CN107240693A - Phosphorous doped silicon graphite composite material and negative material and lithium ion battery containing it - Google Patents
Phosphorous doped silicon graphite composite material and negative material and lithium ion battery containing it Download PDFInfo
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- CN107240693A CN107240693A CN201710524400.6A CN201710524400A CN107240693A CN 107240693 A CN107240693 A CN 107240693A CN 201710524400 A CN201710524400 A CN 201710524400A CN 107240693 A CN107240693 A CN 107240693A
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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
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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
- H01M4/386—Silicon or alloys based on silicon
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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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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
This application discloses a kind of phosphorous doped silicon graphite composite material, N-type silicon and graphite containing phosphorus doping in the phosphorous doped silicon graphite composite material.The phosphorous doped silicon graphite composite material is that negative active core-shell material is used for lithium ion battery, can suppress the huge volumetric expansion of silicon, have the advantages that high power capacity and good cyclical stability.Include step disclosed herein as well is the preparation method of above-mentioned phosphorous doped silicon graphite composite material：First step ball milling：By silicon and phosphorus ball milling in ball grinder；Second step ball milling：By first step ball milling product and powdered graphite further ball milling in ball grinder.Disclosed herein as well is the negative material and lithium ion battery of the material prepared containing above-mentioned phosphorous doped silicon graphite composite material and/or the above method.
Description
Technical field
The application is related to phosphorous doped silicon-graphite composite material, and its is used as in lithium ion battery negative active core-shell material
Using belonging to lithium-ion battery energy field.
Background technology
With society continue to develop and environmental problem it is increasingly serious, develop new cleaning fuel such as solar energy, wind
The focus as social concerns can be waited.Wherein, lithium ion battery act as energy storage and the dual key player of release, because of tool
The features such as having discharge platform stabilization, operating voltage height, good cycle, non-environmental-pollution has become electric automobile, mobile phone, hand
Carry the core of computer, aerospace equipment and Military Electronic Equipment.Therefore new, efficient, cheap electrode material is developed
One of the hot subject of material as Study on Li-ion batteries.Negative pole is used as the important component of lithium ion battery, negative electrode active
Material has important influence to the capacity of lithium ion battery, security, cost etc..Current commercialized negative electrode of lithium ion battery
Material is mainly carbon material, but carbons negative pole has that chemical property is poor in low temperature environment, and irreversible capacity is big first
The characteristics of.The theoretical capacity of carbon material is low (372mAh/g), and can not be improved by process optimization, further as its is limited
The most basic reason of development.Accordingly, it would be desirable to develop with high-energy-density, long circulation life, cheap negative electrode of lithium ion battery material
Material.
It is compared to other negative pole alternative materials, silicon materials not only rich reserves, and possess the theoretical capacity of superelevation
(4200mAh/g) turns into the popular research object for substituting carbon material.But the low electrical conductivity of pure silicon can cause its efficiency for charge-discharge
Lowly, while silicon has diamond lattic structure, exist in charge and discharge process violent Volume Changes (>300%) it is, so huge
Volume Changes will gradually make material produce powder of detached phenomenon, and silicon materials, which depart from collector, causes capacity attenuation, influence cyclicity
Energy.
In order to solve above-mentioned two problems, scientific research personnel proposes numerous solutions.By by silicon materials nanosizing
Method can reduce or even eliminate enormousness change of the silicon materials during embedding lithium/de- lithium, but this method cost compared with
Height, is not suitable for a large amount of productions.The method of porous can also suppress the expansion of silicon volume to a certain extent, but big ratio table
Area can consume a large amount of lithium ion formation solid electrolyte interface films (SEI films).But above method can not solved fundamentally
Certainly the problem of silicon poorly conductive, the electric conductivity of raising silicon is made by doping, and it is combined with carbon, one is coated outside silicon materials
Layer carbon with good conductivity, can not only provide the transmission channel of lithium ion and electronics, carbon matrix can also be played to silicon volumetric expansion
Inhibitory action, while contact of the silicon materials directly with electrolyte can also be prevented, prevents the continuous breaking, regenerating of SEI films, realizes excellent
Different chemical property.Therefore doped silicon/carbon composite had into practical significance as lithium cell negative pole.
