CN105152154A - Olivine type NaFePO4 sodium ion battery positive electrode material preparation method - Google Patents

Olivine type NaFePO4 sodium ion battery positive electrode material preparation method Download PDF

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CN105152154A
CN105152154A CN201510401813.6A CN201510401813A CN105152154A CN 105152154 A CN105152154 A CN 105152154A CN 201510401813 A CN201510401813 A CN 201510401813A CN 105152154 A CN105152154 A CN 105152154A
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sodium
ion battery
olivine
battery positive
nafepo
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CN105152154B (en
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张俊喜
刘瑶
周义荣
戴念维
任平
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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Shanghai University of Electric Power
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to an olivine type NaFePO4 sodium ion battery positive electrode material preparation method, which comprises: (1) adding amorphous nanometer FePO4 and an electric conduction agent to a ball mill tank, and carrying out dry milling and wet milling to prepare an active substance; (2) weighing the active substance, mixing with a binder, stirring to prepare a slurry, coating on the button battery positive electrode shell, compacting, and carrying out vacuum drying; (3) assembling into a button battery; and (4) carrying out constant current charge and discharge cycling at a rate of 0.1 C through an electrochemical method, discharging at a rate of 0.01-0.05 C, placing the button battery into a glove box after completing the discharge, disassembling, taking out the positive electrode material on the button battery positive electrode shell, washing, carrying out ultrasonic dispersion, and drying to prepare the olivine type NaFePO4 sodium ion battery positive electrode material. Compared with the method in the prior art, the method of the present invention has the following characteristics that the amorphous nanometer FePO4 is adopted as the raw material, the raw material sources are abundant, the raw materials are cheap, the preparation method is simple, the high-temperature heat treatment is not required, and the prepared material has excellent electrochemical properties.

Description

A kind of olivine-type NaFePO 4the preparation method of sodium-ion battery positive material
Technical field
The invention belongs to sodium-ion battery technical field, relate to a kind of olivine-type NaFePO 4the preparation method of sodium-ion battery positive material.
Background technology
In recent years, because environmental problem is day by day serious, energy dilemma, the exploitation of new forms of energy and the development of energy storage technology now become the mankind jointly faced by problem.Lithium ion battery, because of the performance of its excellence, has been widely used in portable digital product.Future, lithium ion battery because of the long life, advantages such as high-energy-density and be subject to the attention of energy storage field worker.But lithium ion battery applications is also faced with some challenges in energy storage field.Secondly first, on the earth, lithium source reserves are limited, and the price of metallic lithium can rise gradually along with lithium ion battery large-scale application, develop desirable electrode materials and improve its performance further and seem particularly important.
Be in the sodium of same main group with lithium, have similar chemical property to lithium.Sodium-ion battery and lithium ion battery have similar principle, and importantly sodium reserves are on earth far above lithium.At present, many research work about sodium ion positive electrode material are reported, in succession as Na xcoO 2, Na 0.44mnO 2, Na 0.6mnO 2, NaCrO 2, Na xvO 2, Na 3v 2(PO 4) 3, Na 3v 2(PO 4) 2f 3, Na 3v 2o 2(PO 4) 2f, Na 2fePO 4f, NaFeF 3deng, but the performance of these positive electrode materials still can not meet the requirement of the industrial applications of sodium-ion battery.Therefore, developing desirable electrode materials is the industrialized key of sodium-ion battery.
Iron-based positive electrode material olivine-type (olivine) LiFePO 4as anode material for lithium-ion batteries, be widely used.Relative to LiFePO 4, olivine-type (olivine) NaFePO 4also can as sodium-ion battery positive material.Due to Na +radius ratio Li +greatly, NaFePO is made 4mainly contain maricite and olivine two kinds of crystal formations.Due to the difference of crystalline structure, maricite type NaFePO 4as sodium ion positive electrode material be do not have activated, and olivine type NaFePO 4then there is activity.But, maricite type NaFePO 4more stable.At present, by NaFePO that some thermal treatments or solid state reaction obtain 4be mainly maricite type NaFePO 4.Therefore, olivine-type (olivine) NaFePO how is prepared quickly and easily 4then seem particularly important.
