CN106025194B - A kind of black phosphorus base composite negative pole material and preparation method thereof - Google Patents
A kind of black phosphorus base composite negative pole material and preparation method thereof Download PDFInfo
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- CN106025194B CN106025194B CN201610313380.3A CN201610313380A CN106025194B CN 106025194 B CN106025194 B CN 106025194B CN 201610313380 A CN201610313380 A CN 201610313380A CN 106025194 B CN106025194 B CN 106025194B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of black phosphorus base composite negative pole materials and preparation method thereof, belong to electrochemical power source Material Field.Black phosphorus base composite negative pole material is combined by black phosphorus, germanium oxide and graphite, and the germania particle of sheet is dispersed in the black phosphorus material surface, and the graphite coat is in germanium oxide/black phosphorus surface；Wherein, the mass ratio of the black squama and germanium oxide is 0.25-2:1；The mass percent of the graphite described in the negative electrode material is 5%-80%.The black phosphorus base composite negative pole material is prepared as raw material by two step ball-milling methods using red phosphorus, germanium oxide, graphite.Black phosphorus base composite negative pole material good cycle provided by the invention, at low cost, stable structure；Preparation method technical process is simple, it is time-consuming less, yield it is high, also have the characteristics that cost of material is low, raising composite structure stability, solve the problems, such as black phosphorus based composites poor circulation.
Description
Technical field
The present invention relates to a kind of black phosphorus base composite negative pole materials and preparation method thereof, belong to electrochemical power source Material Field.
Background technique
Lithium ion battery is the novel energy storage cell to grow up 21 century.The features such as due to its high energy low consumption, lithium ion
Battery, which has begun, is widely used in the fields such as mobile phone, electric car, energy storage.With current development, to the energy of battery
Metric density requires higher and higher, the especially release of environmental-protecting type electric automobile, has been greatly facilitated large capacity, high power power battery
Development.Graphite and modified graphite is widely used as negative electrode material in commercial li-ion battery at present, but its theoretical specific capacity is
372mAh/g, actual specific capacity is only 300~330mAh/g, while graphite electrode is big in the presence of irreversible loss for the first time, and multiplying power is put
The problems such as poor electrical performance, therefore it is far from satisfying actual demand, especially requirement of the electric car to cell high-capacity.In addition
This battery is easy to generate SEI (Solid Electrolyte Interface, solid electrolyte in graphite surface in use
Interface), to cause security risk.The research and application of cathode material for high capacity lithium ion battery have become raising battery performance
Key.
The black phosphorus of rhombic form have with fold layer structure as graphite-like, therefore have and electrochemistry as graphite-phase
Embedding lithium reactivity worth.Meanwhile this structure of black phosphorus makes black phosphorus have higher stability compared with white phosphorus and red phosphorus and have
Preferably conductive and thermal conductivity, more practicability.In addition, the structure cell of black phosphorus is much larger than the structure cell of graphite, the embedding lithium reaction of formation
Interchannel is away from for 0.43nm, and greater than 0.335 4nm of graphite, this feature determines that lithium ion has in the black phosphorus of rhombic form
Therefore using black phosphorus as lithium ion battery negative material, higher large current discharging capability may be implemented in high diffusion coefficient.More
Importantly, phosphorus can generate multiple compounds by electrochemical reaction with lithium, such as LiP, Li2P、Li3P etc..When unit phosphorus is embedded in
When 3 lithiums, the specific capacity of 2595mAh/g can be formed up to, considerably beyond graphite electrode material commercialized at present.So
High capacity and high current charge-discharge ability promotes lithium ion battery negative material of the phosphorus as great potential.But use black phosphorus
Electrode makees negative electrode material, is forming lithiated product Li3There are Extremely volume variation when P, while Li3P electric conductivity itself is lower, leads
Blackening phosphorus electrode material the problems such as there are coulombic efficiency difference and low capacity retention ratios.As charge and discharge cycles carry out, biggish body
Product expansion leads to material dusting, and capacity attenuation is rapid.Therefore the cyclical stability for improving black phosphorus based composites is to be badly in need of at present
It solves the problems, such as.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of black phosphorus base composite negative pole material and its preparations
Method.The cyclical stability of black phosphorus base composite negative pole material provided by the invention is good, while also having cost of material low, compound
The good feature of material structure stability；Black phosphorus base composite negative pole material preparation method provided by the invention has technical process letter
It is single, time-consuming less, the high feature of yield.
