CN107611429A - A kind of rich sodium vanadium phosphate ferrisodium material and preparation method thereof and the application in sodium-ion battery - Google Patents
A kind of rich sodium vanadium phosphate ferrisodium material and preparation method thereof and the application in sodium-ion battery Download PDFInfo
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- CN107611429A CN107611429A CN201710681999.4A CN201710681999A CN107611429A CN 107611429 A CN107611429 A CN 107611429A CN 201710681999 A CN201710681999 A CN 201710681999A CN 107611429 A CN107611429 A CN 107611429A
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- 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
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Abstract
Application the invention discloses a kind of rich sodium vanadium phosphate ferrisodium material and preparation method thereof and in sodium-ion battery, Na3+ xFe3+ 1‑xFe2+ xV(PO4)3Material has NASICON type structures, wherein 0.05≤x≤0.9；Its preparation method is utilized using cheap sodium source, source of iron, phosphorus source and vanadium source by ball milling and sinter molding, can obtain that crystalline phase is single, the high Na of electro-chemical activity3+xFe3+ 1‑xFe2+ xV(PO4)3Material；The preparation method is simple and easy, mild condition, and yield is high, when the material of preparation is applied as sodium-ion battery positive material, shows higher first circle charging capacity, height ratio capacity, high working voltage, good stable circulation performance and excellent high rate performance.
Description
Technical field
The present invention relates to a kind of sodium-ion battery positive material, more particularly to a kind of Na3+xFe3+ 1-xFe2+ xV(PO4)3Material
With synthesis in solid state Na3+xFe3+ 1-xFe2+ xV(PO4)3Method, and Na3+xFe3+ 1-xFe2+ xV(PO4)3As sodium ion positive pole material
The application of material, belong to sodium-ion battery field.
Background technology
As lithium ion battery has achieved fast development in 3C Product and electric automobiles, and show good hair
While exhibition prospect, because metal lithium resource is in the scarcity of crustal abundance, lithium ion battery is difficult to meet in large-scale energy storage field
In large-scale application, its manufacturing cost also will be in the trend that constantly rises with the scarcity of lithium resource.Compared with elemental lithium, sodium member
Element rich reserves and source is more extensive in the earth's crust, and sodium element is in same main group with lithium in the periodic table of elements, so
There is similar physicochemical property to lithium.Therefore, the manufacturing cost of relative moderate and the sodium ion electricity to be compared favourably with lithium ion battery
Pond turns into a kind of usable battery system of storage on a large scale of most potential achievable industry.However, the ion due to sodium ion
Radius is bigger than the ionic radius of lithium ion so that in kinetically sodium ion, lithium ion is compared in embedded and abjection in electrode material
It is more difficult, and oxidation-reduction potential of the sodium ion with respect to calibration and larger atomic mass so that sodium-ion battery positive pole material
The low voltage of material, energy density be not high.Therefore, improve sodium-ion battery positive material voltage and turning into for energy density is studied
Emphasis.
Similar with lithium ion battery, in sodium-ion battery positive material, more representational is P2 types and O3 type layers
Shape oxide system, such as P2-Na2/3[Fe1/2Mn1/2]O2, O3-NaFe0.5Co0.5O2, but stratified material in organic electrolyte not
It is stable, easily decompose under high voltages, cause cycle performance of battery poor.In polyanionic positive electrode system,
Na3V2(PO4)3With NASICON types structure and there are good heat endurance and electrochemical stability, sodium ion is brilliant in NASICON
There is excellent conductance, therefore it possesses prominent high rate charge-discharge performance in body structure.Single vanadium source is expensive, the earth's crust
Abundance is low, compares, and source of iron has cheap, wide material sources.The usage amount of v element can be reduced using source of iron, can be effectively
Reduce cost and environmental pressure.But Na3Fe2V(PO4)3Ferric ion in first circle charging process without electrochemistry live
Property, this greatly limits application of the material in full battery, because sodium source is entirely derived from during as full cell positive material
Positive electrode, the quantity of positive electrode deintercalation sodium are reduced, it is meant that in battery can the sodium of deintercalation reduce, battery capacity is low, unfavorable
Used in being commercialized full battery.
