CN101556998A - Metal phosphide used as lithium ion secondary battery cathode material and preparation method thereof - Google Patents
Metal phosphide used as lithium ion secondary battery cathode material and preparation method thereof Download PDFInfo
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- CN101556998A CN101556998A CNA2009100689672A CN200910068967A CN101556998A CN 101556998 A CN101556998 A CN 101556998A CN A2009100689672 A CNA2009100689672 A CN A2009100689672A CN 200910068967 A CN200910068967 A CN 200910068967A CN 101556998 A CN101556998 A CN 101556998A
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Abstract
The invention discloses a metal phosphide used as lithium ion secondary battery cathode material, which consists of phosphorus and metallic element M. The formula is MxPy, wherein x is larger than or equal to 0.15, and less than or equal to 0.85, and y is larger than or equal to 0.15 and less than or equal to 0.85. The invention also discloses a preparation method for the metal phosphide. The metal phosphide used as lithium ion secondary battery cathode material has higher capacity and better cycle performance, and is suitable for being used as lithium ion secondary battery cathode material; simultaneously, the equipment used by the preparation method of the metal phosphide is simple, and technological conditions are easy and convenient, thereby being beneficial for large scale of popularization and application and having great productive practice significance.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, particularly relate to a kind of metal phosphide that is used as ion secondary battery cathode material lithium and preparation method thereof.
Background technology
Along with the raising of people's living standard, the common high-tech consumer goods during electronic products such as mobile phone, notebook computer, Digital Video, digital camera have become people's modernization life and worked.In addition, because emerging of the mobile phone of band camera function, and notebook computer is universal, make the demand of high-capacity lithium-ion secondary cell heighten, thereby its range of application is constantly widened, to energy traffic industry, under water, progressively entered the every field of human society from information industry from space.
Present commercial lithium rechargeable battery all adopts carbon materials as negative material, although carbon materials has advantages such as useful life is long, but its specific capacity is lower, its capacity has reached 350 MAH/grams (mAh/g) in actual battery is used, near the theoretical capacity of its 372mAh/g.Therefore aspect capacity, this carbon materials has not had great room for promotion.The ratio escheat of carbon class material is less in addition, and its real density is 2.2g/cm
3, tap density is at 0.85g/cm
3About, the compacted density that adds man-hour at actual cathode pole piece only is 1.6～1.7g/cm
3
As the substitute of carbon class negative material, the 5th main group (VA) nitrogen group element compound becomes a kind of candidate material of alternative existing carbon class material because its theoretical capacity height, aboundresources, cheap etc.In the 5th main group VA element, what have higher capacity has only nitrogen N and two elements of phosphorus P.Wherein, the nitride of lithium research is more, however its discharge voltage plateau (0.4V) than carbon class material height, and synthesis condition is comparatively harsh; And element phosphor and lithium can form the Li/P atomic ratio up to 3 compound, and its theoretical capacity is 7 times of carbon class materials theory capacity also up to 2600mAh/g.But because the bigger lattice dilatation rate of existence in the lithium process is inhaled/put to the phosphatization lithium in electrochemistry, thereby caused its life-span shorter.
A kind of ternary phosphide and preparation method thereof was once disclosed in the patent No. is the Chinese patent of CN1585171A.This method is to make metal phosphide MP earlier
y(wherein, M is a kind of in copper Cu, cobalt Co, the nickel) is again with itself and lithium nitride Li
3N is ball milling once more, obtains containing the lithium metal phosphide Li of different lithium amount
xMP.Though this ternary phosphide can improve the cycle performance of phosphatization lithium to a certain extent, add the nitride of lithium after, its not only capacity increase not obviously, cycle performance significantly improves, and has increased production cost.In addition, owing to the technical scheme of this patent is to have added lithium in advance to make rich cathode of lithium material in phosphide, therefore the difficulty in poor lithium anode material apolegamy increases greatly, is difficult for finding suitable positive electrode to match with it.
