CN106602020A - Metal phosphide negative electrode material for lithium-ion battery and preparation method of metal phosphide negative electrode material - Google Patents
Metal phosphide negative electrode material for lithium-ion battery and preparation method of metal phosphide negative electrode material Download PDFInfo
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- CN106602020A CN106602020A CN201611199496.5A CN201611199496A CN106602020A CN 106602020 A CN106602020 A CN 106602020A CN 201611199496 A CN201611199496 A CN 201611199496A CN 106602020 A CN106602020 A CN 106602020A
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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
- H01M4/58—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
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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 metal phosphide negative electrode material for a lithium-ion battery and a preparation method, and belongs to the field of electrochemical power source materials. The negative electrode material is formed by compounding metal phosphide and graphite, wherein the graphite coats the surface of the metal phosphide, wherein the mass percent of the graphite in the negative electrode material is 5%-80%. The preparation method provided by the invention comprises the following steps of weighing a specified amount of red phosphorus and metal powder for mixing and then carrying out first ball-milling to obtain a first ball-milling product; and adding a certain amount of graphite, fully mixing and then carrying out second ball-milling to finally obtain the metal phosphide negative electrode material. The negative electrode material provided by the invention is high in specific capacity, good in cycle performance, stable in structure and low in cost and the initial lithium deintercalation capacity is over 1,000mAh.g<-1>; the preparation method is simple in technical process, short in elapsed time and high in yield; the raw material cost is low; and the structure stability of the composite material is improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery metal phosphide negative material and preparation method, belong to electrochemical power source
Material Field.
Background technology
Lithium ion battery is the novel energy storage cell for growing up 21 century.Due to the features such as its high energy low consumption, 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 to battery
Metric density requires more and more higher, and the especially release of environmental-protecting type electric automobile has been greatly facilitated Large Copacity, high power electrokinetic cell
Development.At present the widely used graphite of commercial li-ion battery and modified graphite are used as negative material, but its theoretical specific capacity is
372mAh/g, actual specific capacity is only 300～330mAh/g, while graphite electrode is present, irreversible loss first is big, and multiplying power is put
The problems such as poor electrical performance, therefore actual demand far can not be met, especially requirement of the electric automobile to cell high-capacity.In addition
This battery is in use easily in graphite surface generation SEI (Solid Electrolyte Interface, solid electrolyte
Interface), so as to cause potential safety hazard.The research of cathode material for high capacity lithium ion battery becomes raising battery performance with application
Key.
Metal phosphide has high capacity first, and polarization loss is less, therefore is current lithium ion battery negative material
The focus of material research field.Metal phosphide is as lithium ion battery negative material, reaction mechanism：MxPy+3yLi++3ye-→
xM+yLi3P, the plateau potential of embedding lithium/de- lithium is 1V or so, far above the electro-deposition current potential of lithium metal, is conducive to dendrite inhibition
The formation of lithium.But it is carried out with charge and discharge cycles, larger volumetric expansion occurs causes material efflorescence, and capacity attenuation is fast
Speed.Therefore the cyclical stability for improving phosphide material is current urgent problem.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of lithium ion battery metal phosphide negative pole
Material and preparation method.The specific capacity of the metal phosphide negative material that the present invention is provided is high, cyclical stability is good, while also
With cost of material is low, composite structure good stability the characteristics of；The preparation method that the present invention is provided has technical process letter
It is single, time-consuming less, the characteristics of yield is high.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of lithium ion battery metal phosphide negative material, is composited by metal phosphide and graphite, the stone
Ink is coated on the surface of the metal phosphide；Wherein, in the negative material, the mass percent of the graphite is 5%-
80%.
Above-mentioned lithium ion battery with metal phosphide negative material, as a kind of preferred embodiment, the metal phosphorus
The expression formula of compound is MPx, wherein, metal M is the one kind in Sn, Sb, Ge or its combination, and x is the mol ratio of P and metal M,
0.75≤x≤5。
Above-mentioned lithium ion battery with metal phosphide negative material, as a kind of preferred embodiment, the metal phosphorus
The size of compound is 1-2 μm.
