CN104112858A - Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof - Google Patents
Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof Download PDFInfo
- Publication number
- CN104112858A CN104112858A CN201410298670.6A CN201410298670A CN104112858A CN 104112858 A CN104112858 A CN 104112858A CN 201410298670 A CN201410298670 A CN 201410298670A CN 104112858 A CN104112858 A CN 104112858A
- Authority
- CN
- China
- Prior art keywords
- sodium
- navpo
- source
- carbon
- network structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 network structure nano NaVPO4F/C composite material, and a preparation method thereof. The preparation method comprises the steps of adding a proper amount of alcohol to a mixed aqueous solution of a sodium source, a vanadium source, a fluorine source, a phosphorus source, a reducing agent and a carbon source; carrying out a solvothermal reaction at a temperature of 120-210 DEG C to obtain a carbon coated NaVPO4F precursor; and then calcining at a temperature of 750-900 DEG C under an inert atmosphere. In a high temperature environment, amorphous carbon is partially burned; a degree of graphitization is increased; NaVPO4F particles are fused and crystallized; grains grow; the carbon layer coating the NaVPO4F precursor can inhibit NaVPO4F particles from fusing together to some degree; and finally the network structure nano NaVPO4F/C composite material is formed. The material has a unique network structure and good porosity, and is beneficial to rapid migration of an electrolyte. Electrical conductivity of the whole material is improved due to effective compounding with carbon, and further electrochemical performance of NaVPO4F is increased. The network structure nano NaVPO4F/C composite is an excellent positive electrode material of the sodium ion battery.
Description
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 and electric automobile of consumption electronic product, market to the demand of lithium ion battery in continuous increase.Sodium-ion battery and lithium ion battery have many similarities, and compare with lithium ion battery and also have some obvious advantages, as lower in the cost of raw material, can use electrolyte, fail safe that decomposition voltage is lower better etc.Therefore, sodium-ion battery will be a kind of very promising novel battery.
NaVPO
4f belongs to polyanion shaped material, and its crystal structure is stable, and the two-dimensional channel of ionic conduction can be provided, and is beneficial to the lifting of discharge stability and capacity.2002, Barker synthesized NaVPO first
4f using it as sodium-ion battery positive electrode, when with lithium metal during as negative material, positive electrode NaVPO
4the charge and discharge specific capacity first of F is respectively 101mAh/g and 95mAh/g; When using active carbon as negative material, 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 be only first 50%, its structural stability and comprehensive electrochemical still need to be improved by suitable method.
For this reason, (the sodium-ion battery positive electrode 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 also with two step high temperature solid-state methods, synthesized the sodium-ion battery positive electrode NaVPO of carbon dope
4f after first diammonium hydrogen phosphate, vanadic oxide and glucose being mixed by a certain percentage, calcines and within 8 hours, makes intermediate vanadium phosphate under 750 ℃, inert gas shielding; After again sodium fluoride, intermediate vanadium phosphate and glucose being mixed by a certain percentage, under 750 ℃, inert gas shielding, calcine and within 3 hours, make carbon dope NaVPO
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 respectively 151.5mAh/g and 113mAh/g, 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 also discloses and a kind ofly by collosol and gel, has activated auxiliary two step high temperature solid-state methods and prepare carbon dope sodium-ion battery positive electrode NaVPO
4the method of F, is that vanadium source, phosphorus source, carbon source is soluble in water by a certain percentage, adds thermal agitation, obtains light green color slurry, by after its vacuumize, under 650-850 ℃, inert gas shielding, calcines 2-10 hour, obtains VPO
4/ C presoma, then by VPO
4after/C presoma mixes by a certain percentage with NaF, under 650-850 ℃, inert gas shielding, calcine 2-10 hour, 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 makes
4the pattern of F all presents inhomogeneous structure and is adhered to one another, and particle is too large, carbon coated inhomogeneous, thus cause the shortcomings such as the not high and high rate performance of battery capacity is not good.
Summary of the invention
In view of this, one of object of the present invention is to provide a kind of network structure nanometer NaVPO for preparing
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 that adopts described method to make
4f/C composite material is as the application of sodium-ion battery positive electrode.