To achieve the above object, the invention adopts the following technical scheme:
A kind of black phosphorus base composite negative pole material, is combined by black phosphorus, germanium oxide and graphite, the germanium oxide of sheet
Even particulate dispersion is in the black phosphorus material surface, and graphite coat is in germanium oxide/black phosphorus (GeO2/ P) surface；Wherein, described
The mass ratio of black squama and germanium oxide is 0.25-2:1；In the negative electrode material, the mass percent of the graphite is 5%-
80%.
GeO2Sheet may be uniformly dispersed in black phosphorus surface, prevent its volume expansion and continuation in cyclic process
It crushes；And graphite is in GeO2The surface /P cladding is graphite coat in GeO2Outer surface and P outer surface, further suppress compound
The volume expansion of material, to improve electrochemistry cycle performance.
The preparation method of above-mentioned black phosphorus base composite negative pole material, comprising the following steps:
Step 1 weighs red phosphorus, the germanium oxide of specified amount, after mixing, carries out first time ball milling, obtains the production of the first ball milling
Object；
A certain amount of graphite is added in the first ball milling product step 2, after being sufficiently mixed, carries out second of ball
Mill, obtains the black phosphorus base composite negative pole material.
After first time ball milling, red phosphorus is completely reformed into black phosphorus, forms the combination product of germanium oxide and black phosphorus.Ball milling twice
In, first time ball milling is to need for germanium oxide to be dispersed in black phosphorus surface, and second of ball milling is then by graphite dispersion in germanium oxide/black
Phosphorus composite material surface.Secondary ball milling method can effectively enhance GeO2/ P interfacial contact and carbon coating effect.
Technical principle of the invention is: by ball grinding method realize red phosphorus in-situ preparation black phosphorus, formed effective germanium oxide/
Black phosphorus compound interface improves electronics, ion conduction rate, while can reduce the particle size of active material in the process,
Reduce dusting degree of the material in cyclic process.Cushioning frame is formed using the cladding of carbon, improves conductive channel between particle,
Volume expansion of the inhibitory activity substance in electrochemical process improves material circulation performance.
In the above preparation method, red phosphorus described in step 1 and the germanium oxide as a preferred implementation manner,
Mass ratio is 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 the above preparation method, as a preferred implementation manner, the additional amount of graphite described in step 2 be red phosphorus,
Three kinds of total mass of raw materiales of germanium oxide and graphite 5-80wt% (such as 6wt%, 7wt%, 8wt%, 10wt%, 20wt%,
30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 75wt%, 78wt%).
In the above preparation method, the time of the first time ball milling is 8-20h (ratio as a preferred implementation manner,
Such as 9h, 11h, 13h, 15h, 17h, 19h), revolving speed be 200-500rpm/min (such 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 10-30:1
(such as 11:1,12:1,15:1,18:1,22:1,25:1,28:1,29:1).First time ball milling leads to excessive speeds, prolonged
Ball milling condition realizes that red phosphorus is converted into black phosphorus, reduces black phosphorus size, enhancing germanium oxide and black phosphorus interfacial contact.
