CN107069012A - Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof - Google Patents

Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof Download PDF

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CN107069012A
CN107069012A CN201710272720.7A CN201710272720A CN107069012A CN 107069012 A CN107069012 A CN 107069012A CN 201710272720 A CN201710272720 A CN 201710272720A CN 107069012 A CN107069012 A CN 107069012A
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sodium
source
composite anode
anode materials
preparation
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CN107069012B (en
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赵光金
陈重学
蒲想军
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Wuhan University WHU
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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Wuhan University WHU
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof, including：(1) surfactant is dissolved in polar solvent acquisition surfactant solution, after the pH of surfactant solution is adjusted into 1~4, adds sodium source, source of iron, phosphorus source and carbon source and simultaneously disperses；(2) emulsion obtained by step (1) is transferred to culture dish, and 6h~24h is stood at a temperature of 10 DEG C~40 DEG C, then, in heating 8h~36h at 80 DEG C 120 DEG C, obtains presoma；(3) presoma is placed in inert atmosphere, in 250 DEG C~350 DEG C temperature lower calcination 2h~6h, then raises temperature to 500 DEG C~700 DEG C, continues to calcine 6h~12h.The Volume Changes that sodium ion deintercalation is caused when gained composite anode material of the invention can alleviate discharge and recharge, effectively improve Na4Fe3(PO4)2P2O7Electrical conductivity and stability.

