CN105152154B - A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material - Google Patents
A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material Download PDFInfo
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- CN105152154B CN105152154B CN201510401813.6A CN201510401813A CN105152154B CN 105152154 B CN105152154 B CN 105152154B CN 201510401813 A CN201510401813 A CN 201510401813A CN 105152154 B CN105152154 B CN 105152154B
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Abstract
The present invention relates to a kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material, comprises the following steps：(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, after dry grinding, wet-milling, active material is made；(2) active material is weighed, and is mixed with binding agent, is stirred, slurries are made, and coated on button cell anode cover, be compacted, vacuum drying；(3) it is assembled into button cell；(4) electrochemical method is passed through, constant current charge-discharge circulation is carried out with 0.1C multiplying powers, again with 0.01 0.05C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, dismantled, take out the electrode material on button cell anode cover, cleaning, through ultrasonic disperse, drying, that is, olivine-type NaFePO is made4Sodium-ion battery positive material.Compared with prior art, the present invention is with armorphous nano FePO4For raw material, raw material sources enrich, and inexpensively, preparation method is simple, and without high-temperature heat treatment, obtained material has excellent chemical property.
Description
Technical field
The invention belongs to sodium-ion battery technical field, is related to a kind of olivine-type NaFePO4Sodium-ion battery positive pole material
The preparation method of material.
Background technology
In recent years, due to environmental problem getting worse, energy crisis, the utilization of new energy and the development of energy storage technology
Turn into the problem of mankind face jointly.Lithium ion battery has been widely used for portable digital because of its excellent performance
Product.Future, lithium ion battery were paid attention to the advantages that high-energy-density and by energy storage field worker because of the long life.So
And lithium ion battery applications also face some challenges in energy storage field.First, lithium source reserves are limited, metals on the earth
The price of lithium can be gradually increasing with lithium ion battery large-scale application, secondly, it is further develop preferable electrode material
Its performance is improved to be particularly important.
The sodium of same main group is in lithium, has similar chemical property to lithium.Sodium-ion battery has with lithium ion battery
Similar principle, it is important that the reserves of sodium on earth are far above lithium.At present, many grinding on sodium ion positive electrode
Study carefully work to be reported in succession, such as NaxCoO2, Na0.44MnO2, Na0.6MnO2, NaCrO2, NaxVO2, Na3V2(PO4)3, Na3V2
(PO4)2F3, Na3V2O2(PO4)2F, Na2FePO4F, NaFeF3Deng, but the performance of these positive electrodes still can not meet sodium ion
The requirement of the industrial applications of battery.Therefore, it is the industrialized key of sodium-ion battery to develop preferable electrode material.
Iron-based positive electrode olivine-type (olivine) LiFePO4As anode material for lithium-ion batteries, obtain wide
General application.Relative to LiFePO4, olivine-type (olivine) NaFePO4Sodium-ion battery positive material can also be used as.By
In Na+Radius ratio Li+Greatly so that NaFePO4Mainly there are two kinds of crystal formations of maricite and olivine.Due to the difference of crystal structure
It is different, maricite types NaFePO4It is inactive, and olivine types NaFePO as sodium ion positive electrode4Then have and live
Property.But maricite types NaFePO4But it is more stable.At present, obtained by some heat treatments or solid phase reaction
NaFePO4Predominantly maricite types NaFePO4.Therefore, olivine-type (olivine) NaFePO how is quickly and easily prepared4
Then it is particularly important.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind with armorphous nano
FePO4For raw material, olivine-type NaFePO is quickly and easily prepared4The method of sodium-ion battery positive material.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material, this method is with amorphous nanometer
FePO4As active material, electrode material is made, then pass through electrochemical method so that sodium ion is embedded in amorphous nanometer Fe PO4
In, and then by amorphous nanometer Fe PO4It is converted into olivine-type NaFePO4, specifically include following steps：
(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, ball milling 2-8h, then second is added into ball grinder
Alcohol ball milling 2-8h, is dried as dispersant, that is, active material is made；
(2) active material made from step (1) is weighed, and is mixed with binding agent, is sufficiently stirred, slurries are made, and coat
On button cell anode cover, the pressurize 2-4min under 3MPa pressure, fully compacting, and being dried in vacuo at 100-110 DEG C
10-12h, that is, the button cell anode cover for being loaded with electrode material is made；
(3) in the glove box filled with argon gas, using metallic sodium piece as negative pole, to be loaded with the button cell of electrode material just
Pole shell is positive pole, and is assembled into button cell jointly with electrolyte, barrier film；
(4) by electrochemical method, the button cell being assembled into step (3) carries out 5-20 constant current with 0.1C multiplying powers and filled
Discharge cycles, then with 0.01-0.05C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, dismantles, take
The electrode material gone out on button cell anode cover, cleaning, to remove the electrolyte of electrode material surface residual, then carry out ultrasound point
Dissipate, and at 70-80 DEG C after drying, that is, olivine-type NaFePO is made4Sodium-ion battery positive material.