Graphite prevents its volumetric expansion in cyclic process and continues to crush in metal phosphide Surface coating, so as to
Improve electrochemistry cycle performance.
A kind of lithium ion battery preparation method of metal phosphide negative material, comprises the following steps：
Step one, after weighing red phosphorus, the metal dust mixing of ormal weight, carries out first time ball milling, obtains the first ball milling product
Thing；
Step 2, a certain amount of graphite is added in the first ball milling product, after being sufficiently mixed, carries out second ball
Mill, obtains the metal phosphide negative material.
After first time ball milling, red phosphorus forms phosphide alloy product with metal dust.Twice in ball milling, first time ball milling is
Need to synthesize metal phosphide, second ball milling is then in metal phosphide material surface by graphite dispersion.Ball grinding method twice
The interracial contact and carbon coating effect of metal phosphide can effectively be strengthened.
The present invention know-why be：Realize that red phosphorus generates metal phosphide with in-situ metal by ball grinding method, improve
Electronics, ion conduction rate, while can reduce the particle size of active material in the process, reduce material and are being circulated throughout
Efflorescence degree in journey；Cushioning frame is formed using the cladding of carbon, conductive channel between particle is improved, inhibitory activity material is in electrification
Volumetric expansion during, improves material circulation performance.
In above-mentioned preparation method, as a kind of preferred embodiment, red phosphorus described in step one and the metal dust
Mol ratio be 0.75-5:1 (such as 0.8:1、1:1、1.5:1、2:1、3:1、3.5:1、4:1、4.5:1、4.8:1)；Preferably,
The metal dust is one or more of Sn, Sb, Ge.
In above-mentioned preparation method, as a kind of preferred embodiment, the addition of graphite described in step 2 be red phosphorus,
Three kinds of raw material gross masses of metal dust and graphite 5-80wt% (such as 6wt%, 7wt%, 8wt%, 10wt%, 20wt%,
30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 75wt%, 78wt%).
In above-mentioned preparation method, as a kind of preferred embodiment, the red phosphorus added in step one and metal powder
The particle diameter of the graphite added in end and step 2 is 15-35 μm of (such as 16 μm, 18 μm, 20 μm, 24 μm, 28 μm, 30 μ
M, 32 μm, 34 μm), preferably 20-30 μm.
In above-mentioned preparation method, used as a kind of preferred embodiment, the time of the first time ball milling is 8-20h (ratios
Such as 9h, 11h, 13h, 15h, 17h, 19h), rotating 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 is 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 bar
Part realizes that red phosphorus is metal phosphide with metal dust in-situ preparation, and reduces phosphide size.
In above-mentioned preparation method, used as a kind of preferred embodiment, the time of second ball milling is 10-40h (ratios
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).Second ball milling carries out the doping of C by ball milling conditions such as low speed, forms the cushioning frame based on C, suppresses phosphide
The volumetric expansion of material, forms intergranular conductive channel, improves its cycle performance.
In above-mentioned preparation method, used as a kind of preferred embodiment, the ball milling is in stainless steel jar mill, lazy
Carry out under property atmosphere (such as argon gas).
Compared with prior art, the invention has the beneficial effects as follows：
1) the metal phosphide negative material specific capacity that the present invention is provided is high, and it is 1000mAhg that lithium capacity is taken off first-1With
On, good cycle, Stability Analysis of Structures, low cost；
2) present invention is provided metal phosphide cathode material preparation method technical process is simple, it is time-consuming less, yield it is high；Also
With cost of material it is low, improve composite structure stability the characteristics of.
