CN104600299B - A kind of lithium ion/sodium-ion battery negative active core-shell material, negative pole and battery - Google Patents

A kind of lithium ion/sodium-ion battery negative active core-shell material, negative pole and battery Download PDF

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CN104600299B
CN104600299B CN201510008100.3A CN201510008100A CN104600299B CN 104600299 B CN104600299 B CN 104600299B CN 201510008100 A CN201510008100 A CN 201510008100A CN 104600299 B CN104600299 B CN 104600299B
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compound
negative pole
gep
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active core
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CN104600299A (en
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李会巧
李文武
翟天佑
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Huazhong University of Science and Technology
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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
    • 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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/5805—Phosphides
    • 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
    • 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

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Abstract

The present invention provides a kind of lithium ion/sodium ion secondary battery negative active core-shell material, negative pole and battery, belong to electrochemistry and cell art, negative active core-shell material includes phosphorus germanium compound, or/and the first compound that the phosphorus germanium compound is formed with simple substance P or/and simple substance Ge, or/and the second compound that the phosphorus germanium compound is formed with conductive constituent element；Or/and the triplex thing that first compound is formed with conductive constituent element.The negative pole that the present invention is provided includes negative active core-shell material as described above.Negative pole of the present invention has the advantages that specific capacity is high, initial coulomb efficiency is high, charging/discharging voltage platform differentiation is small, high rate during charging-discharging is good.

Description

A kind of lithium ion/sodium-ion battery negative active core-shell material, negative pole and battery
Technical field
The invention belongs to electrochemistry and cell art, use negative more particularly, to a kind of lithium ion/sodium-ion battery Pole active material, negative pole and battery.
Background technology
Compared with the batteries such as ni-mh, NI-G, lithium ion battery has the characteristic that voltage is high, capacity is high, weight is small.Therefore, In recent years, lithium secondary battery is widely used as mobile communication instrument, portable electronic instrument, electric bicycle, electric two-wheel car, electricity The main power source of electrical automobile etc..But, as the aspects such as communication, electric automobile, electronic equipment and space technology are developed rapidly, to electricity The performance in pond proposes higher and higher requirement, seeks new energy storage system to overcome the traditional fuel energy-storage system to have turned into A current challenge.Chargeable lithium cell has that price is low, has extended cycle life, the invertibity that energy density is high and excellent etc. is excellent Point, its focus for having become many research.
At present, rechargeable lithium ion batteries frequently with graphite as negative material, but, in chargeable lithium cell The capacity of commercial graphite cathode material is only 372mA h/g, and embedded current potential of the lithium ion in graphite is relatively low, is easily formed Li dendrite, in turn results in battery short circuit, so as to bring potential safety hazard.Transition metal oxide also can be used as the negative pole material of battery Material, its specific capacity can reach higher level, general 700-1500mA h/g, but its first coulombic efficiency than relatively low, typically Below 60%, it is also not suitable for making commercial lithium cell cathode material.Silicon, germanium, tin etc. have appearance higher with the alloy that lithium is formed Amount, but its first coulombic efficiency also be difficult to reach 80%, application prospect is not still good.In a word, current secondary lithium battery The middle negative pole for lacking high comprehensive performance.
Although the application prospect of lithium ion battery is quite varied, earth's crust lithium resource is deficienter, and skewness, The lithium resource of China is even more deficient.Compared with lithium resource, sodium resource comparision contents are enriched in the earth's crust, and the sodium resource of China is stored up Amount is very big, therefore develops high performance sodium-ion battery and turn into a weight for reducing secondary cell cost substituting lithium ion battery Want approach.Current room temperature anode material of lithium-ion battery lacks, wherein the hard carbon capacity with commercial application prospect is only 200mA h/g.So low capacity seriously limits the energy density of sodium-ion battery.Therefore, also lack in current room temperature sodium-ion battery The negative pole of weary high comprehensive performance.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of secondary electricity of lithium ion/sodium ion Pond negative active core-shell material, negative pole and battery, high its object is to provide a kind of specific capacity, coulombic efficiency is high first and discharge and recharge Voltage platform difference is small, voltage platform is moderate suitable for lithium ion battery and the negative pole of sodium-ion battery, and there is provided including This kind of lithium ion battery and sodium-ion battery of negative pole, the negative pole for thus solving current lithium ion battery and sodium-ion battery are deposited Off-capacity or first coulombic efficiency than relatively low technical problem.
To achieve these goals, according to one aspect of the present invention, there is provided a kind of lithium ion/sodium-ion battery negative pole Active material, the negative active core-shell material includes：
Phosphorus germanium compound；And/or the first compound that the phosphorus germanium compound is formed with simple substance P and/or simple substance Ge； And/or the second compound that the phosphorus germanium compound is formed with conductive constituent element, the conductive constituent element itself has conductive capability； And/or the triplex thing that first compound is formed with conductive constituent element, wherein, the phosphorus germanium compound includes following thing Matter one or several：
I binary stoichiometric compound that () is formed by P and Ge；
(ii) the binary nonstoichiometric compound formed by P and Ge；
(iii) the polynary phosphorus germanium compound being collectively forming by P and Ge and element M, M takes from Li, Si, Sn, Pb, Zn, Mn, One or more in Fe, Co and Cu.