Amorphous nanometer Fe PO described in step (1)4Mass ratio with conductive agent is (60-70):30, and described lead
Electric agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6, described dispersant is ethanol.
Described amorphous nanometer Fe PO4Particle diameter be 10-100nm, be 60-100m than surface2/ g, tap density are
1.1-1.4g/cm3。
The mass ratio of active material and binding agent described in step (2) is (88-92)：8.
Binding agent described in step (2) is LITHIUM BATTERY polytetrafluoroethylene (PTFE).
Button cell anode cover described in step (2) is the 2016 type button cell anode covers for being welded with stainless (steel) wire.
The solute of electrolyte described in step (3) is NaClO4, the NaClO4Concentration be 1mol/L, and described electricity
The solvent of solution liquid is ethylene carbonate and dimethyl carbonate is 1 by volume:1 mixed solvent, described barrier film are LITHIUM BATTERY
Glass mat.
Described in step (4) constant current charge-discharge circulation condition be：It is 25 DEG C, setting electric current 0.1C to control temperature, electricity
Press as 1.5-4.2V.
The condition of cleaning described in step (4) is：Use ethylene carbonate with dimethyl carbonate by volume for 1:1 it is mixed
Bonding solvent, rinses electrode material surface 3-4 times.
The condition of ultrasonic disperse described in step (4) is：Electrode material after cleaning is placed in alcohol solvent, control is super
Acoustic frequency is 30000-40000Hz, ultrasonic 20-30min, electrode material is thoroughly dispersed in alcohol solvent.
From the point of view of reaction mechanism, active NaFePO is prepared using the inventive method4During, it is not necessary at high temperature
Reason, raw material nano FePO4It is being converted into NaFePO4Afterwards, the particle diameter of material can't change, and this can effectively keep active matter
The bigger serface feature of matter, impedance is advantageously reduced, ensure electrochemical process of the material in charge and discharge process；In addition,
In the electrochemical conversion process of the present invention, mainly while sodium ion is embedded in-moved out process progress, the structure of material is realized
Conversion, the high preferred orientation formed in resulting olivine structural are more beneficial for the follow-up insertion of sodium ion-move out.With showing at present
There is technology to compare, using LiFePO4Sodium ion displacement, due to replace equilibrium reasons, it is impossible to realize putting completely for Li-Na
Change, will necessarily residual fraction LiFePO4, this can reduce the utilization rate of material.In addition, it is prepared at present by solid phase synthesis process
The NaFePO arrived4, be largely Maricite structures NaFePO4, its electro-chemical activity is very low, is even more unable to reach very high
Chemical property.
Compared with prior art, the present invention is with armorphous nano FePO4For raw material, raw material sources enrich, inexpensively, preparation side
Method is simple, without high-temperature heat treatment, obtained NaFePO4The structure of positive electrode is olivine-type structure, and this structure has
Very high electro-chemical activity, excellent chemical property is shown as sodium-ion battery positive material, for example, cycle performance side
Face, under the conditions of 0.1C, manufactured NaFePO4First discharge specific capacity be 147.9mAh/g, reach theoretical capacity
90.8%, after circulation 120 times, remain able to reach 131.3mAh/g, and coulombic efficiency is close to 100%；High rate performance side
Face, under 0.2C, 0.5C, 1.0C discharge-rate, manufactured NaFePO4Specific discharge capacity respectively reach 118.6mAh/g,
90.7mAh/g and 63.1mAh/g.