The content of the invention
According to the one side of the application there is provided a kind of phosphorous doped silicon-graphite composite material, N-type is formed by phosphorus doping
Silicon and graphite it is compound, the change of the electrode volume of charge and discharge process is also inhibits while electric conductivity is improved, it is therefore prevented that silicon
Material is directly contacted with electrolyte, stabilizes the structure of material.Phosphorous doped silicon-the graphite composite material is used as negative electrode active
Material is used for lithium ion battery, has the advantages that height ratio capacity and excellent cycle performance.
N-type silicon and graphite containing phosphorus doping in the phosphorous doped silicon-graphite composite material.
In the application, statement " phosphorous doped silicon-graphite composite material " refers to the material that phosphorous doped silicon is compounded to form with graphite.
Preferably, weight/mass percentage composition of the P elements in the phosphorous doped silicon-graphite composite material be 0.15% to
1.5%.
It is further preferred that weight/mass percentage composition of the P elements in the phosphorous doped silicon-graphite composite material is
0.15% to 1.05%.
Preferably, weight/mass percentage composition of the graphite in the phosphorous doped silicon-graphite composite material is 30% to 70%.
As a preferred embodiment, particle diameter is between particle size range I in the phosphorous doped silicon-graphite composite material
The mass ratio that particle accounts for the whole particles of the phosphorous doped silicon-graphite composite material is not less than 50%.
As a preferred embodiment, particle diameter is between particle size range I in the phosphorous doped silicon-graphite composite material
The mass ratio that particle accounts for the whole particles of the phosphorous doped silicon-graphite composite material is not less than 70%.
As a preferred embodiment, particle diameter is between particle size range I in the phosphorous doped silicon-graphite composite material
The mass ratio that particle accounts for the whole particles of the phosphorous doped silicon-graphite composite material is not less than 80%.
As a preferred embodiment, particle diameter is between particle size range I in the phosphorous doped silicon-graphite composite material
The mass ratio that particle accounts for the whole particles of the phosphorous doped silicon-graphite composite material is not less than 90%.
As a preferred embodiment, particle diameter is between particle size range I in the phosphorous doped silicon-graphite composite material
The mass ratio that particle accounts for the whole particles of the phosphorous doped silicon-graphite composite material is not less than 95%.
As a preferred embodiment, particle diameter is between particle size range I in the phosphorous doped silicon-graphite composite material
The mass ratio that particle accounts for the whole particles of the phosphorous doped silicon-graphite composite material is not less than 99%.
The particle size range upper limit of the particle size range I be selected from 2 μm, 1.8 μm, 1.5 μm, 1.2 μm, 1 μm, 0.8 μm, 0.5 μm,
0.3μm、0.2μm、0.15μm、0.1μm；Lower limit is selected from 0.5 μm, 0.3 μm, 0.2 μm, 0.15 μm, 0.1 μm, 0.08 μm, 0.05 μ
m、0.02μm、0.01μm。
As a preferred embodiment, in the phosphorous doped silicon-graphite composite material particle diameter 0.1 μm~0.5 μm it
Between particle account for the mass ratioes of the whole particles of the phosphorous doped silicon-graphite composite material and be not less than 90%.
According to the another aspect of the application, there is provided a kind of preparation of above-mentioned at least one phosphorous doped silicon-graphite composite material
Method, the preparation method by by secondary preparation doped and compounded, preparing phosphorus doping N-type silicon first, then by phosphorus doping N-type silicon and stone
Ink is compound, the phosphorous doped silicon-graphite composite material of formation, and charge and discharge process is also inhibits while electric conductivity is improved
The change of electrode volume, it is therefore prevented that silicon materials are directly contacted with electrolyte, stabilize the structure of material.The phosphorous doped silicon-
Graphite composite material is used for lithium ion battery as negative active core-shell material, excellent with height ratio capacity and excellent cycle performance etc.
