CN107123790A - A kind of porous silicon-base composite negative pole material, preparation method and lithium ion battery - Google Patents
A kind of porous silicon-base composite negative pole material, preparation method and lithium ion battery Download PDFInfo
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- CN107123790A CN107123790A CN201610101839.3A CN201610101839A CN107123790A CN 107123790 A CN107123790 A CN 107123790A CN 201610101839 A CN201610101839 A CN 201610101839A CN 107123790 A CN107123790 A CN 107123790A
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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
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention provides a kind of porous silicon-base composite negative pole material, its preparation method and lithium ion battery, porous material includes porous agraphitic carbon matrix；It is supported on silicon-containing nano particle and metal particle on the porous agraphitic carbon matrix；The metal particle includes the one or more in Sn, Cu and Mn.Loose structure is conducive to lithium ion in contact surface fast exchange, good cycling stability in the porous material；Metallic particles and porous agraphitic carbon as compound porous negative material support frame, anode material surface is enabled to form stable SEI films, the advantage of the high lithium storage content of silicon materials can be given full play to, electrode is set stably to discharge reversible capacity, therefore, the nano silicon-based composite porous material reversible capacity is high and cycle performance is excellent.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, more particularly to a kind of porous silicon-base are compound
Negative material, its preparation method and lithium ion battery.
Background technology
Lithium ion battery is a kind of secondary cell (rechargeable battery), and it relies primarily on lithium ion in positive pole and negative pole
Between it is mobile come work.In charge and discharge process, Li+Insertion and deintercalation are come and gone between two electrodes:Charging
When, Li+From positive pole deintercalation, negative pole is embedded in by electrolyte, negative pole is in rich lithium state；Then phase during electric discharge
Instead.Battery typically uses the material for containing elemental lithium as electrode, is the representative of modern high performance battery.
The basic composition of lithium ion battery includes positive pole, barrier film, negative pole, electrolyte and battery case.
Excellent lithium ion battery negative material as can improve battery and its cycle life it is important because
Element, is favored by scientific research personnel.Wherein silicon materials are due to higher theoretical specific capacity (=4200mAh/
G), can be as lithium ion battery negative material, but there is huge volume during charge and discharge cycles in it
Effect (>300%) active material particle efflorescence, is caused to be failed, capacity attenuation is very fast so that silicium cathode
It is practical to be obstructed.Research shows, can be significantly improved if silicon grain is reduced into micron or nanoscale
Its cycle performance, the composite of porous has very excellent embedding de- lithium performance.
At present more than the research of porous this respect based on silicon nanowires, although it has excellent embedding lithium
Performance, but its reversible capacity and cycle performance are still poor.
The content of the invention
In view of this, it is an object of the invention to provide a kind of porous silicon-base composite negative pole material, its preparation
Method and lithium ion battery, the porous silicon-base composite negative pole material reversible capacity is high and cycle performance is excellent.
The invention provides including porous agraphitic carbon matrix；
It is supported on silicon-containing nano particle and metal particle on the porous agraphitic carbon matrix；
The metal particle includes the one or more in Sn, Cu and Mn.
Preferably, the specific surface area of the porous silicon-base composite negative pole material is 10~100m2/ g, aperture is
5nm~4 μm.
Preferably, the particle diameter of the metal particle is 5nm~4 μm；
The particle diameter of the silicon-containing nano particle is 5nm~500nm.
Preferably, silicon-containing nano particle includes silicon, SiO2And SiOxIn one or more；
The SiOxMiddle x value is 0<x<2.
The invention provides a kind of preparation side of porous silicon-base composite negative pole material described in above-mentioned technical proposal
Method, comprises the following steps：
Silicon-containing nano particle and solvent are mixed, ball milling obtains slurry；
The slurry and metal particle, carbon source, auxiliary agent are mixed, is sintered after spray drying, obtains porous
Silicon substrate composite negative pole material；The metal particle includes the one or more in Sn, Cu and Mn.
Preferably, the mass content ratio of the silicon-containing nano particle, carbon source and metal particle is
10~70:30~90:3~10.
Preferably, the auxiliary agent be selected from inorganic salts containing sodium, inorganic salts containing potassium, ammonium salt, polyvinyl alcohol, gather
Tie up the one or more in ketone and polyethylene glycol.
Preferably, the carbon source is selected from sodium carboxymethylcellulose, Kynoar, polyvinyl alcohol, phenolic aldehyde
One in resin, epoxy resin, melamine resin, PVP, sucrose, grape sugar and starch
Plant or a variety of.