Description of the drawings
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 embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are these
Some bright embodiments, for those of ordinary skill in the art, without having to pay creative labor, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of phosphatization germanium negative material prepared by the embodiment of the present invention 1；
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of phosphatization tin negative pole material prepared by the embodiment of the present invention 3；
Fig. 3 is X-ray diffraction (XRD) collection of illustrative plates of phosphatization antimony negative material prepared by the embodiment of the present invention 4；
Fig. 4 is ESEM (SEM) figure of phosphatization germanium negative material prepared by the embodiment of the present invention 1；
Fig. 5 is transmission electron microscope (TEM) figure of phosphatization germanium negative material prepared by the embodiment of the present invention 1；
Fig. 6 is the experimental cell that assembles as raw material of phosphatization germanium negative material prepared with the embodiment of the present invention 1 in 0.1A/g
Current density under specific capacity-cycle-index curve；
Fig. 7 is the experimental cell that assembles as raw material of phosphatization germanium negative material prepared with the embodiment of the present invention 1 in 0.1A/g
Current density under voltage-specific capacity curve；
Fig. 8 is that the experimental cell that the phosphatization germanium negative material prepared with the embodiment of the present invention 1 is assembled as raw material is permanent in difference
Curve of double curvature under stream charging or discharging current density.
Specific embodiment
Hereinafter accompanying drawing will be combined by embodiment to be described in further detail present disclosure, the protection of the present invention
Scope is including but not limited to following each embodiments.
Unreceipted specific experiment step or condition person in embodiment, according to the normal experiment described by document in the art
The operation of step or condition can be carried out.Various reagents and raw material used in embodiment are commercially available prod, the raw material for weighing
Number is mass parts.
The GeP of embodiment 13The preparation of/C composite negative pole materials
By ball-milling method, (wherein, the mol ratio of red phosphorus and germanium metal is 3 to the present embodiment:1, graphite addition is red phosphorus, gold
50%) belong to three kinds of raw material gross masses of germanium and graphite prepares metal phosphide negative material, phosphatization germanium and stone in the negative material
The mass ratio of ink is 1:1.
Preparation method is as follows：
(1) 1.28 parts of red phosphorus powder and 1 part of germanium metal powder are weighed, the two obtains mixture for mixing, then by mixture
Being added in stainless steel jar mill carries out first time ball milling, obtains first time ball milling product (phosphatization germanium)；Ball during first time ball milling
Material is than being 20:1 (adding 45.6 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h；
(2) 2.28 parts of graphite powders are weighed, in adding the first time ball milling product that step (1) is obtained, second is then carried out
Ball milling, the product for being obtained is phosphide composite negative pole material；The ratio of grinding media to material 10 of second ball milling:1, rotating speed is 200rpm/
Min, Ball-milling Time 40h.
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the phosphatization germanium negative material prepared by the present embodiment, from the thing phase of the figure
Analysis result may determine that the composite negative pole material composition is phosphatization germanium and graphite, without other impurities.
Fig. 4 is ESEM (SEM) figure of phosphatization germanium negative material prepared by the embodiment of the present invention 1, and Fig. 5 is real for the present invention
Apply transmission electron microscope (TEM) figure of the phosphatization germanium negative material of the preparation of example 1；The chi of phosphatization germanium particle can be observed from Fig. 4 and Fig. 5
It is very little for 1-2 μm, the coated with uniform material with carbon element of phosphatization germanium particle, the phosphatization germanium composite negative pole material can be directly to prepare
Electrode.
The GeP of embodiment 25The preparation of/C composite negative pole materials
The present embodiment passes through ball-milling method (wherein, red phosphorus：The mol ratio of germanium metal is 5:1, graphite addition is red phosphorus, gold
50%) category germanium and graphite three kinds of raw material gross masses prepare phosphide cathode material, phosphatization germanium and graphite in the negative material
Mass ratio is 1:1.
Preparation method is as follows：
(1) 2.13 parts of red phosphorus powder and 1 part of germanium metal powder are weighed, the two obtains mixture for mixing, then by mixture
Being added in stainless steel jar mill carries out first time ball milling, obtains first time ball milling product；Ratio of grinding media to material is 20 during first time ball milling:
1 (adding 62.6 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h；
(2) 3.13 parts of graphite powders are weighed, in adding the first time ball milling product that step (1) is obtained, second is then carried out
Ball milling, the product for being obtained is phosphide cathode material；The ratio of grinding media to material 10 of second ball milling:1, rotating speed is 200rpm/min,
Ball-milling Time 40h.