Summary of the invention
In view of this, the purpose of this invention is to provide a kind of metal phosphide that is used as ion secondary battery cathode material lithium and preparation method thereof, this metal phosphide has higher capacity and excellent cycle performance, and be suitable as the negative material of lithium rechargeable battery, and preparation method's device therefor of this metal phosphide is simple, process conditions are convenient and easy, help applying on a large scale, be of great practical significance.
For this reason, the invention provides a kind of metal phosphide as ion secondary battery cathode material lithium, this metal phosphide is made up of phosphorus and metallic element M, and it forms expression formula is M
xP
y, wherein, 0.15≤x≤0.85,0.15≤y≤0.85.
Preferably, described metallic element M is a kind of in major element and the transition elements.
Preferably, described major element is tin Sn, antimony Sb and bismuth Bi, and described transition elements is vanadium V, chromium Cr, manganese Mn, iron Fe, zinc Zn and silver-colored Ag.
In addition, the present invention also provides a kind of preparation method who is used as the metal phosphide of ion secondary battery cathode material lithium, comprises step:
(1) red phosphorus powder and metal dust are pressed formula M
xP
yCome to put into ball grinder after the proportioning, wherein, 0.15≤x≤0.85,0.15≤y≤0.85, and put into abrading-ball remained in hydrogen or the argon gas atmosphere, with 100～600 rev/mins rotating speed ball millings 10～50 hours;
(2) mixture that ball milling is generated earlier under hydrogen or argon gas atmosphere with 400～1000 ℃ temperature preroast 5-30 hour;
(3) product with above-mentioned preroast naturally cools to room temperature, under hydrogen or argon gas atmosphere, carried out after baking 5～30 hours then, behind natural cooling, promptly obtain described metal phosphide as ion secondary battery cathode material lithium with 100～600 ℃ temperature.
Preferably, the ratio of grinding media to material in the described ball grinder is (5～50): 1.
By above technical scheme provided by the invention as seen, the present invention compared with prior art, the invention provides a kind of metal phosphide that is used as ion secondary battery cathode material lithium and preparation method thereof, this metal phosphide has higher capacity and excellent cycle performance, and be suitable as the negative material of lithium rechargeable battery, and the method for the preparation method of this metal phosphide for adopting high-energy ball milling method to combine with high temperature solid phase synthesis, this preparation method's device therefor is simple, process conditions are convenient and easy, help applying on a large scale, be of great practical significance.
In addition, the preparation process that is used as the metal phosphide of ion secondary battery cathode material lithium provided by the invention is easy to control, for the red phosphorus powder and the metal dust that are used to prepare this metal phosphide, can reduce the granularity of powder to a great extent by mechanical milling process, increase specific area, the reaction between these two kinds of powder is more prone to.Simultaneously, can also improve the uniformity of two kinds of powder to a great extent, help the generation of target product more by mechanical milling process.In addition, the present invention adopts the method for after baking can effectively remove the impurity phase, and helps eliminating the stress in the material and form complete crystal formation.
Description of drawings
Fig. 1 equals at 1: 1 o'clock for manganese phosphorus molar ratio, the X-ray diffractogram of powder behind the ball milling 40h;
Fig. 2 equals at 1: 1 o'clock for manganese phosphorus molar ratio, the X-ray diffractogram of the high-temperature roasting afterproduct of process different time and temperature;
Fig. 3 is the high-resolution transmission electron microscope photo of phosphatization manganese MnP material;
Fig. 4 selects the territory electron diffraction diagram for phosphatization manganese MnP material;
Fig. 5 is the charging and discharging curve figure of phosphatization manganese MnP electrode under different cycle-indexes;
Fig. 6 is the cycle life and the efficiency chart of phosphatization manganese MnP electrode;
Fig. 7 equals at 1: 3 o'clock for manganese phosphorus molar ratio, the X-ray diffractogram of the high-temperature roasting afterproduct of process different time and temperature.
Embodiment
In order to make those skilled in the art person understand the present invention program better, the present invention is described in further detail below in conjunction with drawings and embodiments.