First compound can be surface, or the phosphorus germanium chemical combination that excessive Ge or/and P is coated on phosphorus germanium compound Thing is coated on excessive Ge or/and P surfaces；The solid solution that phosphorus germanium compound is formed with the Ge or/and P of excess is can also be, Simple substance Ge or/and P is may also be to be doped in phosphorus germanium compound.Excessive Ge, P can be it is crystalline state, or amorphous, Phosphorus germanium compound can be crystalline state, or amorphous.
Second/triplex thing is different from general physical mixed, but by answering that the modes such as high-energy mechanical ball milling are obtained Compound, in the compound, active material be uniformly fully combined with conductive constituent element and with strong interaction even into Key, the structure of matter stabilization of this compound, particle size is small, and specific surface area is big, be conducive to the infiltration of electrolyte permeate and Be conducive to the transmission of lithium ion/sodium ion and electronics, while conductive constituent element can be with buffers active composition in charge and discharge process Volumetric expansion.Due to that, containing conductive constituent element relatively higher, can not also be added when doing electrode film and led in second/triplex thing Electric component or conductive agent, are coated on collector after directly being well mixed with binding agent by second/triplex thing.
When phosphorus germanium compound, the first/bis-/triplex thing are used as lithium/anode material of lithium-ion battery, can apply or directly It is grown in two-dimentional conductive substrates as on Copper Foil, it is also possible to coat or be grown directly upon in three conductive substrates, such as nickel foam, carbon Cloth/carbon paper or others can be as the three-dimensional conductive substrates of collector, it is also possible to CNT, nano metal, graphite It is negative to be directly used as lithium/sodium-ion battery that the well mixed rear suction filtration film forming such as alkene turns into the Integrated electrode with self supporting structure Pole.
Further, wherein the binary stoichiometric compound formed by P and Ge includes GeP, GeP2、GeP3、GeP4、 GeP5、Ge2P2、Ge3P、Ge2P3And Ge3P4In one or several.
Further, wherein the binary nonstoichiometric compound formed by P and Ge include one kind of following material or Person is various：
I () chemical general formula is Ge1±aP1±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(ii) chemical general formula is Ge1±a P2±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(iii) chemical general formula is Ge1±a P3±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(iv) chemical general formula is Ge1±a P4±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
V () chemical general formula is Ge2±a P2±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(vi) chemical general formula is Ge3±a P1±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(vii) chemical general formula is Ge2±a P3±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(xiii) chemical general formula is Ge1±a P5±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(ix) chemical general formula is Ge3±a P4±bCompound, wherein 0<A≤0.2, and 0<b≤0.2.
As preferred, the binary nonstoichiometric compound formed by P and Ge include one kind of following material or It is various：
I () chemical general formula is Ge1±aP1±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(ii) chemical general formula is Ge1±a P2±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(iii) chemical general formula is Ge1±a P3±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(iv) chemical general formula is Ge1±a P4±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
V () chemical general formula is Ge2±a P2±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(vi) chemical general formula is Ge3±a P1±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(vii) chemical general formula is Ge2±a P3±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(viii) chemical general formula is Ge1±a P5±bCompound, wherein 0<A≤0.15, and 0<b≤0.15；
(ix) chemical general formula is Ge3±a P4±bCompound, wherein 0<A≤0.15, and 0<b≤0.15.
Used as further preferably, the binary nonstoichiometric compound formed by P and Ge includes following material One or more：
I () chemical general formula is Ge1±aP1±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(ii) chemical general formula is Ge1±a P2±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(iii) chemical general formula is Ge1±a P3±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(iv) chemical general formula is Ge1±a P4±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
V () chemical general formula is Ge2±a P2±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(vi) chemical general formula is Ge3±a P1±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(vii) chemical general formula is Ge2±a P3±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(viii) chemical general formula is Ge1±a P5±bCompound, wherein 0<A≤0.1, and 0<b≤0.1；
(ix) chemical general formula is Ge3±a P4±bCompound, wherein 0<A≤0.1, and 0<b≤0.1.
Further, the binary nonstoichiometric compound for being formed by P and Ge also includes whole comparing chemical combination by what P and Ge were formed Thing and the solid solution that is formed of simple substance P and/or Ge of excess one or more.