Description

Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof
Technical field
The invention belongs to the preparation field of sodium-ion battery positive material, more particularly to a kind of hollow sphere Na4Fe3 (PO4)2P2O7/ C composite anode materials and preparation method thereof.
Background technology
The energy is the important substance basis that human society is depended on for existence and development, but at present traditional fossil energy coal, oil, Natural gas etc. still occupies larger proportion in global energy structure.The increasingly reduction of fossil energy reserves, and it is in utilization During caused by Heavy environmental pollution, force the research of countries in the world Efforts To Develop new energy system and technology.Solar energy, The regenerative resources such as wind energy have aboundresources, it is environment-friendly the features such as.But limited by natural conditions, this class clean energy resource With intermittent and unstability, it is difficult to generate electricity by way of merging two or more grid systems, it is therefore necessary to carry out peak load shifting using large-scale energy storage system, to protect Hinder the stability of power network and the continuity of supply of electric power.Current existing extensive energy storage technology includes energy storage of drawing water, and compression is empty Gas energy storage, flywheel energy storage and electrochemical energy storage etc..Compared with other energy storage technologies, electrochemical energy storage has high conversion efficiency, followed Ring long lifespan, maintenance cost are low, power and the features such as flexible energy response.
Extensive electrochemical energy storage technology has a variety of routes, such as lead-acid battery, flow battery, the high temperature sodium-sulphur battery and lithium Ion battery etc..But there is fatal inherent shortcoming in lead-acid battery, flow battery, the high temperature sodium-sulphur battery so that they are very Difficult sizable application is in energy-storage system.Lithium ion battery energy density is high, have extended cycle life, clean and effective, ought to be energy-storage system First choice.But in recent years, as China's electric automobile market develops rapidly a large amount of consumption of brought lithium metal, and the whole world The skewness (being mainly distributed on South American nations) of lithium resource, the development of following China's lithium ion battery industry will necessarily be by upper Swim the limitation of lithium ore shortage.The sodium-ion battery similar with lithium ion battery operation principle is because close with low cost, energy The features such as degree is higher, may have place to show one's prowess in extensive energy storage field.
Although the research of sodium-ion battery arises from last century the eighties, develop not smooth, the maturity of its technology Also far away from lithium ion battery, the main bottleneck of restriction sodium-ion battery development is a lack of that the long-life of deintercalation sodium ion can be stablized Positive electrode.The positive electrode of current sodium-ion battery mainly includes layered oxide, tunnel type oxide, prussian blue Compound and polyanionic compound etc..Layered oxide NaxMO2With excellent electrochemistry storage sodium activity, preparation method letter Single, energy density is higher, but the structural stability and cycle performance of material are poor.Tunnel type oxide NaxMO2With stabilization Structure and cycle performance, but its first all charging capacity is relatively low, causes the actual specific energy of battery very low.Prussian blue chemical combination Thing KMFe (CN)6With three-dimensional open architecture, storage sodium activity is high, cyclical stability and high rate performance is preferable, cost is relatively low, but Also there is more urgent problem to be solved in the extensive preparation technology of material.Polyanionic compound has open framework knot The many advantages such as structure, good structural stability and heat endurance and stable voltage platform and enjoy favor.
In numerous polyanionic compounds, Na4Fe3(PO4)2P2O7Theoretical specific capacity reach 129mAhg-1, work Voltage is 3.2V, and with low cost, shows excellent combination property, therefore receive significant attention.But Na4Fe3(PO4)2P2O7Electronic conductivity and ionic conductivity it is extremely low, cause that its actual specific capacity is smaller, heavy-current discharge performance is poor.
The content of the invention
It is an object of the invention to provide a kind of hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and its preparation Method.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
First, hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials, wherein carbon and Na4Fe3(PO4)2P2O7Matter Amount is than being 1：(1~49).
2nd, hollow sphere Na4Fe3(PO4)2P2O7The preparation method of/C composite anode materials, including step：
(1) surfactant is dissolved in polar solvent acquisition surfactant solution, and the pH of surfactant solution is adjusted into 1 After~4, add sodium source, source of iron, phosphorus source and carbon source and simultaneously disperse, sodium element in sodium source, source of iron and phosphorus source, ferro element, P elements Mol ratio is 4：3：4；
(2) emulsion obtained by step (1) is transferred to culture dish, and 6h~24h is stood at a temperature of 10 DEG C~40 DEG C, then, in Heat 8h~36h at 80 DEG C -120 DEG C, obtain presoma；
(3) presoma is placed in inert atmosphere, in 250 DEG C~350 DEG C temperature lower calcination 2h~6h, then raises temperature to 500 DEG C~700 DEG C, continue to calcine 6h~12h, produce carbon and Na in target complex, target complex4Fe3(PO4)2P2O7Quality Than for 1：(1~49)；
Na in the consumption and target complex of above-mentioned surfactant4Fe3(PO4)2P2O7Mol ratio be 1：(1~15).
Further, surfactant is fatty glyceride, sodium alkyl benzene sulfonate, PULLRONIC F68-polyoxy One or more in ethene.
Further, polar solvent is the one or more in water, methanol, ethanol, isopropanol, acetone.
Further, sodium source is in disodium hydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium nitrate, sodium citrate, sodium oxalate It is one or more.
Further, source of iron is one kind in ferric nitrate, ferric sulfate, ferric acetate, ferrous oxalate, ferrous sulfate, iron chloride Or it is a variety of.
Further, phosphorus source is phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, burnt phosphorus One or more in sour ammonium, sodium pyrophosphate.
Further, carbon source is the one or more in starch, citric acid, sucrose, glucose, phenolic resin.
Compared to the prior art, the invention has the advantages that and beneficial effect：
(1) surfactant is used for growth templates, is self-assembly of in being formed after spherical structure, removal of surfactant Hollow structure, is shown in Fig. 1；Surface with rounded structures is smooth, and specific surface area is small, can reduce the side reaction occurred with electrolyte；Hollow structure The Volume Changes that sodium ion deintercalation is caused when being conducive to alleviating discharge and recharge.