Preferably, the temperature of the sintering is 450~1200 DEG C；The time of the sintering is 4~10h.
The invention provides a kind of lithium ion battery, including the porous silicon-base described in above-mentioned technical proposal is compound
Porous silicon-base composite negative pole material prepared by preparation method described in negative material or above-mentioned technical proposal.
The invention provides a kind of porous silicon-base composite negative pole material, including porous agraphitic carbon matrix；It is negative
It is loaded in silicon-containing nano particle and metal particle on the porous agraphitic carbon matrix；The metal particle bag
Include the one or more in Sn, Cu and Mn.In the porous silicon-base composite negative pole material that the present invention is provided,
The loose structure of porous agraphitic carbon matrix can provide space for the expansion of silicon-containing nano particle volume, increase
As negative material and the contact surface of electrolyte, be conducive to lithium ion in contact surface fast exchange, circulation
Stability is good；Metallic particles and porous agraphitic carbon matrix are used as the support frame of composite porous material, energy
The integrality of holding electrode conductive network while composite cyclical stability is maintained, such a structure is born
Pole composite material surface can form stable SEI films, can give full play to the high lithium storage content of silicon materials
Advantage, enables electrode stably to discharge reversible capacity, therefore, and the nano silicon-based composite porous material can
Inverse capacity is high and cycle performance is excellent.Test result indicates that：The porous silicon-base composite negative pole that the present invention is provided
Material is assembled into 2032 button batteries, its first discharge capacity be 1600~2620mAh/g, discharge and recharge
Efficiency is 84%~99%, and capability retention is 84%~89% after 100 times.
Brief description of the drawings
Fig. 1 is the nano silicon-based negative material of lithium ion battery porous spherical provided in an embodiment of the present invention
Structural representation；
Fig. 2 is the nano silicon-based negative material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1
XRD；
Fig. 3 is the nano silicon-based negative material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1
TEM figure；
Fig. 4 is the nano silicon-based negative material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1
1200 times of SEM of amplification figures；
Fig. 5 is the nano silicon-based negative material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1
5000 times of SEM of amplification figures；
Fig. 6 is the nano silicon-based negative material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1
First circle and second circle charging and discharging curve figure；
Fig. 7 is the nano silicon-based negative material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1
Cycle performance figure.
Embodiment
The invention provides porous silicon-base composite negative pole material, including porous agraphitic carbon matrix；
It is supported on silicon-containing nano particle and metal particle on the porous agraphitic carbon matrix；
The metal particle includes the one or more in Sn, Cu and Mn.
The porous silicon-base composite negative pole material that the present invention is provided includes porous agraphitic carbon matrix.In the present invention
In, the porous agraphitic carbon matrix is sintered by carbon source and is made；The carbon source is preferably selected from carboxymethyl cellulose
Plain sodium (CMC), Kynoar (PVDF), polyvinyl alcohol, phenolic resin, epoxy resin, trimerization
One or more in cyanamide formaldehyde resin, PVP, sucrose, grape sugar and starch, are more preferably selected from
One or more in phenolic resin, glucose, sodium carboxymethylcellulose, polyvinyl alcohol and starch, most
It is preferably selected from phenolic resin and/or glucose.The present invention originates without special limitation to the carbon source,
Using the carbon source of mentioned kind well known to those skilled in the art, its commercial goods can be such as used.
In the present invention, the temperature that carbon source sintering obtains porous agraphitic carbon matrix is preferably 450~1200 DEG C；Carbon
The time that source sintering obtains porous agraphitic carbon matrix is preferably 4~10h.In the present invention, it is described porous
In agraphitic carbon matrix, loose structure can provide space for the expansion of silicon-containing nano particle volume, increase
As negative material and the contact surface of electrolyte, be conducive to lithium ion in contact surface fast exchange, circulation is steady
It is qualitative good.
The porous silicon-base composite negative pole material that the present invention is provided includes being supported on the porous sizing carbon base body
Silicon-containing nano particle.In the present invention, the silicon-containing nano particle preferably includes silicon, SiO2And SiOx
In one or more；The SiOxMiddle x value is preferably 0<x<2, more preferably x=1, x=0.5
Or x=1.5.In the present invention, the particle diameter of the silicon-containing nano particle is preferably 5nm~500nm, more excellent
Elect 100~400nm as；In an embodiment of the present invention, the particle diameter of the silicon-containing nano particle is specially
100~200nm, 100~500nm or 5~100nm.
