CN105845933A - Doped-state spherical FeF<3>.0.33H<2>O positive electrode material and preparation method therefor - Google Patents
Doped-state spherical FeF<3>.0.33H<2>O positive electrode material and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a doped-state spherical FeF<3>.0.33H<2>O positive electrode material and a preparation method therefor. The chemical expression of the positive electrode material is Fe<1-x>M<x>F<3+(n-3)x>.0.33H<2>O, wherein M is doped elements Mg, Co, Ni or Zn; x is equal to 0.03-0.3; and n is the valance of the corresponding doped elements. The preparation method comprises the steps of putting Fe(NO<3>)<3>.9H<2>O into a reactor, adding nitrate of other doped metal; then adding alcohol, magnetically stirring for 10-20min to obtain a settled solution; then adding an HF water solution in a dropwise manner and stirring for 10-20min; moving the mixture to a hydrothermal reaction kettle to react, then carrying out solid-liquid separation; and carrying out vacuum drying at a temperature of 20-80 DEG C to obtain the doped-state spherical FeF<3>.0.33H<2>O particles. The doped state spherical ferric fluoride obtained by the invention has uniform particles, rough surface, high tap density, high repeatability and excellent electrochemical performance; and the reaction yield can reach greater than 80%.
Description
Technical field
The present invention relates to a kind of doped spherical FeF3·0.33H2O positive electrode and preparation method thereof,
FeF3·0.33H2The doped spherical FeF of O3·0.33H2O material can belong to as the positive electrode of lithium ion battery
In technical field of new energy material preparation.
Background technology
The research of lithium ion battery electrode material is the focus in current investigation of materials field, because energy storage device is
The bottleneck of constraint information era development, the high modern society consumed does not continues the efficient energy and supports the most not
Can continue.By the continuous exploration of whole world scientific research personnel in decades, people are to lithium ion battery
Very familiar, have also been developed many business-like electrode materials, wherein positive electrode has: cobalt acid lithium,
LiMn2O4, ternary material, rich lithium material, LiFePO4 etc..But these materials are each defective, cobalt acid lithium
Actual capacity only has 140mAh g-1, the actual capacity of LiMn2O4 only has 110～120mAh g-1, and putting
In electric process, specific discharge capacity decay is serious, causes its cycle performance poor, and the security performance of ternary material also has
Waiting to improve, the initial coulomb efficiency of rich lithium is low and high rate performance is poor, and LiFePO4 electronic conductivity is low, low temperature
Poor performance and tap density are low.And these materials have a common feature to be exactly that they are all built upon
The battery material of same theoretic, this theory is exactly Li+Deintercalation is theoretical.Will be in the property of battery material
Can go up and obtain bigger breakthrough, to be on the one hand modified existing material improving on the basis of existing,
On the other hand to innovate from the theory of battery material, develop new material.
Metal fluoride is exactly the electrode material that a class is different from simple deintercalation model, and it is at charge and discharge process
In except there being Li+Deintercalation, it can also be by self reversible chemical conversion reaction storing energy.This can
Inverse chemical conversioning reaction can make full use of the various oxidation state of material, exchange material in oxidation-reduction process
In all of electronics, its theoretical specific capacity be significantly larger than tradition outline on Li+Embedding/deintercalation is reacted；Again because of
Electronegativity for fluorine is big, and the running voltage of metal fluoride positive electrode is higher than the oxide material of its correspondence
Material, so metal fluoride has higher energy density.Therefore, metal fluoride positive electrode has the highest
Researching value.
Studying more metal fluoride at present is ferric flouride, and ferric flouride raw material is easy to get, low cost, environment friend
Good, and have good high-temperature stability.The theoretical specific capacity of ferric flouride generation single Electron Transfer Reactions is 237
mAh·g-1, the theoretical specific capacity of 3 electron transfers is 712mAh g-1.By the research to ferric flouride, send out
The shortcoming of its maximum existing is precisely due to band gap width causes its electronic conduction ability the poorest, and high rate performance is poor,
Make its actual specific capacity less than theoretical specific capacity.The electronic conduction ability of ferric flouride to be improved just should be from following
Several aspects are started with: one is to be run business into particular one as far as possible by the granule of material, because the most activity surface of granule is the biggest,
And electronic conduction distance is the shortest；Two be add in material the strong material of some conductive capabilities make ferric flouride and
The composite of conductive agent, the most on the carbon material growth ferric flouride or carbon coated material；Three is at material
Material carries out doped with metal elements, manufactures some defects in lattice, changes the electronic structure of material thus improves
Its conductive capability.Someone makes ferric flouride grain refine by the method for ball milling at present, but be obtained by
Grain is the most uneven and tap density is low, causes volume and capacity ratio low, affects its actual application.Also some are had to close
In doing the report of ferric flouride composite, but it is rough mixing mostly, is not reaching to growth in situ or uniformly
The purpose of cladding, so the chemical property of material does not improve a lot.There is theoretical computational chart bright, right
The wide material of band gap carries out the doping of other elements can effectively reduce the width of band gap, improves electronics
Conductive capability.
