CN106025194A - Black-phosphorus-based composite negative electrode material and preparing method thereof - Google Patents
Black-phosphorus-based composite negative electrode material and preparing method thereof Download PDFInfo
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- CN106025194A CN106025194A CN201610313380.3A CN201610313380A CN106025194A CN 106025194 A CN106025194 A CN 106025194A CN 201610313380 A CN201610313380 A CN 201610313380A CN 106025194 A CN106025194 A CN 106025194A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a black-phosphorus-based composite negative electrode material and a preparing method thereof, and belongs to the field of electrochemistry power supply materials. The black-phosphorus-based composite negative electrode material is prepared by combining black phosphorus, germanium oxide and graphite, flake-like germanium oxide particles are uniformly dispersed on the surface of the black phosphorus material, and the surface of germanium oxide/black phosphorus is coated with graphite, wherein the mass ratio of black phosphorus to germanium oxide is (0.25-2):1, and the mass percentage of graphite in the negative electrode material is 5-80%. The black-phosphorus-based composite negative electrode material is prepared through a two-step ball milling method with black phosphorus, germanium oxide and graphite as raw materials. The black-phosphorus-based composite negative electrode material is good in circulation performance, low in cost and stable in structure; the preparing method is simple in technological process, short in consumed time and high in yield, and has the advantages of being low in raw material cost and improving the structural stability of composites, and the problem that the circulation performance of a black-phosphorus-based composite is poor is solved.
Description
Technical field
The present invention relates to a kind of black phosphorus base composite negative pole material and preparation method thereof, belong to electrochemical power source material
Material field.
Background technology
Lithium ion battery is the novel energy storage cell grown up 21 century.Due to spies such as its high energy low consumptions
Point, lithium ion battery has begun to be widely used in the fields such as mobile phone, electric automobile, energy storage.With
Current development, the energy density of battery is required more and more higher, especially the pushing away of environmental-protecting type electric automobile
Go out, be greatly facilitated Large Copacity, the development of high power electrokinetic cell.Commercial li-ion battery is extensive at present
Employing graphite and modified graphite are as negative material, but its theoretical specific capacity is 372mAh/g, actual specific volume
Amount is only 300～330mAh/g, and to there is irreversible loss first big for graphite electrode simultaneously, multiplying power discharging
The problems such as energy difference, can not meet the most far away actual demand, and especially electric automobile is to cell high-capacity
Requirement.The most this battery in use easily generates SEI (Solid Electrolyte at graphite surface
Interface, solid electrolyte interface), thus cause potential safety hazard.High capacity lithium ion cells cathode material
The research of material has become the key improving battery performance with application.
The black phosphorus of rhombic form have with graphite-like as fold layer structure, therefore have similar to graphite
Electrochemical lithiation reactivity worth.Meanwhile, this structure of black phosphorus makes black phosphorus tool compared with white phosphorus and red phosphorus
There is higher stability and have preferably conduction and heat conductivity, more practicality.It addition, the crystalline substance of black phosphorus
Born of the same parents are much larger than the structure cell of graphite, and the embedding lithium reaction channel spacing of formation is 0.43nm, more than the 0.335 of graphite
4nm, this feature determines lithium ion high diffusion coefficient in the black phosphorus of rhombic form, therefore,
With black phosphorus as lithium ion battery negative material, it is possible to achieve higher large current discharging capability.Prior
It is that phosphorus can generate multiple compounds with lithium by electrochemical reaction, such as LiP, Li2P、Li3P etc..When
When unit phosphorus embeds 3 lithiums, the specific capacity of 2595mAh/g can be formed up to, considerably beyond current business
Industry graphite electrode material.The highest capacity and large current density power promote phosphorus to become great
The lithium ion battery negative material of potentiality.But use black phosphorus electrode to make negative material, produce forming lithiumation
Thing Li3Extremely volume change, Li simultaneously is there is during P3The electric conductivity of P own is relatively low, causes black phosphorus electrode material
There is the problems such as coulombic efficiency difference is low with capability retention in material.Along with charge and discharge cycles is carried out, bigger body
Long-pending expansion causes material efflorescence, and capacity attenuation is rapid.Therefore the stable circulation of black phosphorus based composites is improved
Property is current urgent problem.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of black phosphorus base composite negative pole material
And preparation method thereof.The cyclical stability of the black phosphorus base composite negative pole material that the present invention provides is good, simultaneously
Also have that cost of material is low, the feature of composite structure good stability；The black phosphorus base that the present invention provides is multiple
Close cathode material preparation method and have the advantages that technical process is simple, time-consuming less, yield is high.