Point.
The preparation method, comprises the following steps：
(1) the mixture I containing silicon and phosphorus is subjected to ball milling under protective gas atmosphere, obtains presoma；
(2) presoma and the mixtures II of powdered graphite that will be obtained containing step (1) are carried out under protective gas atmosphere
Ball milling, obtains the phosphorous doped silicon-graphite composite material.
Preferably, weight/mass percentage composition of the silicon in mixture I is 98.5%~99.5% in the step (1).
Preferably, the silicon in the step (1) is crystalline silicon powder.
Preferably, at least model of the particle diameter of the particle of 90% weight/mass percentage composition at 1 μm~3 μm in the crystalline silicon powder
In enclosing.
Preferably, the purity of the crystalline silicon powder crystalline silicon powder is not less than 99.9%.
Preferably, the phosphorus in the step (1) is red phosphorus powder.
Preferably, the purity of the red phosphorus powder is not less than 98.5%.
Preferably, the N-type silicon that the presoma obtained in the step (1) contains phosphorus doping.
Preferably, the particle diameter of at least particle of 90% weight/mass percentage composition exists in the presoma obtained in the step (1)
Between 0.5 μm~2 μm.
Preferably, weight/mass percentage composition of the powdered graphite in mixtures II is 30%~70% in the step (2).
Preferably, in the step (2) granularity of graphite composite powder for can be by the graphite composite powders of 8000 mesh sieves.
Preferably, the purity of graphite composite powder is not less than 99.95% in the step (2).
Preferably, rotational speed of ball-mill is 300rpm~400rpm in the step (1).
Preferably, Ball-milling Time is 4h~8h in the step (1).
Preferably, rotational speed of ball-mill is 400rpm~800rpm in the step (2).
Preferably, Ball-milling Time is 4h~12h in the step (2).
Preferably, protective gas described in the step (1) and step (2) be purity be not less than 99.999% argon gas,
At least one of helium, neon, nitrogen.
Preferably, the ratio of grinding media to material of the step (1) and step (2) described ball milling is 10:1~30:1.
According to the another aspect of the application there is provided a kind of negative material, the negative material is while electric conductivity is improved
Inhibit the change of the electrode volume of charge and discharge process, it is therefore prevented that silicon materials are directly contacted with electrolyte, stabilize material
Structure.The negative material is used for lithium ion battery, has the advantages that height ratio capacity and excellent cycle performance.
Contain at least one of above-mentioned phosphorous doped silicon-graphite composite material and/or the above method in the negative material
At least one of phosphorous doped silicon-graphite composite material prepared.
According to the another aspect of the application there is provided a kind of lithium ion battery, the lithium ion battery improves the conduction of negative pole
Property while also inhibits charge and discharge process electrode volume change, it is therefore prevented that silicon materials and electrolyte are directly contacted, surely
The structure of material is determined.The lithium ion battery, has the advantages that height ratio capacity and excellent cycle performance.
The lithium ion battery, including positive plate, negative plate, barrier film and electrolyte, the negative plate, which contains above-mentioned phosphorus, to be mixed
In phosphorous doped silicon-graphite composite material that at least one of miscellaneous silicon-graphite composite material, the above method are prepared at least
At least one of a kind of and/or above-mentioned negative material.
The beneficial effect of the application includes but is not limited to：
(1) original material used herein is the material for commercially producing maturation, abundant raw material and cheap.
(2) ball-milling method method used herein is easy to operate, efficiency high, technical difficulty are low, can be used to mass produce.
(3) negative active core-shell material that the application is provided, for environmental nonpollution, and with capacity height, cyclical stability
Good advantage.
