CN110335997A - A kind of half/full battery Fe of lithium/sodium ion low temperature7Se8The preparation method of@C negative electrode material - Google Patents

A kind of half/full battery Fe of lithium/sodium ion low temperature7Se8The preparation method of@C negative electrode material Download PDF

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Publication number
CN110335997A
CN110335997A CN201910454663.3A CN201910454663A CN110335997A CN 110335997 A CN110335997 A CN 110335997A CN 201910454663 A CN201910454663 A CN 201910454663A CN 110335997 A CN110335997 A CN 110335997A
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preparation
electrode material
negative electrode
full battery
reaction
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张景萍
范红红
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Northeastern University China
Northeast Normal University
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Northeast Normal 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
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 belongs to novel energy resource material technology fields, are related to a kind of half/full battery Fe of lithium/sodium ion low temperature7Se8The preparation method of@C negative electrode material, in conjunction with simple oil bath reaction and subsequent annealing, the electrode material of preparation has unique coral ball configuration.This unique structure design can improve electrode conductivuty simultaneously and its volume expansion is effectively relieved.Under room temperature (25 DEG C) and cryogenic conditions (- 25 DEG C), half/full battery of assembling shows excellent chemical property.Especially Na3V2(PO4)2O2F//Fe7Se8@C full battery is at -25 DEG C, 0.05A g‑1440 circle of current density circulation, capacity still have 165.6mAh g‑1.Synthesis material of the present invention is cheap and easy to get, and preparation method is simply mild, and reaction yield is high, is expected to realize its business application.

