CN109461911A - A kind of cladded type Li-Si alloy and its preparation method and application - Google Patents
A kind of cladded type Li-Si alloy and its preparation method and application Download PDFInfo
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- CN109461911A CN109461911A CN201811229500.7A CN201811229500A CN109461911A CN 109461911 A CN109461911 A CN 109461911A CN 201811229500 A CN201811229500 A CN 201811229500A CN 109461911 A CN109461911 A CN 109461911A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- 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
- H01M4/36—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
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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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 present invention relates to negative electrode material technical fields, provide a kind of cladded type Li-Si alloy, including Li-Si alloy matrix and clad, and in composition, the clad includes the one or more of lithium carbonate, carbon and lithium fluoride；The clad with a thickness of 3~15nm.Cladded type Li-Si alloy provided by the invention, containing Li-Si alloy matrix, wherein Li-Si alloy matrix first charge-discharge efficiency with higher and capacity, efficiently solve the problems, such as that individual silicium cathode or silicon-based anode first charge-discharge efficiency and capacitance loss are larger；And the present invention coats Li-Si alloy matrix using clad, while ensureing Li-Si alloy matrix first charge discharge efficiency and high capacity, effectively increases the cycle life of Li-Si alloy matrix；In addition, the present invention coats Li-Si alloy matrix using clad, solves the problem of Li-Si alloy matrix activity height, easily react in preparation process, greatly reduce the preparation difficulty of Li-Si alloy electrode material.
Description
Technical field
The present invention relates to negative electrode material technical field more particularly to a kind of cladded type Li-Si alloy and preparation method thereof and answer
With.
Background technique
Lithium ion battery is wide by the performance advantages such as high-energy-density, specific power and operating voltage, long-life, environmental-friendly
It is general to be applied to all kinds of portable electronic devices, it is also shown in terms of some high power batteries such as electric car, accumulation power supply huge
Big application potential.
Current non-carbonaceous material such as silicon, tin and its oxide etc. can form Li with lithium4.4Si、 Li4.4The alloys such as Sn, reason
By charge/discharge capacity up to 1000~4200mAhg-1, there is great potential.But silicon, tin is in charge and discharge process, with
Volume expansion can occur when forming alloy for lithium, reduce the electric conductivity of silicon, tin, cause memory capacity rapid decay, the circulation of electrode
Degradation.
In order to alleviate the volume expansion of alloy material during the charging process, its cyclical stability is improved, is mainly had following several
Kind method: the nanosizing of silicon and porous preparation, silicon and other materials are compound etc..Although the above method can be improved alloy material
Cycle life still can not but effectively improve first charge-discharge efficiency of the alloy material as electrode.
Summary of the invention
The present invention provides a kind of cladded type Li-Si alloys and its preparation method and application.Cladded type lithium provided by the invention
Silicon alloy cyclical stability is higher, and first charge discharge efficiency is higher.
It is described from composition the present invention provides a kind of cladded type Li-Si alloy, including Li-Si alloy matrix and clad
Clad includes one of lithium carbonate, carbon and lithium fluoride or a variety of；The clad with a thickness of 3~15nm.
Preferably, from composition, the Li-Si alloy matrix includes Li2Si、Li13Si4、Li22Si5、 Li12Si7、Li7Si3
And Li15Si4One of or it is a variety of.
Preferably, mass content of the clad in cladded type Li-Si alloy is 8%~30%.
The present invention also provides the preparation methods of cladded type Li-Si alloy described in above-mentioned technical proposal, comprising the following steps:
When the clad is lithium carbonate, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon
Under gas atmosphere, after Li-Si alloy matrix is warming up to 180~400 DEG C, isothermal holding is carried out, room temperature is then down to, is coated
Layer is the cladded type Li-Si alloy of lithium carbonate；The isothermal holding carries out under carbon dioxide atmosphere；
When the clad is carbon, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon gas gas
Under atmosphere, 500~900 DEG C are warming up to after Li-Si alloy matrix and carbon source are mixed, 60~180min is kept the temperature, is then down to room temperature,
Obtain the cladded type Li-Si alloy that clad is carbon；
Alternatively, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon when the clad is carbon
Under the mixed atmosphere of gas and toluene, after silicon powder is warming up to 780~820 DEG C, 55~65min is kept the temperature, room temperature is then down to, obtains
Si-C composite material；Under an argon atmosphere, 650~850 DEG C will be warming up to after Si-C composite material and lithium mix, heat preservation 90~
180 min, are then down to room temperature, obtain the cladded type Li-Si alloy that clad is carbon；
When the clad is lithium fluoride, the preparation method of the cladded type Li-Si alloy is the following steps are included: by complete
After fluorine hexane and Li-Si alloy matrix are stirred, 80~120 DEG C are warming up to, continues to be stirred, obtains clad as fluorination
The cladded type Li-Si alloy of lithium.