The content of the invention
For Na of the prior art3Fe2V(PO4)3The defects of sodium-ion battery material is present, it is an object of the invention to
A kind of property stabilization, the rich sodium Na that crystalline phase is single and electro-chemical activity is high are provided3+xFe3+ 1-xFe2+ xV(PO4)3Material.
Another object of the present invention is to provide one kind to be based on full synthesis in solid state, high-purity N a is realized in a mild condition3+ xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, this method step is short, simple to operate, cost is cheap, can realize extensive
Production.
Third object of the present invention be to provide it is described into Na3+xFe3+ 1-xFe2+ xV(PO4)3Materials application is as sodium
The application of ion battery positive electrode, sodium-ion battery show high first circle coulombic efficiency high-energy-density, high working voltage, good
Good stable circulation performance and excellent high rate performance.
In order to realize above-mentioned technical purpose, the invention provides a kind of Na3+xFe3+ 1-xFe2+ xV(PO4)3Material, the material
With NASICON type structures；Na3+xFe3+ 1-xFe2+ xV(PO4)30.05≤x≤0.9 in material.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Material not only contains ferrous ion, and is rich in sodium ion,
Relatively existing Na3Fe2V(PO4)3Chemical property is greatly enhanced, and has a more preferable high rate performance, and comprising divalence
Iron ion has the first circle coulombic efficiency that higher electro-chemical activity can effectively improve material in first circle charging process, overcomes
Na3Fe2V(PO4)3The problem of first circle coulombic efficiency is low.Na simultaneously3+xFe3+ 1-xFe2+ xV(PO4)3With NASICON (fast ions
Conductor) type crystal structure, and crystal phase structure is single, can realize the quick transmission of sodium ion, so as to have good high rate performance.
Preferable scheme, the Na3+xFe3+ 1-xFe2+ xV(PO4)3Material is the particle that particle diameter is 50~3000nm.
Preferable scheme, Na3+xFe3+ 1-xFe2+ xV(PO4)3With trigonal system, space group is
Present invention also offers a kind of Na3+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, this method be by sodium source,
After phosphorus source, vanadium source, source of iron are by ball milling mixing, it is placed in protective atmosphere or reducing atmosphere, is warming up to 500~750 DEG C of sintering, i.e.,
.
Preferable scheme, the ratio of sodium source, phosphorus source, vanadium source and source of iron is pressed into Na:P:V:Fe mol ratio be 3.05~
4.05:3:1:1 metering.Preferred mol ratio is 3.1~3.8:3:1:1.The dosage of sodium source decides the rich sodium Na of synthesis3+ xFe3+ 1-xFe2+ xV(PO4)3The ratio of phase ferrous ions, it have impact on the first circle coulombic efficiency of material.The ratio of sodium source is incorrect
It can lead to not synthesize rich sodium phase or cause a large amount of dephasigns to produce.
Preferable scheme, the sodium source include sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, sulphur
At least one of sour hydrogen sodium, sodium citrate, sodium hydroxide；Preferred sodium source is sodium carbonate.
Preferable scheme, phosphorus source include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, disodium hydrogen phosphate, biphosphate
At least one of sodium；Preferred phosphorus source is diammonium hydrogen phosphate.
Preferable scheme, the vanadium source include at least one of vanadic anhydride, ammonium metavanadate, vanadium, vanadyl acetylacetonate；
Preferred vanadium source is vanadic anhydride.
Preferable scheme, the source of iron include frerrous chloride, ferrous sulfate, ferric nitrate, iron chloride, ferric citrate, oxygen
Change at least one of ferrous, iron oxide, preferred source of iron is ferrous sulfate.
Preferable scheme, the condition of the ball milling are：Ball material mass ratio is 30~120:1；Engine speed be 300~
1200r/min, Ball-milling Time are 6~24h.Preferred ball material mass ratio is 60~90:1.Preferred engine speed is 500
~1000r/min, Ball-milling Time are 10~14h.Preferable ball milling condition can be sufficiently mixed solid powder, and improve raw material
Reactivity, be advantageous to follow-up solid phase reaction, to reduce the generation of impurities phase.