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. solvent heat carbon is coated NaVPO
4f presoma: sodium source, He Fu source, vanadium source is soluble in water, obtain I liquid; Phosphorus source and the reducing agent carbon source of holding concurrently is soluble in water, obtain II liquid; II liquid is added in I liquid, stir 5～60 minutes, obtain III liquid; Absolute ethyl alcohol is added in III liquid, stirs 5～60 minutes, 120～210 ℃ of solvent thermal reactions 4～72 hours, filter, and collect solid, washing, and 120 ℃ of dry 4～24 hours or freeze dryings, obtain the coated NaVPO of carbon
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;
The described reducing agent carbon source of holding concurrently is one or more in vitamin C, glucose, fructose, maltose and citric acid;
Total sodium 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. high-temperature calcination carbon is coated NaVPO4F presoma: the coated presoma NaVPO of carbon that steps A is made
4f calcines 2～15 hours under 750～900 ℃, inert atmosphere protection, obtains the nanometer NaVPO of network configuration
4f/C composite material.
In said method, in steps A, reducing agent hold concurrently the selection prerequisite of carbon source be under not higher than solvent thermal reaction temperature conditions vanadium can be reverted to+3 valencys or+4 valencys; The concentration in sodium source, He Fu source, vanadium source in I liquid, and in II liquid, phosphorus source and reducing agent are held 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 coated presoma NaVPO of carbon after solvent heat
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
water>=2.5 o'clock, the coated presoma NaVPO of carbon after solvent heat
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 ℃ is phase transition temperature, and under 750 ℃, inert atmosphere protection, calcination time is no more than 4 hours, gained NaVPO
4the crystal formation of F is for mixing phase; Calcination time surpasses 4 hours, gained NaVPO
4the crystal formation of F is monocline type; And under 800～900 ℃, 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 the reducing agent carbon source of holding concurrently is vitamin C.
Further, described steps A is that ammonium metavanadate and sodium fluoride is soluble in water, makes the concentration of ammonium metavanadate and sodium fluoride be respectively 0.2mol/L, obtains I liquid; Ammonium dihydrogen phosphate and vitamin C is soluble in water, and the concentration that makes ammonium dihydrogen phosphate is that 0.2mol/L, ascorbic concentration are 0.3mol/L, obtains II liquid; II liquid is added in I liquid, stir 10 minutes, obtain III liquid; Absolute ethyl alcohol is added in III liquid, and the addition of absolute ethyl alcohol is long-pending 2.5 times of III liquid, stir 10 minutes, and 180 ℃ of solvent thermal reactions 24 hours, filtration washing, solid freeze drying, obtains the coated presoma NaVPO of carbon
4f; Total sodium 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 carbon that steps A is made
4f calcines 6 hours under 750～800 ℃, inert atmosphere protection, obtains the nanometer NaVPO of network configuration
4f/C composite material.
2. the network structure nanometer NaVPO that adopts above-mentioned preparation method to make
4f/C composite material.
3. network structure nanometer NaVPO
4f/C composite material is as the application of sodium-ion battery positive electrode.
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, is to add appropriate alcohol in sodium source, vanadium source, fluorine source, phosphorus source, reducing agent are held concurrently the mixed aqueous solution of carbon source, first at 120～210 ℃ of solvent thermal reactions, makes the coated NaVPO of carbon
4f presoma, then calcine under 750～900 ℃, inert atmosphere protection, in hot environment, amorphous carbon partly burns and loses and degree of graphitization is improved, NaVPO
4f particle fusion, crystallization, grain growth, but be wrapped in NaVPO
4the carbon-coating of F presoma outside can stop NaVPO to a certain extent
4f particle fusion is integral, thereby finally forms a kind of nanometer NaVPO 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 obtaining
4f/C composite material has unique network configuration and good porosity, is conducive to the fast transferring of electrolyte; Effectively compound with carbon, has improved the conductivity of material monolithic, and then has improved NaVPO
4the chemical property of F (first discharge specific capacity is up to 143mAh/g under 0.1C multiplying power), can be used as sodium-ion battery positive electrode, has a good application prospect.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearer, the invention provides following accompanying drawing and describe:
Fig. 1 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of embodiment mono-products obtained therefrom.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment bis-products obtained therefroms.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment tri-products obtained therefroms.