Metal phosphide as ion secondary battery cathode material lithium provided by the invention, this metal phosphide is made up of phosphorus and metallic element M, and it forms expression formula is M
xP
y, wherein, 0.15≤x≤0.85,0.15≤y≤0.85.
In the present invention, described metallic element M is a kind of in major element and the transition elements.On the specific implementation, the major element that the present invention adopts is preferably tin Sn, antimony Sb and bismuth Bi, and the transition elements that is adopted is preferably subgroup elements such as vanadium V, chromium Cr, manganese Mn, iron Fe, zinc Zn and silver-colored Ag.
The metal phosphide as ion secondary battery cathode material lithium of the invention described above can prepare by the following method:
(1) red phosphorus powder and metal dust are pressed formula M
xP
yCome to put into ball grinder after the proportioning, wherein, 0.15≤x≤0.85,0.15≤y≤0.85, and put into abrading-ball remained in hydrogen or the argon gas atmosphere, with 100～600 rev/mins rotating speed ball millings 10～50 hours;
(2) mixture that ball milling is generated earlier under hydrogen or argon gas atmosphere with 400～1000 ℃ temperature preroast 5-30 hour;
(3) product with above-mentioned preroast naturally cools to room temperature, under hydrogen or argon gas atmosphere, carried out after baking 5～30 hours then, behind natural cooling, promptly obtain described metal phosphide as ion secondary battery cathode material lithium with 100～600 ℃ temperature.
In the present invention, the ratio of grinding media to material in the described ball grinder (being weight ratio between abrading-ball and the red phosphorus powder for the treatment of ball milling and the metal dust) is (5～50): 1.
In the present invention, the abrading-ball of above-mentioned preparation method's employing can be the abrading-ball that adopts Polyurethane, pottery or corundum to make; The ball grinder that above-mentioned preparation method adopts can be the ball grinder that adopts Polyurethane, pottery or corundum to make.
The range of speeds that above-mentioned ball mill of the present invention had is 0～700 rev/min.
Embodiment 1
Manganese phosphorus rate of charge (Mn: P) be 50%: 50%.By stoichiometric proportion Mn: P=50%: 50% takes by weighing manganese powder and red phosphorus powder (being that manganese phosphorus molar ratio equals 1: 1), puts into the sealed ceramic ball grinder, and ratio of grinding media to material is 5: 1.Under argon gas atmosphere, carry out ball milling.Ball mill is at room temperature with 400 rev/mins of ball millings of rotating speed 40 hours.Phase structure behind the ball milling is seen Fig. 1.From this figure as can be known, manganese Mn still occurs with crystalline state behind the ball milling, and phosphorus P then is shown as amorphous state.Remove in addition, do not have other to generate mutually.Pressed powder with obtaining behind the ball milling is positioned in the tube furnace.In argon gas atmosphere, progressively be warming up to 980 ℃.Under this temperature, preroast 12 hours.After naturally cooling to room temperature,, be placed in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In argon gas atmosphere, progressively be warming up to 500 ℃.Under this temperature, roasting 24 hours.Roasting finishes, and naturally cools to the phosphatization manganese MnP that room temperature can obtain end product, referring to Fig. 2.Fig. 3 and Fig. 4 are respectively the high-resolution transmission electron microscope photo (HRTEM) of the phosphatization manganese MnP that obtains behind the after baking and select territory electron diffraction diagram (SAED), and from Fig. 3 and Fig. 4 as can be known, this material has the structure of monocrystalline.
After baking product with above-mentioned preparation is an active material, tests its chemical property in button cell.Take by weighing the powder behind a certain amount of after baking, the conductive black that adds 10% (mass percent) is as conductive agent, 5%PVdF (Kynoar) is as binding agent, NMP (N-methyl pyrrolidone) is as solvent, be coated on the Copper Foil after fully mixing, put into vacuum drying chamber and dry 24h.Electrode after the oven dry consists of: 85%MnP, 10% conductive black, 5%PVdF; To electrode is lithium metal; Electrolyte 1 rubs for containing/ethylene carbonate EC/ dimethyl carbonate DMC (volume ratio is 1: the 1) solution of liter (mol/L) lithium hexafluoro phosphate LiPF6, and barrier film is microporous polypropylene membrane Cellgard2400.In the glove box of drying, be assembled into 2032 type button cells.Discharging and recharging cut-ff voltage is 0.01～2V, and current density is 50 microamperes of/square centimeter (μ A/cm
2).