Further, wherein in second/triplex thing, the quality of the conductive constituent element is the second/triplex The 10%~70% of thing gross mass.As further preferably, wherein in second/triplex thing, the conductive constituent element Quality be the 20%~60% of second/triplex thing gross mass.It is total that conductive constituent element quality accounts for second/triplex thing Quality 10%~70% when, when second/triplex thing is as GND, battery performance is relatively good.Repetitious experiment Also confirm, when conductive constituent element quality accounts for the 20%~60% of second/triplex thing gross mass, the thing conduct of second/triplex During secondary battery negative pole, the performance of battery is more excellent.When phosphorus germanium compound is as negative active core-shell material, lithium ion or sodium ion can be embedding Enter in electrode, cause the volumetric expansion of negative pole, so that chemical property is significantly decayed.Adding conductive constituent element has two aspects Effect, on the one hand can improve the transfer of its electronics；On the other hand can also buffer volumes expansion so as to optimize electrode structure Reach the purpose of lifting chemical property.
Further, the conductive constituent element includes activated carbon, native graphite, Delanium, carbon gas with conductive capability Gel, carbon fiber, CNT, graphite oxide, Graphene, reduced graphene, carbon black, acetylene black, W metal, Ni metal, Compound R uO2, compound TiC, polyaniline, one or more in polythiophene and polypyrrole.In fact, conductive constituent element Only there need to be good electric conductivity, you can the chemical property for improving active material.Conductive constituent element herein can be with It is nitrogen, boron, phosphorus, the carbon material of one or more doping of sulphur.
According to another aspect of the present invention, a kind of lithium ion/sodium-ion battery negative pole, the negative pole bag are also provided Contain：Current-collector and anode active material layer, the anode active material layer are formed at least one surface of the current-collector And comprising negative active core-shell material, wherein the negative active core-shell material is negative active core-shell material as defined above.
According to the third aspect of the invention, a kind of lithium ion battery is also provided, it includes positive pole, negative pole and is arranged on Barrier film between the positive pole and the negative pole, wherein the negative pole is negative pole as defined above.
According to the fourth aspect of the invention, a kind of sodium-ion battery is also provided, it includes positive pole, negative pole and is arranged on Barrier film between the positive pole and the negative pole, wherein the negative pole is negative pole as defined above.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show Beneficial effect：
1st, the phosphorus germanium compound prepared by the inventive method simultaneously contain germanium and phosphorus, and phosphorus and germanium all have storage lithium high/ Sodium activity, therefore phosphorus germanium compound has storage lithium/sodium capacity high, also, experiment is proved, phosphorus germanium compound be used for lithium ion/ During the negative material of sodium-ion battery, its charging and discharging curve has the advantages of charge and discharge voltage platform difference is small, and curve is gentle, is easy to Commercial applications.
2nd, the part phosphorus germanium compound in the present invention has class graphite laminate structure or solid solution structure, and experiment is proved, Phosphorus germanium compound or the phosphorus germanium compound of solid solution structure either with class graphite laminate structure, its electric conductivity are superior to Semiconductor.Also containing the metallic element outside germanium in polynary phosphorus germanium compound, on the one hand the metallic element can conduct electronics, separately On the one hand, with the volumetric expansion of buffer electrode, can be conducive to improving the performances such as the high magnification and cycle life of battery.
3rd, in the first compound prepared by the present invention, excessive germanium is coated on the surface of phosphorus germanium compound, germanium metal tool There is electric conductivity higher, while the stable interface between active material and electrolyte can also be formed so as to improve the circulation of battery Stability, such electrode possesses high rate performance higher；Excessive phosphorus can be further when being coated on phosphorus germanium compound surface Capacity is improved, because the storage lithium/sodium Capacity Ratio germanium of phosphorus is also high；The solid solution that phosphorus germanium compound is formed with elemental phosphorous or/and germanium With metallic conductivity, so as to also contribute to improve its chemical property.
4th, it is whole so as to greatly improve due to the introducing of conductive constituent element in the second/triplex thing prepared by the present invention The electron transport ability of individual electrode material, while also add specific surface area, is more beneficial for the infiltration of electrolyte, can shorten lithium from Son/sodium ion transmission range.Due to the introducing of conductive constituent element, the particle size of phosphorus germanium compound becomes smaller or even decrystallized, When the such electrode of lithium/sodium insertion, volumetric expansion change is buffered significantly, and so deintercalation is unlikely to make electrode material repeatedly Material comes off from collector, the electric insulation that will not also cause the crushing of active material to produce, thus avoids cycle performance significantly Degree declines phenomenon.By GeP therein5With C-shaped into the second compound as the negative pole of experimental cell, carry out electrochemistry cyclicity When can test, find its circulation 50 times after, capacity is not almost decayed, and it under the high magnification of 4A/g, battery is still protected Hold the high power capacity of 1400mA h/g.
5th, phosphorus germanium compound can be obtained directly using Ge powder and P powder are carried out into ball milling in electrode of the present invention, ball grinding method with Traditional high-pressure synthesis grind rear high temperature sintering synthetic method and compare, and its processing step is few, and without high-temperature operation, method is more Simply.
6th, simple substance P, simple substance Ge and simple substance C are carried out into high-energy ball milling, can prepare conductive constituent element be C second be combined Thing, this conductive constituent element for C the second compound concrete structure for carbon coating amorphized material, its can directly with bonding Agent mixes for use as electrode, it is no longer necessary to adds conductive agent, greatlys save the preparation flow of electrode.
