 Preparation method for NaFePO4/C nanosheet
CN106684435B (en) * 2016-12-27 2019-03-05 陕西科技大学 A kind of NaFePO4The preparation method of/C nano piece
CN110957490A (en) * 2019-07-30 2020-04-03 哈尔滨工业大学 Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure
CN111362247A (en) * 2020-03-12 2020-07-03 东莞理工学院 Carbon-coated sodium super-ion conductor Na3Fe2(PO4)3/C composite material and preparation method and application thereof
CN113991089A (en) * 2021-11-11 2022-01-28 雅迪科技集团有限公司 Sodium ion battery and preparation method thereof
CN114044504A (en) * 2021-11-11 2022-02-15 雅迪科技集团有限公司 Preparation method of sodium iron phosphate cathode material
CN114044504B (en) * 2021-11-11 2023-02-28 雅迪科技集团有限公司 Preparation method of sodium iron phosphate cathode material
CN114050250A (en) * 2021-11-18 2022-02-15 中国科学技术大学 Carbon-coated sodium iron phosphate sodium ion battery positive electrode material, and preparation method and application thereof

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