In the above preparation method, the time of second of ball milling is 10-40h as a preferred implementation manner,
(such as 12h, 15h, 20h, 25h, 30h, 35h, 38h), revolving speed be 100-250rpm/min (such as 120rpm/min,
150rpm/min, 180rpm/min, 220rpm/min, 240rpm/min), ratio of grinding media to material be 10-15:1 (such as 11:1,12:1,
13:1,14:1).Second of ball milling carries out the doping of C by ball milling conditions such as low speed, forms the suppression using C as the cushioning frame of matrix
The volume expansion of oxygenerating germanium/black phosphorus composite material, forms intergranular conductive channel, improves its cycle performance.
In the above preparation method, the ball milling is carried out in stainless steel jar mill as a preferred implementation manner,.
Compared with prior art, the beneficial effects of the present invention are:
1) black phosphorus base composite negative pole material good cycle provided by the invention, at low cost, stable structure；
2) black phosphorus base composite negative pole material preparation method technical process provided by the invention it is simple, it is time-consuming less, yield it is high；Also
Have the characteristics that cost of material is low, improves composite structure stability, solves black phosphorus based composites poor circulation
Problem.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is this hair
Bright some embodiments for those of ordinary skill in the art without any creative labor, can be with
It obtains other drawings based on these drawings.
Fig. 1 is X-ray diffraction (XRD) map of black phosphorus base composite negative pole material prepared by the embodiment of the present invention 1；
Fig. 2 is scanning electron microscope (SEM) figure of black phosphorus base composite negative pole material prepared by the embodiment of the present invention 1；
Fig. 3 is transmission electron microscope (TEM) figure of black phosphorus base composite negative pole material prepared by the embodiment of the present invention 1；
Fig. 4 is to be existed using black phosphorus base composite negative pole material prepared by the embodiment of the present invention 1 as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g；
Fig. 5 is to be existed using black phosphorus base composite negative pole material prepared by the embodiment of the present invention 1 as the experimental cell that raw material assembles
Voltage-specific capacity curve under the current density of 0.1A/g；
Fig. 6 is to be existed using black phosphorus base composite negative pole material prepared by the embodiment of the present invention 2 as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g；
Fig. 7 is to be existed using black phosphorus base composite negative pole material prepared by the embodiment of the present invention 3 as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g；
Fig. 8 is to be existed using black phosphorus base composite negative pole material prepared by the embodiment of the present invention 4 as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g.
Fig. 9 is to be existed using black phosphorus base composite negative pole material prepared by comparative example 1 of the present invention as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g.
Figure 10 is to be existed using black phosphorus base composite negative pole material prepared by comparative example 2 of the present invention as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g.
Figure 11 is to be existed using black phosphorus base composite negative pole material prepared by comparative example 3 of the present invention as the experimental cell that raw material assembles
Specific capacity-cycle-index curve under the current density of 0.1A/g.
Specific embodiment
The contents of the present invention will be described in further detail by embodiment combination attached drawing below, protection of the invention
Range is including but not limited to following each embodiments.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Various reagents and raw material used in embodiment are commercial product.
Embodiment 1
By ball-milling method, (wherein, red phosphorus: germanium oxide=2:1, graphite additional amount are red squama, germanium oxide and stone to the present embodiment
The 50% of black three kinds of total mass of raw materiales) prepare black phosphorus base composite negative pole material, black squama, germanium oxide and graphite in the negative electrode material
Mass ratio be 2:1:3.
The preparation method is as follows:
(1) 2 parts of red phosphorus powder and 1 part of germanium oxide powder are weighed, both mixing obtain mixture, then feed the mixture into
First time ball milling is carried out into stainless steel jar mill, obtains first time ball milling product；When first time ball milling ratio of grinding media to material be 20:1 (
60 parts of stainless steel balls are added), revolving speed 300rpm/min, Ball-milling Time 20h；
(2) 3 parts of graphite powders are weighed, is added in the first time ball milling product that step (1) obtains, then carries out second of ball
Mill, product obtained is black phosphorus base composite negative pole material；The ratio of grinding media to material 10:1 of second of ball milling, revolving speed 200rpm/
Min, Ball-milling Time 40h.