Brief description of the drawings
Fig. 1 is the x-ray photoelectron spectroscopy figure of phosphorous doped silicon
Fig. 2 is silicon, sample 1#~sample 3#X-ray diffraction pattern.
Fig. 3 is the stereoscan photograph of Si powder.
Fig. 4 is sample 2#Stereoscan photograph.
Fig. 5 is battery C2#Charging and discharging curve.
Fig. 6 is battery C2#Cycle performance curve.
Embodiment
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
D8Advance type X-ray diffractometer of the X-ray powder diffraction material phase analysis (XRD) of sample in Brooker company
It is upper to carry out, Cu targets, K α radiation source.
The stereoscan photograph of sample is shot using the S-4800 types SEM of Hitachi, Ltd.
The electric property of battery is determined on the LAND battery test systems of Lan Bo test equipments Co., Ltd of Wuhan City.
Embodiment 1
Sample 1#Preparation：
It is 99.9% by purity, particle size is 1~3 μm of crystalline silicon powder, purity exists for 98.5% red phosphorus powder
Argon gas protection is lower to carry out first step ball milling；The crystalline silicon powder quality accounts for the 99% of powder gross mass, and drum's speed of rotation is
350rpm, Ball-milling Time is 6h, and the mass ratio of stainless steel ball-milling pearl and powder is 20:1, obtain phosphorous doped silicon powder.
It is 99.95% by phosphorous doped silicon powder obtained above and purity, size is the powdered graphite of 8000 mesh in argon gas
Protection is lower to carry out second step ball milling.The powdered graphite quality accounts for the 70% of powder gross mass, and drum's speed of rotation is 400rpm, ball
Consume time as 12h, the mass ratio of stainless steel ball-milling pearl and powder is 20:1, phosphorous doped silicon-graphite composite material is obtained, sample is designated as
Product 1#。
Battery C1#Preparation：
By obtained 1#Sample and conductive agent (Super P), binding agent (CMC) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N1#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N1#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C1#。
By battery C1#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 911.9mAh/g, and capacity is after circulation 200 is enclosed
518.3mAh/g。
Embodiment 2
Sample 2#Preparation：
It is 99.9% by purity, particle size is 1~3 μm of crystalline silicon powder, purity exists for 98.5% red phosphorus powder
Argon gas protection is lower to carry out first step ball milling；The crystalline silicon powder quality accounts for the 99% of powder gross mass, and drum's speed of rotation is
350rpm, Ball-milling Time is 6h, and the mass ratio of stainless steel ball-milling pearl and powder is 20:1, obtain phosphorous doped silicon powder.
It is 99.95% by phosphorous doped silicon powder obtained above and purity, size is the powdered graphite of 8000 mesh in argon gas
Protection is lower to carry out second step ball milling.The powdered graphite quality accounts for the 50% of powder gross mass, and drum's speed of rotation is 400rpm, ball
Consume time as 12h, the mass ratio of stainless steel ball-milling pearl and powder is 20:1, phosphorous doped silicon-graphite composite material is obtained, sample is designated as
Product 2#。
Battery C2#Preparation：
By obtained 2#Sample and conductive agent (Super P), binding agent (CMC) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N2#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N2#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C2#。
By battery C2#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 1427.1mAh/g, and capacity is after circulation 200 is enclosed
878.5mAh/g。
Embodiment 3
Sample 3#Preparation：
It is 99.9% by purity, particle size is 1~3 μm of crystalline silicon powder, purity exists for 98.5% red phosphorus powder
Argon gas protection is lower to carry out first step ball milling；The crystalline silicon powder quality accounts for the 99% of powder gross mass, drum's speed of rotation is
350rpm, Ball-milling Time is 6h, and the mass ratio of stainless steel ball-milling pearl and powder is 20:1, obtain phosphorous doped silicon powder.