Fig. 5 has provided the charge and discharge curve of MnP electrode under difference circulation cycle.Fig. 6 has provided charge and discharge capacity and the efficient of this electrode under difference circulation cycle.Therefrom as can be known, its first charge-discharge capacity is 904.6mAh/g, and first charge-discharge efficiency is that capacity is 685.7mAh/g after 83.1%, 5 week, and efficiency for charge-discharge is that the capacity after 93%, 10 week is 572mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 2
Manganese phosphorus rate of charge (Mn: P) be 25%: 75%.The preparation method of present embodiment is identical with embodiment 1.(Mn: P=25%: 75%) take by weighing manganese powder and red phosphorus powder (being that manganese phosphorus molar ratio equals 1: 3), put into the ceramic ball grinder of sealing, ratio of grinding media to material is 8: 1 by stoichiometric proportion.Under argon gas atmosphere, carry out ball milling.Ball mill is at room temperature with 400 rev/mins of rotating speeds, 40 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1, and manganese Mn still occurs with crystalline state behind the ball milling, and phosphorus P then is shown as amorphous state, does not have other to generate mutually.Pressed powder with obtaining behind the ball milling is positioned in the tube furnace.In the normal pressure argon gas atmosphere, progressively be warming up to 950 ℃.Under this temperature, preroast 12 hours.After naturally cooling to room temperature,, be placed in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In argon gas atmosphere, progressively be warming up to 500 ℃.Under this temperature, roasting naturally cools to the phosphatization manganese MnP that room temperature can obtain end product after 24 hours
3(see figure 7).The high-resolution transmission electron microscope photo HRTEM of this material and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphatization manganese MnP that is used for electrochemical property test
3The preparation process of electrode is identical with embodiment 1, and the charge and discharge curve of phosphatization manganese MnP electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 924mAh/g, and first charge-discharge efficiency is that capacity is 705mAh/g after 81.2%, 5 week, and efficiency for charge-discharge is that the capacity after 94%, 10 week is 594mAh/g, and efficiency for charge-discharge is 99%.
Tin phosphorus rate of charge (Sn: P) be 15%: 85%.The preparation method of present embodiment is identical with embodiment 1.(Sn: P=15%: 85%) take by weighing glass putty and red phosphorus powder (being that tin phosphorus molar ratio equals 3: 17), put into ceramic ball grinder, ratio of grinding media to material is 10: 1 by stoichiometric proportion.Under argon gas atmosphere, with 100 rev/mins of rotating speeds, 50 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with obtaining behind the ball milling is positioned in the tube furnace.In the normal pressure argon gas atmosphere, progressively be warming up to 400 ℃.Under this temperature, preroast 30 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure argon gas atmosphere, progressively be warming up to 600 ℃.Under this temperature, roasting 5 hours.Roasting finishes, and naturally cools to the phosphorization tin Sn that room temperature can obtain end product
3P
17The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, its high-resolution transmission electron microscope photo HRTEM and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphorization tin Sn that is used for electrochemical property test
3P
17The preparation process of electrode is identical with embodiment 1, phosphorization tin Sn
3P
17The charge and discharge curve of electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 954mAh/g, and first charge-discharge efficiency is that capacity is 755mAh/g after 78%, 5 week, and efficiency for charge-discharge is that the capacity after 92%, 10 week is 564mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 4