In all methods improving ferric flouride chemical property, doping is the primary stage pair at synthetic material
Material is modified, and simpler directly production cost is relatively low, and doping is easier to obtain the material of stable homogeneous
Material.Successfully doping can not only reduce the band gap of ferric flouride the ferric flouride granule of generation can also be made the most even and fine
Little, the pattern of formation rule, improves its tap density, is conducive to reducing the volume of battery.
Therefore with the spherical FeF of a kind of simple efficient method synthesizing blender state3·0.33H2O, improves it simultaneously
Electronic conductivity and tap density, have the highest theory value and using value.
Summary of the invention
Present invention aims to ferric flouride electronic conductivity low, tap density is the highest, chemical property
The problem of difference, it is provided that a kind of doped spherical FeF3·0.33H2O positive electrode and preparation method thereof.
The technical scheme is that
A kind of doped spherical FeF3·0.33H2O positive electrode, molecular formula is Fe1-xMxF3+(n-3)x·0.33H2O,
Wherein M is doped chemical Mg, Co, Ni or Zn, and x=0.03～0.3, n are the quantivalence of doped chemical；
It has spherical morphology, a diameter of 500 nanometers of spheroidal particle～5 microns.
Above-mentioned doped spherical FeF3·0.33H2The preparation method of O positive electrode, comprises the steps:
(1) under room temperature, by Fe (NO3)3·9H2O is placed in reactor, adds the nitric acid of other metal
Salt, is subsequently adding absolute alcohol, magnetic agitation 10～make Fe (NO in 20 minutes3)3·9H2O and the nitre of other metal
Hydrochlorate dissolves, the lower dropping HF aqueous solution of stirring, and the mol ratio controlling iron ion and fluorion is 1:4～4.5,
Stir 10～15 minutes；
(2) moving in hydrothermal reaction kettle by the reactor of sealing, controlling reaction temperature is 90～190 DEG C, instead
It is cooled to room temperature after answering 1～6 hour, obtains bottom and be covered with the mixed liquor of one layer of precipitation top clarification；
(3) outwell the supernatant, precipitation is washed in centrifuge tube centrifugal with ethanol, then wash 2～5 with ethanol
Secondary, centrifugal, 20～80 DEG C are vacuum dried and i.e. obtain doped spherical FeF3·0.33H2O positive electrode, is
Fe1-xMxF3+(n-3)x·0.33H2(M is doped chemical Mg, Co, Ni or Zn to O, and x=0.03～0.3, n are for mixing
The quantivalence of miscellaneous element).
Further, described alcohol is methanol, ethanol, the one in propanol；Add reactant iron ion after alcohol
Concentration control 0.1～0.5mol/L.
Further, the mass fraction of described HF aqueous solution is 20%～50%, preferably 30～40%.
Further, described reactor preferably polytetrafluoroethylene reactor.
Further, other described metal is the one in Mg, Co, Ni, Zn；Control the alcohol formed
In solution, iron ion is 1:0.03～0.3 with the mol ratio of other metal ion.
The present invention has the following technical effect that:
The present invention can by control solvent species, reactant concentration, doping ionic species, dopant ion concentration,
Response time, the structure of reaction temperature regulation product and particle diameter, products therefrom is doped spherical
FeF3·0.33H2O, the more aspheric FeF of its chemical property3·0.33H2O significantly improves, and is a kind of simple
The doped spherical FeF of high-efficiency environment friendly3·0.33H2O preparation method.The preparation method of the present invention enables to produce
Rate more than 80%, the doped spherical FeF of preparation3·0.33H2O purity is high, granularity is little, rough surface,
Epigranular, tap density are high, reproducible, excellent electrochemical performance.
Accompanying drawing explanation
Fig. 1 is spherical Fe prepared by the present invention0.91Mg0.09F2.91·0.33H2Scanning electron microscope (SEM) photograph (the times magnification of O
Number is 30000 times).
Fig. 2 is spherical Fe prepared by the present invention0.87Mg0.13F2.87·0.33H2Scanning electron microscope (SEM) photograph (the times magnification of O
Number is 30000 times).