Summary of the invention
Object of the present invention is exactly provide a kind of with armorphous nano FePO to overcome defect that above-mentioned prior art exists 4for raw material, quickly and easily prepare olivine-type NaFePO 4the method of sodium-ion battery positive material.
Object of the present invention can be achieved through the following technical solutions:
A kind of olivine-type NaFePO 4the preparation method of sodium-ion battery positive material, the method is with amorphous nanometer Fe PO 4as active substance, make electrode materials, then by electrochemical method, make sodium ion embed amorphous nanometer Fe PO 4in, and then by amorphous nanometer Fe PO 4be converted into olivine-type NaFePO 4, specifically comprise the following steps:
(1) by amorphous nanometer Fe PO 4add in ball grinder with conductive agent, ball milling 2-8h, then add ethanol as dispersion agent in ball grinder, ball milling 2-8h, dry, i.e. obtained active substance;
(2) active substance that step (1) is obtained is taken, and mix with binding agent, abundant stirring, make slurries, and be coated on button cell anode cover, pressurize 2-4min under the pressure of 3MPa, abundant compacting, and at 100-110 DEG C vacuum-drying 10-12h, namely obtained load has the button cell anode cover of electrode materials;
(3) in the glove box being filled with argon gas, with sodium Metal 99.5 sheet for negative pole, there is the button cell anode cover of electrode materials for positive pole with load, and be jointly assembled into button cell with electrolytic solution, barrier film;
(4) electrochemical method is passed through, 5-20 constant current charge-discharge circulation is carried out, then with 0.01-0.05C multiplying power discharging, after end to be discharged with 0.1C multiplying power to the button cell that step (3) is assembled into, button cell is placed in glove box, dismounting, takes out the electrode materials on button cell anode cover, cleaning, to remove the residual electrolytic solution of electrode material surface, carry out ultrasonic disperse again, and at 70-80 DEG C after drying, i.e. obtained olivine-type NaFePO 4sodium-ion battery positive material.
Amorphous nanometer Fe PO described in step (1) 4be (60-70) with the mass ratio of conductive agent: 30, and described conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6, and described dispersion agent is ethanol.
Described amorphous nanometer Fe PO 4particle diameter be 10-100nm, specific surface is 60-100m 2/ g, tap density is 1.1-1.4g/cm 3.
Active substance described in step (2) and the mass ratio of binding agent are (88-92): 8.
Binding agent described in step (2) is cell-grade tetrafluoroethylene.
Button cell anode cover described in step (2) is the 2016 type button cell anode covers being welded with stainless (steel) wire.
The solute of the electrolytic solution described in step (3) is NaClO 4, this NaClO 4concentration be 1mol/L, and the solvent of described electrolytic solution is NSC 11801 and methylcarbonate is the mixed solvent of 1:1 by volume, and described barrier film is cell-grade glass mat.
The condition of the constant current charge-discharge circulation described in step (4) is: control temperature is 25 DEG C, and setting electric current is 0.1C, and voltage is 1.5-4.2V.
The condition of the cleaning described in step (4) is: adopt NSC 11801 and methylcarbonate by volume and be the mixed solvent of 1:1, rinse electrode material surface 3-4 time.
The condition of the ultrasonic disperse described in step (4) is: the electrode materials after cleaning is placed in alcohol solvent, and control ultrasonic frequency is 30000-40000Hz, and electrode materials is dispersed in alcohol solvent by ultrasonic 20-30min completely.
From reaction mechanism, the inventive method is adopted to prepare active NaFePO 4in process, do not need through pyroprocessing, raw material nano FePO 4be converted into NaFePO 4after, the particle diameter of material can't change, and this effectively can keep the bigger serface feature of active substance, is conducive to reducing impedance, ensures the electrochemical process of material in charge and discharge process; In addition, in electrochemical conversion process of the present invention, mainly embed-move out while process carries out at sodium ion, realize the thaumatropy of material, the high preferred orientation formed in the olivine structural obtained more is conducive to the follow-up embedding of sodium ion-move out.Compared with currently available technology, adopt LiFePO 4sodium ion displacement, due to displacement equilibrium reasons, the displacement completely of Li-Na can not be realized, will inevitably lingering section LiFePO 4, this can reduce the utilization ratio of material.In addition, at present by NaFePO that solid phase synthesis process prepares 4, major part is the NaFePO of Maricite structure 4, its electrochemical activity is very low, cannot reach very high chemical property especially.