Fig. 4 is the X-ray diffractogram of embodiment mono-, two, three products obtained therefroms.
Fig. 5 is the X-ray diffraction scanning electron microscope (SEM) photograph of embodiment tetra-products obtained therefroms.
Fig. 6 is the constant current charge-discharge curves of embodiment bis-, three products obtained therefroms under 0.1C multiplying power.
Fig. 7 is the cyclic curves of embodiment bis-, three products obtained therefroms 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, conventionally according to normal condition, or the condition of advising according to reagent manufacturer is carried out.
Embodiment mono-, the coated NaVPO of carbon
4synthesizing of F presoma
Take 2mmol NH
4vO
3be dissolved in 10ml deionized water with 2mmol NaF, obtain I liquid; Take 2mmol NH
4h
2pO
4be dissolved in 10ml deionized water with 3mmol vitamin C, obtain II liquid; I liquid is slowly splashed in II liquid, stir 10min, obtain III liquid; 50ml absolute ethyl alcohol is dropped in III liquid, stir 10min, then transfer in solvent thermal reaction still, 180 ℃ are reacted 24 hours, cooled and filtered washing, and solid freeze drying, obtains the coated NaVPO of carbon
4f presoma.
As shown in Figure 1, grain shape is regular for the pattern of products obtained therefrom, particle diameter very little (nanoscale), and surface is evenly coated by carbon.As shown in Figure 4, synthetic is the coated NaVPO of carbon to the component analysis result of products obtained therefrom
4f presoma.
Embodiment bis-, network structure nanometer NaVPO
4synthesizing of F/C composite material
The coated NaVPO of carbon that embodiment mono-is made
4f presoma is calcined 6 hours under 750 ℃, 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, is uniform nano particle.As shown in Figure 4, synthetic is NaVPO to the component analysis result of products obtained therefrom
4f, its crystal formation is monocline type.
Embodiment tri-, network structure nanometer NaVPO
4synthesizing of F/C composite material
The coated NaVPO of carbon that embodiment mono-is made
4f presoma is calcined 6 hours under 800 ℃, 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, is uniform nano particle.As shown in Figure 4, synthetic is NaVPO to the component analysis result of products obtained therefrom
4f, its crystal formation is monocline type.
Embodiment tetra-, calcination time are to network structure nanometer NaVPO
4the impact of F/C composite material pattern
The coated NaVPO of carbon that embodiment mono-is made
4f presoma is calcined respectively 2,6 and 15 hours under 800 ℃, argon shield condition, is cooled to room temperature, obtains network structure nanometer NaVPO
4f/C composite material.
As shown in Figure 5, visible calcination time is longer for the pattern of products obtained therefrom, and product particle is larger.