(2) three-dimensional net structure is formed, by cation in self assembling process as carbon source using oligomer or macromolecular It is fixed on network skeleton, in Na after heat treatment4Fe3(PO4)2P2O7The upper carbon-coating of particle surface cladding, is shown in Fig. 1, effectively improves Na4Fe3(PO4)2P2O7Electrical conductivity and stability.
(3) stable preparation process of the present invention is controllable, favorable reproducibility, it is easy to mass production.
Brief description of the drawings
Fig. 1 is preparation principle figure of the present invention；
Fig. 2~3 are the SEM pictures of the gained target product of embodiment 1；
Fig. 4 is the charging and discharging curve of the gained target product of embodiment 1；
Fig. 5 is the high current cyclic curve of the gained target product of embodiment 1；
Fig. 6 is the charging and discharging curve of the gained target product of embodiment 2；
Fig. 7 is the low current cyclic curve of the gained target product of embodiment 2；
Fig. 8 is the charging and discharging curve of the gained target product of embodiment 3；
Fig. 9 is the low current cyclic curve of the gained target product of embodiment 3；
Figure 10 is the charging and discharging curve of the gained target product of embodiment 4；
Figure 11 is the low current cyclic curve of the gained target product of embodiment 4.
Embodiment
Fig. 1 is preparation principle figure of the present invention, and first, surfactant is in polar solvent by being self-assembly of positive glue Beam.Then, sodium source compound, Fe source compound, P source compound and carbon-source cpd by hydrogen bond action and micella outside Hydrophilic radical is connected.Through Overheating Treatment, surfactant pyrolysis forms hollow ball shape structure after leaving away.
Technical scheme is described in further detail below in conjunction with drawings and Examples.But therefore it not incite somebody to action this Invention is limited among described scope of embodiments.
Embodiment 1
In the present embodiment, raw material include F127, Na4P2O7、Fe(NO3)3、NH4H2PO4, phenolic resin, wherein, F127 is Surfactant, Na4P2O7It is both sodium source and phosphorus source, Fe (NO3)3For source of iron, NH4H2PO4For phosphorus source, phenolic resin is carbon source. F127 and Na in target product4Fe3(PO4)2P2O7Mol ratio be 1：1, Na4P2O7、Fe(NO3)3、NH4H2PO4Mol ratio be 1：3：2.
Using water as polar solvent, gained emulsion is transferred to culture dish, in standing 6h at 40 DEG C, then, in heating at 80 DEG C 8h is handled, presoma is obtained.Presoma is placed in argon gas atmosphere, in 250 DEG C of temperature lower calcination 6h, then raises temperature to 500 DEG C, after Continuous calcining 12h, produces target product.Carbon and Na in gained target product4Fe3(PO4)2P2O7Mass ratio be 1:49.
The SEM pictures of the present embodiment target product are shown in Fig. 2~3, as can be seen from Figure 2, and it has spherical structure, spheric granules Size is 20nm~100nm.From figure 3, it can be seen that it has hollow-core construction, hole diameter is 10nm~80nm.
Fig. 4 is the charging and discharging curve of the present embodiment target product, from this figure, it can be seen that the present embodiment target product has many Individual discharge platform, discharge capacity is 90mAhg-1.Fig. 5 is the high current cyclic curve of the present embodiment target product, the present embodiment Target product is in 200mAg-1Initial capacity 66mAhg under current density-1, 500 circulation volume conservation rates are 68%.
Embodiment 2
In the present embodiment, raw material includes neopelex, Na2HPO4、FeSO4、NH4H2PO4, sucrose, wherein, ten Dialkyl benzene sulfonic acids sodium is surfactant, Na2HPO4It is both sodium source and phosphorus source, NH4H2PO4For phosphorus source, FeSO4For source of iron, Sucrose is carbon source.Neopelex and Na in target product4Fe3(PO4)2P2O7Mol ratio be 1：5, Na2HPO4、 FeSO4、NH4H2PO4Mol ratio be 2：3：2.
Using ethanol as polar solvent, gained emulsion is transferred to culture dish, in standing 8h at 20 DEG C, then, at 90 DEG C plus 10h is heat-treated, presoma is obtained.Presoma is placed in argon gas atmosphere, in 280 DEG C of temperature lower calcination 5h, then raises temperature to 550 DEG C, continue to calcine 10h, produce target product.Carbon and Na in gained target product4Fe3(PO4)2P2O7Mass ratio be 1:19.
Fig. 6 is the charging and discharging curve of the present embodiment target product, from this figure, it can be seen that the present embodiment target product has many Individual discharge platform, discharge capacity is 95mAhg-1.Fig. 7 is the high current cyclic curve of the present embodiment target product, the present embodiment Target product is in 10mAg-1Initial capacity 89mAhg under current density-1, 90 times circulation volume is held essentially constant.
Embodiment 3
In the present embodiment, raw material includes F127, P123, Na4P2O7、FeC2O4, phosphoric acid, glucose, wherein, F127 and P123 For surfactant, Na4P2O7Not only it is sodium source but also be phosphorus source, FeC2O4For source of iron, phosphoric acid is phosphorus source.Surfactant and target production Na in thing4Fe3(PO4)2P2O7Mol ratio be 1:10, Na4P2O7、FeC2O4、H3PO4Mol ratio be 1：3：2.
Using ethanol as polar solvent, gained emulsion is transferred to culture dish, in standing 12h at 30 DEG C, then, at 90 DEG C plus 16h is heat-treated, presoma is obtained.Presoma is placed in argon gas atmosphere, in 300 DEG C of temperature lower calcination 4h, then raises temperature to 600 DEG C, continue to calcine 8h, produce target product.Carbon and Na in gained target product4Fe3(PO4)2P2O7Mass ratio be 1:1.
Fig. 8 is the charging and discharging curve of the present embodiment target product, from this figure, it can be seen that the present embodiment target product has many Individual discharge platform, discharge capacity is 59mAhg-1.Fig. 9 is the high current cyclic curve of the present embodiment target product, the present embodiment Target product is in 20mAg-1Initial capacity 61mAhg under current density-1, capacity attenuation is 53mAhg after 34 circulations-1。
Embodiment 4
In the present embodiment, raw material includes P123, CH3COONa、FeC2O4、NH4H2PO4、(NH4)4P2O7, citric acid, wherein, P123 is surfactant, CH3COONa is sodium source, FeC2O4For source of iron, NH4H2PO4(NH4)4P2O7For P source compound, lemon Lemon acid is carbon source.P123 and Na4Fe3(PO4)2P2O7Mol ratio be 1:15, CH3COONa、NH4H2PO4、(NH4)4P2O7、 FeC2O4Mol ratio be 4:2:1:3.
Using acetone as polar solvent, gained emulsion is transferred to culture dish, in standing 24h at 10 DEG C, then, at 120 DEG C Heat 36h, obtain presoma.Presoma is placed in argon gas atmosphere, in 350 DEG C of temperature lower calcination 2h, then raises temperature to 700 DEG C, continue to calcine 6h, produce target product.Carbon and Na in gained target product4Fe3(PO4)2P2O7Mass ratio be 1:9.
Figure 10 is the charging and discharging curve of the present embodiment target product, from this figure, it can be seen that the present embodiment target product has Multiple discharge platforms, discharge capacity is 102mAhg-1.Figure 11 is the high current cyclic curve of the present embodiment target product, this reality A target product is applied in 10mAg-1Initial capacity 98mAhg under current density-1, capacity is kept not substantially after 100 circulations Become.