More preferably scheme, the ball milling are carried out in organic solvent medium.Preferable organic solvent is acetone and/or nothing
Water-ethanol etc., these organic solvents have more preferable wetability to various solid principles, improve ball milling mixing effect, are various originals
Material is sufficiently mixed uniformly, is reduced dephasign and is produced.
Preferable scheme, after sodium source, phosphorus source, vanadium source, source of iron ball milling mixing, dried at a temperature of being placed in 80~120 DEG C, mistake
100~400 mesh sieves, take minus sieve powder to be sintered.
More preferably scheme, the sintering process are：500~750 DEG C are warming up to 2~10 DEG C/min heating rate,
Sinter 6~48h；The protective atmosphere is nitrogen and/or argon gas；The reducing atmosphere is the gaseous mixture of hydrogen and inert gas
Atmosphere.By controlling sintering temperature and time and heating rate, it is less to obtain dephasign, and crystallization is complete, and particle size is moderate
Na3+xFe3+ 1-xFe2+ xV(PO4)3Material, be advantageous to improve the electric property of material.Sintering atmosphere can be according to the raw material of selection
Suitably adjusted, can be with selective reduction atmosphere when such as selecting ferric iron source, can when selecting divalence source of iron and the ferric iron source to mix
To select protective atmosphere or reducing atmosphere.Calcination atmosphere is preferably the mixed atmosphere (hydrogen of reducing atmosphere, preferably hydrogen and argon gas
Air volume concentration：5%~10%；Most preferably 10%).
Present invention also offers Na3+xFe3+ 1-xFe2+ xV(PO4)3The application of material, it is characterised in that：As sodium ion just
Pole materials application.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Materials application uses existing side as sodium-ion battery positive material
Method is tested its performance to be assembled into sodium-ion battery：Weigh above-mentioned Na3+xFe3+ 1-xFe2+ xV(PO4)3Material, add
10wt.% conductive carbon blacks are ground fully to add a small amount of NMP mixing afterwards as binding agent as conductive agent, 10wt.%PVDF
Uniform black paste slurry is formed, these slurries are coated in aluminum foil current collector as test electrode, made with metallic sodium piece
Button cell is assembled into for comparison electrode, it uses electrolyte system as 1M NaClO4/PC.Filled used in test loop performance
Discharge current density is 100mAh g-1(1C multiplying powers).
Compared with prior art, the advantageous effects that technical scheme is brought：
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Material has the single Fast ion conductor structure of crystalline phase, makes Na3+ xFe3+ 1-xFe2+ xV(PO4)3The increase of material ions electric conductivity, improves its electro-chemical activity.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Material uses Solid phase synthesis, is closed using ball milling mixing associated methods
Into Na3+xFe3+ 1-xFe2+ xV(PO4)3Material, the contact between solid material is improved by high-energy ball milling, reaction is more filled
Point, the generation of impurities phase is reduced, while high-energy mechanical ball milling can improve the reactivity of raw material, be material follow-up sintered
Journey can synthesize rich sodium Na3+xFe3+ 1-xFe2+ xV(PO4)3Phase pure material.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Material is rich in sodium ion, in full battery, the sodium element of deintercalation
From positive electrode, positive electrode deviates from more sodium elements in first circle, it is meant that battery can have higher stable charge and discharge
Capacitance, the first circle coulombic efficiency for effectively improving positive electrode are significant for full battery.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Material first circle charging process has 2.5V corresponding to ferrous ion
Platform, compared to Na3Fe3+ 2V(PO4)3The capacity of material first circle charging, rich sodium Na3.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material is first
The charging platform for having showed 2.5V is irised out, more sodium atoms can be deviate from, so as to which in full battery, the sodium atom of deintercalation can be carried out
Also corresponding increase, capacity increase.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3Material has good high rate performance and excellent cycle performance,
Two discharge platforms of 2.5V and 3.4V make material have higher power density.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3The preparation process of material uses cheap sodium source, phosphorus source, vanadium source, iron
Source is prepared for pure phase Na as raw material by solid-phase ball milling3+xFe3+ 1-xFe2+ xV(PO4)3Material, cost is reduced, simplify synthesis
Technique, it is adapted to large-scale production.
