CN101740777B - ZnO modified phosphide cathode material and preparation method thereof - Google Patents
ZnO modified phosphide cathode material and preparation method thereof Download PDFInfo
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- CN101740777B CN101740777B CN2009102634886A CN200910263488A CN101740777B CN 101740777 B CN101740777 B CN 101740777B CN 2009102634886 A CN2009102634886 A CN 2009102634886A CN 200910263488 A CN200910263488 A CN 200910263488A CN 101740777 B CN101740777 B CN 101740777B
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Abstract
The invention relates to ZnO modified phosphide and a preparation method thereof. The preparation method comprises the following steps of: mixing phosphide powder with Zn-containing substances according to the mol ratio of phosphorus to zinc of (0.5 to 15): 1, and mechanically treating or roasting to prepare the ZnO modified phosphide. The invention solves the problem that the raw materials are difficult to disperse in the preparation process of the phosphide by adopting the phosphide and the Zn-containing substances as raw materials, improves the electrochemical property of the phosphide by utilizing the electronic characteristics of the ZnO, reduces the interface impedance and the reaction impedance of the phosphide and ensures that the phosphide has better rate characteristics and cycle performance and still has more stable cycle performance even under the 12C high current. The invention has low requirements on the device, simple preparation method, less investment and good benefits, and is suitable for producing the ZnO modified phosphide with scale industrialization and low cost.
Description
Technical field
The invention belongs to made technology field, particularly relate to a kind of ZnO modified phosphide and preparation method thereof.
Background technology
Because the metal-P key of low burning attitude, high-tap density, high stable and high electron cloud orientation, the phosphide electrode material has caused people's very big research interest.MnP in research
4, FeP
x, ZnP
2, Cu
3P, CoP
x, GaP, VP
2, NiP
2, SnP
0.94, MoP
2, Li
2In the phosphide such as CuP, Fe-Sn-P, ferrophosphorus is the intermetallic compound that phosphorus and iron reaction form, and does not contain heavy metal element, with Li
xFe
yP
zO
4Similar, be the very promising green energy resource electrode material of a class.When ferrophosphorus is used as lithium ion battery negative material, the tap density height, charge/discharge capacity height, discharge voltage plateau are near graphite, but attenuation ratio is very fast, and cyclical stability is in urgent need to be improved.Because near 0.5V, and the quality Capacity Ratio is higher with respect to the discharge voltage plateau of lithium metal for ferrophosphorus, the operating voltage of the battery of being made up of itself and LiFePO 4 very likely replaces present lead-acid battery, nickel-cadmium cell and Ni-MH battery between 2～3V.
When at present phosphide is as electrode material, have that attenuation ratio is very fast, the common problem of cyclical stability and multiplying power property difference, hindered the practicalization of phosphide electrode material, be difficult to extensive use.Although can reduce the fade performance of ferrophosphorus by the ratio that improves Fe and P, improve cyclical stability [Chem Mater, 2006,18:3531.], the method for this raising ferrophosphorus cyclical stability is very limited, is that capacity with the sacrifice phosphide is a cost.ZnO is a kind of amphoteric oxide, is dissolved in acid, NaOH and ammonium chloride solution, water insoluble or ethanol.In addition, ZnO also is the semiconductor material with wide forbidden band that a kind of band gap is about 3.3eV, comprehensive excellent properties with aspects such as piezoelectric effect, electricity and optics, [Chinese J.Struct.Chem.2009 except self is used as lithium ion battery negative material, 28 (4): 409], also be used for improving the cyclical stability [J Alloy.Compd.2007,436:387] of the positive electrode of operating voltage more than 3.0V.But, up to the present, do not find that also ZnO modifies any research report of the phosphide cathode material of operating voltage below 3.0V.Positive electrode has different operating potentials with negative material, and different electrochemical reactions takes place, and is surface modified different to it.
Summary of the invention
The objective of the invention is in order to solve the technical barrier of decay in the cyclic process of phosphide electrode material fast and multiplying power property difference, improve the chemical property of phosphide cathode material, especially cyclical stability and multiplying power property have proposed a kind of ZnO modified phosphide cathode material and preparation method thereof.
Basic design of the present invention is: at first with the phosphide powder with contain Zn material mix in proportion, can select different material combination for use according to the course of reaction difference, through roasting after the preliminary treatment, concrete step of preparation process is as follows:
(1) be (0.5～15) with phosphide and zinc-containing substance by the mol ratio of phosphorus and zinc at first: 1 carries out mix;
(2) above-mentioned precursor is handled;
(3) precursor of handling is carried out roasting at 400～1100 ℃, heat treatment time is 0.5～30 hour, reduces to room temperature, obtains the ZnO modified phosphide.