Antimony phosphorus rate of charge (Sb: P) be 25%: 75%.The preparation method of present embodiment is identical with embodiment 1.(Sb: P=25%: 75%) take by weighing antimony powder and red phosphorus powder (being that antimony phosphorus molar ratio equals 1: 3), put into ceramic ball grinder, ratio of grinding media to material is 20: 1 by stoichiometric proportion.Under argon gas atmosphere, with 200 rev/mins of rotating speeds, 40 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure hydrogen atmosphere, progressively be warming up to 500 ℃.Under this temperature, preroast 28 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure hydrogen atmosphere, progressively be warming up to 500 ℃.Under this temperature, roasting 8 hours.Roasting finishes, and naturally cools to the phosphatization antimony SbP that room temperature obtains end product
3The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, its high-resolution transmission electron microscope photo HRTEM and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphatization antimony SbP that is used for electrochemical property test
3The preparation process of electrode is identical with embodiment 1, phosphatization antimony SbP
3The charge and discharge curve of electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 914mAh/g, and first charge-discharge efficiency is that capacity is 715mAh/g after 81%, 5 week, and efficiency for charge-discharge is that the capacity after 93%, 10 week is 568mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 5
Bismuth phosphorus rate of charge (Bi: P) be 35%: 65%.The preparation method of present embodiment is identical with embodiment 1.(Bi: P=35%: 65%) claim to remove bismuth meal and red phosphorus powder (being that bismuth phosphorus molar ratio equals 7: 13), put into ceramic ball grinder, ratio of grinding media to material is 30: 1 by stoichiometric proportion.Under hydrogen atmosphere, with 250 rev/mins of rotating speeds, 35 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure hydrogen atmosphere, progressively be warming up to 600 ℃.Under this temperature, preroast 25 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet roasting afterproduct grind into powder.In the normal pressure hydrogen atmosphere, progressively be warming up to 450 ℃.Under this temperature, roasting 12 hours.Roasting finishes, and naturally cools to the phosphatization bismuth Bi that room temperature obtains end product
7P
13The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, its high-resolution transmission electron microscope photo HRTEM and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphatization bismuth Bi that is used for electrochemical property test
7P
13The preparation process of electrode is identical with embodiment 1, phosphatization bismuth Bi
7P
13The charge and discharge curve of electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 878mAh/g, and first charge-discharge efficiency is that capacity is 685mAh/g after 82%, 5 week, and efficiency for charge-discharge is that the capacity after 94%, 10 week is 543mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 6
Alum phosphorus rate of charge (V: P) be 45%: 55%.The preparation method of present embodiment is identical with embodiment 1.(V: P=45%: 55%) take by weighing alum flour and red phosphorus powder (being that vanadium phosphorus molar ratio equals 9: 11), put into ceramic ball grinder, ratio of grinding media to material is 40: 1 by stoichiometric proportion.Under hydrogen atmosphere, with 300 rev/mins of rotating speeds, 30 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure hydrogen atmosphere, progressively be warming up to 700 ℃.Under this temperature, preroast 21 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure hydrogen atmosphere, progressively be warming up to 400 ℃.Under this temperature, roasting 16 hours.Roasting finishes, and naturally cools to the phosphatization alum V that room temperature obtains end product
9P
11The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, high-resolution transmission electron microscope photo HRTEM and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphatization alum V that is used for electrochemical property test
9P
11The preparation process of electrode is identical with embodiment 1, and its charge and discharge curve under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 858mAh/g, and first charge-discharge efficiency is that capacity is 626mAh/g after 85%, 5 week, and efficiency for charge-discharge is that the capacity after 94%, 10 week is 505mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 7