The Sn of embodiment 34P3The preparation of/C composite negative pole materials
The present embodiment passes through ball-milling method (wherein, red phosphorus：The mol ratio of metallic tin is 3:4, graphite addition is red phosphorus, gold
80%) category tin and graphite three kinds of raw material gross masses prepare phosphide cathode material, phosphide and graphite in the negative material
Mass ratio is 2:8.
Preparation method is as follows：
(1) 1 part of red phosphorus powder and 5.11 parts of metallic tin powder are weighed, the two obtains mixture for mixing, then by mixture
Being added in stainless steel jar mill carries out first time ball milling, obtains first time ball milling product；Ratio of grinding media to material is 20 during first time ball milling:
1 (adding 122 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h；
(2) 24.44 parts of graphite powders are weighed, in adding the first time ball milling product that step (1) is obtained, second is then carried out
Ball milling, the product for being obtained is phosphide cathode material；The ratio of grinding media to material 10 of second ball milling:1 (then adds 90 parts of stainless steels
Ball, totally 150 parts of stainless steel balls in ball grinder), rotating speed is 200rpm/min, Ball-milling Time 40h.
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the phosphatization tin negative pole material prepared by the present embodiment, from the thing phase of the figure
Analysis result may determine that the composite negative pole material composition is phosphorization tin and graphite, without other impurities.
The SbP of embodiment 43The preparation of/C composite negative pole materials
The present embodiment passes through ball-milling method (wherein, red phosphorus：The mol ratio of metallic antimony is 3:1, graphite addition is red phosphorus, gold
5%) belong to three kinds of raw material gross masses of antimony and graphite prepares phosphide cathode material, the matter of phosphide and graphite in the negative material
Amount is than being 95:5.
Preparation method is as follows：
(1) 1 part of red phosphorus powder and 1.31 parts of metallic antimony powder are weighed, the two obtains mixture for mixing, then by mixture
Being added in stainless steel jar mill carries out first time ball milling, obtains first time ball milling product；Ratio of grinding media to material is 20 during first time ball milling:
1 (adding 46.2 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h；
(2) 0.12 part of graphite powder is weighed, in adding the first time ball milling product that step (1) is obtained, second is then carried out
Ball milling, the product for being obtained is phosphide cathode material；The ratio of grinding media to material 10 of second ball milling:1, rotating speed is 200rpm/min,
Ball-milling Time 40h.
Fig. 3 is X-ray diffraction (XRD) collection of illustrative plates of the phosphatization antimony negative material prepared by the present embodiment, from the thing phase of the figure
Analysis result may determine that the composite negative pole material composition is phosphatization antimony and graphite, without other impurities.
The GeP of embodiment 55The preparation of/C composite negative pole materials
In the present embodiment, first time rotational speed of ball-mill is 200rpm/min, and Ball-milling Time is 15h；Second rotational speed of ball-mill
For 100rpm/min, Ball-milling Time 30h；Other parameters and condition are same as Example 2.
The GeP of embodiment 65The preparation of/C composite negative pole materials
In the present embodiment, first time rotational speed of ball-mill is 500rpm/min, and Ball-milling Time is 20h；Second rotational speed of ball-mill
For 250rpm/min, Ball-milling Time 20h；Other parameters and condition are same as Example 2.
The GeP of embodiment 75The preparation of/C composite negative pole materials
In the present embodiment, first time rotational speed of ball-mill is 300rpm/min, and Ball-milling Time is 8h；Second rotational speed of ball-mill be
200rpm/min, Ball-milling Time 10h；Other parameters and condition are same as Example 2.
The GeP of embodiment 85The preparation of/C composite negative pole materials
In the present embodiment, the mass ratio of phosphatization germanium and graphite is 95:5, and part of graphite powder is weighed according to this mass ratio
Number；Other parameters and condition are same as Example 2.
The GeP of embodiment 95The preparation of/C composite negative pole materials
In the present embodiment, the mass ratio of phosphatization germanium and graphite is 2:8, and part of graphite powder is weighed according to this mass ratio
Number；Other parameters and condition are same as Example 2.
The SnP of embodiment 105The preparation of/C composite negative pole materials
In the present embodiment, red phosphorus and the mol ratio of metallic tin are 5:1, the mass ratio of phosphorization tin and graphite is 1:1, and root
Accordingly mol ratio and mass ratio weigh the number of red phosphorus, metallic tin and graphite powder；Other parameters and condition are same as Example 3.