The Na of the present invention3+xFe3+ 1-xFe2+ xV(PO4)3When material is applied as sodium-ion battery positive material, height is shown
Coulombic efficiency, high-energy-density, high working voltage, good stable circulation performance and excellent high rate performance.
Brief description of the drawings
【Fig. 1】It is Na prepared by embodiment 13+xFe3+ 1-xFe2+ xV(PO4)3The X-ray diffractogram of material；
【Fig. 2】It is Na prepared by embodiment 13+xFe3+ 1-xFe2+ xV(PO4)3The scanning electron microscope (SEM) photograph of material；
【Fig. 3】It is Na prepared by embodiment 13+xFe3+ 1-xFe2+ xV(PO4)3The first circle charge graph of material.
【Fig. 4】It is Na prepared by comparative example 13Fe3+ 2V(PO4)3The first circle charge graph of material.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material, will
0.0525mol sodium carbonate, 0.09mol diammonium hydrogen phosphates, 0.015mol vanadic anhydrides, 0.0015mol ferrous sulfate, add
1400g zirconium oxide ball milling pearls, add a certain amount of acetone as abrasive media；
Step (2)：The ball milling 12h under rotating speed 1000r/min, it is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na3.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material precursor；
Step (3)：By the presoma obtained by step (2) at 600 DEG C, (containing 10% hydrogen) sintering in hydrogen-argon-mixed atmosphere
12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material；
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, its material table
Chemical property seek peace as shown in the figure：
Fig. 1 shows to successfully synthesize Na3.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material.
The Na of the visible synthesis of Fig. 23.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material, particle diameter distribution is uniform, average grain diameter 400nm.
Fig. 3 is Na3.5Fe3+ 0.5Fe2+ 0.5V(PO4)3Material is assembled into button cell first circle under 1C multiplying powers with sodium piece and charged
Specific capacity is 68.3mAh g-1, with Na in comparative example3Fe3+ 2V(PO4)3The first circle charging of material is compared, rich sodium Na3.5Fe3+ 0.5Fe2 + 0.5V(PO4)3There is 2.5V charging platform in material first circle, can deviate from more sodium atoms, so that in full battery, can
Carrying out the sodium atom of deintercalation also accordingly increases, capacity increase.
Embodiment 2
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na3.2Fe3+ 0.8Fe2+ 0.2V(PO4)3Material, will
0.048mol sodium carbonate, 0.09mol diammonium hydrogen phosphates, 0.015mol vanadic anhydrides, 0.0015mol ferrous sulfate, add
1200g zirconium oxide ball milling pearls, add a certain amount of acetone as abrasive media；
Step (2)：The ball milling 12h under rotating speed 800r/min, it is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na3.2Fe3+ 0.8Fe2+ 0.2V(PO4)3Material precursor；
Step (3)：Presoma obtained by step (2) is sintered into 14h, programming rate in 580 DEG C, high-purity argon gas atmosphere：5
DEG C/min, Na can be obtained after natural cooling3.2Fe3+ 0.8Fe2+ 0.2V(PO4)3Material；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3.2Fe3+ 0.8Fe2+ 0.2V
(PO4)3Material average grain diameter is 500nm.Initial charge specific capacity is 63mAh g-1。
Embodiment 3
Step (1)：The present embodiment design generation 0.03mol target products Na3.7Fe3+ 0.3Fe2+ 0.7V(PO4)3Material, will
0.0555mol sodium carbonate, 0.09mol diammonium hydrogen phosphates, 0.03mol ammonium metavanadates, 0.0015mol frerrous chlorides, add 1000g
Zirconium oxide ball milling pearl, a certain amount of acetone is added as abrasive media；
Step (2)：The ball milling 14h under rotating speed 800r/min, it is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na3.7Fe3+ 0.3Fe2+ 0.7V(PO4)3Material precursor；
Step (3)：Presoma obtained by step (2) is sintered into 12h, programming rate in 580 DEG C, high-purity argon gas atmosphere：3
DEG C/min, Na can be obtained after natural cooling3.7Fe3+ 0.3Fe2+ 0.7V(PO4)3Material；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3.7Fe3+ 0.3Fe2+ 0.7V
(PO4)3Material average grain diameter is 450nm.Initial charge specific capacity is 70mAh g-1,
Comparative example 1
Starting material element content is adjusted to Na:P:V:Fe mol ratio is 3:3:1:1
Step (1)：The present embodiment design generation 0.03mol target products Na3FeV(PO4)3Material, by 0.045mol carbonic acid
Sodium, 0.09mol ammonium dihydrogen phosphates, 0.015mol vanadic anhydrides, 0.03mol ferrous sulfate, add 1400g zirconium oxide ball millings
Pearl, a certain amount of acetone is added as abrasive media；
Step (2)：The ball milling 12h under rotating speed 800r/min, it is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~
400 mesh sieves, obtain Na3FeV(PO4)3Material precursor；
Step (3)：Presoma obtained by step (2) is warming up to 600 DEG C of sintering under 350 DEG C, high-purity argon gas atmosphere
12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling3FeV(PO4)3Material.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na3FeV(PO4)3Material is averaged
Particle diameter is 800nm.Initial charge specific capacity is 56mAh g-1, as shown in Figure 4.