In a word, electrode of the present invention has that theoretical capacity is high, coulombic efficiency is high, charging/discharging voltage platform differentiation is small first, follows Ring property is excellent, long lifespan the advantages of, and be able to maintain that high discharge capacity, coulombic efficiency high, high magnification and low voltage Platform, it has excellent chemical property, is that one kind has potential electrode very much, and the electrode is for realizing safe and effective, performance It is significant for the battery of stabilization.Also, electrode of the present invention mainly includes Ge, P and the compound being made up of Ge and P, Can be prepared using ball milling method, the electrode material is abundant, cheap, preparation method is simple, be easy to promote and extensive Production, is a kind of great application potential, the electrode suitable for lithium ion battery and sodium-ion battery.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of GeP prepared by the use ball milling method included in electrode of the present invention；
Fig. 2 is GeP prepared by the use ball milling method included in electrode of the present invention5X-ray diffractogram；
Fig. 3 is GeP in the embodiment of the present invention5Energy spectrum diagram；
Fig. 4 is by GeP in the embodiment of the present invention5With C-shaped into the second compound energy spectrum diagram；
Fig. 5 is by GeP in the embodiment of the present invention5With C-shaped into the second compound face surface sweeping figure, (a) in the figure, (b), C () and (d) is respectively the SEM pictures of the compound, Ge element distribution map, P elements distribution map and carbon distribution map；
Fig. 6 is the GeP prepared using ball milling method in the embodiment of the present invention5SEM figure；
Fig. 7 is the storage lithium performance map of the GeP included in embodiment of the present invention electrode；
Fig. 8 is the storage sodium performance map of the GeP included in embodiment of the present invention electrode；
Fig. 9 is the GeP included in embodiment of the present invention electrode5Storage lithium performance map；
Figure 10 is the GeP included in embodiment of the present invention electrode5Storage sodium performance map.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method Not constituting conflict each other can just be mutually combined.
Lithium ion/sodium ion secondary battery negative active core-shell material that the present invention is provided, is a kind of diversified material of composition Material, it is mainly comprising one or more in following four major classes material：
(1) phosphorus germanium compound；
(2) first compounds；
(3) second compounds；
(4) triplex things；
Phosphorus germanium compound includes the binary stoichiometric compound formed by P and Ge, the binary non-stoichiometric formed by P and Ge Compound and the polynary phosphorus germanium compound being collectively forming by P and Ge and element M；First compound is phosphorus germanium compound and list Compound or solid solution that matter P and/or simple substance Ge are formed；Second compound is the phosphorus germanium compound and conductive constituent element institute The compound of formation；The compound that triplex thing is formed by the first compound with conductive constituent element.
More specific description is carried out to negative material of the invention by the following examples, but, the present invention is not limited In these embodiments.
The embodiment ＞ of ＜ phosphorus germanium compounds
(1) the binary stoichiometric compound formed by P and Ge
By in the phosphorus powder that purity is 99.8% and the germanium that purity is 99.9% addition ball grinder, the ratio of grinding media to material for using is 13: 1, rotating speed is 350~600 revs/min, and the binary stoichiometric compound formed by P and Ge is obtained after ball milling 2-20 hours.Pass through The mass ratio of adjustment phosphorus powder and elemental Germanium, the various whole ratioizations of binary formed by P and Ge can be prepared with the ball milling method Compound, through X-ray diffraction detectable substance phase, the binary stoichiometric compound has following several：GeP、GeP2、GeP3、GeP4、GeP5、 Ge2P2, Ge3P, Ge2P3 and Ge3P4.According to the change of phosphorus powder and the mass ratio and Ball-milling Time of elemental Germanium, product may be used also Can be various mixtures in above binary stoichiometric compound, now, through X-ray diffraction detectable substance phase, may occur in which multiple materials Phase diffraction maximum.Table 1 by the embodiment of the present invention in binary stoichiometric compound is formed by P and Ge.Not by 9 in the form The various possible combined situation of kind of binary stoichiometric compound lists one by one, but can not be thus be excluded that not listed in table 1 Other may be combined.
Fig. 1 is the X-ray diffractogram of GeP prepared by the use ball milling method included in electrode of the present invention, it can be seen that All of diffraction maximum can be corresponding with the PDF cards (numbering of the card is 44-1125) of standard, illustrates to obtain pure phase GeP。
Table 1 by the embodiment of the present invention part binary stoichiometric compound formed by P and Ge
Embodiment The thing phase that XRD analysis are obtained
Embodiment 1 GeP
Embodiment 2 GeP2
Embodiment 3 GeP3
Embodiment 4 GeP4
Embodiment 5 GeP5
Embodiment 6 Ge2P2
Embodiment 7 Ge3P4
Embodiment 8 Ge2P3
Embodiment 9 Ge3P
Embodiment 10 GeP4、Ge3P and GeP5It is 10%, 30% and 60% mixing according to mass ratio
Embodiment 11 Ge3P4、GeP2And GeP5It is 20%, 5% and 75% mixing according to mass ratio
Fig. 2 is GeP prepared by the use ball milling method included in electrode of the present invention5X-ray diffractogram, can from figure Know, all of diffraction maximum can be corresponding with the PDF cards (numbering of the card is 24-0455) of standard, illustrate to obtain pure The GeP of phase5。
Fig. 3 is GeP in the embodiment of the present invention5Energy spectrum diagram, it can be seen that it is made up of element Ge and P, and Ge and P Atomic ratio be 1:5, and other oligo-element such as copper, come from the copper mesh for being TEM, and carbon comes from pollution carbon.