Brief description of the drawings
Fig. 1 is NaFePO produced by the present invention4XRD spectrum；
Fig. 2 is NaFePO produced by the present invention4High power transmission electron microscope collection of illustrative plates；
Fig. 3 is NaFePO produced by the present invention4Selected area electron diffraction collection of illustrative plates；
Fig. 4 is NaFePO produced by the present invention4Electronic energy spectrum；
Fig. 5 is NaFePO produced by the present invention4Cyclic voltammetry curve collection of illustrative plates；
Fig. 6 is NaFePO produced by the present invention4Loop test figure；
Fig. 7 is NaFePO produced by the present invention4Multiplying power test chart；
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
Armorphous nano FePO4With conductive agent (graphite (upper marine products, AR)：Carbon black (upper marine products, AR)=4:6) in mass ratio
For 62:30 are mixed to join in ball grinder, and planetary ball mill is dry grinded two hours, then small by the use of alcohol as dispersant wet-milling two
When, obtained active material is dried in thermostatic drying chamber.Weigh 15mg active materials and PTFE (Japan produces, LITHIUM BATTERY) (matter
Measure ratio 92:8) slurries are mixed into, are coated on the 2016 type button cell anode covers for being welded with stainless (steel) wire.Vacuum is placed in after compacting to do
In dry case, 12h is dried under the conditions of 100 DEG C, is then filling Ar2It is negative pole with metal Na (upper marine products, CP) piece in glove box, electrolysis
Liquid is 1mol/L NaClO4(upper marine products, AR) (is dissolved in volume ratio as 1：1 EC (is produced from Tianjin, AR)/DMC (upper marine products, AR)
In), it is barrier film with glass felt fiber (Fujian dragon's fountain produces, LITHIUM BATTERY), is assembled into 2016 type button cells.
10 circulations of constant current charge-discharge test, test temperature control are carried out with Land battery test systems (China, Wuhan)
In 25 DEG C of constant temperature, test voltage is between 1.5-4.2V.Then in glove box (meter Kai Luo that), by positive electrode from button electricity
Taken out in pond, the electrolyte for removing electrode surface residual three times is cleaned with EC/DMC.Then electrode is placed in spirit solvent,
Ultrasonic 20min so that the positive electrode on electrode is thoroughly dispersed in alcohol, is then dried under the conditions of 70 DEG C.So,
NaFePO4Positive electrode just obtains.
Fig. 1 is synthesized NaFePO4The XRD spectrum of material, it can be seen that there is very strong olivine-type
NaFePO4Diffraction maximum.
The NaFePO of table 1.4Lattice parameter
It is NaFePO corresponding to Fig. 2-34High power transmission electron microscope picture and selected area electron diffraction collection of illustrative plates, can be with from figure
Find out, high power transmission shows obvious lattice fringe, and electronic diffraction has obvious diffraction ring to occur, illustrates armorphous nano
FePO4Material is transformed into NaFePO in electrochemical process4Crystallite.
It is EDS collection of illustrative plates corresponding to Fig. 4, Na therein：Fe：P ratio is 1：1：1, the results showed that this electrochemistry formated
The material composition that method is synthesized is NaFePO4。
By Olivine-NaFePO made of the present embodiment4As sodium ion positive electrode, 15mg NaFePO is weighed4With
PTEF(92：8) slurries are mixed into, are coated on the 2016 type button cell anode covers for being welded with stainless (steel) wire.Vacuum is placed in after compacting
In drying box, 12h is dried under the conditions of 100 DEG C, is then filling Ar2In glove box, using metal Na pieces as negative pole, electrolyte 1mol/L
NaClO4, using glass felt fiber as barrier film, it is assembled into 2016 type button cells.
Constant current charge-discharge test is done in Land battery test systems.
In 0.1C, 0.2C, 0.5C, the test of 1C different multiplyings, electrochemical window 1.5V-4.2V.
Fig. 5 is NaFePO4The cyclic voltammogram of positive electrode, redox spike potential are respectively 2.83V and 2.43V, this
Individual redox spike potential very close to, the results showed that go out NaFePO4There is excellent electrochemical reversibility.
Fig. 6 is NaFePO4Charge and discharge cycles collection of illustrative plates of the positive electrode under the conditions of 0.1C.NaFePO4Electric discharge specific volume first
Measure as 147.9mAh/g, reach the 90.8% of theoretical capacity, after circulation 120 times, remain able to reach 131.3mAh/g, and
Coulombic efficiency is close to 100%.As a result NaFePO is shown4The cycle performance of excellent point is shown as sodium-ion battery positive material
And volumetric properties.
Analyzed from Fig. 7, NaFePO4Positive electrode is under 0.2C, 0.5C, 1.0C discharge-rate, specific discharge capacity point
Do not reach 118.6mAh/g, 90.7mAh/g, 63.1mAh/g, the results showed that, NaFePO4There is the high rate performance of excellent point.