Fig. 3 is spherical Fe prepared by the present invention0.83Mg0.17F2.83·0.33H2Scanning electron microscope (SEM) photograph (the times magnification of O
Number is 30000 times).
Fig. 4 is spherical Fe prepared by the present invention0.95Co0.05F2.95·0.33H2Scanning electron microscope (SEM) photograph (the amplification of O
It it is 1000 times).
Fig. 5 is spherical Fe prepared by the present invention0.95Ni0.05F3·0.33H2(amplification is the scanning electron microscope (SEM) photograph of O
1000 times).
Fig. 6 is spherical Fe prepared by the present invention0.95Zn0.05F3·0.33H2(amplification is the scanning electron microscope (SEM) photograph of O
1000 times).
Fig. 7 is spherical Fe prepared by the present invention0.87Mg0.13F2.87·0.33H2The transmission electron microscope picture of O.
Fig. 8 is spherical Fe prepared by the present invention0.87Mg0.13F2.87·0.33H2The X-ray diffractogram of O.
Fig. 9 is spherical Fe prepared by the present invention0.95Co0.05F2.95·0.33H2The X-ray diffractogram of O.
Figure 10 is spherical Fe prepared by the present invention0.95Ni0.05F2.95·0.33H2The X-ray diffractogram of O.
Figure 11 is spherical Fe prepared by the present invention0.95Zn0.05F2.95·0.33H2The X-ray diffractogram of O.
Figure 12 is the spherical Fe prepared by the present invention0.87Mg0.13F2.87·0.33H2O and FeF3·0.33H2O divides
Not Wei positive electrode, lithium sheet is negative material, is assembled into button cell, at room temperature with 47.4mA/g's
Electric current density, the cycle life curve in the voltage range of 1.5-4.5V.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described
Embodiment 1
Under room temperature, weigh 4.04g Fe (NO3)3·9H2O、0.384g Mg(NO3)2·6H2O is placed in polytetrafluoroethyl-ne
In alkene reaction device, add 50mL absolute methanol, magnetic agitation, dissolve, be stirred continuously lower dropping 2mL matter
Amount mark is the HF aqueous solution of 40%, stirs 15 minutes.Reactor is placed in hydrothermal reaction kettle sealing,
180 DEG C are heated 6 hours, obtain bottom and are covered with the mixed liquor of one layer of precipitation top clarification, outwell supernatant,
With dehydrated alcohol precipitation washed and centrifugal in centrifuge tube obtain white precipitate, then wash 2 times with ethanol, centrifugal,
80 DEG C of vacuum drying i.e. obtain white Fe in 12 hours0.87Mg0.13F2.87·0.33H2O powder, being found by test should
Fe0.87Mg0.13F2.87·0.33H2O is spheroidal particle, and particle diameter is at 500 ran.
Embodiment 2
Under room temperature, weigh 4.04g Fe (NO3)3·9H2O、0.256g Mg(NO3)2·6H2O is placed in polytetrafluoroethyl-ne
In alkene reaction device, add 50mL absolute methanol, magnetic agitation, dissolve, be stirred continuously lower dropping 2mL matter
Amount mark is the HF aqueous solution of 40%, stirs 10 minutes.Reactor is placed in hydrothermal reaction kettle sealing,
180 DEG C are heated 6 hours, obtain bottom and are covered with the mixed liquor of one layer of precipitation top clarification, outwell supernatant,
With dehydrated alcohol precipitation washed and centrifugal in centrifuge tube obtain white precipitate, then wash 2 times with ethanol, centrifugal,
60 DEG C of vacuum drying i.e. obtain white Fe in 16 hours0.91Mg0.09F2.91·0.33H2O powder, being found by test should
Fe0.91Mg0.09F2.91·0.33H2O is spheroidal particle, and particle diameter is at 1 microns.
Embodiment 3
Under room temperature, weigh 4.04g Fe (NO3)3·9H2O、0.512g Mg(NO3)2·6H2O is placed in polytetrafluoroethyl-ne
In alkene reaction device, add 50mL absolute methanol, magnetic agitation, dissolve, be stirred continuously lower dropping 2.1mL
Mass fraction is the HF aqueous solution of 45%, stirs 15 minutes.Reactor is placed in hydrothermal reaction kettle close
Envelope, 190 DEG C are heated 6 hours, obtain bottom and are covered with the mixed liquor of one layer of precipitation top clarification, outwell supernatant
Liquid, washes precipitation with dehydrated alcohol and centrifugal in centrifuge tube obtains white precipitate, then wash 3 times with ethanol, from
The heart, 80 DEG C of vacuum drying i.e. obtain white Fe in 12 hours0.83Mg0.17F2.83·0.33H2O powder, is sent out by test
Now this Fe0.83Mg0.17F2.83·0.33H2O is spheroidal particle, and particle diameter is at 600 ran.