Fig. 6 is the GeP prepared using ball milling method in the embodiment of the present invention5SEM figures, GeP as we know from the figure5Pattern It is nano particle, the particle is the second particle reunited by less primary particle, the side of second particle one for so being formed Face is conducive to being impregnated with for electrolyte on the other hand to also have tap density higher, is conducive to improving the energy density of whole electrode.
(2) the binary nonstoichiometric compound formed by P and Ge
By in the phosphorus powder that purity is 99.8% and the germanium that purity is 99.9% addition ball grinder, it is 15 to use ratio of grinding media to material:1, Rotating speed is 450 revs/min, and the ball milling mode of 15 hours obtains the binary nonstoichiometric compound formed by P and Ge.By adjustment The mass ratio of phosphorus powder and elemental Germanium, the various binary non-stoichiometrics formed by P and Ge can be prepared with the ball milling method Compound, such compound tests and analyzes and is scanned through by X-ray diffraction the Surface scan function that Electronic Speculum carries and carries out composition Analysis, finds diffraction maximum, list with the binary stoichiometric compound formed by P and Ge in the corresponding diffraction maximum of such compound The diffraction maximum of matter phosphorus and elemental Germanium, but ESEM carry Surface scan component analysis function detection and analysis, find it is elemental phosphorous, Elemental Germanium is uniformly distributed, and illustrates that binary nonstoichiometric compound middle part is divided into solid solution structure.By quantitative constituent analysis, learn It is following several that the binary nonstoichiometric compound has：
I () chemical general formula is Ge1±aP1±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high-energy ball milling side After prepared by formula, according to analysis of experiments, it was demonstrated that there is Ge0.8P1.2、Ge1.2P0.8And Ge1.2P1.2；
(ii) chemical general formula is Ge1±aP2±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high-energy ball milling After prepared by mode, according to analysis of experiments, it was demonstrated that there is Ge0.8P2.2、Ge1.2P1.8And Ge1P1.9；
(iii) chemical general formula is Ge1±a P3±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high energy ball After prepared by mill mode, according to analysis of experiments, it was demonstrated that there is Ge0.8P3.2、Ge1.2P2.8And Ge1P2.9；
(iv) chemical general formula is Ge1±a P4±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high-energy ball milling After prepared by mode, according to analysis of experiments, it was demonstrated that there is Ge0.8P4.2、Ge1.2P3.8And Ge1P3.9；
V () chemical general formula is Ge2±a P2±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high-energy ball milling After prepared by mode, according to analysis of experiments, it was demonstrated that there is Ge1.8P2.2、Ge2.2P1.8And Ge1.9P2.1；
(vi) chemical general formula is Ge3±a P1±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high-energy ball milling After prepared by mode, according to analysis of experiments, it was demonstrated that there is Ge2.8P1.2、Ge3.2P0.8And Ge2.9P1.1；
(vii) chemical general formula is Ge2±a P3±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high energy ball After prepared by mill mode, according to analysis of experiments, it was demonstrated that there is Ge1.8P3.2、Ge2.2P2.8And Ge1.9P3.1；
(xiii) chemical general formula is Ge1±a P5±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high energy ball After prepared by mill mode, according to analysis of experiments, it was demonstrated that there is Ge0.8P5.2、Ge1.2P4.8And Ge0.9P5.1；
(ix) chemical general formula is Ge3±a P4±bCompound, wherein 0<A≤0.2, and 0<B≤0.2, wherein, high-energy ball milling After prepared by mode, according to analysis of experiments, it was demonstrated that there is Ge2.8P4.2、Ge3.2P3.8And Ge2.9P4.1；
Table 2 by the binary nonstoichiometric compound formed by P and Ge in the embodiment of the present invention, in the form, not by two In first nonstoichiometric compound it is various possible proportioning list one by one, but can not thus be excluded that do not listed in table 2 its His possible proportioning.
(3) the polynary phosphorus germanium compound being collectively forming by P and Ge and element M
It is when preparation, phosphorus powder, germanium and the Li simple substance of one or more, Si powder, Sn powder, Pb simple substance, Zn simple substance, Mn is mono- Mixed in matter, Fe powder, Co powder and Cu powder, be added into ball grinder, be filled with argon gas protection, it is 20 to use ratio of grinding media to material： 1, rotating speed is 500 revs/min, and ball milling prepares the polynary phosphorus germanium compound for 20 hours.