Chromium phosphorus rate of charge (Cr: P) be 55%: 45%.The preparation method of present embodiment is identical with embodiment 1.(Cr: P=55%: 45%) take by weighing chromium powder and red phosphorus powder (being that chromium phosphorus molar ratio equals 11: 9), put into ceramic ball grinder, ratio of grinding media to material is 45: 1 by stoichiometric proportion.Under hydrogen atmosphere, with 400 rev/mins of rotating speeds, 25 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure hydrogen atmosphere, progressively be warming up to 800 ℃.Under this temperature, preroast 15 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure hydrogen atmosphere, progressively be warming up to 300 ℃.Under this temperature, roasting 21 hours.Roasting finishes, and naturally cools to the phosphatization chromium Cr that room temperature obtains end product
11P
9The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, its high-resolution transmission electron microscope photo HRTEM and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphatization chromium Cr that is used for electrochemical property test
11P
9The preparation process of electrode is identical with embodiment 1, phosphatization chromium Cr
11P
9The charge and discharge curve of electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 788mAh/g, and first charge-discharge efficiency is that capacity is 529mAh/g after 86%, 5 week, and efficiency for charge-discharge is that the capacity after 94%, 10 week is 455mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 8
Iron phosphorus rate of charge (Fe: P) be 65%: 35%.The preparation method of present embodiment is identical with embodiment 1.(Fe: P=65%: 35%) take by weighing iron powder and red phosphorus powder (being that iron phosphorus molar ratio equals 13: 7), put into ceramic ball grinder, ratio of grinding media to material is 50: 1 by stoichiometric proportion.Under argon gas atmosphere, with 450 rev/mins of rotating speeds, 20 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure argon gas atmosphere, progressively be warming up to 900 ℃.Under this temperature, preroast 13 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure hydrogen atmosphere, progressively be warming up to 250 ℃.Under this temperature, roasting 25 hours.Roasting finishes, and naturally cools to the iron phosphide Fe that room temperature obtains end product
13P
7The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, the high-resolution transmission electron microscope photo HRTEM of this material and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The iron phosphide Fe that is used for electrochemical property test
13P
7The preparation process of electrode is identical with embodiment 1, iron phosphide Fe
13P
7The charge and discharge curve of electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 762mAh/g, and first charge-discharge efficiency is that capacity is 512mAh/g after 86%, 5 week, and efficiency for charge-discharge is that the capacity after 95%, 10 week is 425mAh/g, and efficiency for charge-discharge is 99%.
Embodiment 9
Zinc phosphorus rate of charge (Zn: P) be 75%: 25%.The preparation method of present embodiment is identical with embodiment 1.(Zn: P=75%: 25%) take by weighing zinc powder and red phosphorus powder (being that zinc phosphorus molar ratio equals 3: 1), put into ceramic ball grinder, ratio of grinding media to material is 15: 1 by stoichiometric proportion.Under argon gas atmosphere, with 500 rev/mins of rotating speeds, 15 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure argon gas atmosphere, progressively be warming up to 980 ℃.Under this temperature, preroast 8 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure hydrogen atmosphere, progressively be warming up to 200 ℃.Under this temperature, roasting 28 hours.Roasting finishes, and naturally cools to the zinc phosphide Zn that room temperature obtains end product
3P.The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, the high-resolution transmission electron microscope photo HRTEM of this material and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The zinc phosphide Zn that is used for electrochemical property test
3The preparation process of P electrode is identical with embodiment 1, zinc phosphide Zn
3The charge and discharge curve of P electrode under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 618mAh/g, and first charge-discharge efficiency is that capacity is 423mAh/g after 87%, 5 week, and efficiency for charge-discharge is that the capacity after 95%, 10 week is 375mAh/g, and efficiency for charge-discharge is 99%.