Raw material of the present invention can adopt dry method in mixing, and also can adopt wet method, can also add other materials, as: carbonaceous material, doped chemical, conductive agent, complexing agent, dispersant, stabilizer.
In the precursor processing procedure of the present invention, roasting again after can handling through low temperature preroast also can be through directly carrying out roasting behind the mechanical treatments such as abrading-ball or atomizing.
In the preparation process of the present invention, the oxygen element among the ZnO can be from reaction raw materials, also can be from air, oxygen, ozone.
The present invention can control pattern, degree of crystallinity and particle size and the distribution thereof of product by process conditions, also can carry out ball milling or processing such as comminution by gas stream, modification to product as required.
The phosphide dephosphorization that the present invention uses contains a kind of metallic element outward at least, and wide material sources can be the accessory substances of mineral or its smelting product and phosphorous chemical industry or silicate chemical industry etc.
The present invention compared with prior art, adopting phosphide and containing the Zn material is feedstock production ZnO modified phosphide, solve raw material in the phosphide preparation process and evenly disperseed difficult problem, technology is simple, have the following advantages and the high-lighting effect: adopt phosphide and contain the Zn material after mechanical treatment or preroast again roasting obtain the ZnO modified phosphide, element is evenly distributed in the phosphide, can with contain the Zn material and better mix, react easily; Used phosphide and contain Zn material wide material sources, cost is lower; The mixing preliminary treatment of raw material can be adopted dry method (as ball milling, atomizing), also can adopt wet method (as rheology phase, class collosol and gel), and is lower to the requirement of equipment; The oxygen element wide material sources that need in the course of reaction can also can adopt the mode of diffuse type or centralized oxygen supply can effectively solve the difficult problem of oxygen amount control in the course of reaction from air or oxygen or ozone from reaction raw materials; The creationary ZnO modified phosphide of using, help reducing the interface impedance and the reaction impedance of phosphide, overcome the shortcoming of phosphide electrode material cyclical stability and multiplying power property difference, make phosphide that multiplying power property and cycle performance preferably be arranged, even under the big electric current of 12C, still have more stable cycle performance.
Description of drawings
Fig. 1 ZnO modifies the XRD figure of ferrophosphorus.
Fig. 2 ZnO modifies the nanotopography figure of ferrophosphorus.
Fig. 3 ferrophosphorus and ZnO modify the typical charging and discharging curve of ferrophosphorus.
Fig. 4 ferrophosphorus and ZnO modify the cycle performance of ferrophosphorus under different multiplying.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing; described content only is the basic explanation of the present invention under conceiving; but the present invention is not limited to following example, and any equivalent transformation according to technical scheme of the present invention is done all belongs to protection scope of the present invention.
Embodiment 1
Adopt rheology phase method with ferrophosphorus Fe
3P
2Modify ferrophosphorus Fe with the Zn powder for feedstock production ZnO
3P
2Negative material at first is crushed to ferrophosphorus about 60 orders, then with ferrophosphorus Fe
3P
2Powder, Zn powder and reduction carbon dust are to mix at 8: 1: 0.5 in molar ratio, add ethanol and be ground to formation homogeneous rheology phase, be transferred in the corundum crucible with cover, earlier in～200 ℃ of Muffle furnaces, carry out preroast, utilize airborne oxygen to be oxygen source, Zn in the crucible obtains oxygen by the oxygen flow function of corundum ceramic film from air, then again～600 ℃ of roastings 8～11 hours, be cooled to and obtain ZnO after the room temperature and modify ferrophosphorus Fe
3P
2, its crystal structure and forming as shown in Figure 1, nano particle pattern as shown in Figure 2, with former Fe
1.5P and ZnO modify ferrophosphorus Fe
3P
2The work electrode that is used separately as 2032 simulated batteries carries out the chemical property evaluation, its typical charging and discharging curve as shown in Figure 3, the cycle performance under the different multiplying is as shown in Figure 4.Be not difficult to find, adopt method of the present invention successfully to prepare ZnO and modify ferrophosphorus Fe
3P
2Obtained nanometer torispherical particle, discharge capacity, cyclical stability and the multiplying power property of former ferrophosphorus have greatly been improved, 0.05C under discharge capacity increased about 190mAh/g, capability retention after repeatedly circulating under the different multiplying has almost improved 200%, and the capacity restoration performance has also obtained very big improvement.
