CN104112858B - Network structure nanometer NaVPO 4the preparation method and application of F/C composite material - Google Patents

Network structure nanometer NaVPO 4the preparation method and application of F/C composite material Download PDF

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CN104112858B
CN104112858B CN201410298670.6A CN201410298670A CN104112858B CN 104112858 B CN104112858 B CN 104112858B CN 201410298670 A CN201410298670 A CN 201410298670A CN 104112858 B CN104112858 B CN 104112858B
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navpo
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CN104112858A (en
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徐茂文
程传俊
包淑娟
李长明
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Southwest University
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a kind of network structure nanometer NaVPO 4f/C composite material and preparation method thereof, be to sodium source, vanadium source, fluorine source, phosphorus source and reducing agent hold concurrently carbon source mixed aqueous solution in add appropriate alcohol, first obtain the coated NaVPO of carbon at 120 ~ 210 DEG C of solvent thermal reactions 4f presoma, then 750 ~ 900 DEG C, calcine under inert atmosphere, in hot environment, amorphous carbon part is burnt and to be lost and degree of graphitization is improved, NaVPO 4f particle fusion, crystallization, grain growth, be wrapped in NaVPO 4carbon-coating outside F presoma can stop NaVPO to a certain extent 4f particle fusion is integral, thus a kind of network structure nanometer NaVPO of final formation 4f/C composite material.This material has unique network configuration and good porosity, is conducive to the fast transferring of electrolyte; Effective compound with carbon, improves the conductivity of material monolithic, and then improves NaVPO 4the chemical property of F is a kind of excellent sodium-ion battery positive material.

Description

Network structure nanometer NaVPO 4the preparation method and application of F/C composite material
Technical field
The invention belongs to Material Field, relate to a kind of fluorophosphoric acid vanadium sodium (NaVPO 4f) material, and preparation method thereof and in the application of field of batteries.
Background technology
Along with the rise of the universal of consumption electronic product and electric automobile, market to the demand of lithium ion battery in continuous increase.Sodium-ion battery and lithium ion battery have many similarities, and also have some obvious advantages compared with lithium ion battery, and as lower in the cost of raw material, the electrolyte that can decomposition voltage be used lower, fail safe are better etc.Therefore, sodium-ion battery will be the very promising novel battery of one.
NaVPO 4f belongs to polyanion shaped material, and its crystal structure is stablized, and can provide the two-dimensional channel of ionic conduction, is beneficial to the lifting of discharge stability and capacity.2002, Barker synthesized NaVPO first 4f also it can be used as sodium-ion battery positive material, when with lithium metal as negative material time, positive electrode NaVPO 4the charge and discharge specific capacity first of F is respectively 101mAh/g and 95mAh/g; When with active carbon as negative material time, positive electrode NaVPO 4the charge and discharge specific capacity first of F is respectively 82mAh/g and 79mAh/g, and discharge platform is 3.7V; But NaVPO 4the discharge capacity of F after 30 charge and discharge cycles is only first 50%, and its structural stability and comprehensive electrochemical still need to be improved by suitable method.
For this reason, (the sodium-ion battery positive material NaVPO of carbon dope such as Zhang Chuanxiang 4the chemical property of F. Chinese Journal of Inorganic Chemistry, 2007,23 (4): 649-654) add appropriate glucose and synthesized the sodium-ion battery positive material NaVPO of carbon dope with two step high temperature solid-state methods 4f, after first diammonium hydrogen phosphate, vanadic oxide and glucose being mixed by a certain percentage, at 750 DEG C, calcining 8 hours obtained intermediate phosphate vanadium under inert gas shielding; After again sodium fluoride, intermediate phosphate vanadium and glucose being mixed by a certain percentage, at 750 DEG C, calcining 3 hours obtained carbon dope NaVPO under inert gas shielding 4f.Constant current charge-discharge test result shows, the NaVPO of carbon dope 10wt% 4f charge and discharge specific capacity first under 0.1C multiplying power reaches 151.5mAh/g and 113mAh/g respectively, and charge and discharge platform is respectively 3.8V and 3.6V, and after 20 circulations, specific discharge capacity is initial 91.6%.