It is 99.95% by phosphorous doped silicon powder obtained above and purity, size is the powdered graphite of 8000 mesh in argon gas
Protection is lower to carry out second step ball milling.The powdered graphite quality accounts for the 30% of powder gross mass, and drum's speed of rotation is 400rpm, ball
Consume time as 12h, the mass ratio of stainless steel ball-milling pearl and powder is 20:1, phosphorous doped silicon-graphite composite material is obtained, sample is designated as
Product 3#。
Battery C3#Preparation：
By obtained 3#Sample and conductive agent (Super P), binding agent (CMC) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N3#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N3#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C3#。
By battery C3#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 2320.7mAh/g, and capacity is after circulation 200 is enclosed
723.8mAh/g。
Embodiment 4
The specimen in use of embodiment 4 is 1#。
Battery C4#Preparation：
By obtained 1#Sample and conductive agent (Super P), binding agent (PVDF) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N4#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N4#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C4#。
By battery C4#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 994.8mAh/g, and capacity is after circulation 200 is enclosed
594.6mAh/g。
Embodiment 5
The specimen in use of embodiment 5 is 2#。
Battery C5#Preparation：
By obtained 2#Sample and conductive agent (Super P), binding agent (PVDF) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N5#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N5#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C5#。
By battery C5#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 1532.4mAh/g, and capacity is after circulation 200 is enclosed
886.2mAh/g。
Embodiment 6
The specimen in use of embodiment 6 is 3#。
Battery C6#Preparation：
By obtained 3#Sample and conductive agent (Super P), binding agent (PVDF) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N6#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N6#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C6#。
By battery C6#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 1879.7mAh/g, and capacity is after circulation 200 is enclosed
725.8mAh/g。
Embodiment 7
The preparation method of specimen in use is same as Example 1, and simply crystalline silicon powder quality accounts for powder in first step ball milling
The 99.5% of gross mass, drum's speed of rotation is 300rpm, and Ball-milling Time is 8h, and the mass ratio of stainless steel ball-milling pearl and powder is
10:1.Obtained presoma has peak through x-ray photoelectron spectroscopy map analysis in 100EV or so, shows to contain N-type in presoma
Silicon.Presoma accounts for the 90% of presoma gross mass through particle size distribution analysis, particle of the particle diameter between 0.5 μm~2 μm.
Powdered graphite quality described in second step ball milling accounts for the 70% of powder gross mass, and drum's speed of rotation is 600rpm, ball
Consume time as 8h, the mass ratio of stainless steel ball-milling pearl and powder is 10:1, finally obtained phosphorous doped silicon-graphite composite wood
Material, is designated as sample 7#。
Battery C7#Preparation：
By obtained sample 7#With conductive agent (Super P), binding agent (PVDF) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N7#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N4#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C7#。
By battery C7#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 994.8mAh/g, and capacity is after circulation 200 is enclosed
594.6mAh/g。
Embodiment 8
The preparation method of specimen in use is same as Example 3, and simply crystalline silicon powder quality accounts for powder in first step ball milling
The 98.5% of gross mass, drum's speed of rotation is 400rpm, and Ball-milling Time is 4h, and the mass ratio of stainless steel ball-milling pearl and powder is
30:1.The presoma arrived has peak through x-ray photoelectron spectroscopy map analysis in 100EV or so, shows to contain N-type in presoma
Silicon.Presoma accounts for the 95% of presoma gross mass through particle size distribution analysis, particle of the particle diameter between 0.5 μm~2 μm.