The porous silicon-base composite negative pole material that the present invention is provided includes being supported on the porous agraphitic carbon matrix
On metal particle；The metal particle includes the one or more in Sn, Cu and Mn.In the present invention
In, the particle diameter of the metal particle is preferably 5nm~4 μm, more preferably 100nm~3 μm, most preferably
For 500nm~1000nm；In a particular embodiment of the present invention, the particle diameter of the metal particle is specially
500nm。
In the present invention, metallic particles and porous agraphitic carbon matrix as composite porous material support rib
Frame, can maintain composite cyclical stability while holding electrode conductive network integrality, it is such a
Structure anode material surface can form stable SEI films, can give full play to silicon materials height storage lithium
The advantage of capacity, enables electrode stably to discharge reversible capacity.
Fig. 1 is the structural representation of porous silicon-base composite negative pole material provided in an embodiment of the present invention, wherein,
1 is silicon-containing nano particle, and 2 be metallic particles, and 3 be loose structure, and 4 be agraphitic carbon.
In the present invention, the loose structure 3 of silicon-containing nano particle 1 and metal particle 2 in agraphitic carbon 4
In.In the present invention, the loose structure can provide space for the expansion of silicon-containing nano particle volume, increase
It is big as negative material and the contact surface of electrolyte, be conducive to lithium ion in contact surface fast exchange, follow
Ring stability is good.The porous silicon-base composite negative pole material that the present invention is provided is elliposoidal or spherical.At this
In invention, the specific surface area of the porous silicon-base composite negative pole material is 10~100m2/ g, preferably 20~95
m2/g；The aperture of the silicon-based anode composite porous material is 5nm~4 μm, preferably 100nm~1 μm.
In the present invention, the D50 of the silicon-based anode composite porous material is preferably 5~45 μm, more excellent
Elect 10~35 μm as.
The invention provides a kind of preparation side of porous silicon-base composite negative pole material described in above-mentioned technical proposal
Method, comprises the following steps：
Silicon-containing nano particle and solvent are mixed, ball milling obtains slurry；
The slurry and metal particle, carbon source and auxiliary agent are mixed, is sintered after spray drying, obtains porous
Silicon substrate composite negative pole material；
The metal particle includes the one or more in Sn, Cu and Mn.
The present invention mixes silicon-containing nano particle and solvent, and ball milling obtains slurry.In the present invention, institute
State silicon-containing nano particle and preferably include silicon, SiO2And SiOxIn one or more；The SiOxMiddle x's
Value is preferably 0<x<2, more preferably x=1, x=0.5 or x=1.5.In the present invention, it is described siliceous to receive
The particle diameter of rice grain is preferably 5nm~500nm, more preferably 100~400nm；In the implementation of the present invention
In example, the particle diameter of the silicon-containing nano particle is specially 100~200nm, 100~500nm or 5~100nm.
In the present invention, the solvent is preferably selected from water, ethanol, third intoxicated, tetrahydrofuran, benzene, toluene, two
One or more in toluene and dimethylformamide, are more preferably selected from water, ethanol and dimethylformamide
One or more, most preferably water.The present invention is to the source of the silicon-containing nano particle and solvent without spy
Different limitation, using above-mentioned silicon-containing nano particle and solvent well known to those skilled in the art, such as may be used
To use its commercial goods.In the present invention, the quality of the silicon-containing nano particle and the volume ratio of water are excellent
Elect 1g as：(100~1000) mL, more preferably 1g：(200~800) mL.
After the present invention preferably mixes silicon-containing nano particle and water, obtained mixture is first subjected to high energy ball
Mill, then the ball milling in sand mill, obtain slurry.In the present invention, the rotating speed of the high-energy ball milling is preferred
For 400~2000 turns/min, more preferably 500~1800 turns/min；The time of the high-energy ball milling is preferably
3~10h, more preferably 5~9h；In a particular embodiment of the present invention, the rotating speed of the high-energy ball milling is
1800 turns/min, 2000 turns/min, 1500 turns/min；The time of the high-energy ball milling is 8h.In this hair
In bright, the rotating speed of sand mill is preferably 1500~2500 turns/min during ball milling in the sand mill, more preferably
1700~2400 turns/min；The time of ball milling is preferably 4~10h in the sand mill, more preferably 4~8h,
Most preferably 4h.