The preparation of embodiment five, battery and electrochemical property test
Get respectively the network structure nanometer NaVPO that embodiment bis-, three makes
4f/C composite material, by its with conductive black, PVDF binding agent in mass ratio 70:20:10 mix, add again appropriate 1-Methyl-2-Pyrrolidone (NMP), in agate mortar, be ground to pasty state, be coated in (every aluminium foil laod network structure nano NaVPO on the aluminium foil that diameter is 19mm
4the about 2mg of F/C composite material), then by aluminium foil in 120 ℃ of vacuumizes 12 hours, obtain positive plate, be transferred to the assembling of carrying out button cell in the glove box that is full of argon gas, button cell model is CR2025, negative pole is sodium metal sheet, and barrier film is microporous polypropylene membrane Celgard2325, the NaPF that electrolyte is 1mol/L
6solution (solvent is ethylene carbonate and the dimethyl carbonate mixed liquor that 1:1 forms by volume).The battery assembling carries out electrochemical property test after placing more than 6 hours on Land test macro, 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 bis-makes
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 tri-makes
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 bis-makes
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 tri-makes
4f/C composite material rear specific discharge capacity of 100 circulations under 0.1C multiplying power is 79mAh/g.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can to it, make various changes in the form and details, and not depart from the claims in the present invention book 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. solvent heat carbon is coated NaVPO
4f presoma: sodium source, He Fu source, vanadium source is soluble in water, obtain I liquid; Phosphorus source and the reducing agent carbon source of holding concurrently is soluble in water, obtain II liquid; II liquid is added in I liquid, stir 5～60 minutes, obtain III liquid; Absolute ethyl alcohol is added in III liquid, stirs 5～60 minutes, 120～210 ℃ of solvent thermal reactions 4～72 hours, filter, and collect solid, washing, and 120 ℃ of dry 4～24 hours or freeze dryings, obtain the coated NaVPO of carbon
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;
The described reducing agent carbon source of holding concurrently is one or more in vitamin C, glucose, fructose, maltose and citric acid;
Total sodium 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. high-temperature calcination carbon is coated NaVPO4F presoma: the coated presoma NaVPO of carbon that steps A is made
4f calcines 2～15 hours under 750～900 ℃, 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 the 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 is that ammonium metavanadate and sodium fluoride is soluble in water, makes the concentration of ammonium metavanadate and sodium fluoride be respectively 0.2mol/L, obtains I liquid; Ammonium dihydrogen phosphate and vitamin C is soluble in water, and the concentration that makes ammonium dihydrogen phosphate is that 0.2mol/L, ascorbic concentration are 0.3mol/L, obtains II liquid; II liquid is added in I liquid, stir 10 minutes, obtain III liquid; Absolute ethyl alcohol is added in III liquid, and the addition of absolute ethyl alcohol is long-pending 2.5 times of III liquid, stir 10 minutes, and 180 ℃ of solvent thermal reactions 24 hours, filtration washing, solid freeze drying, obtains the coated NaVPO of carbon
4f presoma; Total sodium 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 carbon that steps A is made
4f calcines 6 hours under 750～800 ℃, inert atmosphere protection, obtains network structure nanometer NaVPO
4f/C composite material.
5. adopt the network structure nanometer NaVPO that in claim 1 to 4, described in any one, preparation method makes
4f/C composite material.
6. network structure nanometer NaVPO claimed in claim 5
4f/C composite material is as the application of sodium-ion battery positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298670.6A CN104112858B (en) | 2014-06-26 | 2014-06-26 | Network structure nanometer NaVPO 4the preparation method and application of F/C composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410298670.6A CN104112858B (en) | 2014-06-26 | 2014-06-26 | Network structure nanometer NaVPO 4the preparation method and application of F/C composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104112858A true CN104112858A (en) | 2014-10-22 |
| CN104112858B CN104112858B (en) | 2016-04-13 |
Family