Embodiment 4
Under room temperature, weigh 4.04g Fe (NO3)3·9H2O、0.1455g Co(NO3)2·6H2O is placed in polytetrafluoro
In ethylene reaction device, add 50mL absolute methanol, magnetic agitation, dissolve, be stirred continuously lower dropping 2mL
Mass fraction is the HF aqueous solution of 40%, stirs 15 minutes.Reactor is placed in hydrothermal reaction kettle close
Envelope, 180 DEG C are heated 1 hour, obtain bottom and are covered with the mixed liquor of one layer of precipitation top clarification, outwell supernatant
Liquid, washes precipitation with dehydrated alcohol and centrifugal in centrifuge tube obtains pale yellow precipitate, then wash 2 times with ethanol,
Centrifugal, 60 DEG C of vacuum drying i.e. obtain faint yellow Fe in 12 hours0.95Co0.05F2.95·0.33H2O powder, by surveying
Examination finds this Fe0.95Co0.05F2.95·0.33H2O is spheroidal particle, and particle diameter is at 5 microns.
Embodiment 5
Under room temperature, weigh 4.04g Fe (NO3)3·9H2O、0.1455g Ni(NO3)2·6H2O is placed in polytetrafluoroethyl-ne
In alkene reaction device, add 50mL absolute methanol, magnetic agitation, dissolve, be stirred continuously lower dropping 2mL matter
Amount mark is the HF aqueous solution of 40%, stirs 15 minutes.Reactor is placed in hydrothermal reaction kettle sealing,
180 DEG C are heated 1 hour, obtain bottom and are covered with the mixed liquor of one layer of precipitation top clarification, outwell supernatant,
With dehydrated alcohol, precipitation is washed the centrifugal light green that obtains in centrifuge tube to precipitate, then wash 2 times with ethanol, centrifugal,
60 DEG C of vacuum drying i.e. obtain light green Fe in 12 hours0.95Ni0.05F2.95·0.33H2O powder, is found by test
This Fe0.95Ni0.05F2.95·0.33H2O is spheroidal particle, and particle diameter is at 5 microns.
Embodiment 6
Under room temperature, weigh 4.04g Fe (NO3)3·9H2O、0.149g Zn(NO3)2·6H2O is placed in polytetrafluoroethyl-ne
In alkene reaction device, add 50mL absolute methanol, magnetic agitation, dissolve, be stirred continuously lower dropping 2.2mL matter
Amount mark is the HF aqueous solution of 35%, stirs 10 minutes.Reactor is placed in hydrothermal reaction kettle sealing,
180 DEG C are heated 1 hour, obtain bottom and are covered with the mixed liquor of one layer of precipitation top clarification, outwell supernatant,
With dehydrated alcohol precipitation washed and centrifugal in centrifuge tube obtain white precipitate, then wash 2 times with ethanol, centrifugal,
60 DEG C of vacuum drying i.e. obtain white Fe in 12 hours0.95Zn0.05F2.95·0.33H2O powder, being found by test should
Fe0.95Zn0.05F2.95·0.33H2O is spheroidal particle, and particle diameter is at 5 microns.
As shown in Figures 1 to 3, it can be seen that can to obtain hundreds of nanometer big by doping Mg element
Little doped spherical FeF3·0.33H2O granule, and particle size distribution is uniform, spherical surface is coarse, can be bright
Showing and see the secondary particle being constituted hundreds of nanometer by the first stage particles of tens nanometers, such structure can be bright
The aobvious specific surface increasing particle, also helps the infiltration of electrolyte simultaneously, shorten the electronic conduction of ferric flouride away from
From, favourable to the chemical property of material.
As shown in figures 4-6, it can be seen that by adulterate at different conditions Co, Ni, Zn,
Have also been obtained the particle diameter doped spherical FeF within several microns3·0.33H2O。
As it is shown in fig. 7, it can be seen that the bright dark of many replaces from transmission electron microscope picture, the spherical of gained is described
Fe0.87Mg0.13F2.87·0.33H2O is molecular by the nanoparticle that many is less, has pore structure, has
It is beneficial to infiltration and the transmission of electric charge of electrolyte.
As shown in Fig. 8～11, it can be seen that doped spherical FeF from the XRD figure after doping3·0.33H2O
X-ray diffraction peak well can coincide with standard card (76-1262), illustrate that doping is successful,
It is not to generate solid mixture.