The SbP of embodiment 115The preparation of/C composite negative pole materials
In the present embodiment, red phosphorus and the mol ratio of metallic antimony are 5:1, the mass ratio of phosphatization antimony and graphite is 1:1, and root
Accordingly mol ratio and mass ratio weigh the number of red phosphorus, metallic antimony and graphite powder；Other parameters and condition are same as Example 4.
The GeP of comparative example 10.5The preparation of/C composite negative pole materials
This comparative example passes through ball-milling method (wherein, red phosphorus：The mol ratio of germanium metal is 1:2, graphite addition is red phosphorus, gold
50%) the preparation phosphatization germanium negative material of category three kinds of raw material gross masses of antimony germanium and graphite, phosphide and graphite in the negative material
Mass ratio be 1:1.
Preparation method is as follows：
(1) 1 part of red phosphorus powder and 4.69 parts of germanium metal powder are weighed, the two obtains mixture for mixing, then by mixture
Being added in stainless steel jar mill carries out first time ball milling, obtains first time ball milling product；Ratio of grinding media to material is 20 during first time ball milling:
1 (adding 113.8 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h；
(2) 5.69 parts of graphite powders are weighed, in adding the first time ball milling product that step (1) is obtained, second is then carried out
Ball milling, the product for being obtained is phosphatization germanium composite negative pole material；The ratio of grinding media to material 10 of second ball milling:1, rotating speed is 200rpm/
Min, Ball-milling Time 40h.
The GeP of comparative example 23The preparation of/C composite negative pole materials
Red phosphorus powder, germanium metal powder and graphite powder are prepared phosphatization germanium negative pole material by this comparative example by a ball-milling method
Material.
Preparation method is as follows：
1.28 parts of red phosphorus powder, 1 part of germanium metal powder and 2.28 parts of graphite powders are weighed, mixing three obtains mixture, so
After add mixture to and carry out in stainless steel jar mill ball milling, obtain ball milling product；Ratio of grinding media to material is 20 during ball milling:1 (adds
91 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h.
The GeP of comparative example 33The preparation of composite negative pole material
Red phosphorus powder and germanium metal powder are prepared phosphatization germanium negative material by this comparative example by a ball-milling method.
Preparation method is as follows：
1.28 parts of red phosphorus powder and 1 part of germanium metal powder are weighed, the two obtains mixture for mixing, then feeds the mixture into
Ball milling is carried out in stainless steel jar mill, phosphatization germanium composite negative pole material is obtained；Ratio of grinding media to material is 20 during first time ball milling:1 (i.e. plus
Enter 45.6 parts of stainless steel balls), rotating speed is 300rpm/min, and Ball-milling Time is 20h.
Experimental example
By embodiment 1～9 and comparative example 1～3 prepare phosphide cathode material sample number consecutively for A～I and J～
L, and above-mentioned sample A～L is carried out into performance test for lithium ion battery electrode material.
Method of testing is：Phosphide cathode material prepared by the embodiment of the present invention presses 7 with acetylene black and Kynoar:
2:1 mass ratio grinds in 1-METHYLPYRROLIDONE (NMP) medium and makes slurry, is coated with Copper Foil, is dried, section.With
Metal lithium sheet is that, to electrode, polypropylene screen is barrier film, 1M LiPF6/ (EC+DMC+EMC) is electrolyte, assembles 2025 model realities
Electrical verification pond, under the current density of 0.1A/g, carries out charge-discharge test in the voltage range of 0.01～3V.
The electric performance test result of sample A～L is as shown in table 1.