ID=51709568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410298670.6A Active CN104112858B (en) | 2014-06-26 | 2014-06-26 | Network structure nanometer NaVPO 4the preparation method and application of F/C composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104112858B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655565A (en) * | 2016-04-08 | 2016-06-08 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN105762356A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院过程工程研究所 | Sodium vanadium fluorophosphate, and preparation method and use thereof |
| CN106058212A (en) * | 2016-08-03 | 2016-10-26 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN106374104A (en) * | 2016-10-10 | 2017-02-01 | 济南大学 | Method for preparing sodium fluorine vanadium phosphate material in air atmosphere |
| CN107482180A (en) * | 2017-07-10 | 2017-12-15 | 三峡大学 | A kind of NaVPO4F/C anode material for compound lithium ion battery and preparation method thereof |
| CN108199028A (en) * | 2018-01-10 | 2018-06-22 | 中南大学 | A kind of NaVPO4F/C composite materials and preparation method thereof |
| CN108417792A (en) * | 2018-02-01 | 2018-08-17 | 桂林理工大学 | The preparation method of high-performance aluminum potassium codope fluorophosphoric acid vanadium sodium/carbon composite |
| CN109037621A (en) * | 2018-07-12 | 2018-12-18 | 西安交通大学 | A kind of preparation method of the sodium-ion battery cathode material of high power high stable |
| CN109659505A (en) * | 2017-10-10 | 2019-04-19 | 中国科学院大连化学物理研究所 | A kind of NaVP2O7Application in sodium-ion battery anode |
| CN109841800A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application |
| CN109841801A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of carbon coating NaxRyM2(PO4)3Material and its preparation and application |
| CN110371950A (en) * | 2019-08-12 | 2019-10-25 | 苏州大学 | A kind of preparation method of hollow carbon material |
| CN111446449A (en) * | 2020-03-10 | 2020-07-24 | 西安交通大学 | Multi-electron-transmission vanadium-based oxygen sodium fluophosphate battery material and preparation method thereof |
| CN113690398A (en) * | 2021-08-04 | 2021-11-23 | 中国电子科技集团公司第十八研究所 | Preparation method of super-ion conductor structure type material-coated high-nickel single crystal ternary material |
| CN116425414A (en) * | 2022-01-04 | 2023-07-14 | 福建省德化县鑫洋陶瓷有限公司 | Crystal speckled ceramic glaze and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002097907A2 (en) * | 2001-04-06 | 2002-12-05 | Valence Technology, Inc. | Sodium ion batteries |
| CN101087018A (en) * | 2007-06-28 | 2007-12-12 | 复旦大学 | A water solution Na ion chargeable battery |
| 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 |
| CN103594716A (en) * | 2013-11-21 | 2014-02-19 | 天津工业大学 | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates |
-
2014
- 2014-06-26 CN CN201410298670.6A patent/CN104112858B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002097907A2 (en) * | 2001-04-06 | 2002-12-05 | Valence Technology, Inc. | Sodium ion batteries |
| CN101087018A (en) * | 2007-06-28 | 2007-12-12 | 复旦大学 | A water solution Na ion chargeable battery |
| CN103594716A (en) * | 2013-11-21 | 2014-02-19 | 天津工业大学 | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| YAO LU等: "Preparation and characterization of carbon-coated NaVPO4F as cathode material for rechargeable sodium-ion batteries", 《JOURNAL OF POWER SOURCES》, vol. 247, 14 September 2013 (2013-09-14), pages 770 - 777 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762356A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院过程工程研究所 | Sodium vanadium fluorophosphate, and preparation method and use thereof |
| CN105762356B (en) * | 2014-12-15 | 2019-10-11 | 中国科学院过程工程研究所 | A kind of fluorophosphoric acid vanadium sodium salt, preparation method and its usage |
| CN105655565A (en) * | 2016-04-08 | 2016-06-08 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN105655565B (en) * | 2016-04-08 | 2018-01-09 | 苏州大学 | A kind of sodium-ion battery composite positive pole and preparation method thereof |
| CN106058212B (en) * | 2016-08-03 | 2018-11-20 | 苏州大学 | A kind of sodium-ion battery composite positive pole and preparation method thereof |
| CN106058212A (en) * | 2016-08-03 | 2016-10-26 | 苏州大学 | Composite cathode material of sodium-ion battery and preparation method of composite cathode material |
| CN106374104B (en) * | 2016-10-10 | 2019-12-03 | 济南大学 | A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material |
| CN106374104A (en) * | 2016-10-10 | 2017-02-01 | 济南大学 | Method for preparing sodium fluorine vanadium phosphate material in air atmosphere |
| CN107482180B (en) * | 2017-07-10 | 2019-12-06 | 三峡大学 | NaVPO4F/C composite lithium ion battery anode material and preparation method thereof |
| CN107482180A (en) * | 2017-07-10 | 2017-12-15 | 三峡大学 | A kind of NaVPO4F/C anode material for compound lithium ion battery and preparation method thereof |
| CN109659505A (en) * | 2017-10-10 | 2019-04-19 | 中国科学院大连化学物理研究所 | A kind of NaVP2O7Application in sodium-ion battery anode |