Powdered graphite quality described in second step ball milling accounts for the 30% of powder gross mass, and drum's speed of rotation is 800rpm, ball
Consume time as 4h, the mass ratio of stainless steel ball-milling pearl and powder is 30:1, finally obtained phosphorous doped silicon-graphite composite wood
Material, is designated as sample 8#。
Battery C8#Preparation：
By obtained sample 8#With conductive agent (Super P), binding agent (PVDF) in mass ratio 7:2:1 ratio mixing is applied
It is overlying on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece N8#.In the glove box full of argon gas
Assembled battery in (water, oxygen content are less than 1ppm)：N5#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/poly- third
Alkene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid diformazan
Ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as battery C8#。
By battery C8#Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, discharge and recharge cut-off
Voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 2456.7mAh/g, and capacity is after circulation 200 is enclosed
732.6mAh/g。
Embodiment 9
The specimen in use of embodiment 9 does not add P and first step ball milling, directly carries out ball milling by silicon and graphite, remaining with
Embodiment 4 is identical, and the sample of acquisition is designated as sample D1#。
Battery DC1#Preparation：
By obtained sample D1#With conductive agent (Super P), binding agent (PVDF) in mass ratio 7:2:1 ratio mixing
It is coated on copper foil, pole piece (diameter is made in 100 DEG C of vacuum drying 12h：14mm) it is designated as pole piece DN1#.In the gloves full of argon gas
Assembled battery in case (water, oxygen content are less than 1ppm)：DN1#For working electrode, lithium metal is to electrode；Polypropylene, polyethylene/
Polypropylene sandwich diaphragm (being abbreviated as PP/PE/PP, Celgard 2400) is barrier film；In electrolyte, organic solvent is by carbonic acid
Dimethyl ester (being abbreviated as DMC), fluorinated ethylene carbonate (being abbreviated as FEC) and methyl ethyl carbonate (being abbreviated as EMC) are according to volume ratio
For FEC:DMC:EMC=1:1:1 ratio is mixed to get, LiPF6Concentration is 1mol/L；Gained battery is designated as batteryDC1# 。
By batteryDC1# Charge-discharge test is carried out, test condition is：Charging and discharging currents density is 200mA/g, and discharge and recharge is cut
Only voltage is 0.01~2V (vs.Li+/Li).Its initial charge capacity is 1562.8mAh/g, and capacity is after circulation 200 is enclosed
189.5mAh/g。
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, but and be not used to limit the application, any those skilled in the art are not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (10)
1. a kind of phosphorous doped silicon-graphite composite material, it is characterised in that contain phosphorus in the phosphorous doped silicon-graphite composite material
The N-type silicon and graphite of doping.
2. phosphorous doped silicon-graphite composite material according to claim 1, it is characterised in that P elements are in the phosphorus doping
Weight/mass percentage composition in silicon-graphite composite material is 0.15% to 1.5%；
Weight/mass percentage composition of the graphite in the phosphorous doped silicon-graphite composite material is 30% to 70%.
3. phosphorous doped silicon-graphite composite material according to claim 1, it is characterised in that the phosphorous doped silicon-graphite is multiple
Particle of the particle diameter between 0.1 μm~0.5 μm accounts for the quality of the whole particles of the phosphorous doped silicon-graphite composite material in condensation material
Than being not less than 90%.
4. the preparation method of any one of claims 1 to 3 phosphorous doped silicon-graphite composite material, it is characterised in that including such as
Lower step：
(1) the mixture I containing silicon and phosphorus is subjected to ball milling under protective gas atmosphere, obtains presoma；
(2) mixtures II of the presoma obtained containing step (1) and powdered graphite is subjected to ball milling under protective gas atmosphere,
Obtain the phosphorous doped silicon-graphite composite material.
5. preparation method according to claim 4, it is characterised in that quality of the silicon in mixture I in the step (1)
Percentage composition is 98.5%~99.5%；
Silicon in the step (1) is crystalline silicon powder；At least particle of 90% weight/mass percentage composition in the crystalline silicon powder
Particle diameter in the range of 1 μm~3 μm；The purity of the crystalline silicon powder crystalline silicon powder is not less than 99.9%；
Phosphorus in the step (1) is red phosphorus powder；The purity of the red phosphorus powder is not less than 98.5%.