Fig. 1 is X-ray diffraction (XRD) map of black phosphorus base composite negative pole material prepared by the present embodiment, from the figure
Material phase analysis result may determine that the black phosphorus base composite negative pole material ingredient is black phosphorus, germanium oxide and graphite, without other oxides
Impurity.
Fig. 2 is scanning electron microscope (SEM) figure of black phosphorus base composite negative pole material prepared by the embodiment of the present invention 1, and Fig. 3 is this
Transmission electron microscope (TEM) figure of black phosphorus base composite negative pole material prepared by inventive embodiments 1；Piece can be observed from Fig. 2 and Fig. 3
The germania particle of stratiform is dispersed in black phosphorus material surface, which can be directly to prepare electricity
Pole.
Black phosphorus base composite negative pole material and acetylene black and Kynoar prepared by the embodiment of the present invention 1 is by 7:2:1's
Mass ratio grinds in N-Methyl pyrrolidone (NMP) medium and slurry is made, and is coated on copper foil, dry, slice.With lithium metal
Piece is to electrode, and polypropylene screen is diaphragm, 1M LiPF6/ (EC+DMC+EMC) is electrolyte, assembles 2025 model experimental cells,
Under the current density of 0.1A/g, charge-discharge test is carried out in the voltage range of 0.01~3V.Specific capacity-circulation shown in Fig. 4
It is 1242mAh/g, charging capacity that frequency curve and voltage shown in fig. 5-specific capacitance curve, which can be seen that discharge capacity for the first time,
For 950mAh/g, charge/discharge capacity still may remain in 860mAh/g after 60 circulations.
Embodiment 2
The present embodiment by ball-milling method (wherein, red phosphorus: germanium oxide=0.25:1, graphite additional amount be red squama, germanium oxide and
The 50% of three kinds of total mass of raw materiales of graphite) prepare black phosphorus base composite negative pole material, black squama, germanium oxide and stone in the negative electrode material
The mass ratio of ink is 0.25:1:1.25.
The preparation method is as follows:
(1) 1 part of red phosphorus powder and 4 parts of germanium oxide powders are weighed, both mixing obtain mixture, then feed the mixture into
First time ball milling is carried out into stainless steel jar mill, obtains first time ball milling product；When first time ball milling ratio of grinding media to material be 20:1 (
100 parts of stainless steel balls are added), revolving speed 300rpm/min, Ball-milling Time 20h；
(2) 5 parts of graphite powders are weighed, is added in the first time ball milling product that step (1) obtains, then carries out second of ball
Mill, product obtained is black phosphorus base composite negative pole material；The ratio of grinding media to material 10:1 of second of ball milling, revolving speed 200rpm/
Min, Ball-milling Time 40h.
The charge-discharge performance of black phosphorus base composite negative pole material manufactured in the present embodiment is tested: with black phosphorus manufactured in the present embodiment
Base composite negative pole material is that raw material is assembled into experimental cell, and assemble method is with embodiment 1, from specific capacity-circulation shown in fig. 6 time
Number curve can be seen that for the first time discharge capacity be 1248mAh/g, charging capacity 876mAh/g, still by 15 circulation volumes
It so may remain in 990mAh/g.
Embodiment 3
By ball-milling method, (wherein, red phosphorus: germanium oxide=2:1, graphite additional amount are red squama, germanium oxide and stone to the present embodiment
The 80% of black three kinds of total mass of raw materiales) prepare black phosphorus base composite negative pole material, black squama, germanium oxide and graphite in the negative electrode material
Mass ratio be 2:1:12.