For achieving the above object, the present invention is by the following technical solutions:
A kind of black phosphorus base composite negative pole material, is composited by black phosphorus, germanium oxide and graphite, sheet
Described germania particle is dispersed in described black phosphorus material surface, and graphite coat is in germanium oxide/black phosphorus
(GeO2/ P) surface；Wherein, the mass ratio of described black squama and germanium oxide is 0.25-2:1；Described
In negative material, the mass percent of described graphite is 5%-80%.
GeO2Sheet may be uniformly dispersed in black phosphorus surface, stop its volume in cyclic process swollen
Swollen and continuation is pulverized；And graphite is at GeO2/ P Surface coating i.e. graphite coat is in GeO2Outer surface and P
Outer surface, suppress further the volumetric expansion of composite, thus improve electrochemistry cycle performance.
The preparation method of above-mentioned black phosphorus base composite negative pole material, comprises the following steps:
Step one, weighs the red phosphorus of ormal weight, germanium oxide, after mixing, carries out ball milling for the first time, obtains
First ball milling product；
Step 2, adds a certain amount of graphite in described first ball milling product, after being sufficiently mixed, carries out
Ball milling for the second time, obtains described black phosphorus base composite negative pole material.
For the first time after ball milling, red phosphorus is completely reformed into black phosphorus, forms germanium oxide and the combination product of black phosphorus.
In twice ball milling, ball milling is to need to be dispersed in germanium oxide black phosphorus surface for the first time, and ball milling is then for the second time
By graphite dispersion at germanium oxide/black phosphorus composite material surface.Secondary ball milling method can effectively strengthen GeO2/P
Interracial contact and carbon covered effect.
The know-why of the present invention is: realize red phosphorus in-situ preparation black phosphorus by ball grinding method, is formed effectively
Germanium oxide/black phosphorus compound interface, improve electronics, ion conduction rate, can subtract in the process simultaneously
The particle size of few active substance, reduces material efflorescence degree in cyclic process.Utilize the bag of carbon
Cover formation cushioning frame, improve conductive channel between granule, inhibitory activity material body in electrochemical process
Long-pending expansion, improves material circulation performance.
In above-mentioned preparation method, as a kind of preferred implementation, red phosphorus described in step one and described
The mass ratio of germanium oxide be 0.25-2:1 (such as 0.25:1,0.3:1,0.5:1,0.8:1,1.2:1,1.6:1,
1.8:1、2.0:1)。
In above-mentioned preparation method, as a kind of preferred implementation, the addition of graphite described in step 2
Amount is red phosphorus, the 5-80wt% of germanium oxide and three kinds of raw material gross masses of graphite (such as 6wt%, 7wt%,
8wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 75wt%,
78wt%).
In above-mentioned preparation method, as a kind of preferred implementation, the time of described first time ball milling is
8-20h (such as 9h, 11h, 13h, 15h, 17h, 19h), rotating speed is 200-500rpm/min (ratio
As 202rpm/min, 205rpm/min, 208rpm/min, 210rpm/min, 215rpm/min,
220rpm/min、250rpm/min、300rpm/min、350rpm/min、400rpm/min、450rpm/min、
480rpm/min, 490rpm/min, 495rpm/min), ratio of grinding media to material be 10-30:1 (such as 11:1,
12:1、15:1、18:1、22:1、25:1、28:1、29:1).Ball milling for the first time, logical excessive speeds, length
The ball milling condition of time realizes red phosphorus and is converted into black phosphorus, reduces black phosphorus size, enhancing germanium oxide and black phosphorus circle
Face contacts.