Compared with prior art, the present invention is with armorphous nano FePO 4for raw material, abundant raw material source, cheap, preparation method is simple, without the need to high-temperature heat treatment, and obtained NaFePO 4the structure of positive electrode material is olivine-type structure, and this structure has very high electrochemical activity, shows excellent chemical property as sodium-ion battery positive material, such as, cycle performance aspect, under 0.1C condition, the NaFePO made 4first discharge specific capacity be 147.9mAh/g, reach 90.8% of theoretical capacity, circulate after 120 times, still can reach 131.3mAh/g, and coulombic efficiency is close to 100%; High rate performance aspect, under 0.2C, 0.5C, 1.0C discharge-rate, the NaFePO made 4specific discharge capacity reach 118.6mAh/g, 90.7mAh/g and 63.1mAh/g respectively.
Accompanying drawing explanation
Fig. 1 is the NaFePO that the present invention obtains 4xRD figure spectrum;
Fig. 2 is the NaFePO that the present invention obtains 4high power transmission electron microscope collection of illustrative plates;
Fig. 3 is the NaFePO that the present invention obtains 4selected area electron diffraction collection of illustrative plates;
Fig. 4 is the NaFePO that the present invention obtains 4electronic energy spectrum;
Fig. 5 is the NaFePO that the present invention obtains 4cyclic voltammetry curve collection of illustrative plates;
Fig. 6 is the NaFePO that the present invention obtains 4loop test figure;
Fig. 7 is the NaFePO that the present invention obtains 4multiplying power test pattern;
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
Armorphous nano FePO 4with conductive agent (graphite (upper marine products, AR): carbon black (upper marine products, AR)=4:6) in mass ratio for 62:30 is mixed to join in ball grinder, planetary ball mill is dry grinded two hours, then use alcohol as dispersion agent wet-milling two hours, the active substance obtained is dry in thermostatic drying chamber.Take 15mg active material and PTFE (Japan produces, cell-grade) (mass ratio 92:8) and be mixed into slurries, be coated in and be welded with on 2016 type button cell anode covers of stainless (steel) wire.Compacting is placed in vacuum drying oven, dries 12h, then filling Ar under 100 DEG C of conditions 2in glove box, be negative pole with metal Na (upper marine products, CP) sheet, electrolytic solution is the NaClO of 1mol/L 4(upper marine products, AR) (is dissolved in EC (is produced from Tianjin, AR)/DMC (the upper marine products that volume ratio is 1:1, AR) in), be barrier film with glassmat fiber (Fujian dragon's fountain produce, cell-grade), be assembled into 2016 type button cells.
Carry out constant current charge-discharge with Land battery test system (China, Wuhan) and test 10 circulations, probe temperature controls constant temperature 25 DEG C, and test voltage is between 1.5-4.2V.Then in glove box (meter Kai Luo that), positive electrode material is taken out from button cell, cleans three times with EC/DMC, the ionogen that removing electrode surface is residual.Then electrode is placed in spirit solvent, ultrasonic 20min, the positive electrode material on electrode is dispersed in alcohol completely, then dries under 70 DEG C of conditions.Like this, NaFePO 4positive electrode material just obtains.
Fig. 1 is synthesized NaFePO 4, as can be seen from the figure, there is very strong olivine-type NaFePO in the XRD figure spectrum of material 4diffraction peak.
Table 1.NaFePO 4lattice parameter
That Fig. 2-3 is corresponding is NaFePO 4high power transmission electron microscope picture and selected area electron diffraction collection of illustrative plates, as can be seen from the figure, high power transmission demonstrates obvious lattice fringe, and electron diffraction has obvious diffraction ring to occur, armorphous nano FePO is described 4material is transformed into NaFePO in electrochemical process 4crystallite.