Obtain after slurry, the present invention mixes the slurry and metal particle, carbon source, auxiliary agent, and spraying is dry
Sintered after dry, obtain porous silicon-base composite negative pole material；The metal particle is included in Sn, Cu and Mn
One or more.
In the present invention, the metal particle includes the one or more in Sn, Cu and Mn；The gold
The particle diameter for belonging to particulate is preferably 5nm~4 μm, more preferably 100nm~3 μm, most preferably 500
Nm~1000nm.The present invention originates without special limitation to the metal particle, using this area skill
Above-mentioned metal particle known to art personnel, can such as use its commercial goods.
In the present invention, the carbon source is preferably selected from sodium carboxymethylcellulose, Kynoar, polyethylene
Alcohol, phenolic resin, epoxy resin, melamine resin, PVP, sucrose, glucose and shallow lake
One or more in powder；It is more preferably selected from one in glucose, phenolic resin, polyvinyl alcohol and starch
Plant or a variety of；It is most preferably selected from glucose and/or phenolic resin.In one embodiment of the invention, institute
Carbon source specially phenolic resin is stated, the phenolic resin is bought in Chemical Reagent Co., Ltd., Sinopharm Group；
In another embodiment of the present invention, the carbon source is specially glucose；The glucose is bought in state
Chemical reagent Co., Ltd of medicine group.
In the present invention, the auxiliary agent is preferably selected from inorganic salts containing sodium, inorganic salts containing potassium, ammonium salt, poly- second
One or more in enol, PVP and polyethylene glycol；Be more preferably selected from polyvinyl alcohol, PVP,
One kind in polyethylene glycol, ammonium hydrogen carbonate, ammonium carbonate, sodium chloride, sodium nitrate, potassium chloride and potassium nitrate
Or it is a variety of；It is most preferably selected from the one or more in ammonium carbonate, sodium chloride and sodium sulphate.
The present invention is preferably carried out the slurry and metal particle, carbon source, auxiliary agent in the form of ultrasonic disperse
Mixing.In the present invention, the slurry and metal particle, carbon source, the time of auxiliary agent mixing are preferably 3h~6
H, more preferably 4~5h.
In the present invention, the mass ratio of the silicon-containing nano particle, carbon source and metal particle is preferably
10~70:30~90:3~10, more preferably 10~70:35~90:4~9；In a particular embodiment of the present invention,
The mass ratio of the silicon-containing nano particle, carbon source and metal particle is specially 10:40:3、70:90:10、15:35:4
Or 65:85:9.The mass ratio of the silicon-containing nano particle and auxiliary agent is preferably 1:1~1:10, more preferably
1:2~1:5.
The mixture spray drying that the present invention is mixed to get to the slurry and metal particle, carbon source, auxiliary agent
After re-sinter.In the present invention, the temperature of air inlet is preferably 220 DEG C~280 DEG C during the spray drying；
The temperature of air outlet is preferably 90 DEG C~120 DEG C during the spray drying；The atomizer during spray drying
Rotating speed is preferably 19000~21000 turns/min, more preferably 20000 turns/min；Under above-mentioned rotating speed, mesh
Be in order that slurry and metal particle, carbon source, auxiliary agent are well mixed.Obtained after spray drying
Globular material tap density be 0.6~2.2g/cm3.The round that mixture is obtained after spray drying
That expects is shaped as elliposoidal and/or spherical.
The present invention is preferably sintered in resistance furnace well known to those skilled in the art.The present invention preferably exists
It is sintered under protective atmosphere；The protective atmosphere includes the one or more in nitrogen, argon gas and hydrogen.
In the present invention, the temperature of the sintering is preferably 450 DEG C~1200 DEG C, more preferably 500~1100 DEG C,
In a particular embodiment of the present invention, the temperature of the sintering is specially 800 DEG C；The time of the sintering is excellent
Elect 4~10h, more preferably 5~10h as；In a particular embodiment of the present invention, the time of the sintering
Specially 5h, 8h or 10h.
Sintered product is preferably washed, dried and sieved by the present invention successively, is obtained porous silicon-base and is combined
Negative material.The present invention does not have special limitation to the method for washing, is known using those skilled in the art
Washing technology scheme.Washed present invention preferably employs the mode of centrifuge washing；The centrifugation
The solvent that washing is used is preferably the alcoholic solution of deionized water or water.