6. preparation method according to claim 4, it is characterised in that the presoma obtained in the step (1) contains phosphorus
The N-type silicon of doping；
In the presoma obtained in the step (1) at least the particle diameter of the particle of 90% weight/mass percentage composition 0.5 μm~2 μm it
Between.
7. preparation method according to claim 4, it is characterised in that powdered graphite is in mixtures II in the step (2)
In weight/mass percentage composition be 30%~70%；
The granularity of graphite composite powder is can be by the graphite composite powder of 8000 mesh sieves in the step (2)；
The purity of graphite composite powder is not less than 99.95% in the step (2).
8. preparation method according to claim 4, it is characterised in that in the step (1) rotational speed of ball-mill be 300rpm~
400rpm, Ball-milling Time is 4h~8h；
Rotational speed of ball-mill is 400rpm~800rpm in the step (2), and Ball-milling Time is 4h~12h；
Protective gas described in the step (1) and step (2) be purity be not less than 99.999% argon gas, helium, neon, nitrogen
At least one of gas；
The ratio of grinding media to material of the step (1) and step (2) described ball milling is 10:1~30:1.
9. a kind of negative material, it is characterised in that contain any one of claims 1 to 3 phosphorous doped silicon-graphite composite material
At least one of and/or phosphorous doped silicon-graphite composite material for being prepared according to any one of claim 4 to 8 method in
At least one.
10. a kind of lithium ion battery, including positive plate, negative plate, barrier film and electrolyte, it is characterised in that the negative plate contains
Have the right at least one of described phosphorous doped silicon-graphite composite material of any one of requirement 1 to 3, according to claim 4 to 8 times
Negative material described at least one of phosphorous doped silicon-graphite composite material that one method is prepared and/or claim 9
At least one of.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110380017A (en) * | 2019-06-12 | 2019-10-25 | 星恒电源股份有限公司 | A kind of high capacity high rate lithium ionic cell cathode n-type silicon material |
| CN110649243A (en) * | 2019-09-29 | 2020-01-03 | 杭州电子科技大学 | Preparation method and application of superfine phosphorus-doped porous silicon nano material |
| CN113644238A (en) * | 2020-04-27 | 2021-11-12 | 溧阳天目先导电池材料科技有限公司 | Phosphorus-doped silicon-based lithium ion battery cathode material and preparation method and application thereof |
| CN114784251A (en) * | 2022-05-13 | 2022-07-22 | 中国科学技术大学 | Phosphorus-coated negative electrode material and preparation method and application thereof |
| CN115036497A (en) * | 2022-06-22 | 2022-09-09 | 山东大学 | Graphite and ammonium polyphosphate co-modified silicon negative electrode material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110380017A (en) * | 2019-06-12 | 2019-10-25 | 星恒电源股份有限公司 | A kind of high capacity high rate lithium ionic cell cathode n-type silicon material |
| CN110380017B (en) * | 2019-06-12 | 2022-08-16 | 星恒电源股份有限公司 | N-type silicon material for high-capacity high-rate lithium ion battery cathode |
| CN110649243A (en) * | 2019-09-29 | 2020-01-03 | 杭州电子科技大学 | Preparation method and application of superfine phosphorus-doped porous silicon nano material |
| CN110649243B (en) * | 2019-09-29 | 2022-05-06 | 杭州电子科技大学 | Preparation method and application of superfine phosphorus-doped porous silicon nano material |
| CN113644238A (en) * | 2020-04-27 | 2021-11-12 | 溧阳天目先导电池材料科技有限公司 | Phosphorus-doped silicon-based lithium ion battery cathode material and preparation method and application thereof |
| CN114784251A (en) * | 2022-05-13 | 2022-07-22 | 中国科学技术大学 | Phosphorus-coated negative electrode material and preparation method and application thereof |
| CN115036497A (en) * | 2022-06-22 | 2022-09-09 | 山东大学 | Graphite and ammonium polyphosphate co-modified silicon negative electrode material and preparation method thereof |
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