The binary nonstoichiometric compound formed by P and Ge in the embodiment of the present invention of table 2
The constituent analysis of the Surface scan function that Electronic Speculum is carried is tested and analyzed and is scanned through by X-ray diffraction, it is known that, The chemical formula of polynary phosphorus germanium compound is：Li5GeP3、ZnGeP2、MnGeP2、Zn1-xMnxGeP2, polynary phosphorus germanium compound can be with It is CdGeP2、GexPxS1-2x、Cd1-xMnxGeP2、Zn1-xMnxGeP2.Table 3 lists part by P and Ge and the common shape of element M Into polynary phosphorus germanium compound.Only list a limited number of kind of polynary phosphorus germanium compound in the table, but can not therefore by The ternary phosphorus germanium compound that other are not listed forecloses.
The polynary phosphorus germanium compound that the part of table 3 is collectively forming by P and Ge and element M
Embodiment The thing phase that XRD analysis are obtained
Embodiment 36 Li5GeP3
Embodiment 37 ZnGeP2
Embodiment 38 MnGeP2
Embodiment 39 Zn1-xMnxGeP2
＜ the first compound embodiments ＞
The composition and mass percent of the first compound of part of table 4
Unit：Wt.%
Embodiment GeP GeP2 GeP3 GeP5 Simple substance P Simple substance Ge
Embodiment 40 / / / 80 20 /
Embodiment 41 / / / 70 / 30
Embodiment 42 30 50 / 10 5 5
Embodiment 43 20 / / / 80 /
Embodiment 44 25 / / 30 / 45
Embodiment 45 / / 40 10 30 20
Embodiment 46 50 8 10 / 20 12
Embodiment 47 2 3 5 60 / 30
The phosphorus germanium compound of acquisition made above and the phosphorus powder that purity is 99.8% or/and germanium that purity is 99.9% are added Enter in ball grinder, it is 18 to use ratio of grinding media to material:1, rotating speed is 700 revs/min, and ball milling obtains the first compound in 19 hours.Penetrated by X Line diffraction tests and analyzes and is scanned through the Surface scan function that Electronic Speculum carries and carries out constituent analysis, finds to have in diffraction maximum single The peak of matter phosphorus, elemental Germanium, and also with the peak of above-described phosphorus germanium compound.
Table 4 is the compound of part first, and several first compounds are only listed in table, but can not therefore by other The first compound do not listed forecloses.
＜ the second compound embodiments ＞
After the phosphorus germanium compound of acquisition made above mix with conductive constituent element in addition ball grinder, the ratio of grinding media to material for using for 19:1, determine that rotating speed is 400 revs/min, ball milling obtains the second compound in 10 hours.Wherein, conductive constituent element can be with conduction The activated carbon of ability, native graphite, Graphene, graphite flake, Delanium, carbon aerogels, carbon fiber, CNT, graphite oxygen Compound, Graphene, reduced graphene, conductive black, acetylene black, W metal, Ni metal, compound R uO2, it is compound TiC, poly- The carbon material of one or more doping in aniline, polythiophene and polypyrrole, or nitrogen, boron, phosphorus, sulphur.
Table 5 is the compound of part second, and several second compounds are only listed in table, but can not therefore by other The second compound do not listed forecloses.List the composition and size of several conductive constituent elements in table 6, but can not be because This constituent element and composition for will not having row in table foreclose.In fact, conductive constituent element need to only have good electric conductivity, use Can be used to improve the chemical property of active material in the conduction of electronics.Conductive constituent element herein can also be nitrogen, boron, phosphorus, Other not referred in carbon materials or the present invention of one or more doping of sulphur have the material of conductive capability.
The composition and mass percent of the second compound of part of table 5
Unit：Wt.%
Embodiment GeP GeP2 GeP3 GeP5 Conductive constituent element
Embodiment 48 / 5 25 60 10
Embodiment 49 70 5 5 / 20
Embodiment 50 / 5 65 / 30
Embodiment 51 5 5 / 70 20
Embodiment 52 10 40 / / 50
Embodiment 53 20 5 / 15 60
Embodiment 54 20 10 / / 70
Embodiment 55 25 10 / 30 35
Embodiment 56 / 30 / 10 60
Embodiment 57 10 10 10 5 65
Embodiment 58 2 3 5 40 50
Table 5 is the compound of part second, and several second compounds are only listed in table, but can not therefore by other The second compound do not listed forecloses.List the composition and size of several conductive constituent elements in table 6, but can not be because This constituent element and composition for will not having row in table foreclose.In fact, conductive constituent element need to only have good electric conductivity, use Can be used to improve the chemical property of active material in the conduction of electronics.Conductive constituent element herein can also be nitrogen, boron, phosphorus, Other not referred in carbon materials or the present invention of one or more doping of sulphur have the material of conductive capability.