The preparation method is as follows:
(1) 2 parts of red phosphorus powder and 1 part of germanium oxide powder are weighed, both mixing obtain mixture, then feed the mixture into
First time ball milling is carried out into stainless steel jar mill, obtains first time ball milling product；When first time ball milling ratio of grinding media to material be 20:1 (
60 parts of stainless steel balls are added), revolving speed 300rpm/min, Ball-milling Time 20h；
(2) 12 parts of graphite powders are weighed, is added in the first time ball milling product that step (1) obtains, then carries out second of ball
Mill, product obtained is black phosphorus base composite negative pole material；Second of ball milling ratio of grinding media to material 10:1 (then add 90 parts it is stainless
Steel ball, totally 150 parts of stainless steel balls in ball grinder), revolving speed 200rpm/min, Ball-milling Time 40h.
The charge-discharge performance of black phosphorus base composite negative pole material manufactured in the present embodiment is tested: with black phosphorus manufactured in the present embodiment
Base composite negative pole material is that raw material is assembled into experimental cell, and assemble method is the same as embodiment 1, specific capacity-circulation shown in Fig. 7 time
Number curve can be seen that for the first time discharge capacity be 895mAh/g, charging capacity 656mAh/g, still by 30 circulation volumes
It may remain in 524mAh/g.
Embodiment 4
By ball-milling method, (wherein, red phosphorus: germanium oxide=2:1, graphite additional amount are red squama, germanium oxide and stone to the present embodiment
The 5% of black three kinds of total mass of raw materiales) prepare black phosphorus base composite negative pole material, black squama, germanium oxide and graphite in the negative electrode material
Mass ratio be 2:1:0.166.
The preparation method is as follows:
(1) 12 parts of red phosphorus powder and 6 parts of germanium oxide powders are weighed, both mixing obtain mixture, then add mixture
Enter into stainless steel jar mill and carry out first time ball milling, obtains first time ball milling product；Ratio of grinding media to material is 20:1 when first time ball milling
(360 parts of stainless steel balls are added), revolving speed 300rpm/min, Ball-milling Time 20h；
(2) 1 part of graphite powder is weighed, is added in the first time ball milling product that step (1) obtains, then carries out second of ball
Mill, product obtained is black phosphorus base composite negative pole material；The ratio of grinding media to material 10:1 of second of ball milling, revolving speed 200rpm/
Min, Ball-milling Time 40h.
The charge-discharge performance of black phosphorus base composite negative pole material manufactured in the present embodiment is tested: with black phosphorus manufactured in the present embodiment
Base composite negative pole material is that raw material is assembled into experimental cell, and assemble method is with embodiment 1, from specific capacity-circulation shown in Fig. 8 time
Number curve can be seen that for the first time discharge capacity be 1062mAh/g, charging capacity 634mAh/g, still by 27 circulation volumes
It so may remain in 498mAh/g.
Comparative example 1
This comparative example prepares black phosphorus base composite negative pole material by ball-milling method.
The preparation method is as follows:
(1) 8 parts of red phosphorus powder and 1 part of germanium oxide powder are weighed, both mixing obtain mixture, then feed the mixture into
First time ball milling is carried out into stainless steel jar mill, obtains first time ball milling product；When first time ball milling ratio of grinding media to material be 20:1 (
180 parts of stainless steel balls are added), revolving speed 300rpm/min, Ball-milling Time 20h；
(2) 1 part of graphite powder is weighed, is added in the first time ball milling product that step (1) obtains, then carries out second of ball
Mill, product obtained is black phosphorus base composite negative pole material；The ratio of grinding media to material 10:1 (subtracting 80 parts of steel balls) of second of ball milling,
Revolving speed is 200rpm/min, Ball-milling Time 40h.
The charge-discharge performance of black phosphorus base composite negative pole material manufactured in the present embodiment is tested: with black phosphorus manufactured in the present embodiment
Base composite negative pole material is that raw material is assembled into experimental cell, and assemble method is with embodiment 1, from specific capacity-circulation shown in Fig. 9 time
It is 1687mAh/g, charging capacity 1435mAh/g that number curve, which can be seen that discharge capacity for the first time, by 200 circulation volumes
Decay to 150mAh/g, and after 15 circulations charge/discharge capacity rapid attenuation to 400mAh/g or less.