Description

A kind of half/full battery Fe of lithium/sodium ion low temperature7Se8The preparation method of@C negative electrode material
Technical field
The invention belongs to novel energy resource material technology fields, are related to a kind of half/full battery Fe of lithium/sodium ion low temperature7Se8@C is negative The preparation method of pole material, prepared material have coral ball configuration, show excellent half at low ambient temperatures/full electricity Pond chemical property, and synthesize simple, yield height, low raw-material cost.
Background technique
A large amount of Fossil fuel consumptions and serious environmental problem promote researcher to focus more on and develop novel green Energy storage system.High efficient energy sources system of the lithium ion battery (LIBs) as a kind of great development prospect, in many fields Applied (such as mancarried device and power grid application).Up to the present, sodium-ion battery (SIBs) because of it geographically It is widely distributed also to have attracted more and more interest.In addition, reported chemical property also shows sodium-ion battery application Potentiality.However, Na+Radius (1.02A) essentially greater than Li+(0.76A), and Na+/ Na oxidation-reduction potential (- 2.71V) it is relatively higher than Li+/ Li (- 3.04V) directly inhibits the storage performance of sodium.In general, graphite is as commercial cathode material Material, capacity is about 372mAh g-1, but be used as SIBs negative electrode material when because being difficult to generate insertion graphite compound, reversible capacity Only 30mAh g-1.Fundamentally, it is extremely important that exploration, which suitably has superior lithium/sodium storage performance electrode material, 's.Currently, the material for L/SIBs cathode is broadly divided into three classes: conversion class material (sulfide compound), alloying material (tin/antimony sill) and intercalation class material (carbon material).In these electrode materials, transient metal sulfide/selenides is based on Electron rich reaction mechanism has higher theoretical capacity and seems especially prominent.Compared with corresponding metal sulfide, transition Metal selenide has higher electric conductivity, better high rate performance.Unfortunately, metal selenide is in charge and discharge process Volume change is larger, and chemical property is poor.
The storage of low temperature lithium/sodium is the widely applied major criterion of L/SIBs, especially for the application of full battery. Regrettably, the dynamics of oxidation reduction of room temperature lower electrode material still needs to improve, needless to say it is in low temperature environment.In order to Simultaneously improve the dynamics of electrode material and inhibit its volume change, most effective strategy first is that construct suitable frame with Shorten the gentle solution volume change of ion diffusion path.Recently, a series of biomimetic features, such as class watermelon type, class grape type, class Cherry type, class neuron pattern and class geologic structure type have become interesting structure design model to assign material excellent electricity Chemical reactivity.Wherein, these biomimetic materials generally have hybrid heterojunctions structure, can effectively shorten the expansions of electrons/ions Path is dissipated, active site is increased.Therefore, these advantages promote that electrode material has good cyclical stability and high-energy is close Degree.Therefore, we devise a kind of novel coralloid Fe of class7Se8@C heterojunction structure, composite material therein are by orderly Nanometer rods assemble.Open channel between nanometer rods can be used as " channel " of electrolyte ion fast transfer, receive simultaneously Bore clearance between rice grain can increase active site.Importantly, the conductive carbon obtained in situ from surfactant These nanometer rods of tight to effectively improve the conductivity of composite material accelerate dynamics of oxidation reduction mistake Journey
Here, we have synthesized a kind of advanced cathode by the subsequent annealing of simple oil bath reaction bonded first Material Fe7Se8@C, the material have excellent low temperature lithium/sodium storage performance, are suitable for half/full battery of lithium/sodium ion.Gained The electrode material arrived is in coral structures, wherein Fe7Se8Stick is limited in the conductive carbon layer with open channel.This preparation Fe7Se8Under the conditions of@C is from -25 DEG C to room temperature (25 DEG C), all there is excellent chemical property.Such as it is being used as lithium ion The test of half-cell negative electrode material, novel Fe7Se8@C is in 5A g-1200 circle of circulation, capacity still have 791.6mAh g under current density-1.In addition, Fe7Se8@C is being used as the test of half/full battery negative electrode material of lithium/sodium ion equally with outstanding electrochemistry Matter.With Na3V2(PO4)2O2The matching of F anode is used as sodium ion full battery, in 5A g-1Under current density, capacity still has 188.9 mAh g-1, 1A g-1200 circle of circulation, capacity still have 232.1mAh g-1。Na3V2(PO4)2O2F//Fe7Se8@C full battery is -25 At DEG C, 0.05 A g-1440 circle of current density circulation, capacity still have 165.6mAh g-1.Demonstrate the full weather of the negative electrode material Applicability.
Summary of the invention
The purpose of the present invention is designs to synthesize a kind of negative electrode material that can apply to low temperature environment, and this design is using simple Oil bath reaction bonded annealing, be successfully prepared carbon-coated eight selenizings, seven iron (Fe7Se8@C) compound.Effectively tie The electric conductivity of carbon frame and the opening duct of hierarchical structure and advantageous electrochemical reaction site are closed, what is prepared is compound Object shows excellent low temperature and room temperature chemical property, Er Qiehe when being used as half/full battery negative electrode material of lithium/sodium ion At low in cost, operating process is simple, is expected to realize full weather electrode material application.
The preparation method of carbon-coated eight selenizings, seven iron of the invention, the specific steps are as follows:
(1) source of iron, selenium source and organic reagent are mixed, obtain uniform dark solution by magnetic agitation.It will be black Color solution is packed into round-bottomed flask.
(2) round-bottomed flask is transferred in oil bath pan, in oil bath reaction a period of time.
(3) after reaction, round-bottomed flask is taken out, isolates the black product in round-bottomed flask with centrifuge, and use second Alcohol cleans for several times.
(4) washed black product is put into 70 DEG C of baking ovens dry 15h.
(5) it is put into magnetic boat after grinding, is then made annealing treatment in tube furnace.