Chinese patent application CN103594716A is also disclosed a kind of activation by collosol and gel and assists two step high temperature solid-state methods to prepare carbon dope sodium-ion battery positive material NaVPO 4the method of F, is that vanadium source, phosphorus source, carbon source is soluble in water by a certain percentage, adds thermal agitation, obtain light green color slurry, after its vacuumize, 650-850 DEG C, calcine 2-10 hour under inert gas shielding, obtain VPO 4/ C presoma, then by VPO 4after/C presoma mixes by a certain percentage with NaF, 650-850 DEG C, calcine 2-10 hour under inert gas shielding, obtain carbon dope positive electrode NaVPO 4f/C.This positive electrode NaVPO 4f/C first discharge specific capacity under 0.05C multiplying power is 112mAh/g, and the specific discharge capacity conservation rate from 0.05C to 0.2C is 62.6%, and occurs two constant voltage platforms near 3.7V and 3.25V voltage.
But, the carbon dope NaVPO that said method is obtained 4the pattern of F all presents uneven structure and is adhered to one another, and particle is too large, carbon coated uneven, thus the shortcoming such as cause the not high and high rate performance of battery capacity not good.
Summary of the invention
In view of this, an object of the present invention is to provide one to prepare network structure nanometer NaVPO 4the new method of F/C composite material, the method is easy and simple to handle, the cycle is short, cost is low, gained NaVPO 4the advantages such as F/C composite material has unique network configuration, even particle distribution, porosity is high, carbon plyability is good, chemical property is good; Two of object is to provide the network structure nanometer NaVPO adopting described method obtained 4f/C composite material is as the application of sodium-ion battery positive material.
After deliberation, the invention provides following technical scheme:
1.network structure nanometer NaVPO 4the preparation method of F/C composite material, comprises the following steps:
A. the coated NaVPO of solvent heat carbon 4f presoma: by soluble in water to sodium source, vanadium source and fluorine source, obtain I liquid; Carbon source of being held concurrently in phosphorus source and reducing agent is soluble in water, obtains II liquid; II liquid is added in I liquid, stir 5 ~ 60 minutes, obtain III liquid; Be added to by absolute ethyl alcohol in III liquid, stir 5 ~ 60 minutes, 120 ~ 210 DEG C of solvent thermal reactions 4 ~ 72 hours, filter, collect solid, washing, 120 DEG C of dryings 4 ~ 24 hours or freeze drying, obtain the NaVPO that carbon is coated 4f presoma;
Described sodium source is one or more in sodium metavanadate, sodium vanadate, sodium pyrovanadate, sodium fluoride, sodium dihydrogen phosphate, NaOH, sodium carbonate and sodium acid carbonate;
Described vanadium source is the oxide of vanadic salts or vanadium; Vanadic salts is one or more in ammonium metavanadate, sodium metavanadate, sodium vanadate and sodium pyrovanadate; The oxide of vanadium is one or more in vanadic oxide, vanadium dioxide and vanadium trioxide;
Described fluorine source is sodium fluoride or ammonium fluoride;
Described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and sodium dihydrogen phosphate;
Described reducing agent carbon source of holding concurrently is one or more in vitamin C, glucose, fructose, maltose and citric acid;
Sodium total in solvent thermal reaction system: vanadium: fluorine: phosphonium ion mol ratio is 1:1:1:1; The hold concurrently consumption of carbon source of reducing agent is 1 ~ 2 times of vanadium ion mole dosage;
B. the coated NaVPO of high-temperature calcination carbon 4f presoma: the presoma NaVPO that carbon steps A obtained is coated 4f, 750 ~ 900 DEG C, calcining 2 ~ 15 hours under inert atmosphere protection, obtains the nanometer NaVPO of network configuration 4f/C composite material.
In said method, in steps A, the hold concurrently selection prerequisite of carbon source of reducing agent vanadium can be reverted to+3 valencys or+4 valencys under not higher than solvent thermal reaction temperature conditions; The concentration in sodium source in I liquid, vanadium source and fluorine source, and in II liquid, phosphorus source and reducing agent hold concurrently the concentration of carbon source all without strict requirement; In III liquid, the addition of absolute ethyl alcohol is to product (the presoma NaVPO that carbon is coated 4f) crystal formation has impact, works as V alcohol: V waterduring < 2.5, the presoma NaVPO that after solvent heat, carbon is coated 4the XRD that F is corresponding does not have peak, and follow-up high-temperature calcination also can not get corresponding monoclinic form NaVPO 4f, and work as V alcohol: V waterwhen>=2.5, the presoma NaVPO that after solvent heat, carbon is coated 4the XRD that F is corresponding has peak, and follow-up high-temperature calcination can obtain corresponding monoclinic form NaVPO 4f.In step B, 750 DEG C is phase transition temperature, 750 DEG C, calcination time is no more than 4 hours, gained NaVPO under inert atmosphere protection 4the crystal formation of F is mixed phase; Calcination time more than 4 hours, gained NaVPO 4the crystal formation of F is monocline type; And 800 ~ 900 DEG C, under inert atmosphere protection, the length of calcination time only affects gained NaVPO 4the pattern of F, more long crystal growth is larger for calcination time, gained NaVPO 4f particle is larger, and does not affect its crystal formation.
Further, described sodium source is sodium fluoride, and vanadium source is ammonium metavanadate, and fluorine source is sodium fluoride, and phosphorus source is ammonium dihydrogen phosphate, and reducing agent carbon source of holding concurrently is vitamin C.
Further, described steps A be by ammonium metavanadate and sodium fluoride soluble in water, make the concentration of ammonium metavanadate and sodium fluoride be respectively 0.2mol/L, obtain I liquid; By ammonium dihydrogen phosphate and vitamin C soluble in water, make that the concentration of ammonium dihydrogen phosphate is 0.2mol/L, ascorbic concentration is 0.3mol/L, obtain II liquid; II liquid is added in I liquid, stir 10 minutes, obtain III liquid; Be added to by absolute ethyl alcohol in III liquid, the addition of absolute ethyl alcohol is long-pending 2.5 times of III liquid, stirs 10 minutes, and 180 DEG C of solvent thermal reactions 24 hours, filtration washing, solid freeze drying, obtains the presoma NaVPO that carbon is coated 4f; Sodium total in solvent thermal reaction system: vanadium: fluorine: phosphonium ion mol ratio is 1:1:1:1; Described ascorbic consumption is 1.5 times of vanadium ion mole dosage.
Further, described step B is the coated presoma NaVPO of the carbon that steps A obtained 4f, 750 ~ 800 DEG C, calcining 6 hours under inert atmosphere protection, obtains the nanometer NaVPO of network configuration 4f/C composite material.
Adopt the network structure nanometer NaVPO that above-mentioned preparation method obtains 4f/C composite material.
Network structure nanometer NaVPO 4f/C composite material is as the application of sodium-ion battery positive material.
Beneficial effect of the present invention is: the present invention utilizes solvent heat assisted with high-temperature calcination method to prepare network structure nanometer NaVPO 4f/C composite material, be to sodium source, vanadium source, fluorine source, phosphorus source, reducing agent hold concurrently carbon source mixed aqueous solution in add appropriate alcohol, first obtain the coated NaVPO of carbon at 120 ~ 210 DEG C of solvent thermal reactions 4f presoma, then 750 ~ 900 DEG C, calcine under inert atmosphere protection, in hot environment, amorphous carbon part is burnt and to be lost and degree of graphitization is improved, NaVPO 4f particle fusion, crystallization, grain growth, but be wrapped in NaVPO 4carbon-coating outside F presoma can stop NaVPO to a certain extent 4f particle fusion is integral, thus the final nanometer NaVPO forming a kind of network configuration 4f/C composite material.This preparation method is easy and simple to handle, the cycle is short, cost is low, the network structure nanometer NaVPO obtained 4f/C composite material has unique network configuration and good porosity, is conducive to the fast transferring of electrolyte; Effective compound with carbon, improves the conductivity of material monolithic, and then improves NaVPO 4the chemical property (first discharge specific capacity is up to 143mAh/g under 0.1C multiplying power) of F, can be used as sodium-ion battery positive material, has a good application prospect.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing and being described:
Fig. 1 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of embodiment one products obtained therefrom.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment two products obtained therefrom.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment three products obtained therefrom.
Fig. 4 is the X-ray diffractogram of embodiment one, two, three products obtained therefrom.
Fig. 5 is the X-ray diffraction scanning electron microscope (SEM) photograph of embodiment four products obtained therefrom.
Fig. 6 is the constant current charge-discharge curve of embodiment two, three products obtained therefrom under 0.1C multiplying power.
Fig. 7 is the cyclic curve of embodiment two, three products obtained therefrom under 0.1C multiplying power.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in preferred embodiment, usually conveniently condition, or carry out according to the condition that reagent manufacturer advises.
the NaVPO that embodiment one, carbon are coated 4 the synthesis of F presoma
Take 2mmolNH 4vO 3be dissolved in 10ml deionized water with 2mmolNaF, obtain I liquid; Take 2mmolNH 4h 2pO 4be dissolved in 10ml deionized water with 3mmol vitamin C, obtain II liquid; I liquid is slowly instilled in II liquid, stir 10min, obtain III liquid; Dropped to by 50ml absolute ethyl alcohol in III liquid, stir 10min, then transfer in solvent thermal reaction still, 180 DEG C are reacted 24 hours, and cooled and filtered is washed, and solid freeze drying, obtains the NaVPO that carbon is coated 4f presoma.
As shown in Figure 1, grain shape is regular, particle diameter very little (nanoscale), and surface is evenly coated by carbon for the pattern of products obtained therefrom.As shown in Figure 4, synthetic is the coated NaVPO of carbon to the composition analysis result of products obtained therefrom 4f presoma.
embodiment two, network structure nanometer NaVPO 4 the synthesis of F/C composite material
By NaVPO coated for carbon obtained for embodiment one 4f presoma, 750 DEG C, calcining 6 hours under argon shield condition, is cooled to room temperature, obtains network structure nanometer NaVPO 4f/C composite material.
The pattern of products obtained therefrom as shown in Figure 2, in uniform nano particle.As shown in Figure 4, synthetic is NaVPO to the composition analysis result of products obtained therefrom 4f, its crystal formation is monocline type.
embodiment three, network structure nanometer NaVPO 4 the synthesis of F/C composite material
By NaVPO coated for carbon obtained for embodiment one 4f presoma, 800 DEG C, calcining 6 hours under argon shield condition, is cooled to room temperature, obtains network structure nanometer NaVPO 4f/C composite material.
The pattern of products obtained therefrom as shown in Figure 3, in uniform nano particle.As shown in Figure 4, synthetic is NaVPO to the composition analysis result of products obtained therefrom 4f, its crystal formation is monocline type.
embodiment four, calcination time are to network structure nanometer NaVPO 4 the impact of F/C composite material pattern
By NaVPO coated for carbon obtained for embodiment one 4f presoma 800 DEG C, calcine 2,6 and 15 hours respectively under argon shield condition, be cooled to room temperature, obtain network structure nanometer NaVPO 4f/C composite material.
As shown in Figure 5, visible calcination time is longer, and product particle is larger for the pattern of products obtained therefrom.
the preparation of embodiment five, battery and electrochemical property test
The network structure nanometer NaVPO that Example two, three is obtained respectively 4f/C composite material, by its with conductive black, PVDF binding agent in mass ratio 70:20:10 mix, add appropriate 1-Methyl-2-Pyrrolidone (NMP) again, in agate mortar, be ground to pasty state, be coated in (every sheet aluminium foil laod network structure nano NaVPO on aluminium foil that diameter is 19mm 4f/C composite material is about 2mg), then by aluminium foil in 120 DEG C of vacuumizes 12 hours, obtain positive plate, be transferred to the assembling carrying out button cell in the glove box being full of argon gas, button cell model is CR2025, negative pole is sodium metal sheet, and barrier film is microporous polypropylene membrane Celgard2325, and electrolyte is the NaPF of 1mol/L 6solution (solvent is ethylene carbonate and the dimethyl carbonate mixed liquor that forms of 1:1 by volume).The battery assembled is placed after more than 6 hours, and Land test macro carries out electrochemical property test, and voltage range is 2.5 ~ 4.2V, and size of current is 0.1C.Gained constant current charge-discharge curve as shown in Figure 6, the network structure nanometer NaVPO that embodiment two is obtained 4the first discharge specific capacity of F/C composite material under 0.1C multiplying power is 143mAh/g, the network structure nanometer NaVPO that embodiment three is obtained 4the first discharge specific capacity of F/C composite material under 0.1C multiplying power is 101mAh/g.Gained cyclic curve as shown in Figure 7, the network structure nanometer NaVPO that embodiment two is obtained 4f/C composite material rear specific discharge capacity of 100 circulations under 0.1C multiplying power is 94mAh/g, the network structure nanometer NaVPO that embodiment three is obtained 4f/C composite material rear specific discharge capacity of 100 circulations under 0.1C multiplying power is 79mAh/g.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.

Claims (6)

1. network structure nanometer NaVPO 4the preparation method of F/C composite material, is characterized in that, comprises the following steps:
A. the coated NaVPO of solvent heat carbon 4f presoma: by soluble in water to sodium source, vanadium source and fluorine source, obtain I liquid; Carbon source of being held concurrently in phosphorus source and reducing agent is soluble in water, obtains II liquid; II liquid is added in I liquid, stir 5 ~ 60 minutes, obtain III liquid; Be added to by absolute ethyl alcohol in III liquid, stir 5 ~ 60 minutes, 120 ~ 210 DEG C of solvent thermal reactions 4 ~ 72 hours, filter, collect solid, washing, 120 DEG C of dryings 4 ~ 24 hours or freeze drying, obtain the NaVPO that carbon is coated 4f presoma;
Described sodium source is one or more in sodium metavanadate, sodium vanadate, sodium pyrovanadate, sodium fluoride, sodium dihydrogen phosphate, NaOH, sodium carbonate and sodium acid carbonate;
Described vanadium source is the oxide of vanadic salts or vanadium; Vanadic salts is one or more in ammonium metavanadate, sodium metavanadate, sodium vanadate and sodium pyrovanadate; The oxide of vanadium is one or more in vanadic oxide, vanadium dioxide and vanadium trioxide;
Described fluorine source is sodium fluoride or ammonium fluoride;
Described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and sodium dihydrogen phosphate;
Described reducing agent carbon source of holding concurrently is one or more in vitamin C, glucose, fructose, maltose and citric acid;
Sodium total in solvent thermal reaction system: vanadium: fluorine: phosphonium ion mol ratio is 1:1:1:1; The hold concurrently consumption of carbon source of reducing agent is 1 ~ 2 times of vanadium ion mole dosage;
B. the coated NaVPO of high-temperature calcination carbon 4f presoma: the presoma NaVPO that carbon steps A obtained is coated 4f, 750 ~ 900 DEG C, calcining 2 ~ 15 hours under inert atmosphere protection, obtains network structure nanometer NaVPO 4f/C composite material.
2. network structure nanometer NaVPO as claimed in claim 1 4the preparation method of F/C composite material, is characterized in that, described sodium source is sodium fluoride, and vanadium source is ammonium metavanadate, and fluorine source is sodium fluoride, and phosphorus source is ammonium dihydrogen phosphate, and reducing agent carbon source of holding concurrently is vitamin C.
3. network structure nanometer NaVPO as claimed in claim 2 4the preparation method of F/C composite material, is characterized in that, described steps A be by ammonium metavanadate and sodium fluoride soluble in water, make the concentration of ammonium metavanadate and sodium fluoride be respectively 0.2mol/L, obtain I liquid; By ammonium dihydrogen phosphate and vitamin C soluble in water, make that the concentration of ammonium dihydrogen phosphate is 0.2mol/L, ascorbic concentration is 0.3mol/L, obtain II liquid; II liquid is added in I liquid, stir 10 minutes, obtain III liquid; Be added to by absolute ethyl alcohol in III liquid, the addition of absolute ethyl alcohol is long-pending 2.5 times of III liquid, stirs 10 minutes, and 180 DEG C of solvent thermal reactions 24 hours, filtration washing, solid freeze drying, obtains the NaVPO that carbon is coated 4f presoma; Sodium total in solvent thermal reaction system: vanadium: fluorine: phosphonium ion mol ratio is 1:1:1:1; Described ascorbic consumption is 1.5 times of vanadium ion mole dosage.
4. network structure nanometer NaVPO as claimed in claim 3 4the preparation method of F/C composite material, is characterized in that, described step B is the coated presoma NaVPO of the carbon that steps A obtained 4f, 750 ~ 800 DEG C, calcining 6 hours under inert atmosphere protection, obtains network structure nanometer NaVPO 4f/C composite material.
5. adopt the network structure nanometer NaVPO that according to any one of Claims 1-4, preparation method obtains 4f/C composite material.
6. network structure nanometer NaVPO according to claim 5 4f/C composite material is as the application of sodium-ion battery positive material.
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CN103594707A (en) * 2013-11-29 2014-02-19 西南大学 High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2

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