In above-mentioned preparation method, as a kind of preferred implementation, the time of described second time ball milling is
10-40h (such as 12h, 15h, 20h, 25h, 30h, 35h, 38h), rotating speed is 100-250rpm/min
(such as 120rpm/min, 150rpm/min, 180rpm/min, 220rpm/min, 240rpm/min),
Ratio of grinding media to material is 10-15:1 (such as 11:1,12:1,13:1,14:1).Ball milling is by low speed etc. for the second time
Ball milling condition carries out the doping of C, forms the cushioning frame with C as matrix, and inhibited oxidation germanium/black phosphorus is multiple
The volumetric expansion of condensation material, forms intergranular conductive channel, improves its cycle performance.
In above-mentioned preparation method, as a kind of preferred implementation, described ball milling is in stainless steel ball-milling
Tank is carried out.
Compared with prior art, the invention has the beneficial effects as follows:
1) the black phosphorus base composite negative pole material good cycle of present invention offer, low cost, Stability Analysis of Structures；
The black phosphorus base composite negative pole material preparation method technical process that 2) present invention provides is simple, time-consuming less,
Yield is high；Also there is the feature that cost of material is low, improve composite structure stability, solve black phosphorus
The problem of based composites cycle performance difference.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to reality
Execute the required accompanying drawing used in example or description of the prior art to be briefly described, it should be apparent that under,
Accompanying drawing during face describes is some embodiments of the present invention, for those of ordinary skill in the art,
On the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the X-ray diffraction (XRD) of the black phosphorus base composite negative pole material of the embodiment of the present invention 1 preparation
Collection of illustrative plates；
Fig. 2 is the scanning electron microscope (SEM) of the black phosphorus base composite negative pole material of the embodiment of the present invention 1 preparation
Figure；
Fig. 3 is the transmission electron microscope (TEM) of the black phosphorus base composite negative pole material of the embodiment of the present invention 1 preparation
Figure；
Fig. 4 is the experiment that the black phosphorus base composite negative pole material prepared with the embodiment of the present invention 1 assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g；
Fig. 5 is the experiment that the black phosphorus base composite negative pole material prepared with the embodiment of the present invention 1 assembles for raw material
Battery voltage-specific capacity curve under the electric current density of 0.1A/g；
Fig. 6 is the experiment that the black phosphorus base composite negative pole material prepared with the embodiment of the present invention 2 assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g；
Fig. 7 is the experiment that the black phosphorus base composite negative pole material prepared with the embodiment of the present invention 3 assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g；
Fig. 8 is the experiment that the black phosphorus base composite negative pole material prepared with the embodiment of the present invention 4 assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g.
Fig. 9 is the experiment that the black phosphorus base composite negative pole material prepared with comparative example 1 of the present invention assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g.
Figure 10 is the experiment that the black phosphorus base composite negative pole material prepared with comparative example 2 of the present invention assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g.
Figure 11 is the experiment that the black phosphorus base composite negative pole material prepared with comparative example 3 of the present invention assembles for raw material
Battery specific capacity-cycle-index curve under the electric current density of 0.1A/g.
Detailed description of the invention
Hereinafter will combine accompanying drawing by embodiment present disclosure is described in further detail, this
Bright protection domain is including but not limited to following each embodiment.
Unreceipted specific experiment step or condition person in embodiment, described by the document in this area
The operation of normal experiment step or condition can be carried out.The various reagent and the raw material that use in embodiment are
Commercially available prod.
Embodiment 1
The present embodiment by ball-milling method (wherein, red phosphorus: germanium oxide=2:1, graphite addition be red squama,
Germanium oxide and the 50% of three kinds of raw material gross masses of graphite) prepare black phosphorus base composite negative pole material, this negative pole material
In material, the mass ratio of black squama, germanium oxide and graphite is 2:1:3.