| CN109841800B (en) * | 2017-11-28 | 2022-07-05 | 中国科学院大连化学物理研究所 | Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof |
| CN109841800A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application |
| CN109841801A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of carbon coating NaxRyM2(PO4)3Material and its preparation and application |
| CN108199028A (en) * | 2018-01-10 | 2018-06-22 | 中南大学 | A kind of NaVPO4F/C composite materials and preparation method thereof |
| CN108417792A (en) * | 2018-02-01 | 2018-08-17 | 桂林理工大学 | The preparation method of high-performance aluminum potassium codope fluorophosphoric acid vanadium sodium/carbon composite |
| CN109037621A (en) * | 2018-07-12 | 2018-12-18 | 西安交通大学 | A kind of preparation method of the sodium-ion battery cathode material of high power high stable |
| CN110371950A (en) * | 2019-08-12 | 2019-10-25 | 苏州大学 | A kind of preparation method of hollow carbon material |
| CN110371950B (en) * | 2019-08-12 | 2023-06-23 | 苏州大学 | Preparation method of hollow carbon material |
| CN111446449A (en) * | 2020-03-10 | 2020-07-24 | 西安交通大学 | Multi-electron-transmission vanadium-based oxygen sodium fluophosphate battery material and preparation method thereof |
| CN113690398A (en) * | 2021-08-04 | 2021-11-23 | 中国电子科技集团公司第十八研究所 | Preparation method of super-ion conductor structure type material-coated high-nickel single crystal ternary material |
| CN116425414A (en) * | 2022-01-04 | 2023-07-14 | 福建省德化县鑫洋陶瓷有限公司 | Crystal speckled ceramic glaze and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104112858B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104112858B (en) | Network structure nanometer NaVPO 4the preparation method and application of F/C composite material | |
| Zhao et al. | Environment-friendly synthesis of high-voltage LiNi0. 5Mn1. 5O4 nanorods with excellent electrochemical properties | |
| CN103594716A (en) | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates | |
| CN103066265B (en) | Sodium ion battery negative pole active substance and preparation method and application thereof | |
| CN103258994B (en) | Positive material for lithium ion battery, preparation method of material, and lithium ion battery | |
| KR20200138198A (en) | Microwave assisted sol-gel method for manufacturing in-situ carbon-coated electrode material and product thereof | |
| CN102315444B (en) | A kind of preparation method of nano-modified polyanionic cathode active material | |
| CN105236486B (en) | A kind of high performance lithium ion battery anode material vanadium pentoxide hollow microsphere and preparation method | |
| CN111293307B (en) | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof | |
| CN103682244B (en) | A kind of surface coating method of lithium ion battery electrode material | |
| CN104538207A (en) | Method for preparing titanium niobate and carbon nanotube composite material and lithium ion capacitor with material as negative electrode | |
| CN104477870A (en) | Porous sheet lithium ion battery LiTi2(PO4)3 electrode material and preparation method thereof | |
| CN104577120A (en) | Preparation method of lithium vanadium phosphate and fluorination lithium vanadium phosphate composite positive pole material | |
| CN102249297A (en) | Method for preparing lithium titanate powder | |
| Li et al. | Synthesis and electrochemical properties of LiFePO4 cathode material by ionic thermal method using eutectic mixture of tetramethyl ammonium chloride–urea | |
| CN108698828A (en) | Olivine compounds, preparation method and the purposes in the cathode material of sodium-ion battery | |
| CN102332582B (en) | Preparation method for novel lithium vanadium phosphate/bamboo charcoal composite cathode material | |
| CN102208646B (en) | LiFePO4/C anode material repaired and coated by AlPO4 and preparation method thereof | |
| CN102267692B (en) | Self-sacrificing template method for preparing nanoscale lithium ferrous phosphate | |
| CN105826522A (en) | Method for preparing in-situ carbon coated manganese carbonate for negative electrode of lithium ion battery | |
| CN104916840A (en) | Three-dimensional porous grading carbon modified LMP-LVP/C electrode material, and preparation method and application thereof | |
| CN103296251B (en) | The preparation method of the anode material for lithium-ion batteries of the coated sulphur compound of lithium titanate | |
| CN105449174A (en) | Anode active material, sodium ion battery and lithium ion battery | |
| CN105439200B (en) | Negative electrode active material, sodium-ion battery and lithium ion battery | |
| JP6252553B2 (en) | Negative electrode active material, sodium ion battery and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |