CN109659505A - A kind of NaVP2O7Application in sodium-ion battery anode - Google Patents

A kind of NaVP2O7Application in sodium-ion battery anode Download PDF

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Publication number
CN109659505A
CN109659505A CN201710935249.5A CN201710935249A CN109659505A CN 109659505 A CN109659505 A CN 109659505A CN 201710935249 A CN201710935249 A CN 201710935249A CN 109659505 A CN109659505 A CN 109659505A
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CN
China
Prior art keywords
compound
navp
sodium
ion battery
room temperature
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Pending
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CN201710935249.5A
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Chinese (zh)
Inventor
冯凯
张华民
宋子晗
李先锋
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN201710935249.5A priority Critical patent/CN109659505A/en
Publication of CN109659505A publication Critical patent/CN109659505A/en
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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
    • H01M4/364—Composites as mixtures
    • 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
    • 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 present invention relates to a kind of NaVP2O7Application in sodium-ion battery anode.The NaVP2O7Compound is applied in sodium-ion battery anode as active material.With highest average working voltage in known phosphate sodium-ion battery positive material, there is preferable sodium-ion battery charge-discharge performance, high rate performance is excellent, can be used as sodium-ion battery positive material.

Description

A kind of NaVP2O7Application in sodium-ion battery anode
Technical field
It is NaVP the present invention relates to chemical formula2O7Sodium-ion battery positive material, preparation method and utilize the material system Make sodium-ion battery.
Background technique
It is increasingly serious with energy problem, non-renewable resources increasingly deficient and people recognize environmentally friendly importance The continuous enhancing known, demand of the society to new energy is increasingly enhanced, and energy storage plays more and more important work in energy system With.Before, the sodium-ion battery as energy storage device important in new energy has attracted numerous resourcess for research.
Mainly there is Na applied to the positive electrode of sodium-ion battery at present0.4MnO2And Na3V2(PO4)3Deng (Nano Energy 2015,16,186-195；Advanced materials 2015,27(42),6670-6676).However, these materials are still deposited In many problems: specific capacity and operating voltage are lower, and cyclical stability difference and preparation difficulty etc., this severely limits these materials Practical application (AngewandteChemie 2013,52 (17), 4633-6).Therefore, novel sodium-ion battery anode is explored Material is still the hot and difficult issue of sodium-ion battery research.In polyanion class positive electrode, pyrophosphate is higher because of it Voltage platform and higher specific capacity and higher energy density is presented, to get growing concern for.
Summary of the invention
For technical problem set forth above, it is an object of that present invention to provide a kind of NaVP2O7Sodium is used for as positive electrode In ion battery.Specific technical solution is as follows:
A kind of NaVP2O7Application in sodium-ion battery anode, the NaVP2O7Compound is as active material application In sodium-ion battery anode.
The sodium-ion battery positive electrode active materials are NaVP2O7Material.
NaVP provided by the invention2O7Sodium-ion battery positive material.
NaVP is prepared using solid reaction process2O7, its step are as follows:
1) ingredient: will contain Na compound, the compound of V containing trivalent and be rubbing for (1-1.1): 1:2 by Na:V:P containing P-compound You mix and are pre-processed than ingredient；
The pretreatment for configured raw material is poured into crucible after mixing, in Muffle furnace from room temperature to 200-500 DEG C of heating 2-10 hours or more, after be cooled to room temperature；
2) control parameters carry out materials synthesis: the crucible for filling above-mentioned ingredient is placed in Muffle furnace；With 1-10 DEG C Rate rise to 600-1000 DEG C from room temperature；Heat preservation 10-40 hours；After reaction sufficiently, room temperature is down to the rate of 1-50 DEG C/h, Obtain NaVP2O7Material；
The compound containing Na is the oxide of Na, the carbonate of Na, the phosphate of Na, the nitrate of Na or the oxalic acid of Na One of salt or two kinds or more；
The compound containing V is one of oxalates of the oxide of trivalent V, V or two kinds or more；
The P-compound that contains is NH4H2PO4, (NH4)2HPO4, P2O5Or H3PO4One of or two kinds or more.
NaVP is prepared using sol-gal process2O7Sodium-ion battery positive material, its step are as follows:
1) ingredient: will contain Na compound, the compound of V containing trivalent and containing P-compound by Na:V:P: oxalic acid is (1-1.1): 1: The molar ratio of 2:3 is added in 50-100 DEG C of deionized water and stirs to uniform blue solution is formed, and it is molten to being formed to continue stirring Glue；
2) colloidal sol is transferred in 100-150 DEG C of baking oven, is dried to gel, gel abrasive is transferred to porcelain boat at powder In, it is pre-processed；
The pretreatment is small from room temperature to 200-500 DEG C of heating 2-10 in Muffle furnace for by the raw material in porcelain boat When more than, after be cooled to room temperature；
3) control parameters carry out materials synthesis: the porcelain boat for filling above-mentioned ingredient is placed in Muffle furnace；With 1-10 DEG C Rate rise to 600-1000 DEG C；Heat preservation 10-40 hours；After reaction sufficiently, room temperature is down to the rate of 1-50 DEG C/h, is obtained NaVP2O7Material；
The compound containing Na is the oxide of Na, the carbonate of Na, the phosphate of Na, the nitrate of Na or the oxalic acid of Na One of salt or two kinds or more；
The compound containing V is one of oxalates of the oxide of trivalent V, V or two kinds or more；
The P-compound that contains is NH4H2PO4, (NH4)2HPO4, P2O5Or H3PO4One of or two kinds or more.
It is listed below and several typically can be obtained NaVP2O7The chemical equation of compound:
(1)Na2CO3+V2O3+2P2O5=2NaVP2O7+CO2↑
(2)2NaOH+4H3PO4+V2O3=2NaVP2O7+7H2O
(3)2NaOH+2VOC2O4+4H3PO4+H2=2NaVP2O7+4CO2↑+8H2O
The present invention has the advantages that obtained NaVP2O7Blackish green powder (Fig. 1) is presented in positive electrode, has preferable crystallization It spends (Fig. 2), specific capacity (Fig. 4), high rate performance (Fig. 5) and cyclical stability with higher.NaVP2O7Sodium-ion battery anode Material specific capacity with higher reaches 100mAh/g；Its operating voltage is to be currently known sodium-ion battery just in 3.5V or so Higher one kind in the material of pole, 100 circulation after specific capacity be still able to maintain 95% or more.
Detailed description of the invention
Fig. 1 is NaVP of the present invention2O7The SEM picture of sodium-ion battery positive material.
Fig. 2 is NaVP of the present invention2O7Polycrystal powder X ray diffracting spectrum.
Fig. 3 is NaVP of the present invention2O7Crystal structure figure.
Fig. 4 is NaVP of the present invention2O7The charging and discharging curve of sodium positive electrode 1C multiplying power, 1.5-4.3V.
Fig. 5 is NaVP of the present invention2O7The high rate performance curve of sodium positive electrode.
Specific embodiment
1 NaVP of embodiment2O7It is prepared by the high temperature solid-state of positive electrode
By the Na of 0.01mol2CO3, 0.01mol V2O3With the H of 0.04mol3PO4It is put into agate mortar, grinding half is small When.It is transferred in crucible, crucible is put into Muffle furnace.Stove is risen to 200-500 DEG C with the heating rate of 1-10 DEG C/min, Heat preservation 2-10 hours, is finally down to room temperature with the speed of 1-50 DEG C/min.The material of synthesis is taken out, is turned again after pulverizing It moves on in crucible, is put into Muffle furnace.Stove is risen to 600-1000 DEG C with the heating rate of 1-10 DEG C/min, keeps the temperature 10-40 Hour, room temperature is finally down to the speed of 1-50 DEG C/min.Product taking-up grinding ingredient will be obtained and arrive NaVP to obtain the final product2O7Compound.
As shown in Figure 1, it is blackish green powder, tap density 2.5g/cm3, 900 DEG C of fusing point.Its X ray diffracting spectrum is such as Shown in Fig. 2, crystal structure figure is as shown in Figure 3.It can be seen in figure 3 that its basic structural unit is VO6Polyhedron and PO4 Tetrahedron, PO4Tetrahedron is by VO6Polyhedron is interconnected to form three-dimensional net structure, and Na ion is interspersed among network.
2 NaVP of embodiment2O7It is prepared by the sol-gel of positive electrode
By the dissolving oxalic acid of 0.03mol in the beaker equipped with deionized water, the V of 0.01mol is then added2O5, in 70- In 80 DEG C of water bath with thermostatic control then the H of 0.04mol is added to solution blue in stirring3PO4, 0.01mol Na2CO3, continue to stir It mixes to form glaucous pyrophosphoric acid vanadium sodium colloidal sol.The colloidal sol is placed in 80 DEG C of baking ovens and is dried before 10h or so obtains blue puffy Body is driven, presoma grinding is placed in crucible in powder, crucible is put into Muffle furnace.With the heating speed of 1-10 DEG C/min Stove is risen to 200-500 DEG C by degree, is kept the temperature 2-10 hours, is finally down to room temperature with the speed of 1-50 DEG C/min.By the material of synthesis Material takes out, and is transferred again into crucible, is put into Muffle furnace after pulverizing.With the heating rate of 1-10 DEG C/min by stove liter To 600-1000 DEG C, 10-40 hours are kept the temperature, room temperature is finally down to the speed of 1-50 DEG C/min.Product will be obtained and take out grinding Ingredient obtains NaVP2O7Compound.
By Examples 1 and 2 resulting materials, the mass ratio according to active material, conductive black, binder three is 8:1:1 It is dissolved in appropriate N-Methyl pyrrolidone and being uniformly mixed, be coated into the electrode film with a thickness of 0.15mm, vacuum with wet film maker It is cut into the electrode slice that diameter is 12mm with slicer after drying, weighs and calculate the quality of active material.Simultaneously using sodium piece as Cathode, using Celgard 2500 as diaphragm, the NaPF of 1mol/L6EC+DMC (volume ratio 1:1) solution be electrolyte, Button cell is dressed up in the glove box full of argon gas.Then the battery of assembly is subjected to electro-chemical test, respectively in 1.5- It is tested under 4.3V constant current conditions.Test result is as shown in Figures 4 and 5, it can be seen that NaVP2O7With very high in sodium-ion battery Platform between 3.5-4V, while specific discharge capacity with higher reaches 105mAhg-1, and have it is good follow it is forthright again Can, still there is 97mAhg under 20 multiplying powers-1Specific capacity.
The present invention has preferable sodium-ion battery charge-discharge performance, and cyclical stability is good.

Claims (7)

1. a kind of NaVP2O7Application in sodium-ion battery anode.
2. application described in accordance with the claim 1, it is characterised in that: it is characterized by: the NaVP2O7Compound is as activity Material is applied in sodium-ion battery anode.
3. application described in accordance with the claim 1, it is characterised in that: the sodium-ion battery positive electrode active materials are NaVP2O7Material Material.
4. application described in accordance with the claim 1, it is characterised in that: the quality group of sodium-ion battery anode becomes NaVP2O7: it leads Electrical carbon=99:1~1:1.
5. according to any application of claim 1-4, it is characterised in that: NaVP2O7It is prepared, is walked using solid reaction process It is rapid as follows:
1) Na compound, the compound of V containing trivalent and the molar ratio containing P-compound by Na:V:P for (1-1.1): 1:2 ingredient: will be contained Ingredient is mixed and is pre-processed；
The pretreatment for by configured raw material after mixing from room temperature to 200-500 DEG C of heating 2-10 hours with On, after be cooled to room temperature；
2) control parameters carry out materials synthesis: pretreated ingredient is risen to the rate of 1-10 DEG C/min from room temperature 600-1000℃；Heat preservation 10-40 hours；After reaction sufficiently, room temperature is down to the rate of 1-50 DEG C/h, obtains NaVP2O7Material；
The compound containing Na is in the oxide of Na, the carbonate of Na, the phosphate of Na, the nitrate of Na or the oxalates of Na One or two or more kinds；
The compound containing V is one of oxalates of the oxide of trivalent V, V or two kinds or more；
The P-compound that contains is NH4H2PO4, (NH4)2HPO4, P2O5Or H3PO4One of or two kinds or more.
6. according to any application of claim 1-4, which is characterized in that prepare NaVP using sol-gal process2O7Sodium ion Cell positive material, its step are as follows:
1) ingredient: will contain Na compound, the compound of V containing trivalent and containing P-compound by Na:V:P: oxalic acid is (1-1.1): 1:2:3 Molar ratio be added in 50-100 DEG C of deionized water and stir to uniform blue solution is formed, continue stirring to forming colloidal sol；
2) colloidal sol is transferred in 100-200 DEG C of baking oven, is dried to gel, gel abrasive Cheng Fenhou is pre-processed；
The pretreatment for from room temperature to 200-500 DEG C of heating 2-10 hours or more, after be cooled to room temperature；
3) control parameters carry out materials synthesis: by the pretreated material of step 2)；600- is risen to 1-10 DEG C of rate 1000℃；Heat preservation 10-40 hours；After reaction sufficiently, room temperature is down to the rate of 1-50 DEG C/h, obtains NaVP2O7Material；
The compound containing Na is in the oxide of Na, the carbonate of Na, the phosphate of Na, the nitrate of Na or the oxalates of Na One or two or more kinds；
The compound containing V is one of oxalates of the oxide of trivalent V, V or two kinds or more；
The P-compound that contains is NH4H2PO4, (NH4)2HPO4, P2O5Or H3PO4One of or two kinds or more.
7. according to application described in claim 5 or 6, it is characterised in that: the molar concentration of V in aqueous solution is 0.1-2mol.
CN201710935249.5A 2017-10-10 2017-10-10 A kind of NaVP2O7Application in sodium-ion battery anode Pending CN109659505A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676796A (en) * 2022-11-08 2023-02-03 西北大学 Monoclinic-phase vanadium sodium oxygen pyrophosphate, preparation method thereof and application thereof in sodium-ion battery

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CN106450300A (en) * 2016-11-01 2017-02-22 中南大学 Na2Fe2P2O7 material with flower-like structure and preparation method and application thereof
CN107017398A (en) * 2017-06-01 2017-08-04 中南大学 A kind of pyrophosphoric acid vanadium sodium/carbon composite anode material, preparation and its application
KR20170098625A (en) * 2016-02-22 2017-08-30 한국원자력연구원 Cathode material for na-ion batteries and method for producing the same
CN107195886A (en) * 2017-06-01 2017-09-22 中南大学 A kind of pyrophosphoric acid vanadium sodium@carbon composite anode materials, preparation and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112858A (en) * 2014-06-26 2014-10-22 西南大学 Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof
KR20170098625A (en) * 2016-02-22 2017-08-30 한국원자력연구원 Cathode material for na-ion batteries and method for producing the same
CN106450300A (en) * 2016-11-01 2017-02-22 中南大学 Na2Fe2P2O7 material with flower-like structure and preparation method and application thereof
CN107017398A (en) * 2017-06-01 2017-08-04 中南大学 A kind of pyrophosphoric acid vanadium sodium/carbon composite anode material, preparation and its application
CN107195886A (en) * 2017-06-01 2017-09-22 中南大学 A kind of pyrophosphoric acid vanadium sodium@carbon composite anode materials, preparation and application

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676796A (en) * 2022-11-08 2023-02-03 西北大学 Monoclinic-phase vanadium sodium oxygen pyrophosphate, preparation method thereof and application thereof in sodium-ion battery
CN115676796B (en) * 2022-11-08 2024-04-16 西北大学 Monoclinic-phase sodium vanadyl pyrophosphate, preparation method thereof and application thereof in sodium ion battery

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Application publication date: 20190419