The present invention does not have special limitation to the method that the sintered product after washing is dried, using ability
Dry technology scheme known to field technique personnel.In the present invention, the sintered product after washing is carried out
Dry temperature is preferably 50~120 DEG C.
The present invention does not have special limitation to the method for the screening, using well known to those skilled in the art
Material sieving technology scheme.In the present invention, the silicon-based anode composite porous material obtained after the screening
D50 be preferably 5~45 μm, more preferably 10~35 μm.
The invention provides a kind of lithium ion battery, including the porous silicon-base described in above-mentioned technical proposal is compound
Porous silicon-base composite negative pole material prepared by preparation method described in negative material or above-mentioned technical proposal.
It is button-shaped that silicon-based anode composite porous material described in above-mentioned technical proposal is fabricated to 2030 by the present invention
Battery carries out electrochemical property test, and the manufacturing process of 2030 button batteries is specially：
It is 80 to weigh mass ratio:10:10 silicon-based anode composite porous material, acetylene black and Kynoar；
Kynoar and 1-METHYLPYRROLIDONE are mixed, the poly- inclined fluorine that mass concentration is 0.02g/mL is configured to
Vinyl solution；Load weighted silicon-based anode composite porous material and acetylene black are well mixed, then added
Above-mentioned Kynoar solution, is coated on Cu paper tinsels, small in 120 DEG C of vacuum drying 8 in vacuum drying chamber
When, take a diameter of 1.6 centimetres of electrode slice as working electrode, metal lithium sheet is that electrolyte is to electrode
LiPF6(wherein, EC is ethylene carbonate to/EC-DMC-EMC, and DMC is dimethyl carbonate, EMC
For methyl ethyl ester, volume ratio 1:1:1) 2032 knobs, are assembled into the glove box full of Ar gas
Button cell.
Test result indicates that：It is button-shaped that the porous silicon-base composite negative pole material that the present invention is provided is assembled into 2032
Battery, its first discharge capacity be 1600~2620mAh/g, efficiency for charge-discharge be 84%~99%, pass through
Capability retention is 84%~89% after 100 times.
In order to further illustrate the present invention, a kind of porous silicon-base provided with reference to embodiment the present invention
Composite negative pole material, its preparation method and lithium ion battery are described in detail, but can not manage them
Solve as limiting the scope of the present invention.
Embodiment 1
By silica flour and the 50mL aqueous solution under an inert atmosphere, 2000 turns/min high-energy ball millings 8 hours, then
Transfer them to 1000 turns/min ball millings 4 hours in sand mill；It is 5~100nm by the 2.5g particle diameters of acquisition
Silicon slurry, the mass ratio of silica flour, glucose and Sn is 10:40:3rd, the mass ratio of silica flour and sodium chloride is
1:Ultrasonic disperse 5 hours after 1 mixing, spray drying is granulated, 20000 turns of atomizer rotating speed with up to
The uniform purpose of grain, it is 220 DEG C to dry intake air temperature, and air outlet temperature is 110 DEG C, and what is obtained is spherical
Material is placed in resistance furnace again carries out 800 DEG C of sintering 5h in an inert atmosphere, obtained globular material centrifugation
Water washing, dries, the nano silicon-based negative material of lithium ion battery porous spherical is obtained after screening, i.e., many
Hole silicon substrate composite negative pole material.
Crystalline phase point is carried out with the nano silicon-based negative material of porous spherical to lithium ion battery manufactured in the present embodiment
Analysis and morphology analysis, respectively as shown in Figures 2 and 3：If Fig. 2 is lithium prepared by the embodiment of the present invention 1
The XRD of the ion battery nano silicon-based negative material of porous spherical, as can be seen from Figure 2 embodiment
The nano silicon-based negative material of porous spherical prepared by 1 is pure phase silicon composite.Fig. 3 is implemented for the present invention
Lithium ion battery prepared by example 1 is schemed with the TEM of the nano silicon-based negative material of porous spherical, can from Fig. 3
To find out the particle of black as silicon grain, size is between 100nm~150nm, the inside and surface of particle
There is the structure of hole, the size of hole is between 100nm~200nm.Fig. 4 and Fig. 5 is embodiment 1
The lithium ion battery of preparation is schemed with the SEM of the nano silicon-based negative material of porous spherical, and Fig. 4 is real for the present invention
Apply 1200 times of SEM of amplification of the lithium ion battery nano silicon-based negative material of porous spherical of the preparation of example 1
Figure；It is the nano silicon-based negative pole material of lithium ion battery porous spherical prepared by the embodiment of the present invention 1 from Fig. 5
5000 times of SEM figures of amplification of material；As can be seen that also having for particle surface is a large amount of from Fig. 4 and Fig. 5
Hole exist, the size of hole is between 100nm~1 μm.