Preferably, the preparation method of the Li-Si alloy matrix according to lithium silicon the following steps are included: under an argon atmosphere, close
The atom mass rate of auri body mixes silicon powder and lithium piece, after being warming up to 380~420 DEG C, keeps the temperature 160~200min, then drops
To room temperature, Li-Si alloy matrix is obtained.
Preferably, when the clad is carbon, the mixing of the Li-Si alloy matrix and carbon source includes: by Li-Si alloy
Matrix and carbon source mix in tetrahydrofuran, then again remove tetrahydrofuran.
Preferably, when the clad is carbon, the molar ratio of silicon atom is in the lithium atom and Si-C composite material
1.7~4.4:1.
Preferably, when the clad is lithium fluoride, the mass ratio of the perflexane and Li-Si alloy matrix is 1:1
~1.5.
The present invention also provides prepare described in cladded type Li-Si alloy described in above-mentioned technical proposal and above-mentioned technical proposal
Application of the cladded type Li-Si alloy that method is prepared as negative electrode material.
It is in composition, described the present invention provides a kind of cladded type Li-Si alloy, including Li-Si alloy matrix and clad
Clad includes lithium carbonate, carbon or lithium fluoride；The clad with a thickness of 3~15nm.Cladded type lithium silicon provided by the invention
Alloy, containing Li-Si alloy matrix, wherein Li-Si alloy matrix first charge-discharge efficiency with higher and capacity, are effectively solved
Individual silicium cathode or silicon-based anode first charge discharge efficiency and the larger problem of capacitance loss；And the present invention uses clad pair
Li-Si alloy matrix is coated, and while ensureing Li-Si alloy matrix first charge discharge efficiency and high capacity, effectively increases lithium silicon
The cycle life of alloy substrate；In addition, the present invention coats Li-Si alloy matrix using clad, solves Li-Si alloy
The problem of matrix activity is high, easily reacts in preparation process, greatly reduces the preparation difficulty of Li-Si alloy electrode material.
Detailed description of the invention
Fig. 1 is the XRD diagram for the Li-Si alloy matrix that the embodiment of the present invention 1 is prepared；
Fig. 2 is the scanning electron microscope (SEM) photograph for the cladded type Li-Si alloy that the embodiment of the present invention 1 is prepared；
Fig. 3 is the scanning electron microscope (SEM) photograph for the cladded type Li-Si alloy that the embodiment of the present invention 2 is prepared；
Fig. 4 is the transmission electron microscope picture for the cladded type Li-Si alloy that the embodiment of the present invention 2 is prepared；
Fig. 5 is the XRD figure for the cladded type Li-Si alloy that the embodiment of the present invention 2 and 3 is prepared；
Fig. 6 is the first charge-discharge curve graph for the cladded type Li-Si alloy that the embodiment of the present invention 2 is prepared；
Fig. 7 is the cyclic curve figure for the cladded type Li-Si alloy that the embodiment of the present invention 2 is prepared；
Fig. 8 is the first charge-discharge curve graph for the cladded type Li-Si alloy that the embodiment of the present invention 4 is prepared；
Fig. 9 is the cyclic curve figure for the cladded type Li-Si alloy that the embodiment of the present invention 4 is prepared.
Specific embodiment
The present invention provides a kind of cladded type Li-Si alloys, including Li-Si alloy matrix and clad.
In the present invention, in composition, the Li-Si alloy matrix preferably includes Li2Si、Li13Si4、 Li22Si5、
Li12Si7、Li7Si3And Li15Si4One of or it is a variety of.