Embodiment 2：
The present embodiment olivine-type NaFePO4The preparation method of sodium-ion battery positive material, specifically includes following steps：
(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, ball milling 2h, then ethanol is added into ball grinder
As dispersant, continue ball milling 2h, dry, that is, active material is made；
(2) active material made from step (1) is weighed, and is mixed with binding agent, is sufficiently stirred, slurries are made, and coat
On button cell anode cover, pressurize 3min under 3MP pressure, fully compacting, and 12h is dried in vacuo at 100 DEG C, that is, make
The button cell anode cover of electrode material must be loaded with；
(3) in the glove box filled with argon gas, using sodium piece as negative pole, the button cell anode cover for being loaded with electrode material is
Positive pole, and button cell is assembled into jointly with electrolyte, barrier film；
(4) by electrochemical method, the button cell being assembled into step (3) carries out 20 constant current charge and discharges with 0.1C multiplying powers
Electricity circulation, then with 0.01C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, is dismantled, and takes out button
Electrode material on anode shell, cleaning, to remove the electrolyte of electrode material surface residual, then ultrasonic disperse is carried out, and
After being dried at 70 DEG C, that is, olivine-type NaFePO is made4Sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO4Particle diameter be 100nm, be 60m than surface2/ g, tap density 1.1g/
cm3；Button cell anode cover is the 2016 type button cell anode covers for being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO4Mass ratio with conductive agent is 60:30, and conductive agent is by stone
Ink mixes with carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active material and binding agent is 88：8, binding agent is LITHIUM BATTERY polytetrafluoroethylene (PTFE).
In step (3), the solute of electrolyte is NaClO4, the NaClO4Concentration be 1mol/L, solvent is ethylene carbonate
It is 1 by volume with dimethyl carbonate:1 mixed solvent, barrier film are LITHIUM BATTERY glass mat.
In step (4), the condition of cleaning is：Use ethylene carbonate with dimethyl carbonate by volume for 1:1 mixing
Solvent, rinses electrode material surface 3 times；The condition of ultrasonic disperse is：Electrode material after cleaning is placed in alcohol solvent, controlled
Supersonic frequency processed is 40000Hz, ultrasonic 20min, electrode material is thoroughly dispersed in alcohol solvent.
Embodiment 3：
The present embodiment olivine-type NaFePO4The preparation method of sodium-ion battery positive material, specifically includes following steps：
(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, ball milling 4h, then ethanol is added into ball grinder
As dispersant, continue ball milling 4h, dry, that is, active material is made；
(2) active material made from step (1) is weighed, and is mixed with binding agent, is sufficiently stirred, slurries are made, and coat
On button cell anode cover, pressurize 4min under 3MP pressure, fully compacting, and 10h is dried in vacuo at 110 DEG C, that is, it is made
It is loaded with the button cell anode cover of electrode material；
(3) in the glove box filled with argon gas, using sodium piece as negative pole, the button cell anode cover for being loaded with electrode material is
Positive pole, and button cell is assembled into jointly with electrolyte, barrier film；
(4) by electrochemical method, the button cell being assembled into step (3) carries out 15 constant current charge and discharges with 0.1C multiplying powers
Electricity circulation, then with 0.05C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, is dismantled, and takes out button
Electrode material on anode shell, cleaning, to remove the electrolyte of electrode material surface residual, then ultrasonic disperse is carried out, and
After being dried at 80 DEG C, that is, olivine-type NaFePO is made4Sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO4Particle diameter be 10nm, be 100m than surface2/ g, tap density 1.4g/
cm3；Button cell anode cover is the 2016 type button cell anode covers for being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO4Mass ratio with conductive agent is 70:30, and conductive agent is by stone
Ink mixes with carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active material and binding agent is 90：8, binding agent is LITHIUM BATTERY polytetrafluoroethylene (PTFE).
In step (3), the solute of electrolyte is NaClO4, the NaClO4Concentration be 1mol/L, solvent is ethylene carbonate
It is 1 by volume with dimethyl carbonate:1 mixed solvent, barrier film are LITHIUM BATTERY glass mat.
In step (4), the condition of cleaning is：Use ethylene carbonate with dimethyl carbonate by volume for 1:1 mixing
Solvent, rinses electrode material surface 4 times；The condition of ultrasonic disperse is：Electrode material after cleaning is placed in alcohol solvent, controlled
Supersonic frequency processed is 30000Hz, ultrasonic 30min, electrode material is thoroughly dispersed in alcohol solvent.