The source of iron of initial feed is four water frerrous chlorides, ferrous sulfate heptahydrate, nine water ferric nitrates, ferric trichloride etc.；Selenium source For selenium dioxide, selenium powder, sodium selenite etc.；The solvent of selection is dimethyl acetamide, acetone, isopropanol, ethylene glycol, ethyl alcohol Amine, diethylene glycol, dimethylformamide, oleyl amine dimethyl sulfoxide and water etc.；Oil bath reaction temperature be 120 DEG C, 150 DEG C, 160 DEG C, 180 DEG C etc.；The oil bath reaction time is 6h, 8h, 10h, 12h etc.；Tube furnace calcination temperature be 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 800 DEG C.
Fe is provided in the present invention7Se8The preparation of@C negative electrode material, it is preferable that the source of iron used is nine water ferric nitrate.
Fe is provided in the present invention7Se8The preparation of@C negative electrode material, it is preferable that the selenium source used is selenium powder.
Fe is provided in the present invention7Se8The preparation of@C negative electrode material, it is preferable that the reaction dissolvent used is oleyl amine.
Fe is provided in the present invention7Se8The preparation of@C negative electrode material, it is preferable that the oil bath reaction temperature used is 150 DEG C.
Fe is provided in the present invention7Se8The preparation of@C negative electrode material, it is preferable that the calcination temperature used is 600 DEG C.
The compound of carbon-coated eight selenizings, seven iron prepared by the present invention, appearance structure is coral spherical structure, ultra-thin Carbon is wrapped in the outside of eight selenizings, seven iron.The Na being assembled into3V2(PO4)2O2F//Fe7Se8@C full battery is tested, room temperature item Under part, 5A g-1Under current density, capacity still has 188.9mAh g-1, 1A g-1200 circle of circulation, capacity still have 232.1mAh g-1。Na3V2(PO4)2O2F//Fe7Se8@C full battery is at -25 DEG C, 0.05A g-1440 circle of current density circulation, capacity still have 165.6mAh g-1。
Bath oiling of the invention combines the compound of carbon-coated eight selenizings, seven iron of annealing synthesis, the advantage is that:
(1) experimental facilities and synthesis technology are simple to operation, and low raw-material cost used, synthetic yield height is easy to implement Commercial applications.
(2) the generated in-situ ultra-thin carbon-coating of this method, can not only effectively enhance the electric conductivity of compound, and can effectively delay Volume expansion in solution reaction, ensure that structural intergrity.The coral structures of design effectively shorten ion and electronics simultaneously Transmission path enhances the dynamics of reaction.
(3) negative electrode material of this method preparation all has in room temperature and low temperature environment through Series Electrochemical performance test The storage lithium and storage sodium performance of excellent half-cell and full battery, it was confirmed that its potential practicability.
Detailed description of the invention
The present invention is further detailed below with reference to case study on implementation and attached drawing:
Attached drawing 1 is that the SEM of carbon-coated eight selenizings, seven iron made from embodiment 1 schemes (a), (b), pattern schematic diagram (c), TEM schemes (d), and (e) and HRTEM schemes (f) and its distribution diagram of element (g-j)；
Attached drawing 2 is the cyclic voltammetric (a) of carbon-coated eight selenizings, seven iron made from embodiment 1, constant current charge-discharge curve (b), cycle performance (c), electrons/ions react schematic diagram (d) and high rate performance figure (e)；
Attached drawing 3 is carbon-coated eight selenizings, seven iron made from embodiment 1 in room temperature and -25 DEG C of full battery performance map；
Specific implementation method
Embodiment 1
The nine water ferric nitrates and 154mg selenium powder of 404mg are added in beaker, and oleyl amine then is added to the inside, stir one section It is poured into round-bottomed flask after time.Flask is transferred in oil bath pan, 150 DEG C of reaction 10h.After reaction, tube furnace is used It is heat-treated at 600 DEG C, finally obtains the Fe with coral structures7Se8@C compound.The Fe of preparation7Se8@C compound level-one The ball that structure is about 1.3 μm of size, secondary structure is the carbon coating Fe of pole shape7Se8.It is assembled into Na3V2(PO4)2O2F// Fe7Se8@C full battery is tested, under room temperature, 5A g-1Under current density, capacity still has 188.9mAh g-1, 1A g-1 200 circle of circulation, capacity still have 232.1mAh g-1。Na3V2(PO4)2O2F//Fe7Se8@C full battery is at -25 DEG C, 0.05A g-1 440 circle of current density circulation, capacity still have 165.6mAh g-1.(attached drawing 1-3).
Embodiment 2
The nine water ferric nitrates and 154mg selenium powder of 404mg are added in beaker, and oleyl amine then is added to the inside, stir one section It is poured into round-bottomed flask after time.Flask is transferred in oil bath pan, 150 DEG C of reaction 8h.After reaction, tube furnace is used It is heat-treated at 600 DEG C, obtains the Fe of uniform spherical shape7Se8@C compound.It is assembled into Na3V2(PO4)2O2F//Fe7Se8@C is complete Battery is tested, under room temperature, 5A g-1Under current density, capacity still has 128.9mAh g-1, at -25 DEG C, 0.05A g-1100 circle of current density circulation, capacity still have 115.5mAh g-1。
Embodiment 3
The nine water ferric nitrates and 118mg selenium powder of 404mg are added in beaker, and oleyl amine then is added to the inside, stir one section It is poured into round-bottomed flask after time.Flask is transferred in oil bath pan, 150 DEG C of reaction 10h.After reaction, tube furnace is used It is heat-treated at 600 DEG C.It is assembled into Na3V2(PO4)2O2F//Fe7Se8@C full battery is tested, under room temperature, 5A g-1 Under current density, capacity still has 158.3mAh g-1, at -25 DEG C, 0.05A g-1100 circle of current density circulation, capacity still have 149.2mAh g-1。
Embodiment 4
The nine water ferric nitrates and 118mg selenium powder of 404mg are added in beaker, and oleyl amine then is added to the inside, stir one section It is poured into round-bottomed flask after time.Flask is transferred in oil bath pan, 150 DEG C of reaction 8h.After reaction, tube furnace is used It is heat-treated at 600 DEG C.It is assembled into Na3V2(PO4)2O2F//Fe7Se8@C full battery is tested, under room temperature, 5A g-1 Under current density, capacity still has 138.8mAh g-1, at -25 DEG C, 0.05A g-1100 circle of current density circulation, capacity still have 125.1mAh g-1。
Embodiment 5
The nine water ferric nitrates and 154mg selenium powder of 404mg are added in beaker, and oleyl amine then is added to the inside, stir one section It is poured into round-bottomed flask after time.Flask is transferred in oil bath pan, 150 DEG C of reaction 10h.After reaction, tube furnace is used It is heat-treated at 400 DEG C, obtains the Fe of uniform spherical shape7Se8@C compound.It is assembled into Na3V2(PO4)2O2F//Fe7Se8@C is complete Battery is tested, under room temperature, 5A g-1Under current density, capacity still has 165.1mAh g-1, at -25 DEG C, 0.05A g-1100 circle of current density circulation, capacity still have 100.1mAh g-1。