Preparation method is as follows:
(1) weighing 2 parts of red phosphorus powder and 1 part of germanium oxide powder, both mixing obtain mixture, then
Add mixture to and stainless steel jar mill carries out ball milling for the first time, obtain ball milling product for the first time；The
During ball milling, ratio of grinding media to material is 20:1 (adding 60 parts of stainless steel balls), and rotating speed is 300rpm/min,
Ball-milling Time is 20h；
(2) weigh 3 parts of graphite powders, add in the first time ball milling product that step (1) obtains, then
Carrying out second time ball milling, the product obtained is black phosphorus base composite negative pole material；The ball of ball milling for the second time
Material ratio 10:1, rotating speed is 200rpm/min, Ball-milling Time 40h.
Fig. 1 is X-ray diffraction (XRD) figure of the black phosphorus base composite negative pole material prepared by the present embodiment
From the material phase analysis result of this figure, spectrum, may determine that this black phosphorus base composite negative pole material composition is black phosphorus, oxygen
Change germanium and graphite, without other oxide impurities.
Fig. 2 is the scanning electron microscope (SEM) of the black phosphorus base composite negative pole material of the embodiment of the present invention 1 preparation
Figure, Fig. 3 is the transmission electron microscope (TEM) of the black phosphorus base composite negative pole material of the embodiment of the present invention 1 preparation
Figure；Can observe that the germania particle of sheet is dispersed in black phosphorus material surface from Fig. 2 and Fig. 3,
This black phosphorus base composite negative pole material can be directly in order to prepare electrode.
The black phosphorus base composite negative pole material embodiment of the present invention 1 prepared is pressed with acetylene black and Kynoar
The mass ratio of 7:2:1 grinds in N-Methyl pyrrolidone (NMP) medium and makes slurry, on Copper Foil
Coating, is dried, section.With metal lithium sheet for electrode, polypropylene screen is barrier film, 1M
LiPF6/ (EC+DMC+EMC) is electrolyte, assembles 2025 model experimental cells, at the electricity of 0.1A/g
Under current density, in the voltage range of 0.01～3V, carry out charge-discharge test.Specific capacity-circulation shown in Fig. 4
Voltage shown in frequency curve and Fig. 5-than capacitance curve it can be seen that first discharge capacity be
1242mAh/g, charging capacity is 950mAh/g, and after 60 circulations, charge/discharge capacity is the most permissible
It is maintained at 860mAh/g.
Embodiment 2
The present embodiment by ball-milling method (wherein, red phosphorus: germanium oxide=0.25:1, graphite addition be red squama,
Germanium oxide and the 50% of three kinds of raw material gross masses of graphite) prepare black phosphorus base composite negative pole material, this negative pole material
In material, the mass ratio of black squama, germanium oxide and graphite is 0.25:1:1.25.
Preparation method is as follows:
(1) weighing 1 part of red phosphorus powder and 4 parts of germanium oxide powder, both mixing obtain mixture, then
Add mixture to and stainless steel jar mill carries out ball milling for the first time, obtain ball milling product for the first time；The
During ball milling, ratio of grinding media to material is 20:1 (adding 100 parts of stainless steel balls), and rotating speed is 300rpm/min,
Ball-milling Time is 20h；
(2) weigh 5 parts of graphite powders, add in the first time ball milling product that step (1) obtains, then
Carrying out second time ball milling, the product obtained is black phosphorus base composite negative pole material；The ball of ball milling for the second time
Material ratio 10:1, rotating speed is 200rpm/min, Ball-milling Time 40h.
The charge-discharge performance test of black phosphorus base composite negative pole material prepared by the present embodiment: with the present embodiment system
Standby black phosphorus base composite negative pole material is that raw material is assembled into experimental cell, assemble method with embodiment 1, from
Specific capacity shown in Fig. 6-cycle-index curve it can be seen that first discharge capacity be 1248mAh/g, fill
Capacitance is 876mAh/g, still may remain in 990mAh/g through 15 circulation volumes.