Embodiment 4：
The present embodiment olivine-type NaFePO4The preparation method of sodium-ion battery positive material, specifically includes following steps：
(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, ball milling 5h, then ethanol is added into ball grinder
As dispersant, continue ball milling 5h, dry, that is, active material is made；
(2) active material made from step (1) is weighed, and is mixed with binding agent, is sufficiently stirred, slurries are made, and coat
On button cell anode cover, pressurize 2min under 3MP pressure, fully compacting, and 10h is dried in vacuo at 100 DEG C, that is, it is made
It is loaded with the button cell anode cover of electrode material；
(3) in the glove box filled with argon gas, using sodium piece as negative pole, the button cell anode cover for being loaded with electrode material is
Positive pole, and button cell is assembled into jointly with electrolyte, barrier film；
(4) by electrochemical method, the button cell being assembled into step (3) carries out 5 constant current charge and discharges with 0.1C multiplying powers
Electricity circulation, then with 0.02C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, is dismantled, and takes out button
Electrode material on anode shell, cleaning, to remove the electrolyte of electrode material surface residual, then ultrasonic disperse is carried out, and
After being dried at 75 DEG C, that is, olivine-type NaFePO is made4Sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO4Particle diameter be 60nm, be 80m than surface2/ g, tap density 1.2g/
cm3；Button cell anode cover is the 2016 type button cell anode covers for being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO4Mass ratio with conductive agent is 64:30, and conductive agent is by stone
Ink mixes with carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active material and binding agent is 91：8, binding agent is LITHIUM BATTERY polytetrafluoroethylene (PTFE).
In step (3), the solute of electrolyte is NaClO4, the NaClO4Concentration be 1mol/L, solvent is ethylene carbonate
It is 1 by volume with dimethyl carbonate:1 mixed solvent, barrier film are LITHIUM BATTERY glass mat.
In step (4), the condition of cleaning is：Use ethylene carbonate with dimethyl carbonate by volume for 1:1 mixing
Solvent, rinses electrode material surface 3 times；The condition of ultrasonic disperse is：Electrode material after cleaning is placed in alcohol solvent, controlled
Supersonic frequency processed is 38000Hz, ultrasonic 25min, electrode material is thoroughly dispersed in alcohol solvent.
Embodiment 5：
The present embodiment olivine-type NaFePO4The preparation method of sodium-ion battery positive material, specifically includes following steps：
(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, ball milling 8h, then ethanol is added into ball grinder
As dispersant, continue ball milling 8h, dry, that is, active material is made；
(2) active material made from step (1) is weighed, and is mixed with binding agent, is sufficiently stirred, slurries are made, and coat
On button cell anode cover, pressurize 3min under 3MP pressure, fully compacting, and 11h is dried in vacuo at 105 DEG C, that is, it is made
It is loaded with the button cell anode cover of electrode material；
(3) in the glove box filled with argon gas, using sodium piece as negative pole, the button cell anode cover for being loaded with electrode material is
Positive pole, and button cell is assembled into jointly with electrolyte, barrier film；
(4) by electrochemical method, the button cell being assembled into step (3) carries out 10 constant current charge and discharges with 0.1C multiplying powers
Electricity circulation, then with 0.03C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, is dismantled, and takes out button
Electrode material on anode shell, cleaning, to remove the electrolyte of electrode material surface residual, then ultrasonic disperse is carried out, and
After being dried at 78 DEG C, that is, olivine-type NaFePO is made4Sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO4Particle diameter be 40nm, be 95m than surface2/ g, tap density 1.3g/
cm3；Button cell anode cover is the 2016 type button cell anode covers for being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO4Mass ratio with conductive agent is 65:30, and conductive agent is by stone
Ink mixes with carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active material and binding agent is 89：8, binding agent is LITHIUM BATTERY polytetrafluoroethylene (PTFE).
In step (3), the solute of electrolyte is NaClO4, the NaClO4Concentration be 1mol/L, solvent is ethylene carbonate
It is 1 by volume with dimethyl carbonate:1 mixed solvent, barrier film are LITHIUM BATTERY glass mat.
In step (4), the condition of cleaning is：Use ethylene carbonate with dimethyl carbonate by volume for 1:1 mixing
Solvent, rinses electrode material surface 3 times；The condition of ultrasonic disperse is：Electrode material after cleaning is placed in alcohol solvent, controlled
Supersonic frequency processed is 40000Hz, ultrasonic 30min, electrode material is thoroughly dispersed in alcohol solvent.