Claims (7)

1. a kind of half/full battery Fe of lithium/sodium ion low temperature7Se8The preparation method of@C negative electrode material, the preparation method include following Step:
(1) source of iron, selenium source and organic reagent are mixed, obtain uniform dark solution by magnetic stirring apparatus.
(2) reaction solution is transferred in round-bottomed flask, a period of time is reacted in oil bath pan.
(3) after reaction, round-bottomed flask is taken out, isolates the black product in round-bottomed flask with centrifuge, and clear with ethyl alcohol It washes for several times.
(4) washed black product is put into 70 DEG C of baking ovens dry 15h, is put into after grinding in magnetic boat, then in tube furnace Annealing.
2. Fe according to claim 17Se8The preparation method of@C negative electrode material, wherein source of iron be four water frerrous chlorides, seven Aqueous ferrous sulfate, nine water ferric nitrates, one of ferric trichloride.
3. Fe according to claim 17Se8The preparation method of@C negative electrode material, wherein selenium source is selenium dioxide, selenium powder, One of sodium selenite.
4. Fe according to claim 17Se8The preparation method of@C negative electrode material, wherein the solvent of selection is dimethyl second Amide, acetone, isopropanol, ethylene glycol, ethanol amine, diethylene glycol, dimethylformamide, dimethyl sulfoxide, oleyl amine and water it One.
5. Fe according to claim 17Se8The preparation method of@C negative electrode material, wherein oil bath reaction temperature is 120 DEG C, 150 DEG C, 160 DEG C, one of 180 DEG C.
6. Fe according to claim 17Se8The preparation method of@C negative electrode material, wherein the oil bath reaction time be 6h, 8h, One of 10h, 12h.
7. Fe according to claim 17Se8The preparation method of@C negative electrode material, wherein calcination temperature be 300-700 DEG C it One.
CN201910454663.3A 2019-05-29 2019-05-29 A kind of half/full battery Fe of lithium/sodium ion low temperature7Se8The preparation method of@C negative electrode material Pending CN110335997A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112786853A (en) * 2020-12-22 2021-05-11 山西大学 High-rate composite negative electrode material of sodium ion battery and preparation method thereof
CN115207344A (en) * 2021-04-12 2022-10-18 南京工业大学 Fe x Se y Preparation of @ CN composite material and electrochemical energy storage application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112786853A (en) * 2020-12-22 2021-05-11 山西大学 High-rate composite negative electrode material of sodium ion battery and preparation method thereof
CN112786853B (en) * 2020-12-22 2022-03-18 山西大学 High-rate composite negative electrode material of sodium ion battery and preparation method thereof
CN115207344A (en) * 2021-04-12 2022-10-18 南京工业大学 Fe x Se y Preparation of @ CN composite material and electrochemical energy storage application thereof

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Application publication date: 20191015