What Fig. 4 was corresponding is EDS collection of illustrative plates, and the ratio of Na:Fe:P is wherein 1:1:1, and result shows that the material that the method for this electrochemical synthesis is synthesized consists of NaFePO 4.
The Olivine-NaFePO that the present embodiment is made 4as sodium ion positive electrode material, take the NaFePO of 15mg 4be mixed into slurries with PTEF (92:8), be coated in and be welded with on 2016 type button cell anode covers of stainless (steel) wire.Compacting is placed in vacuum drying oven, dries 12h, then filling Ar under 100 DEG C of conditions 2in glove box, with metal Na sheet for negative pole, electrolytic solution is the NaClO of 1mol/L 4, with glassmat fiber for barrier film, be assembled into 2016 type button cells.
Constant current charge-discharge test is done at Land battery test system.
In the test of 0.1C, 0.2C, 0.5C, 1C different multiplying, electrochemical window is 1.5V-4.2V.
Fig. 5 is NaFePO 4the cyclic voltammogram of positive electrode material, redox spike potential is respectively 2.83V and 2.43V, and this redox spike potential is very close, and result indicates NaFePO 4there is excellent electrochemical reversibility.
Fig. 6 is NaFePO 4the charge and discharge cycles collection of illustrative plates of positive electrode material under 0.1C condition.NaFePO 4first discharge specific capacity be 147.9mAh/g, reach 90.8% of theoretical capacity, circulate after 120 times, still can reach 131.3mAh/g, and coulombic efficiency is close to 100%.Result shows NaFePO 4cycle performance and the volumetric properties of excellent point is shown as sodium-ion battery positive material.
Analyzed from Fig. 7, NaFePO 4positive electrode material is under 0.2C, 0.5C, 1.0C discharge-rate, and specific discharge capacity reaches 118.6mAh/g, 90.7mAh/g, 63.1mAh/g respectively, and result shows, NaFePO 4there is the high rate performance of excellent point.
Embodiment 2:
The present embodiment olivine-type NaFePO 4the preparation method of sodium-ion battery positive material, specifically comprises the following steps:
(1) by amorphous nanometer Fe PO 4add in ball grinder with conductive agent, ball milling 2h, then add ethanol as dispersion agent in ball grinder, continue ball milling 2h, dry, i.e. obtained active substance;
(2) active substance that step (1) is obtained is taken, and mix with binding agent, abundant stirring, make slurries, and be coated on button cell anode cover, pressurize 3min under the pressure of 3MP, abundant compacting, and at 100 DEG C vacuum-drying 12h, namely obtained load has the button cell anode cover of electrode materials;
(3) in the glove box being filled with argon gas, with sodium sheet for negative pole, load has the button cell anode cover of electrode materials to be positive pole, and is jointly assembled into button cell with electrolytic solution, barrier film;
(4) electrochemical method is passed through, 20 constant current charge-discharge circulations are carried out, then with 0.01C multiplying power discharging, after end to be discharged with 0.1C multiplying power to the button cell that step (3) is assembled into, button cell is placed in glove box, dismounting, takes out the electrode materials on button cell anode cover, cleaning, to remove the residual electrolytic solution of electrode material surface, carry out ultrasonic disperse again, and at 70 DEG C after drying, i.e. obtained olivine-type NaFePO 4sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO 4particle diameter be 100nm, specific surface is 60m 2/ g, tap density is 1.1g/cm 3; Button cell anode cover is the 2016 type button cell anode covers being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO 4be 60:30 with the mass ratio of conductive agent, and conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active substance and binding agent is 88:8, and binding agent is cell-grade tetrafluoroethylene.
In step (3), the solute of electrolytic solution is NaClO 4, this NaClO 4concentration be 1mol/L, solvent is NSC 11801 and methylcarbonate is the mixed solvent of 1:1 by volume, and barrier film is cell-grade glass mat.
In step (4), the condition of cleaning is: adopt NSC 11801 and methylcarbonate by volume and be the mixed solvent of 1:1, rinse electrode material surface 3 times; The condition of ultrasonic disperse is: the electrode materials after cleaning is placed in alcohol solvent, and control ultrasonic frequency is 40000Hz, and electrode materials is dispersed in alcohol solvent by ultrasonic 20min completely.
Embodiment 3:
The present embodiment olivine-type NaFePO 4the preparation method of sodium-ion battery positive material, specifically comprises the following steps:
(1) by amorphous nanometer Fe PO 4add in ball grinder with conductive agent, ball milling 4h, then add ethanol as dispersion agent in ball grinder, continue ball milling 4h, dry, i.e. obtained active substance;
(2) active substance that step (1) is obtained is taken, and mix with binding agent, abundant stirring, make slurries, and be coated on button cell anode cover, pressurize 4min under the pressure of 3MP, abundant compacting, and at 110 DEG C vacuum-drying 10h, namely obtained load has the button cell anode cover of electrode materials;
(3) in the glove box being filled with argon gas, with sodium sheet for negative pole, load has the button cell anode cover of electrode materials to be positive pole, and is jointly assembled into button cell with electrolytic solution, barrier film;
(4) electrochemical method is passed through, 15 constant current charge-discharge circulations are carried out, then with 0.05C multiplying power discharging, after end to be discharged with 0.1C multiplying power to the button cell that step (3) is assembled into, button cell is placed in glove box, dismounting, takes out the electrode materials on button cell anode cover, cleaning, to remove the residual electrolytic solution of electrode material surface, carry out ultrasonic disperse again, and at 80 DEG C after drying, i.e. obtained olivine-type NaFePO 4sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO 4particle diameter be 10nm, specific surface is 100m 2/ g, tap density is 1.4g/cm 3; Button cell anode cover is the 2016 type button cell anode covers being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO 4be 70:30 with the mass ratio of conductive agent, and conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active substance and binding agent is 90:8, and binding agent is cell-grade tetrafluoroethylene.
In step (3), the solute of electrolytic solution is NaClO 4, this NaClO 4concentration be 1mol/L, solvent is NSC 11801 and methylcarbonate is the mixed solvent of 1:1 by volume, and barrier film is cell-grade glass mat.
In step (4), the condition of cleaning is: adopt NSC 11801 and methylcarbonate by volume and be the mixed solvent of 1:1, rinse electrode material surface 4 times; The condition of ultrasonic disperse is: the electrode materials after cleaning is placed in alcohol solvent, and control ultrasonic frequency is 30000Hz, and electrode materials is dispersed in alcohol solvent by ultrasonic 30min completely.
Embodiment 4:
The present embodiment olivine-type NaFePO 4the preparation method of sodium-ion battery positive material, specifically comprises the following steps:
(1) by amorphous nanometer Fe PO 4add in ball grinder with conductive agent, ball milling 5h, then add ethanol as dispersion agent in ball grinder, continue ball milling 5h, dry, i.e. obtained active substance;
(2) active substance that step (1) is obtained is taken, and mix with binding agent, abundant stirring, make slurries, and be coated on button cell anode cover, pressurize 2min under the pressure of 3MP, abundant compacting, and at 100 DEG C vacuum-drying 10h, namely obtained load has the button cell anode cover of electrode materials;
(3) in the glove box being filled with argon gas, with sodium sheet for negative pole, load has the button cell anode cover of electrode materials to be positive pole, and is jointly assembled into button cell with electrolytic solution, barrier film;
(4) electrochemical method is passed through, 5 constant current charge-discharge circulations are carried out, then with 0.02C multiplying power discharging, after end to be discharged with 0.1C multiplying power to the button cell that step (3) is assembled into, button cell is placed in glove box, dismounting, takes out the electrode materials on button cell anode cover, cleaning, to remove the residual electrolytic solution of electrode material surface, carry out ultrasonic disperse again, and at 75 DEG C after drying, i.e. obtained olivine-type NaFePO 4sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO 4particle diameter be 60nm, specific surface is 80m 2/ g, tap density is 1.2g/cm 3; Button cell anode cover is the 2016 type button cell anode covers being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO 4be 64:30 with the mass ratio of conductive agent, and conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active substance and binding agent is 91:8, and binding agent is cell-grade tetrafluoroethylene.
In step (3), the solute of electrolytic solution is NaClO 4, this NaClO 4concentration be 1mol/L, solvent is NSC 11801 and methylcarbonate is the mixed solvent of 1:1 by volume, and barrier film is cell-grade glass mat.
In step (4), the condition of cleaning is: adopt NSC 11801 and methylcarbonate by volume and be the mixed solvent of 1:1, rinse electrode material surface 3 times; The condition of ultrasonic disperse is: the electrode materials after cleaning is placed in alcohol solvent, and control ultrasonic frequency is 38000Hz, and electrode materials is dispersed in alcohol solvent by ultrasonic 25min completely.
Embodiment 5:
The present embodiment olivine-type NaFePO 4the preparation method of sodium-ion battery positive material, specifically comprises the following steps:
(1) by amorphous nanometer Fe PO 4add in ball grinder with conductive agent, ball milling 8h, then add ethanol as dispersion agent in ball grinder, continue ball milling 8h, dry, i.e. obtained active substance;
(2) active substance that step (1) is obtained is taken, and mix with binding agent, abundant stirring, make slurries, and be coated on button cell anode cover, pressurize 3min under the pressure of 3MP, abundant compacting, and at 105 DEG C vacuum-drying 11h, namely obtained load has the button cell anode cover of electrode materials;
(3) in the glove box being filled with argon gas, with sodium sheet for negative pole, load has the button cell anode cover of electrode materials to be positive pole, and is jointly assembled into button cell with electrolytic solution, barrier film;
(4) electrochemical method is passed through, 10 constant current charge-discharge circulations are carried out, then with 0.03C multiplying power discharging, after end to be discharged with 0.1C multiplying power to the button cell that step (3) is assembled into, button cell is placed in glove box, dismounting, takes out the electrode materials on button cell anode cover, cleaning, to remove the residual electrolytic solution of electrode material surface, carry out ultrasonic disperse again, and at 78 DEG C after drying, i.e. obtained olivine-type NaFePO 4sodium-ion battery positive material.
In the present embodiment, amorphous nanometer Fe PO 4particle diameter be 40nm, specific surface is 95m 2/ g, tap density is 1.3g/cm 3; Button cell anode cover is the 2016 type button cell anode covers being welded with stainless (steel) wire.
Wherein, in step (1), amorphous nanometer Fe PO 4be 65:30 with the mass ratio of conductive agent, and conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
In step (2), the mass ratio of active substance and binding agent is 89:8, and binding agent is cell-grade tetrafluoroethylene.
In step (3), the solute of electrolytic solution is NaClO 4, this NaClO 4concentration be 1mol/L, solvent is NSC 11801 and methylcarbonate is the mixed solvent of 1:1 by volume, and barrier film is cell-grade glass mat.
In step (4), the condition of cleaning is: adopt NSC 11801 and methylcarbonate by volume and be the mixed solvent of 1:1, rinse electrode material surface 3 times; The condition of ultrasonic disperse is: the electrode materials after cleaning is placed in alcohol solvent, and control ultrasonic frequency is 40000Hz, and electrode materials is dispersed in alcohol solvent by ultrasonic 30min completely.