In the present invention, in composition, the clad includes one of lithium carbonate, carbon and lithium fluoride or a variety of；Institute
State clad with a thickness of 3~15nm, preferably 5~10nm；Mass content of the clad in cladded type Li-Si alloy
Preferably 8%~30%, further preferably 10%~20%.
Cladded type Li-Si alloy provided by the invention, containing Li-Si alloy matrix, wherein Li-Si alloy matrix has higher
First charge-discharge efficiency and capacity, efficiently solve individual silicium cathode or silicon-based anode first charge discharge efficiency and capacitance loss compared with
Big problem；And the present invention coats Li-Si alloy matrix using clad, imitates for the first time in guarantee Li-Si alloy matrix
While rate and high capacity, the cycle life of Li-Si alloy matrix is effectively increased；In addition, the present invention is using clad to lithium silicon
Alloy substrate is coated, and is solved the problem of Li-Si alloy matrix activity height, easily react in preparation process, is dropped significantly
The low preparation difficulty of Li-Si alloy electrode material.
The present invention also provides the preparation methods of cladded type Li-Si alloy described in above-mentioned technical proposal, comprising the following steps:
When the clad is lithium carbonate, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon
Under gas atmosphere, after Li-Si alloy matrix is warming up to 180~400 DEG C, isothermal holding is carried out, room temperature is then down to, is coated
Layer is the cladded type Li-Si alloy of lithium carbonate；The isothermal holding carries out under carbon dioxide atmosphere；
When the clad is carbon, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon gas gas
Under atmosphere, 500~900 DEG C are warming up to after Li-Si alloy matrix and carbon source are mixed, 60~180min is kept the temperature, is then down to room temperature,
Obtain the cladded type Li-Si alloy that clad is carbon；
Alternatively, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon when the clad is carbon
Under the mixed atmosphere of gas and toluene, after silicon powder is warming up to 780~820 DEG C, 55~65min is kept the temperature, room temperature is then down to, obtains
Si-C composite material；Under an argon atmosphere, 650~850 DEG C will be warming up to after Si-C composite material and lithium mix, heat preservation 90~
180 min, are then down to room temperature, obtain the cladded type Li-Si alloy that clad is carbon；
When the clad is lithium fluoride, the preparation method of the cladded type Li-Si alloy is the following steps are included: by complete
After fluorine hexane and Li-Si alloy matrix are stirred, 80~120 DEG C are warming up to, continues to be stirred, obtains clad as fluorination
The cladded type Li-Si alloy of lithium.
The present invention does not specially require the source of the Li-Si alloy matrix, can be commercially available Li-Si alloy, can also
To be homemade.In the present invention, the preparation method of the Li-Si alloy matrix preferably includes following steps: in argon atmosphere
Under, silicon powder and lithium piece are mixed according to the atom mass rate of Li-Si alloy matrix, after being warming up to 380~420 DEG C, heat preservation 160~
Then 200min is down to room temperature, obtain Li-Si alloy matrix.In the present invention, the target temperature of the heating be preferably 390~
410 DEG C, further preferably 400 DEG C；The rate of the heating is preferably 1~3 DEG C/min, further preferably 2 DEG C/min；Institute
The time for stating heat preservation is preferably 170~190 min, further preferably 180min.
In the present invention, when the clad be lithium carbonate when, the preparation method of the cladded type Li-Si alloy include with
Lower step: under an argon atmosphere, after Li-Si alloy matrix is warming up to 180~400 DEG C, isothermal holding is carried out, is then down to often
Temperature obtains the cladded type Li-Si alloy that clad is lithium carbonate.In the present invention, the target temperature of the heating is preferably 190
~380 DEG C, further preferably 200~350 DEG C, more preferably 250~300 DEG C；The rate of the heating is preferably 1~3 DEG C/
Min, further preferably 2 DEG C/min.In the present invention, the isothermal holding carries out under carbon dioxide atmosphere；The heat preservation
Time be 25~35min, preferably 28~32min, further preferably 30min.The present invention is during isothermal holding, institute
The lithium and carbon dioxide gas for stating Li-Si alloy matrix surface react, and generate lithium carbonate, are covered on Li-Si alloy matrix table
Face forms the cladded type Li-Si alloy that clad is lithium carbonate.The present invention preferably carries out cooling processing under an argon atmosphere, obtains
Clad is the cladded type Li-Si alloy of lithium carbonate.