Embodiment 2
Adopt the reaction comminuting method with phosphatization two bronze medal Cu
2P, CuO and Zn powder are modified phosphatization three bronze medal Cu for feedstock production ZnO
3P is at first with phosphatization two bronze medal Cu
2P and CuO are crushed to about 80 orders, then with phosphatization two bronze medal Cu
2P powder, CuO powder, Zn powder are to carry out ball milling at 1: 1: 1 to mix in molar ratio, then the precursor that mixes is transferred in the closed ball milling jar that has safety valve, adopt intermittent mode with the ball-milling treatment of 300～500rpm rotating speed after 3～10 hours, be cooled to and obtain ZnO after the room temperature and modify phosphatization three bronze medal Cu
3P, through electrochemical property test, ZnO can improve phosphatization three bronze medal Cu
3The cyclical stability of P and multiplying power property.
Embodiment 3
Adopt spray drying process with iron phosphide FeP, phosphorization tin SnP, Fe powder and ZnCO
3For feedstock production ZnO modifies iron phosphide tin Fe
3SnP
2, then with the iron phosphide FeP about 100 orders, phosphorization tin SnP, Fe powder and ZnCO
3Be 1: 1: 2 in molar ratio: 1 carry out the atomization drying mixed processing after, be transferred to 500～800 ℃ tubular type kiln roasting 15～20 hours, adopt the N of 5mL/min flow
2Protect, be cooled to and obtain ZnO after the room temperature and modify iron phosphide tin Fe
3SnP
2, through electrochemical property test, ZnO can reduce iron phosphide tin Fe
3SnP
2The reaction internal resistance, improve cyclical stability and multiplying power property.
Embodiment 4
Adopt microwave method with iron phosphide FeP, phosphatization vanadium VP
2, nickel phosphide NiP
2, Fe
2O
3Modify phosphatization ferrovanadium nickel Fe with FeZn for feedstock production ZnO
6VNiP
5, at first with about raw material pulverizing to 120 order, then with iron phosphide FeP, phosphatization vanadium VP
2, nickel phosphide NiP
2, Fe
2O
3With FeZn be 1: 1: 1 in molar ratio: carry out at 1: 3 dry mixed evenly after, be transferred in 600～800 watts the microwave reactor and heated 3～5 hours, protect with Ar, be cooled to and obtain ZnO after the room temperature and modify phosphatization ferrovanadium nickel Fe
6VNiP
5
Adopt the class sol-gal process with iron phosphide FeP, phosphatization manganese MnP
2, nickel phosphide NiP
2, phosphatization cobalt CoP
2(CH
3COO)
2Zn modifies iron phosphide manganese nickel cobalt FeMnNiCoP for feedstock production ZnO
7/ C compound is a chelating agent with the citric acid, with iron phosphide FeP, phosphatization manganese MnP
2, nickel phosphide NiP
2, phosphatization cobalt CoP
2, (CH
3COO)
2Zn and citric acid are 1: 1: 1 in molar ratio: after evenly mixing at 1: 1: 1, adding low amounts of water disperses and the furnishing slurry, with planetary stainless steel ball grinding machine with behind 100～300rpm ball milling～5 hour, be transferred in the tube furnace and carry out preroast at 80～100 ℃, subsequently at 600～800 ℃ the airtight tubular type kiln roasting that has safety valve, be cooled to porphyrize after the room temperature, obtain ZnO and modify phosphatization iron phosphide manganese nickel cobalt FeMnNiCoP
7/ C compound.
Claims (1)
1. the preparation method of a ZnO modified phosphide is characterized in that: adopt the reaction comminuting method with phosphatization two bronze medal Cu
2P, CuO and Zn powder are modified phosphatization three bronze medal Cu for feedstock production ZnO
3P is at first with phosphatization two bronze medal Cu
2P and CuO are crushed to about 80 orders, then with phosphatization two bronze medal Cu
2P powder, CuO powder, Zn powder are to carry out ball milling at 1: 1: 1 to mix in molar ratio, then the precursor that mixes is transferred in the closed ball milling jar that has safety valve, adopt intermittent mode with the ball-milling treatment of 300～500rpm rotating speed after 3～10 hours, be cooled to and obtain ZnO after the room temperature and modify phosphatization three bronze medal Cu
3P.
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| CN101740777B true CN101740777B (en) | 2011-11-09 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219783A (en) * | 2008-01-23 | 2008-07-16 | 四川大学 | Method for producing electrode material with ferrophosphorus |
| CN101373667A (en) * | 2008-09-17 | 2009-02-25 | 四川大学 | High potential super capacitor electrode material and preparing method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219783A (en) * | 2008-01-23 | 2008-07-16 | 四川大学 | Method for producing electrode material with ferrophosphorus |
| CN101373667A (en) * | 2008-09-17 | 2009-02-25 | 四川大学 | High potential super capacitor electrode material and preparing method thereof |
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