Claims (10)

1. an olivine-type NaFePO 4the preparation method of sodium-ion battery positive material, is characterized in that, the method is with amorphous nanometer Fe PO 4as active substance, make electrode materials, then by electrochemical method, make sodium ion embed amorphous nanometer Fe PO 4in, and then by amorphous nanometer Fe PO 4be converted into olivine-type NaFePO 4, specifically comprise the following steps:
(1) by amorphous nanometer Fe PO 4add in ball grinder with conductive agent, ball milling 2-8h, then add ethanol as dispersion agent in ball grinder, ball milling 2-8h, dry, i.e. obtained active substance;
(2) active substance that step (1) is obtained is taken, and mix with binding agent, abundant stirring, make slurries, and be coated on button cell anode cover, pressurize 2-4min under the pressure of 3MPa, abundant compacting, and at 100-110 DEG C vacuum-drying 10-12h, namely obtained load has the button cell anode cover of electrode materials;
(3) in the glove box being filled with argon gas, with sodium Metal 99.5 sheet for negative pole, there is the button cell anode cover of electrode materials for positive pole with load, and be jointly assembled into button cell with electrolytic solution, barrier film;
(4) electrochemical method is passed through, 5-20 constant current charge-discharge circulation is carried out, then with 0.01-0.05C multiplying power discharging, after end to be discharged with 0.1C multiplying power to the button cell that step (3) is assembled into, button cell is placed in glove box, dismounting, takes out the electrode materials on button cell anode cover, cleaning, to remove the residual electrolytic solution of electrode material surface, carry out ultrasonic disperse again, and at 70-80 DEG C after drying, i.e. obtained olivine-type NaFePO 4sodium-ion battery positive material.
2. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, is characterized in that, the amorphous nanometer Fe PO described in step (1) 4be (60-70) with the mass ratio of conductive agent: 30, and described conductive agent is mixed by graphite and carbon black, wherein, the mass ratio of graphite and carbon black is 4:6.
3. a kind of olivine-type NaFePO according to claim 1 and 2 4the preparation method of sodium-ion battery positive material, is characterized in that, described amorphous nanometer Fe PO 4particle diameter be 10-100nm, specific surface is 60-100m 2/ g, tap density is 1.1-1.4g/cm 3.
4. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, is characterized in that, the active substance described in step (2) and the mass ratio of binding agent are (88-92): 8.
5. a kind of olivine-type NaFePO according to claim 4 4the preparation method of sodium-ion battery positive material, is characterized in that, the binding agent described in step (2) is cell-grade tetrafluoroethylene.
6. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, is characterized in that, the button cell anode cover described in step (2) is the 2016 type button cell anode covers being welded with stainless (steel) wire.
7. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, is characterized in that, the solute of the electrolytic solution described in step (3) is NaClO 4, this NaClO 4concentration be 1mol/L, and the solvent of described electrolytic solution is NSC 11801 and methylcarbonate is the mixed solvent of 1:1 by volume, and described barrier film is cell-grade glass mat.
8. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, is characterized in that, the condition of the constant current charge-discharge circulation described in step (4) is: control temperature is 25 DEG C, and setting electric current is 0.1C, and voltage is 1.5-4.2V.
9. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, is characterized in that, the condition of the cleaning described in step (4) is: adopt NSC 11801 and methylcarbonate by volume and be the mixed solvent of 1:1, rinse electrode material surface 3-4 time.
10. a kind of olivine-type NaFePO according to claim 1 4the preparation method of sodium-ion battery positive material, it is characterized in that, the condition of the ultrasonic disperse described in step (4) is: the electrode materials after cleaning is placed in alcohol solvent, control ultrasonic frequency is 30000-40000Hz, ultrasonic 20-30min, is dispersed in alcohol solvent completely by electrode materials.
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CN109786744A (en) * 2019-01-24 2019-05-21 中南大学 A method of phosphoric acid ferrisodium electrode is prepared using industrial by-product ferrous sulfate
CN114368736A (en) * 2022-01-28 2022-04-19 中南大学 Preparation method of olivine type sodium iron phosphate cathode material
CN114784270A (en) * 2022-03-05 2022-07-22 四川龙蟒磷化工有限公司 Preparation method of sodium ion battery material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109786744A (en) * 2019-01-24 2019-05-21 中南大学 A method of phosphoric acid ferrisodium electrode is prepared using industrial by-product ferrous sulfate
CN114368736A (en) * 2022-01-28 2022-04-19 中南大学 Preparation method of olivine type sodium iron phosphate cathode material
CN114784270A (en) * 2022-03-05 2022-07-22 四川龙蟒磷化工有限公司 Preparation method of sodium ion battery material
CN114784270B (en) * 2022-03-05 2023-09-19 四川龙蟒磷化工有限公司 Preparation method of sodium ion battery material

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