In the present invention, when the clad is carbon, the preparation method of the cladded type Li-Si alloy includes following step
It is rapid: under an argon atmosphere, to be warming up to 500~900 DEG C after Li-Si alloy matrix and carbon source are mixed, keep the temperature 60~180min, so
After be down to room temperature, obtain clad be carbon cladded type Li-Si alloy.In the present invention, the Li-Si alloy matrix and carbon source are mixed
The mode of conjunction is preferred are as follows: mixes Li-Si alloy matrix and carbon source in tetrahydrofuran, then again removes tetrahydrofuran.At this
In invention, the mass ratio of the Li-Si alloy matrix and carbon source is preferably 5~7:1, further preferably 6:1；The carbon source is excellent
It is selected as Kynoar (PVDF).In the present invention, the target temperature of the heating is preferably 640~660 DEG C, further preferably
It is 650 DEG C；The rate of the heating is preferably 1~3 DEG C/min, further preferably 2 DEG C/min；The time of the heat preservation is excellent
It is selected as 110~130min, further preferably 120min.The present invention will heat up after temperature and soaking time control in above-mentioned model
In enclosing, be conducive to carbon source and be coated on Li-Si alloy surface, forms the cladded type Li-Si alloy that clad is carbon.
The present invention also provides a kind of preparation methods for the cladded type Li-Si alloy that clad is carbon.In the present invention, when
When the clad is carbon, the preparation method of the cladded type Li-Si alloy the following steps are included: under argon gas and toluene atmosphere,
After silicon powder is warming up to 780~820 DEG C, 55~65min is kept the temperature, room temperature is then down to, obtains Si-C composite material；In argon gas gas
Under atmosphere, after Si-C composite material and lithium are mixed, 700~850 DEG C are warming up to, 90~180min is kept the temperature, is then down to room temperature, obtains
It is the cladded type Li-Si alloy of carbon to clad.
Silicon powder is preferably warming up to 720~810 DEG C, further preferably 750~800 DEG C by the present invention；The speed of the heating
Rate is preferably 8~12 DEG C/min, further preferably 10 DEG C/min；What the silicon powder was kept the temperature under argon gas and toluene mixed atmosphere
Time is preferably 50~70min, further preferably 60min.Volume of the present invention to toluene in argon gas and toluene mixed atmosphere
Score does not specially require.In the present invention, the toluene is vapor-deposited at the temperature disclosed above, is coated on silicon powder surface,
Generate Si-C composite material.
After obtaining Si-C composite material, the present invention mixes Si-C composite material and lithium, obtains mixture.In the present invention
In, the molar ratio of silicon atom is preferably 1.7~4.4:1 in the lithium atom and Si-C composite material, further preferably 2.0~
4.0:1, more preferably 2.0~3.5:1.The mixture of Si-C composite material and lithium is preferably warming up to 650~800 by the present invention
DEG C, further preferably 700~750 DEG C；The rate of the heating is preferably 3~7 DEG C/min, further preferably 5 DEG C/
min；Soaking time after the heating of the mixture of the Si-C composite material and lithium is preferably 110~130min, further preferably
For 120min.In the present invention, the lithium at the temperature disclosed above, gradually penetrates into Si-C composite material, by silicon-carbon composite wood
Carbon in material is coated, and the cladded type Li-Si alloy that clad is carbon is formed.
In the present invention, when the clad be lithium fluoride when, the preparation method of the cladded type Li-Si alloy include with
Lower step: after perflexane and Li-Si alloy matrix are stirred, 80~120 DEG C are warming up to, continues to be stirred, be wrapped
Coating is the cladded type Li-Si alloy of lithium fluoride.In the present invention, the mass ratio of the perflexane and Li-Si alloy matrix is excellent
It is selected as 1:1~1.5, further preferably 1:1.2~1.3；The time that the perflexane and Li-Si alloy matrix are stirred
Preferably 3~6h, further preferably 4~5h；Temperature after the heating is preferably 90~110 DEG C, further preferably 100
℃；The time for continuing to be stirred is preferably 15~25min, further preferably 20min.In the present invention, the lithium
The lithium and perflexane of silicon alloy matrix surface react at the temperature disclosed above, generate lithium fluoride, and the lithium fluoride is coated on
Li-Si alloy surface forms the cladded type Li-Si alloy that clad is lithium fluoride.