Comparative example 2
Raw material mixing is changed into：Common grinding
Step (1)：The present embodiment design generation 0.03mol target product materials, by 0.0555mol sodium carbonate, 0.09mol
Diammonium hydrogen phosphate, 0.03mol ammonium metavanadates, 0.0015mol frerrous chlorides, 1000g zirconium oxide ball milling pearls are added, added a certain amount of
Acetone as abrasive media；
Step (2)：It is ground using to raw material, 100~400 mesh sieves is crossed after grinding, obtain Na3.7Fe3+ 0.3Fe2+ 0.7V
(PO4)3Material precursor；
Step (3)：Presoma obtained by step (2) is sintered into 12h, programming rate in 580 DEG C, high-purity argon gas atmosphere：3
DEG C/min, Na can be obtained after natural cooling3.7Fe3+ 0.3Fe2+ 0.7V(PO4)3Material；
This comparative example resulting materials contain not well-known dephasign, assemble them into half-cell, battery assembling and method of testing and
Embodiment 1 is identical, and material average grain diameter is 2000nm.Initial charge specific capacity is 30mAh g-1。
Claims (10)
- A kind of 1. Na3+xFe3+ 1-xFe2+ xV(PO4)3Material, it is characterised in that：With NASICON type structures；Na3+xFe3+ 1-xFe2+ xV(PO4)30.05≤x≤0.9 in material.
- A kind of 2. Na according to claim 13+xFe3+ 1-xFe2+ xV(PO4)3Material, it is characterised in that：The Na3+xFe3+ 1-xFe2+ xV(PO4)3Material is the particle that particle diameter is 50~3000nm.
- 3. the Na described in claim 1 or 23+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, it is characterised in that：By sodium source, phosphorus source, vanadium source, source of iron by ball milling mixing after, be placed in protective atmosphere or reducing atmosphere, be warming up to 500~ 750 DEG C of sintering, are produced.
- 4. Na according to claim 33+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, it is characterised in that：Sodium source, phosphorus The ratio in source, vanadium source and source of iron presses Na:P:V:Fe mol ratio is 3.05~4.05:3:1:1 metering.
- 5. Na according to claim 43+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, it is characterised in that：The sodium source includes sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, niter cake, citric acid At least one of sodium, sodium hydroxide；Phosphorus source includes at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate；The vanadium source includes at least one of vanadic anhydride, ammonium metavanadate, vanadium, vanadyl acetylacetonate；The source of iron is included in frerrous chloride, ferrous sulfate, ferric nitrate, iron chloride, ferric citrate, ferrous oxide, iron oxide At least one.
- 6. according to the Na described in any one of claim 3~53+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, its feature exist In：The condition of the ball milling is：Ball material mass ratio is 30~120:1；Engine speed is 300~1200r/min, and Ball-milling Time is 6~24h.
- 7. Na according to claim 63+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, it is characterised in that：The ball Mill is carried out in organic solvent medium.
- 8. according to the Na described in claim 3~5,7 any one3+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, its feature It is：After sodium source, phosphorus source, vanadium source, source of iron ball milling mixing, dried at a temperature of being placed in 80~120 DEG C, cross 100~400 mesh sieves, take Minus sieve powder is sintered.