Embodiment 3
The present embodiment by ball-milling method (wherein, red phosphorus: germanium oxide=2:1, graphite addition be red squama,
Germanium oxide and the 80% of three kinds of raw material gross masses of graphite) prepare black phosphorus base composite negative pole material, this negative pole material
In material, the mass ratio of black squama, germanium oxide and graphite is 2:1:12.
Preparation method is as follows:
(1) weighing 2 parts of red phosphorus powder and 1 part of germanium oxide powder, both mixing obtain mixture, then
Add mixture to and stainless steel jar mill carries out ball milling for the first time, obtain ball milling product for the first time；The
During ball milling, ratio of grinding media to material is 20:1 (adding 60 parts of stainless steel balls), and rotating speed is 300rpm/min,
Ball-milling Time is 20h；
(2) weigh 12 parts of graphite powders, add in the first time ball milling product that step (1) obtains, so
After carry out second time ball milling, the product obtained is black phosphorus base composite negative pole material；Ball milling for the second time
Ratio of grinding media to material 10:1 (then add 90 parts of stainless steel balls, in ball grinder totally 150 parts of stainless steel balls), rotating speed
For 200rpm/min, Ball-milling Time 40h.
The charge-discharge performance test of black phosphorus base composite negative pole material prepared by the present embodiment: with the present embodiment system
Standby black phosphorus base composite negative pole material is that raw material is assembled into experimental cell, assemble method with embodiment 1, from
Specific capacity shown in Fig. 7-cycle-index curve it can be seen that first discharge capacity be 895mAh/g, fill
Capacitance is 656mAh/g, still may remain in 524mAh/g through 30 circulation volumes.
Embodiment 4
The present embodiment by ball-milling method (wherein, red phosphorus: germanium oxide=2:1, graphite addition be red squama,
Germanium oxide and the 5% of three kinds of raw material gross masses of graphite) prepare black phosphorus base composite negative pole material, this negative pole material
In material, the mass ratio of black squama, germanium oxide and graphite is 2:1:0.166.
Preparation method is as follows:
(1) weighing 12 parts of red phosphorus powder and 6 parts of germanium oxide powder, both mixing obtain mixture, so
After add mixture to stainless steel jar mill carry out for the first time ball milling, obtain ball milling product for the first time；
During ball milling, ratio of grinding media to material is 20:1 (adding 360 parts of stainless steel balls) for the first time, and rotating speed is 300rpm/min,
Ball-milling Time is 20h；
(2) weigh 1 part of graphite powder, add in the first time ball milling product that step (1) obtains, then
Carrying out second time ball milling, the product obtained is black phosphorus base composite negative pole material；The ball of ball milling for the second time
Material ratio 10:1, rotating speed is 200rpm/min, Ball-milling Time 40h.
The charge-discharge performance test of black phosphorus base composite negative pole material prepared by the present embodiment: with the present embodiment system
Standby black phosphorus base composite negative pole material is that raw material is assembled into experimental cell, assemble method with embodiment 1, from
Specific capacity shown in Fig. 8-cycle-index curve it can be seen that first discharge capacity be 1062mAh/g, fill
Capacitance is 634mAh/g, still may remain in 498mAh/g through 27 circulation volumes.
Comparative example 1
This comparative example prepares black phosphorus base composite negative pole material by ball-milling method.
Preparation method is as follows:
(1) weighing 8 parts of red phosphorus powder and 1 part of germanium oxide powder, both mixing obtain mixture, then
Add mixture to and stainless steel jar mill carries out ball milling for the first time, obtain ball milling product for the first time；The
During ball milling, ratio of grinding media to material is 20:1 (adding 180 parts of stainless steel balls), and rotating speed is 300rpm/min,
Ball-milling Time is 20h；
(2) weigh 1 part of graphite powder, add in the first time ball milling product that step (1) obtains, then
Carrying out second time ball milling, the product obtained is black phosphorus base composite negative pole material；The ball of ball milling for the second time
Material ratio 10:1 (i.e. deducting 80 parts of steel balls), rotating speed is 200rpm/min, Ball-milling Time 40h.