The specific capacity of each sample under the 0.1A/g current densities of table 1
From table 1 it follows that when charging and discharging currents are 0.1A/g, first specific capacity is up to for sample A, B, C, D
More than 1110mAh/g；And from fig. 6, it can be seen that for sample A, when current density is 0.1A/g, after 50 circulations, than
Capacity is also decayed without obvious, so as to good cycle performance is presented (see Fig. 6)；For sample A, B, C, D, when discharge and recharge electricity
Flow for 0.1A/g when, specific capacity is respectively 1286mAh/g, 1325mAh/g, 1224mAh/g, 1185mAh/g, and when through 50 times
After circulation, the specific capacity of sample A, B, C, D still reaches respectively 840mAh/g, 910mAh/g, 750mAh/g, 613mAh/g；And it is right
In sample J, K, L, when charging and discharging currents are 0.1A/g, and when after 50 circulations, the specific capacity of sample J, K, L decays
Seriously.It follows that the good cycle of the phosphide electrode material of present invention preparation, specific capacity height should in lithium ion battery
There is good application prospect with field.
Fig. 6 is the phosphide electrode material (sample A) of the preparation of the embodiment of the present invention 1 under the conditions of current density is 0.1A/g
The cyclical stability figure of the discharge and recharge of measure, it can be seen that when current density is 0.1A/g, after 50 circulations, specific capacity
Also without significantly decay, specific capacity reaches 840, and good cycle performance is presented.
Fig. 7 is phosphide electrode material (sample A) voltage-specific capacitance curve prepared by the embodiment of the present invention 1, can from figure
To find out：Under 0.01～3V scopes, first discharge capacity is 1286mAh/g, and charging capacity is 947mAh/g, and first efficiency reaches
To 73.6%.
Fig. 8 is the phosphide electrode material (sample A) of the preparation of the embodiment of the present invention 1 under different constant current charge-discharge current densitys
High rate performance.It can be seen that when current density is respectively 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g and 5A/
During g, the specific capacity of sample A is higher, and capacity is returned to 800mAh/g or so again after current density returns to 0.1A/g from 5A/g, can
See that the composite has good high rate performance.
Claims (10)
1. a kind of lithium ion battery metal phosphide negative material, it is characterised in that the negative material is by metal phosphide
It is composited with graphite, the graphite coat is in the surface of the metal phosphide；Wherein, it is described in the negative material
The mass percent of graphite is 5%-80%.
2. negative material according to claim 1, it is characterised in that the expression formula of the metal phosphide is MPx, wherein, gold
Category M is one kind in Sn, Sb, Ge or its combination, and x is the mol ratio of P and metal M, 0.75≤x≤5.
3. negative material according to claim 1 or claim 2, it is characterised in that the size of the metal phosphide is 1-2 μm.
4. a kind of lithium ion battery preparation method of metal phosphide negative material, it is characterised in that comprise the following steps：
Step one, after weighing red phosphorus, the metal dust mixing of ormal weight, carries out first time ball milling, obtains the first ball milling product；
Step 2, a certain amount of graphite is added in the first ball milling product, after being sufficiently mixed, carries out second ball milling, is obtained
To the metal phosphide negative material.
5. preparation method according to claim 4, it is characterised in that red phosphorus described in step one and the metal dust rub
You are than being 0.75-5:1；Preferably, the metal dust is one or more of Sn, Sb, Ge.
6. preparation method according to claim 4, it is characterised in that the addition of graphite described in step 2 is red phosphorus, gold
The 5-80wt% of category three kinds of raw material gross masses of powder and graphite.
7. the preparation method according to any one of claim 4-6, it is characterised in that the red phosphorus that adds in step one and
The particle diameter of the graphite added in metal dust and step 2 is 15-35 μm, preferably 20-30 μm.
8. the preparation method according to any one of claim 4-6, it is characterised in that the time of the first time ball milling is 8-
20h, rotating speed is 200-500rpm/min, and ratio of grinding media to material is 10-30:1.
9. the preparation method according to any one of claim 4-6, it is characterised in that the time of second ball milling is
10-40h, rotating speed is 100-250rpm/min, and ratio of grinding media to material is 10-15:1.
10. preparation method according to claim 4, it is characterised in that the ball milling is in stainless steel jar mill, in inertia
Carry out under atmosphere.
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| CN115676801A (en) * | 2022-11-22 | 2023-02-03 | 无锡零一未来新材料技术研究院有限公司 | Conductive agent coated positive electrode material, preparation method thereof and electrochemical energy storage device |
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