As shown in figure 12, it can be seen that with spherical Fe0.87Mg0.13F2.87·0.33H2O is positive pole material
Material, lithium sheet is negative material, is assembled into button cell, at room temperature with the electric current density of 47.4mA/g,
In the voltage range of 1.5-4.5V, circulate 100 specific discharge capacities also have 159mAh/g, circulate 200 times
Also has 139mAh/g；And FeF under the same conditions3·0.33H2O is at the specific discharge capacity of the 100th circulation
For 99mAh/g, the 200th time is 81.5mAh/g；Illustrate that magnesium-doped element significantly improves
FeF3·0.33H2The chemical property of O.
Claims (6)
1. a doped spherical FeF3·0.33H2O positive electrode, it is characterised in that: molecular formula is
Fe1-xMxF3+(n-3)x·0.33H2O, wherein M is doped chemical Mg, Co, Ni or Zn, x=0.03～0.3,
N is the quantivalence of doped chemical；It has spherical morphology, a diameter of 500 nanometers of spheroidal particle～5 microns.
2. the doped spherical FeF described in claim 13·0.33H2The preparation method of O positive electrode, its
It is characterised by, comprises the steps:
(1) under room temperature, by Fe (NO3)3·9H2O is placed in reactor, adds the nitric acid of other metal
Salt, is subsequently adding absolute alcohol, magnetic agitation 10～make Fe (NO in 20 minutes3)3·9H2O and the nitre of other metal
Hydrochlorate dissolves, the lower dropping HF aqueous solution of stirring, and the mol ratio controlling iron ion and fluorion is 1:4～4.5,
Stir 10～15 minutes；
(2) moving in hydrothermal reaction kettle by the reactor of sealing, controlling reaction temperature is 90～190 DEG C, instead
It is cooled to room temperature after answering 1～6 hour, obtains bottom and be covered with the mixed liquor of one layer of precipitation top clarification；
(3) outwell the supernatant, precipitation is washed in centrifuge tube centrifugal with ethanol, then wash 2～5 with ethanol
Secondary, centrifugal, 20～80 DEG C are vacuum dried and i.e. obtain doped spherical FeF3·0.33H2O positive electrode, is
Fe1-xMxF3+(n-3)x·0.33H2O, wherein M is doped chemical Mg, Co, Ni or Zn, x=0.03～0.3,
N is the quantivalence of doped chemical.
Doped spherical FeF the most according to claim 23·0.33H2The preparation method of O positive electrode,
It is characterized in that, described alcohol is methanol, ethanol, the one in propanol；Add reactant iron ion after alcohol
Concentration controls 0.1～0.5mol/L.
Doped spherical FeF the most according to claim 23·0.33H2The preparation method of O positive electrode,
It is characterized in that, the mass fraction of described HF aqueous solution is 20%～50%.
Doped spherical FeF the most according to claim 23·0.33H2The preparation method of O positive electrode,
It is characterized in that, described reactor is politef reactor.
Doped spherical FeF the most according to claim 23·0.33H2The preparation method of O positive electrode,
It is characterized in that, other described metal is the one in Mg, Co, Ni, Zn；The alcohol controlling to be formed is molten
In liquid, iron ion is 1:0.03～0.3 with the mol ratio of other metal ion.
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| CN106099074A (en) * | 2016-08-19 | 2016-11-09 | 广东工业大学 | A kind of modified fluorinated ferrum nano composite anode material and its preparation method and application |
| CN113241444A (en) * | 2020-12-28 | 2021-08-10 | 中国科学院过程工程研究所 | FeF3Base composite positive electrode material, preparation method thereof and lithium ion battery |
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| LI LIU等: "Excellent cycle performance of Co-doped FeF3/C nanocomposite cathode", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| R.S. RAO等: "Facile synthesis and reversible lithium insertion studies on hydrated iron trifluoride FeF3•0.33H2O", 《SOLID STATE SCIENCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099074A (en) * | 2016-08-19 | 2016-11-09 | 广东工业大学 | A kind of modified fluorinated ferrum nano composite anode material and its preparation method and application |
| CN106099074B (en) * | 2016-08-19 | 2019-03-22 | 广东工业大学 | A kind of modified fluorinated iron nano composite anode material and its preparation method and application |
| CN113241444A (en) * | 2020-12-28 | 2021-08-10 | 中国科学院过程工程研究所 | FeF3Base composite positive electrode material, preparation method thereof and lithium ion battery |
| CN113241444B (en) * | 2020-12-28 | 2022-09-27 | 中国科学院过程工程研究所 | FeF 3 Base composite positive electrode material, preparation method thereof and lithium ion battery |
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| Publication number | Publication date |
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| CN105845933B (en) | 2019-08-27 |
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