Comparative example 2
Red phosphorus powder, germanium oxide powder and graphite powder are prepared black phosphorus base composite negative pole by a ball-milling method by this comparative example
Material.
The preparation method is as follows:
2 parts of red phosphorus powder, 1 part of germanium oxide powder and 3 parts of graphite powders are weighed, mixing three obtains mixture, then will mix
Conjunction object, which is added in stainless steel jar mill, carries out ball milling, obtains ball milling product；Ratio of grinding media to material is that 20:1 (is added 120 parts when ball milling
Stainless steel ball), revolving speed 300rpm/min, Ball-milling Time 20h.
The charge-discharge performance test of the black phosphorus base composite negative pole material of this comparative example preparation: the black phosphorus prepared with this comparative example
Base composite negative pole material is that raw material is assembled into experimental cell, and assemble method is with embodiment 1, from specific capacity-circulation shown in Fig. 10
It is 1645mAh/g, charging capacity 1310mAh/g that frequency curve, which can be seen that discharge capacity for the first time, by 50 circulation volumes
Decay to 252mAh/g.
Comparative example 3
Red phosphorus powder and germanium oxide powder are prepared black phosphorus base composite negative pole material by a ball-milling method by this comparative example.
The preparation method is as follows:
2 parts of red phosphorus powder and 1 part of germanium oxide powder are weighed, both mixing obtain mixture, then add mixture to
Ball milling is carried out in stainless steel jar mill, obtains black phosphorus base composite negative pole material；Ratio of grinding media to material is that 20:1 (is added when first time ball milling
60 parts of stainless steel balls), revolving speed 300rpm/min, Ball-milling Time 20h.
The charge-discharge performance test of the black phosphorus base composite negative pole material of this comparative example preparation: the black phosphorus prepared with this comparative example
Base composite negative pole material is that raw material is assembled into experimental cell, and assemble method is with embodiment 1, specific capacity-circulation shown in Figure 11
It is 1404mAh/g, charging capacity 1195mAh/g that frequency curve, which can be seen that discharge capacity for the first time, is held by 100 circulations
Amount decays to 179mAh/g.
Claims (5)
1. a kind of black phosphorus base composite negative pole material, which is characterized in that the negative electrode material by black phosphorus, germanium oxide and graphite it is compound and
At the germania particle of sheet is dispersed in the black phosphorus material surface, and the graphite coat is in germanium oxide/black phosphorus
Surface；Wherein, the mass ratio of the black squama and germanium oxide is 0.25-2:1；The quality of the graphite described in the negative electrode material
Percentage is 5%-80%.
2. the preparation method of black phosphorus base composite negative pole material described in a kind of claim 1, which comprises the following steps:
Step 1 weighs red phosphorus, the germanium oxide of specified amount, after mixing, carries out first time ball milling, obtains the first ball milling product；Institute
The time for stating first time ball milling is 8-20h, revolving speed 200-500rpm/min, ratio of grinding media to material 10-30:1；
A certain amount of graphite is added in the first ball milling product step 2, after being sufficiently mixed, carries out second of ball milling, obtains
To the black phosphorus base composite negative pole material；The time of second of ball milling is 10-40h, revolving speed 100-250rpm/min, ball
Material is than being 10-15:1.
3. preparation method according to claim 2, which is characterized in that the matter of red phosphorus described in step 1 and the germanium oxide
Amount is than being 0.25-2:1.
4. preparation method according to claim 2, which is characterized in that the additional amount of graphite described in step 2 be red phosphorus,
The 5-80wt% of three kinds of total mass of raw materiales of germanium oxide and graphite.
5. preparation method according to claim 2, which is characterized in that the ball milling is carried out in stainless steel jar mill.
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| CN113401897A (en) * | 2021-08-19 | 2021-09-17 | 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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| 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 |
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