The charge-discharge performance test of black phosphorus base composite negative pole material prepared by the present embodiment: with the present embodiment system
Standby black phosphorus base composite negative pole material is that raw material is assembled into experimental cell, assemble method with embodiment 1, from
Specific capacity shown in Fig. 9-cycle-index curve it can be seen that first discharge capacity be 1687mAh/g, fill
Capacitance is 1435mAh/g, through 200 Capacity fadings to 150mAh/g, and through 15 times
After circulation, charge/discharge capacity rapid attenuation is to below 400mAh/g.
Comparative example 2
Red phosphorus powder, germanium oxide powder and graphite powder are prepared black phosphorus base by a ball-milling method by this comparative example
Composite negative pole material.
Preparation method is as follows:
Weighing 2 parts of red phosphorus powder, 1 part of germanium oxide powder and 3 parts of graphite powders, mixing three is mixed
Thing, then adds mixture to and carries out ball milling in stainless steel jar mill, obtain ball milling product；During ball milling
Ratio of grinding media to material is 20:1 (i.e. adding 120 parts of stainless steel balls), and rotating speed is 300rpm/min, and Ball-milling Time is
20h。
The charge-discharge performance test of black phosphorus base composite negative pole material prepared by this comparative example: with this comparative example system
Standby black phosphorus base composite negative pole material is that raw material is assembled into experimental cell, assemble method with embodiment 1, from
Specific capacity shown in Figure 10-cycle-index curve it can be seen that first discharge capacity be 1645mAh/g,
Charging capacity is 1310mAh/g, through 50 Capacity fadings to 252mAh/g.
Comparative example 3
Red phosphorus powder and germanium oxide powder are prepared black phosphorus base composite negative pole by a ball-milling method by this comparative example
Material.
Preparation method is as follows:
Weighing 2 parts of red phosphorus powder and 1 part of germanium oxide powder, both mixing obtain mixture, then will be mixed
Compound joins and carries out ball milling in stainless steel jar mill, obtains black phosphorus base composite negative pole material；Ball for the first time
During mill, ratio of grinding media to material is 20:1 (adding 60 parts of stainless steel balls), and rotating speed is 300rpm/min, during ball milling
Between be 20h.
The charge-discharge performance test of black phosphorus base composite negative pole material prepared by this comparative example: with this comparative example system
Standby black phosphorus base composite negative pole material is that raw material is assembled into experimental cell, assemble method with embodiment 1, from
Specific capacity shown in Figure 11-cycle-index curve it can be seen that first discharge capacity be 1404mAh/g,
Charging capacity is 1195mAh/g, through 100 Capacity fadings to 179mAh/g.
Claims (7)
1. a black phosphorus base composite negative pole material, it is characterised in that described negative material is by black phosphorus, oxidation
Germanium and graphite are composited, and the described germania particle of sheet is dispersed in described black phosphorus material surface,
Described graphite coat is in the surface of germanium oxide/black phosphorus；Wherein, the mass ratio of described black squama and germanium oxide is
0.25-2:1；Described in described negative material, the mass percent of graphite is 5%-80%.
2. the preparation method of black phosphorus base composite negative pole material described in a claim 1, it is characterised in that
Comprise the following steps:
Step one, weighs the red phosphorus of ormal weight, germanium oxide, after mixing, carries out ball milling for the first time, obtains
First ball milling product；
Step 2, adds a certain amount of graphite in described first ball milling product, after being sufficiently mixed, carries out
Ball milling for the second time, obtains described black phosphorus base composite negative pole material.
Preparation method the most according to claim 2, it is characterised in that red phosphorus described in step one and
The mass ratio of described germanium oxide is 0.25-2:1.
Preparation method the most according to claim 2, it is characterised in that graphite described in step 2
Addition is red phosphorus, germanium oxide and the 5-80wt% of three kinds of raw material gross masses of graphite.