The composition and content of the partially electronically conductive constituent element of table 6
Fig. 4 is by GeP in the embodiment of the present invention5With C-shaped into the second compound energy spectrum diagram, it can be seen that its wrap Ge containing element, P, C, and other oligo-elements, such as copper come from the copper mesh for being TEM.
Fig. 5 is by GeP in the embodiment of the present invention5With C-shaped into the second compound face surface sweeping figure, (a) in the figure, (b), C () and (d) is respectively the SEM pictures of the compound, Ge element distribution map, P elements distribution map and carbon distribution map, It can be seen that carbon and GeP5Compound uniformly mixes, and entirety shows amorphous feature.
＜ triplex thing embodiments ＞
First compound is carried out into ball milling with conductive constituent element, moreover it is possible to obtain triplex thing, the of part is listed in table 7 The composition and content of triplex thing, simply show several triplex things, but therefore will can have in table in the table Other triplex things discharge listed is outside.Also, mass percent, the matter of phosphorus germanium compound of conductive constituent element in the form The mass percent sum of amount percentage, the mass percent of simple substance P and simple substance Ge is 100%.
The composition and content of the part triplex thing of table 7
Unit：Wt.%
Embodiment GeP GeP2 GeP3 GeP5 Simple substance P Simple substance Ge Conductive constituent element
Embodiment 59 / / 70 10 / Native graphite
Embodiment 60 / / / 70 10 Delanium
Embodiment 61 3 5 / 5 5 5 Graphite oxide
Embodiment 62 20 / / / / / W metal
Embodiment 63 25 / / 30 / / Ni metal
Embodiment 64 / / / 10 30 / Reduced graphene
Embodiment 65 / 8 10 / / 12 Polythiophene
Embodiment 66 2 3 5 / / 30 Polypyrrole
Lithium ion or sodium ion secondary battery negative pole are prepared using negative active core-shell material of the present invention, the negative pole includes current collection Device and anode active material layer, anode active material layer are formed on 4 surfaces of current-collector, but negative pole is lived in the present invention The number of surfaces that property material layer is formed in current-collector is not limited specifically, and phosphorus germanium chemical combination is included in anode active material layer One or more in thing, the first compound, the second compound and triplex thing.
In the present invention, electrochemical property test is carried out as negative pole prepared by negative active core-shell material using GeP, obtain its storage The charging and discharging curve of lithium and storage sodium, as shown in Figure 7 and Figure 8, it in the embodiment of the present invention with GeP is active material preparation that Fig. 7 is Storage lithium performance map in electrode, it can be seen that its lithium storage content is about 1897mA h/g, it has more than 90% first Coulombic efficiency.Fig. 8 is the storage sodium performance map in the electrode prepared as active material with GeP in the embodiment of the present invention, can from figure Know, its storage sodium capacity is about 850mA h/g, and it has the coulombic efficiency first close to 90%.
In the present invention, using GeP5The negative pole prepared as negative active core-shell material carries out electrochemical property test, obtains it The charging and discharging curve of storage lithium and storage sodium, as shown in Figure 9 and Figure 10, Fig. 9 is with GeP in the embodiment of the present invention5For active material system The storage lithium performance map of standby electrode, it can be seen that its lithium storage content is about 2289mA h/g, it has more than 90% first Coulombic efficiency.Figure 10 is with GeP in the embodiment of the present invention5It is the storage sodium performance map of electrode prepared by active material, can from figure Know, its storage sodium capacity is about 1250mA h/g, and it has the coulombic efficiency first close to 90%.
Table 8 lists the storage of the electrode that part phosphorus germanium compound and the compound of part second are prepared as electrode active material Lithium capacity.Knowable to from the table, the GeP in phosphorus germanium compound5Lithium storage content it is maximum, reach about 2289mA h/g, also, In the second compound, GeP5With C-shaped into compound lithium storage content it is maximum, reach about 2389mA h/g.In the table only Only give a limited number of kind of germanium compound and a limited number of kind of the second compound, but can not therefore by do not list other Phosphorus germanium compound and other second compounds foreclose.
Table 9 lists the storage of the electrode that part phosphorus germanium compound and the compound of part second are prepared as electrode active material Sodium capacity.Knowable to from the table, the GeP in phosphorus germanium compound5Storage sodium capacity it is maximum, reach 1250mA h/g, also, the In two compounds, GeP5With C-shaped into compound storage sodium capacity it is maximum, reach about 1300mA h/g.Only given in the table A limited number of kind of phosphorus germanium compound and a limited number of kind of the second compound, but other phosphorus that therefore will can not do not list Germanium compound and other second compounds foreclose.
The storage lithium of the electrode that the part phosphorus germanium compound of table 8 and the compound of part second are prepared as electrode active material holds Amount.
The storage sodium of the electrode that the part phosphorus germanium compound of table 9 and the compound of part second are prepared as electrode active material holds Amount
The lithium ion or sodium-ion battery prepared with Top electrode are used, comprising positive pole, negative pole and the positive pole is arranged on And the barrier film between the negative pole, wherein the negative pole is negative pole as defined above, the negative pole includes phosphorus germanium compound, first Compound, the second compound and triplex thing, i.e. as long as comprising with the sodium-ion battery or lithium-ion electric of Top electrode Pond, belongs to the scope of protection of present invention, as long as phosphorus germanium compound, the first compound, second comprising the above in electrode Compound and triplex thing belong to the scope of protection of present invention.