Silver phosphorus rate of charge (Ag: P) be 85%: 15%.The preparation method of present embodiment is identical with embodiment 1.(Ag: P=85%: 15%) take by weighing silver powder and red phosphorus powder (being that silver-colored phosphorus molar ratio equals 17: 3), be dosed in the ceramic ball grinder of sealing, ratio of grinding media to material is 10: 1 by stoichiometric proportion.Under argon gas atmosphere, with 600 rev/mins of rotating speeds, 10 hours ball milling time.Phase structure behind the ball milling is similar to Fig. 1.At ambient temperature, the pressed powder with behind the ball milling is positioned in the tube furnace.In the normal pressure argon gas atmosphere, progressively be warming up to 1000 ℃.Under this temperature, preroast 5 hours.After naturally cooling to room temperature,, place in the tube furnace once more behind the compressing tablet preroast afterproduct grind into powder.In the normal pressure argon gas atmosphere, progressively be warming up to 100 ℃.Under this temperature, roasting 30 hours.Roasting finishes, and naturally cools to the phosphatization silver Ag that room temperature obtains end product
17P
3The X-ray diffractogram of this material and embodiment 2 similar (promptly similar) to Fig. 7, the high-resolution transmission electron microscope photo HRTEM of this material and the display result of selecting territory electron diffraction diagram SAED and embodiment 1 similar (promptly similar with Fig. 4 to Fig. 3), the material behind the after baking has mono-crystalline structures.
The phosphatization silver Ag that is used for electrochemical property test
17P
3The preparation process of electrode is identical with embodiment 1, and its charge and discharge curve under difference circulation cycle is similar with Fig. 6 to Fig. 5 with charge and discharge capacity and efficiency curve.The first charge-discharge capacity is 523mAh/g, and first charge-discharge efficiency is that capacity is 384mAh/g after 89%, 5 week, and efficiency for charge-discharge is that the capacity after 96%, 10 week is 345mAh/g, and efficiency for charge-discharge is 99%.
In sum, the present invention compared with prior art, the invention provides a kind of metal phosphide that is used as ion secondary battery cathode material lithium and preparation method thereof, this metal phosphide has higher capacity and excellent cycle performance, and be suitable as the negative material of lithium rechargeable battery, and the method for the preparation method of this metal phosphide for adopting high-energy ball milling method to combine with high temperature solid phase synthesis, this preparation method's device therefor is simple, process conditions are convenient and easy, help applying on a large scale, be of great practical significance.
In addition, the preparation process that is used as the metal phosphide of ion secondary battery cathode material lithium provided by the invention is easy to control, for the red phosphorus powder and the metal dust that are used to prepare this metal phosphide, can reduce the granularity of powder to a great extent by mechanical milling process, increase specific area, the reaction between these two kinds of powder is more prone to.Simultaneously, can also improve the uniformity of two kinds of powder to a great extent, help the generation of target product more by mechanical milling process.In addition, the present invention adopts the method for after baking can effectively remove the impurity phase, and helps eliminating the stress in the material and form complete crystal formation.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1, a kind of metal phosphide as ion secondary battery cathode material lithium is characterized in that this metal phosphide is made up of phosphorus and metallic element M, and it forms expression formula is M
xP
y, wherein, 0.15≤x≤0.85,0.15≤y≤0.85.
2, metal phosphide as claimed in claim 1 is characterized in that, described metallic element M is a kind of in major element and the transition elements.
3, metal phosphide as claimed in claim 2 is characterized in that, described major element is tin Sn, antimony Sb and bismuth Bi, and described transition elements is vanadium V, chromium Cr, manganese Mn, iron Fe, zinc Zn and silver-colored Ag.
4, a kind of preparation method who is used as the metal phosphide of ion secondary battery cathode material lithium is characterized in that, comprises step:
(1) red phosphorus powder and metal dust are pressed formula M
xP
yCome to put into ball grinder after the proportioning, wherein, 0.15≤x≤0.85,0.15≤y≤0.85, and put into abrading-ball remained in hydrogen or the argon gas atmosphere, with 100～600 rev/mins rotating speed ball millings 10～50 hours;
(2) mixture that ball milling is generated earlier under hydrogen or argon gas atmosphere with 400～1000 ℃ temperature preroast 5-30 hour;
(3) product with above-mentioned preroast naturally cools to room temperature, under hydrogen or argon gas atmosphere, carried out after baking 5～30 hours then, behind natural cooling, promptly obtain described metal phosphide as ion secondary battery cathode material lithium with 100～600 ℃ temperature.
5, preparation method as claimed in claim 4 is characterized in that, the ratio of grinding media to material in the described ball grinder is (5～50): 1.
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