- 9. according to the Na described in claim 3~5,7 any one3+xFe3+ 1-xFe2+ xV(PO4)3The preparation method of material, its feature It is：The sintering process is：500~750 DEG C are warming up to 2~10 DEG C/min heating rate, sinters 6~48h；The guarantor It is nitrogen and/or argon gas to protect atmosphere；The reducing atmosphere is the mixed atmosphere of hydrogen and inert gas.
- 10. the Na described in claim 1 or 23+xFe3+ 1-xFe2+ xV(PO4)3The application of material, it is characterised in that：As sodium ion Positive electrode application.
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Cited By (7)
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| CN109103431A (en) * | 2018-08-19 | 2018-12-28 | 王子韩 | A kind of preparation method of sodium ion battery electrode material vanadium phosphate ferrisodium composite material |
| CN110085862A (en) * | 2019-04-26 | 2019-08-02 | 北京金羽新能科技有限公司 | A kind of sode cell electrode material Na1+xFexTi2-x(PO4)3And its preparation method and application |
| CN110165183A (en) * | 2019-05-30 | 2019-08-23 | 广东电网有限责任公司 | A kind of preparation method of vanadium phosphate sodium sodium-ion battery composite material |
| CN110993942A (en) * | 2020-01-02 | 2020-04-10 | 同济大学 | High-performance sodium-deficient cathode material and sodium-ion battery |
| CN114156470A (en) * | 2021-11-30 | 2022-03-08 | 电子科技大学 | Sodium-rich phase zinc vanadium sodium phosphate composite material, preparation and application thereof |
| CN115432686A (en) * | 2022-09-14 | 2022-12-06 | 鞍钢集团北京研究院有限公司 | Vanadium iron sodium phosphate material and preparation method and application thereof |
| CN115520849A (en) * | 2022-11-10 | 2022-12-27 | 无锡零一未来新材料技术研究院有限公司 | Preparation process of sodium ion battery positive electrode material, positive plate and sodium ion battery |
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| CN109103431A (en) * | 2018-08-19 | 2018-12-28 | 王子韩 | A kind of preparation method of sodium ion battery electrode material vanadium phosphate ferrisodium composite material |
| CN110085862A (en) * | 2019-04-26 | 2019-08-02 | 北京金羽新能科技有限公司 | A kind of sode cell electrode material Na1+xFexTi2-x(PO4)3And its preparation method and application |
| CN110165183A (en) * | 2019-05-30 | 2019-08-23 | 广东电网有限责任公司 | A kind of preparation method of vanadium phosphate sodium sodium-ion battery composite material |
| CN110165183B (en) * | 2019-05-30 | 2022-08-19 | 广东电网有限责任公司 | Preparation method of sodium vanadium phosphate sodium ion battery composite material |
| CN110993942A (en) * | 2020-01-02 | 2020-04-10 | 同济大学 | High-performance sodium-deficient cathode material and sodium-ion battery |
| CN114156470A (en) * | 2021-11-30 | 2022-03-08 | 电子科技大学 | Sodium-rich phase zinc vanadium sodium phosphate composite material, preparation and application thereof |
| CN114156470B (en) * | 2021-11-30 | 2023-04-25 | 电子科技大学 | Sodium-rich phase zinc-vanadium-sodium phosphate composite material, preparation and application |
| CN115432686A (en) * | 2022-09-14 | 2022-12-06 | 鞍钢集团北京研究院有限公司 | Vanadium iron sodium phosphate material and preparation method and application thereof |
| CN115432686B (en) * | 2022-09-14 | 2024-04-16 | 鞍钢集团北京研究院有限公司 | Sodium vanadium phosphate material, and preparation method and application thereof |
| CN115520849A (en) * | 2022-11-10 | 2022-12-27 | 无锡零一未来新材料技术研究院有限公司 | Preparation process of sodium ion battery positive electrode material, positive plate and sodium ion battery |
| CN115520849B (en) * | 2022-11-10 | 2023-08-22 | 无锡零一未来新材料技术研究院有限公司 | Preparation process of sodium ion battery positive electrode material, positive electrode plate and sodium ion battery |
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