In the embodiment of the present invention, size, the specific composition of conductive constituent element and conductive constituent element and change for conductive constituent element The specific proportioning of compound with combine or compound and simple substance P or simple substance Ge specific proportioning and combine and be not limited to the above Specific embodiment, in fact, conductive constituent element is preferred in the embodiment of the present invention, can also select the thing of other electric conductivity Matter, the size of conductive constituent element can be feasible in principle with smaller or greater, and the quality of the conductive constituent element accounts for described The 10%~70% of two/triplex thing gross mass, is feasible, and be defined to the concrete numerical value in above example.Repeatedly Experiment repeatedly is also confirmed, when conductive constituent element quality accounts for the 20%~60% of second/triplex thing gross mass, the second/tri- When compound is as secondary battery negative pole, the performance of battery is more excellent.In electrode of the present invention, to compound, the first compound, second Specific proportioning in compound and triplex thing is not defined.
Those skilled in the art is readily appreciated that, the foregoing is only presently preferred embodiments of the present invention, is not used to limit The system present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., should be included in Within protection scope of the present invention.

Claims (3)

1. a kind of lithium ion/sodium-ion battery negative pole, the negative pole is included：
Current-collector；With
Anode active material layer, the anode active material layer is formed at least one surface of the current-collector and comprising negative Pole active material,
Wherein described negative active core-shell material by any one of following 7 negative active core-shell materials for limiting,
(1) negative active core-shell material includes：
Phosphorus germanium compound,
The first compound that the phosphorus germanium compound and simple substance P and/or simple substance Ge are formed,
The second compound that the phosphorus germanium compound is formed with conductive constituent element,
One or more in the triplex thing that first compound is formed with conductive constituent element, the conductive constituent element from Body has conductive capability,
Wherein, the phosphorus germanium compound includes one or several of following material：
I binary stoichiometric compound that () is formed by P and Ge；
(ii) the binary nonstoichiometric compound formed by P and Ge；
(iii) the polynary phosphorus germanium compound being collectively forming by P and Ge and element M, M takes from Li, Si, Sn, Pb, Mn, Fe, Co and One or more in Cu,
(2) on the basis of the negative active core-shell material described in (1st) item, further, wherein the binary formed by P and Ge Stoichiometric compound includes GeP, GeP2、GeP3、GeP4、GeP5、Ge2P2、Ge2P3、Ge3P and Ge3P4In one or several,
(3) on the basis of the negative active core-shell material described in (1st) item, further, wherein the binary formed by P and Ge Nonstoichiometric compound includes one or more of following material：
I () chemical general formula is Ge1±aP1±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(ii) chemical general formula is Ge1±aP2±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(iii) chemical general formula is Ge1±aP3±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(iv) chemical general formula is Ge1±aP4±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
V () chemical general formula is Ge2±aP2±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(vi) chemical general formula is Ge3±aP1±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(vii) chemical general formula is Ge2±aP3±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(viii) chemical general formula is Ge1±aP5±bCompound, wherein 0<A≤0.2, and 0<b≤0.2；
(ix) chemical general formula is Ge3±aP4±bCompound, wherein 0<A≤0.2, and 0<B≤0.2,
(4) on the basis of the negative active core-shell material described in (1st) item, further, wherein, it is described formed by P and Ge two First nonstoichiometric compound includes the stoichiometric compound formed by P and Ge with consolidating that the simple substance P and/or simple substance Ge of excess are formed One or more of solution,
(5) on the basis of the negative active core-shell material described in (1st) item, further, wherein in the second/the triplex thing, The quality of the conductive constituent element is the 10%~70% of the second compound gross mass,
(6) on the basis of the negative active core-shell material described in (1st) item, further, wherein in the second/the triplex thing, The quality of the conductive constituent element is the 20%~60% of the second compound gross mass,
(7) on the basis of the negative active core-shell material described in (1st) item, further, wherein the conductive constituent element includes having leading The activated carbon of electric energy power, native graphite, Graphene, graphite flake, Delanium, carbon aerogels, carbon fiber, CNT, graphite Oxide, reduced graphene, carbon black, acetylene black, W metal, Ni metal, compound R uO2, compound TiC, polyaniline, poly- thiophene One or more in fen and polypyrrole.
2. a kind of lithium ion battery, it is included：
Positive pole；
Negative pole；With
The barrier film between the positive pole and the negative pole is arranged on,
Wherein described negative pole is the negative pole defined in claim 1.
3. a kind of sodium-ion battery, it is included：
Positive pole；
Negative pole；With
The barrier film between the positive pole and the negative pole is arranged on,
Wherein described negative pole is the negative pole defined in claim 1.
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