Claims (8)
- A kind of 1. olivine-type NaFePO4The preparation method of sodium-ion battery positive material, it is characterised in that this method is with without fixed Shape nanometer Fe PO4As active material, electrode material is made, then pass through electrochemical method so that sodium ion insertion is amorphous to be received Rice FePO4In, and then by amorphous nanometer Fe PO4It is converted into olivine-type NaFePO4, specifically include following steps：(1) by amorphous nanometer Fe PO4Added with conductive agent in ball grinder, ball milling 2-8h, then ethanol conduct is added into ball grinder Dispersant, ball milling 2-8h, dry, that is, active material is made；(2) active material made from step (1) is weighed, and is mixed with binding agent, is sufficiently stirred, slurries are made, and be coated in knob Detain on anode shell, the pressurize 2-4min under 3MPa pressure, fully compacting, and 10- is dried in vacuo at 100-110 DEG C 12h, that is, the button cell anode cover for being loaded with electrode material is made；(3) in the glove box filled with argon gas, using metallic sodium piece as negative pole, to be loaded with the button cell anode cover of electrode material For positive pole, and button cell is assembled into jointly with electrolyte, barrier film；(4) by electrochemical method, the button cell being assembled into step (3) carries out 5-20 constant current charge-discharge with 0.1C multiplying powers Circulation, then with 0.01-0.05C multiplying power dischargings, after end to be discharged, button cell is placed in glove box, is dismantled, and takes out knob The electrode material on anode shell is detained, cleaning, to remove the electrolyte of electrode material surface residual, then carries out ultrasonic disperse, And after being dried at 70-80 DEG C, that is, olivine-type NaFePO is made4Sodium-ion battery positive material；Described amorphous nanometer Fe PO4Particle diameter be 10-100nm, specific surface area 60-100m2/ g, tap density 1.1- 1.4g/cm3；The condition of ultrasonic disperse described in step (4) is：Electrode material after cleaning is placed in alcohol solvent, controls supersonic frequency Rate is 30000-40000Hz, ultrasonic 20-30min, electrode material is thoroughly dispersed in alcohol solvent.
- A kind of 2. olivine-type NaFePO according to claim 14The preparation method of sodium-ion battery positive material, it is special Sign is, the amorphous nanometer Fe PO described in step (1)4Mass ratio with conductive agent is (60-70):30, and described lead Electric agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
- A kind of 3. olivine-type NaFePO according to claim 14The preparation method of sodium-ion battery positive material, it is special Sign is that the mass ratio of active material and binding agent described in step (2) is (88-92)：8.
- A kind of 4. olivine-type NaFePO according to claim 34The preparation method of sodium-ion battery positive material, it is special Sign is that the binding agent described in step (2) is LITHIUM BATTERY polytetrafluoroethylene (PTFE).
- A kind of 5. olivine-type NaFePO according to claim 14The preparation method of sodium-ion battery positive material, it is special Sign is that the button cell anode cover described in step (2) is the 2016 type button cell anode covers for being welded with stainless (steel) wire.
- A kind of 6. olivine-type NaFePO according to claim 14The preparation method of sodium-ion battery positive material, it is special Sign is that the solute of the electrolyte described in step (3) is NaClO4, the NaClO4Concentration be 1mol/L, and described electrolysis The solvent of liquid is ethylene carbonate and dimethyl carbonate is 1 by volume:1 mixed solvent, described barrier film are LITHIUM BATTERY glass Glass fibrofelt.
- A kind of 7. olivine-type NaFePO according to claim 14The preparation method of sodium-ion battery positive material, it is special Sign is that the condition of the constant current charge-discharge circulation described in step (4) is：It is 25 DEG C, setting electric current 0.1C to control temperature, voltage For 1.5-4.2V.
- A kind of 8. olivine-type NaFePO according to claim 14The preparation method of sodium-ion battery positive material, it is special Sign is that the condition of the cleaning described in step (4) is：Use ethylene carbonate with dimethyl carbonate by volume for 1:1 it is mixed Bonding solvent, rinses electrode material surface 3-4 times.
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| CN201510401813.6A CN105152154B (en) | 2015-07-09 | 2015-07-09 | A kind of olivine-type NaFePO4The preparation method of sodium-ion battery positive material |
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