Claims (8)

1. a kind of hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials, it is characterized in that：
Na4Fe3(PO4)2P2O7Carbon and Na in/C composite anode materials4Fe3(PO4)2P2O7Mass ratio be 1：(1~49).
2. a kind of hollow sphere Na4Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is characterized in that, including step：
(1) surfactant is dissolved in polar solvent acquisition surfactant solution, and the pH of surfactant solution is adjusted into 1~4 Afterwards, sodium source, source of iron, phosphorus source and carbon source are added and is disperseed, mole of sodium element, ferro element, P elements in sodium source, source of iron and phosphorus source Than for 4：3：4；
(2) emulsion obtained by step (1) is transferred to culture dish, and 6h~24h is stood at a temperature of 10 DEG C~40 DEG C, then, in 80 DEG C- Heat 8h~36h at 120 DEG C, obtain presoma；
(3) presoma is placed in inert atmosphere, in 250 DEG C~350 DEG C temperature lower calcination 2h~6h, then raise temperature to 500 DEG C~ 700 DEG C, continue to calcine 6h~12h, produce carbon and Na in target complex, target complex4Fe3(PO4)2P2O7Mass ratio be 1：(1~49)；
Na in the consumption and target complex of above-mentioned surfactant4Fe3(PO4)2P2O7Mol ratio be 1：(1~15).
3. hollow sphere Na as claimed in claim 24Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is special Levying is：
Described surfactant is in fatty glyceride, sodium alkyl benzene sulfonate, polyoxyethylene-poly-oxypropylene polyoxyethylene One or more.
4. hollow sphere Na as claimed in claim 24Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is special Levying is：
Described polar solvent is the one or more in water, methanol, ethanol, isopropanol, acetone.
5. hollow sphere Na as claimed in claim 24Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is special Levying is：
Described sodium source is one kind or many in disodium hydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium nitrate, sodium citrate, sodium oxalate Kind.
6. hollow sphere Na as claimed in claim 24Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is special Levying is：
Described source of iron is the one or more in ferric nitrate, ferric sulfate, ferric acetate, ferrous oxalate, ferrous sulfate, iron chloride.
7. hollow sphere Na as claimed in claim 24Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is special Levying is：
Described phosphorus source is phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium pyrophosphate, Jiao One or more in sodium phosphate.
8. hollow sphere Na as claimed in claim 24Fe3(PO4)2P2O7The preparation method of/C composite anode materials, it is special Levying is：
Described carbon source is the one or more in starch, citric acid, sucrose, glucose, phenolic resin.
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CN108046231A (en) * 2017-11-13 2018-05-18 中南大学 A kind of sodium-ion battery positive material and preparation method thereof
CN108565418A (en) * 2018-04-03 2018-09-21 武汉大学 A kind of novel sodium-ion battery positive material and preparation method thereof
CN110098383A (en) * 2018-01-29 2019-08-06 宁德新能源科技有限公司 Positive electrode and preparation method thereof, anode and lithium ion battery
CN110226252A (en) * 2018-07-27 2019-09-10 辽宁星空钠电电池有限公司 A kind of polyanionic sodium-ion battery positive material and preparation method thereof
CN113060714A (en) * 2021-02-25 2021-07-02 湖北万润新能源科技股份有限公司 Slave FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) Method (2)
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CN113285072A (en) * 2021-07-24 2021-08-20 南杰智汇(深圳)科技有限公司 Pyrophosphate composite material, sodium ion battery anode, sodium ion battery cathode and sodium ion battery
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CN116404154A (en) * 2023-03-31 2023-07-07 华南理工大学 High-entropy sodium ferric pyrophosphate sodium ion battery anode material and preparation method thereof
CN116534829A (en) * 2023-05-29 2023-08-04 浙江鑫钠新材料科技有限公司 From FePO 4 Method for preparing double-layer coated sodium ion battery anode material by liquid phase method

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