Preparation method the most according to claim 2, it is characterised in that described first time ball milling time
Between be 8-20h, rotating speed is 200-500rpm/min, and ratio of grinding media to material is 10-30:1.
Preparation method the most according to claim 2, it is characterised in that described second time ball milling time
Between be 10-40h, rotating speed is 100-250rpm/min, and ratio of grinding media to material is 10-15:1.
Preparation method the most according to claim 2, it is characterised in that described ball milling is at rustless steel
Ball grinder is carried out.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602020A (en) * | 2016-12-22 | 2017-04-26 | 安泰科技股份有限公司 | Metal phosphide negative electrode material for lithium-ion battery and preparation method of metal phosphide negative electrode material |
| CN106784615A (en) * | 2016-11-18 | 2017-05-31 | 深圳大学 | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery |
| CN107039647A (en) * | 2017-04-19 | 2017-08-11 | 安徽师范大学 | Good compounding simple-substance phosphorus of crystallinity and preparation method thereof and application |
| CN108987707A (en) * | 2018-07-18 | 2018-12-11 | 顺德职业技术学院 | A kind of lithium ion battery phosphor-copper negative electrode material and preparation method thereof |
| CN109301209A (en) * | 2018-09-27 | 2019-02-01 | 三峡大学 | A kind of preparation method of titania modified phosphorus/carbon compound cathode materials |
| CN109332708A (en) * | 2018-09-30 | 2019-02-15 | 宁波瑞丰汽车零部件有限公司 | A kind of automobile steering power cylinder fulcrum bearing |
| CN112864351A (en) * | 2021-03-12 | 2021-05-28 | 天津市捷威动力工业有限公司 | Negative electrode and lithium secondary battery comprising same |
| CN113582148A (en) * | 2021-07-28 | 2021-11-02 | 澳门大学 | Phosphate-doped metal phosphide, preparation method and application thereof, metal phosphide composite material, preparation method and application thereof |
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| CN113401897B (en) * | 2021-08-19 | 2021-11-19 | 湖南金阳烯碳新材料有限公司 | Preparation method of black phosphorus-based graphite composite lithium ion battery negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106784615A (en) * | 2016-11-18 | 2017-05-31 | 深圳大学 | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery |
| CN106784615B (en) * | 2016-11-18 | 2020-08-04 | 深圳大学 | Flexible lithium ion battery cathode, preparation method thereof and flexible lithium ion battery |
| CN106602020A (en) * | 2016-12-22 | 2017-04-26 | 安泰科技股份有限公司 | Metal phosphide negative electrode material for lithium-ion battery and preparation method of metal phosphide negative electrode material |
| CN107039647A (en) * | 2017-04-19 | 2017-08-11 | 安徽师范大学 | Good compounding simple-substance phosphorus of crystallinity and preparation method thereof and application |
| CN107039647B (en) * | 2017-04-19 | 2019-06-25 | 安徽师范大学 | Good compounding simple-substance phosphorus of crystallinity and preparation method thereof and application |
| CN108987707A (en) * | 2018-07-18 | 2018-12-11 | 顺德职业技术学院 | A kind of lithium ion battery phosphor-copper negative electrode material and preparation method thereof |
| CN108987707B (en) * | 2018-07-18 | 2021-10-26 | 顺德职业技术学院 | Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof |
| CN109301209A (en) * | 2018-09-27 | 2019-02-01 | 三峡大学 | A kind of preparation method of titania modified phosphorus/carbon compound cathode materials |
| CN109332708A (en) * | 2018-09-30 | 2019-02-15 | 宁波瑞丰汽车零部件有限公司 | A kind of automobile steering power cylinder fulcrum bearing |
| CN112864351A (en) * | 2021-03-12 | 2021-05-28 | 天津市捷威动力工业有限公司 | Negative electrode and lithium secondary battery comprising same |
| CN113582148A (en) * | 2021-07-28 | 2021-11-02 | 澳门大学 | Phosphate-doped metal phosphide, preparation method and application thereof, metal phosphide composite material, preparation method and application thereof |
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