Electrochemistry is carried out with porous spherical nano silicon-based negative material to lithium ion battery manufactured in the present embodiment
Performance test.2030 button batteries make, electrochemical property test is as follows:Lithium ion battery is with porous
The mass ratio of ball shaped nano silicon based anode material, acetylene black and PVDF (Kynoar) is 80:10:10,
Lithium ion battery is well mixed with the nano silicon-based negative material of porous spherical and acetylene black, then adds and contains
(the PVDF/NMP solution that the solution containing PVDF is the 0.02g/mL prepared is applied PVDF solution
Overlay on Cu paper tinsels, be dried in vacuo 8 hours in 120 DEG C in vacuum drying chamber, take a diameter of 1.6 centimetres
Electrode slice as working electrode, metal lithium sheet is that electrolyte is LiPF to electrode6/EC-DMC-EMC
(volume ratio 1:1:1) 2032 button batteries, are assembled into the glove box full of Ar gas.Discharge and recharge electricity
Pressure scope is 2.0~0.005V, and the charging and discharging currents of first circle are charge and discharge after 200mA/g (0.1C), first circle
Electric current density is 400mA/g (0.2C).After tested, test chart such as Fig. 6, Fig. 6 are implemented for the present invention
Lithium ion battery prepared by example 1 is bent with the nano silicon-based negative material first circle of porous spherical and the second circle discharge and recharge
Line chart, as can be seen from Figure 6：Discharge capacity is 2618.7mAh/g first, and initial charge capacity is
2253.9mAh/g, first charge-discharge efficiency is 86.1%, and the second circle discharge capacity is 2229mAh/g, is filled
Capacitance is 2167.8mAh/g, and efficiency for charge-discharge is 97.3%.Fig. 7 is prepared by the embodiment of the present invention 1
The lithium ion battery nano silicon-based negative material cycle performance curve map of porous spherical, as can be seen from Figure 7：
Under 0.2C multiplying power, after 100 times circulate, discharge capacity is 1897.4mAh/g, charging capacity
For 1874.2mAh/g, efficiency for charge-discharge is 99.0%, and capability retention is 86%.
Embodiment 2
By silica flour and the 50mL aqueous solution 1800 turns/min high-energy ball millings 8 hours under an inert atmosphere, then
Transfer them to 1500 turns/min ball millings 4 hours in sand mill；It is 100~500 by the 2.5g particle diameters of acquisition
The silicon slurry of nanometer, the mass ratio of silica flour, phenolic resin and Sn is 70:90:10th, silica flour and (NH4)2CO3The mass ratio of (ammonium carbonate) is 1:Ultrasonic disperse 5 hours after 10 mixing, spray drying is granulated,
20000 turns/min of atomizer rotating speed is so that up to evengranular purpose, it is 220 DEG C to dry intake air temperature, is gone out
Draught temperature is 110 DEG C.Obtained globular material is placed in resistance furnace again carries out 800 DEG C in an inert atmosphere
10h is sintered, obtained globular material centrifugation water washing is dried, lithium ion battery is obtained after screening with porous
Ball shaped nano copper silicon negative material, i.e. porous silicon-base composite negative pole material.
Electrochemistry is carried out with porous spherical nanometer copper silicon negative material to lithium ion battery manufactured in the present embodiment
Performance test.2030 button batteries make, electrochemical property test is as follows:Lithium ion battery porous ball
The mass ratio of shape nanometer copper silicon negative material, acetylene black and PVDF (Kynoar) is 80:10:10,
Lithium ion battery is well mixed with porous spherical nanometer copper silicon negative material and acetylene black, then adds and contains
PVDF solution, the PVDF/NMP solution that the solution containing PVDF is the 0.02g/mL prepared is applied
Overlay on Cu paper tinsels, be dried in vacuo 8 hours in 120 DEG C in vacuum drying chamber, take a diameter of 1.6 centimetres
Electrode slice as working electrode, metal lithium sheet is that electrolyte is LiPF to electrode6/EC-DMC-EMC
(volume ratio 1:1:1) 2032 button batteries, are assembled into the glove box full of Ar gas.Discharge and recharge electricity
Pressure scope is 2.0~0.005V, and the charging and discharging currents of first circle are discharge and recharge after 200mA/g (0.1C), first circle
Current density is 400mA/g (0.2C).After tested, discharge capacity is 2300mAh/g, discharge and recharge effect first
Rate is 85%, and capability retention is 84% after 100 times.
Embodiment 3
By silica flour and the 50mL aqueous solution 1500 turns/min high-energy ball millings 8 hours, then will under an inert atmosphere
It is transferred to 2000 turns/min ball millings 4 hours in sand mill；It is 100 by the 2.5g particle diameters of acquisition
Nm~200nm nanometers of silicon slurry, the mass ratio of silica flour, phenolic resin and copper powder is 65:85:9th, silica flour
With Na2SO4The mass ratio of (sodium sulphate) is 1:Ultrasonic disperse 5 hours after 5 mixing, spray drying is carried out
Granulation, 20000 turns of atomizer rotating speed is 220 DEG C up to evengranular purpose, to dry intake air temperature,
Air outlet temperature is 110 DEG C.Obtained globular material is placed in resistance furnace and carried out in an inert atmosphere again
800 DEG C of sintering 8h, obtained globular material centrifugation water washing, dry, lithium ion battery use are obtained after screening
Porous spherical nanometer copper silicon negative material, i.e. porous silicon-base composite negative pole material.
Electrochemistry is carried out with porous spherical nano-silicon aluminum honeycomb material to lithium ion battery manufactured in the present embodiment
Performance test.2030 button batteries make, electrochemical property test is as follows:The spherical porous silicon of high power capacity
The mass ratio of base composite negative pole material, acetylene black and PVDF (Kynoar) is 80:10:10, by lithium from
Sub- battery porous spherical nano-silicon aluminum honeycomb material and second:Block is black well mixed, then adds and contains PVDF
Solution, (the PVDF/NMP solution that the solution containing PVDF is the 0.02g/mL prepared, is coated in
On Cu paper tinsels, it is dried in vacuo 8 hours in 120 DEG C in vacuum drying chamber, takes a diameter of 1.6 centimetres of electricity
Pole piece is as working electrode, and metal lithium sheet is that electrolyte is LiPF to electrode6/ EC-DMC-EMC (volumes
Than 1:1:1) 2032 button batteries, are assembled into the glove box full of Ar gas.Charging/discharging voltage model
Enclose for 2.0~0.005V, the charging and discharging currents of first circle are charging and discharging currents after 200mA/g (0.1C), first circle
Density is 400mA/g (0.2C).After tested, discharge capacity is 2000mAh/g first, and efficiency for charge-discharge is
83%, capability retention is 89% after 100 times.
Embodiment 4
By SiO powder and the 50mL aqueous solution 1800 turns/min high-energy ball millings 8 hours under an inert atmosphere, then
Transfer them to 1500 turns/min ball millings 4 hours in sand mill；It is 10nm~100 by the 2.5g particle diameters of acquisition
The SiO slurries of nanometer, the mass ratio of silica flour, phenolic resin and Mn is 15:35:4th, silica flour and Na2SO4
The mass ratio of (sodium sulphate) is 1:Ultrasonic disperse 5 hours after 2 mixing, spray drying is granulated, mist
It is 220 DEG C, air outlet temperature up to evengranular purpose, to dry intake air temperature to change 20000 turns of device rotating speed
Spend for 110 DEG C, obtained globular material is placed in resistance furnace again carries out 800 DEG C of sintering 5h in an inert atmosphere,
Obtained globular material centrifugation water washing, dries, lithium ion battery porous spherical nanometer is obtained after screening
SiO negative materials, i.e. porous silicon-base composite negative pole material.
Electrochemistry is carried out with porous spherical Nano-meter SiO_2 negative material to lithium ion battery manufactured in the present embodiment
Performance test.2030 button batteries make, electrochemical property test is as follows:Lithium ion battery porous ball
The mass ratio of shape Nano-meter SiO_2 negative material, acetylene black and PVDF (Kynoar) is 80:10:10, will
Lithium ion battery porous spherical Nano-meter SiO_2 negative material and second:Block is black well mixed, then adds and contains
PVDF solution, (the PVDF/NMP solution that the solution containing PVDF is the 0.02g/mL prepared is applied
Overlay on Cu paper tinsels, be dried in vacuo 8 hours in 120 DEG C in vacuum drying chamber, take a diameter of 1.6 centimetres
Electrode slice as working electrode, metal lithium sheet is that, to electrode, electrolyte is Li PF6/EC-DMC-EMC
(volume ratio 1:1:1) 2032 button batteries, are assembled into the glove box full of Ar gas.Discharge and recharge electricity
Pressure scope is 2.0~0.005V, and the charging and discharging currents of first circle are charge and discharge after 200mA/g (0.1C), first circle
Electric current density is 400mA/g (0.2C).After tested, discharge capacity is 1600mAh/g, discharge and recharge first
Efficiency is 84%, and capability retention is 89% after 100 times.
As seen from the above embodiment, the invention provides a kind of porous silicon-base composite negative pole material, including it is many
Hole agraphitic carbon matrix；The silicon-containing nano particle and metal being supported on the porous agraphitic carbon matrix are micro-
Grain；The metal particle includes the one or more in Sn, Cu and Mn.The porous silicon that the present invention is provided
In the porous agraphitic carbon matrix of base composite negative pole material, loose structure can be silicon-containing nano particle volume
Expansion provides space, increases the contact surface as negative material and electrolyte, is conducive to lithium ion connecing
Contacting surface fast exchange, good cycling stability；Metallic particles and porous agraphitic carbon are used as composite porous material
Support frame, can maintain composite cyclical stability while holding electrode conductive network it is complete
Property, such a structure anode material surface can form stable SEI films, can give full play to silicon material
Expect the advantage of high lithium storage content, electrode is stably discharged reversible capacity, therefore, this is nano silicon-based
Composite porous material reversible capacity is high and cycle performance is excellent.Test result indicates that：It is many that the present invention is provided
Hole silicon substrate composite negative pole material is assembled into 2032 button batteries, its first discharge capacity be 1600~2620
MAh/g, efficiency for charge-discharge is 84%~99%, and capability retention is 84%~89% after 100 times.
Described above is only the preferred embodiment of the present invention, it is noted that for the general of the art
For logical technical staff, under the premise without departing from the principles of the invention, some improvement and profit can also be made
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of porous silicon-base composite negative pole material, including porous agraphitic carbon matrix；
It is supported on silicon-containing nano particle and metal particle on the porous agraphitic carbon matrix；
The metal particle includes the one or more in Sn, Cu and Mn.
2. porous silicon-base composite negative pole material according to claim 1, it is characterised in that described porous
The specific surface area of silicon substrate composite negative pole material is 10~100m2/ g, aperture is 5nm~4 μm.
3. porous silicon-base composite negative pole material according to claim 2, it is characterised in that the metal
The particle diameter of particulate is 5nm~4 μm；
The particle diameter of the silicon-containing nano particle is 5nm~500nm.
4. porous silicon-base composite negative pole material according to claim 1, it is characterised in that silicon-containing nano
Particle includes silicon, SiO2And SiOxIn one or more；
The SiOxMiddle x value is 0<x<2.
5. the preparation method of porous silicon-base composite negative pole material described in a kind of Claims 1 to 4 any one,
Comprise the following steps：
Silicon-containing nano particle and solvent are mixed, ball milling obtains slurry；
The slurry and metal particle, carbon source, auxiliary agent are mixed, is sintered after spray drying, obtains porous
Silicon substrate composite negative pole material；The metal particle includes the one or more in Sn, Cu and Mn.
6. preparation method according to claim 5, it is characterised in that the silicon-containing nano particle,
The mass ratio of carbon source and metal particle is 10~70:30~90:3~10.
7. preparation method according to claim 5, it is characterised in that the auxiliary agent be selected from containing sodium without
One or more in machine salt, inorganic salts containing potassium, ammonium salt, polyvinyl alcohol, PVP and polyethylene glycol.
8. preparation method according to claim 5, it is characterised in that the carbon source is selected from carboxymethyl
Sodium cellulosate, Kynoar, polyvinyl alcohol, phenolic resin, epoxy resin, melamino-formaldehyde tree
One or more in fat, PVP, sucrose, grape sugar and starch.
9. preparation method according to claim 5, it is characterised in that the temperature of the sintering is
450~1200 DEG C；The time of the sintering is 4~10h.
10. a kind of lithium ion battery, it is characterised in that including described in Claims 1 to 4 any one
Porous silicon prepared by preparation method described in porous silicon-base composite negative pole material or claim 5~9 any one
Base composite negative pole material.
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