The present invention also provides any one of cladded type Li-Si alloy and above-mentioned technical proposal institutes described in above-mentioned technical proposal
State the application of cladded type Li-Si alloy that preparation method is prepared as negative electrode material.
Concrete application method of the present invention to cladded type Li-Si alloy as negative electrode material is not particularly limited, using ability
Method commonly used by field technique personnel.
This is clearly and completely described the technical solution in the present invention below in conjunction with the embodiment in the present invention.
Embodiment 1
Full of in argon gas glove box, silicon powder and lithium piece that molar ratio is 1:2 are placed in stainless steel boat.Sample will be housed
Stainless steel boat be transferred in quartz ampoule, be placed in tube furnace, be warming up to 400 DEG C in argon atmosphere with 2 DEG C/min speed, and
3h is kept the temperature in argon atmosphere, room temperature is finally cooled in argon atmosphere, obtains Li-Si alloy Li2Si.By gained Li-Si alloy
Li2Si continuation is warming up to 400 DEG C under an argon atmosphere with 2 DEG C/min speed, and in CO22h is kept the temperature in atmosphere, finally in argon gas
Room temperature is cooled in atmosphere, obtains the cladded type Li-Si alloy that clad is lithium carbonate.
XRD analysis is carried out to the Li-Si alloy that embodiment 1 obtains, analysis result is as shown in Figure 1.As shown in Figure 1, of the invention
Contain Li in the Li-Si alloy being prepared2The peak Si illustrates to form Li-Si alloy.
Electron microscope analysis is scanned to the cladded type Li-Si alloy that the clad that embodiment 1 is prepared is lithium carbonate, is tied
Fruit is as shown in Figure 2.As shown in Figure 2, lithium carbonate cladded type Li-Si alloy distribution of particles is more uniform, grain diameter be 200~
500nm。
Embodiment 2
Full of in argon gas glove box, 0.200g nano silica fume is placed in corundum boat, under toluene/argon atmosphere, with
10 DEG C/min speed is warming up to 800 DEG C, keeps the temperature 60min, then cools to room temperature under an argon atmosphere, obtain silicon-carbon composite wood
Material.Then in glove box, 0.1726g Si-C composite material and 0.0432g lithium piece are weighed, is placed in stainless steel boat, with 5 DEG C/
Min speed is warming up to 750 DEG C, and 2h is kept the temperature in argon atmosphere, and room temperature is finally cooled in argon atmosphere, is coated
Layer is the cladded type Li-Si alloy of carbon.
The clad that embodiment 2 is prepared is that the cladded type Li-Si alloy of carbon is scanned electron microscope analysis and thoroughly respectively
Electron microscope analysis is penetrated, scanning electron microscope analysis result is as shown in Figure 3；Transmission electron microscope analysis result is as shown in Figure 4.It is tested by Fig. 3 and Fig. 4
As a result it is found that the structure of cladded type Li-Si alloy is successively from outside to inside: carbon, Li-Si alloy and silicon.
Embodiment 3
It is tested according to the method for embodiment 2, difference is, the temperature for respectively reacting Si-C composite material and lithium piece
It is adjusted to 600 DEG C, 650 DEG C and 700 DEG C.
XRD analysis is carried out to the cladded type Li-Si alloy that embodiment 2 and embodiment 3 obtain, test results are shown in figure 5.
As shown in Figure 5, when reaction temperature is 600 DEG C, the peak of Li-Si alloy disappears.It follows that when reaction temperature is 600 DEG C,
Cladded type Li-Si alloy of the present invention can not be prepared.
Embodiment 4
With commercially available Li-Si alloy Li13Si40.0755g is weighed in the glove box full of argon atmosphere for raw material
Li13Si4It in corundum boat, is then transferred in tube furnace, is warming up to 400 DEG C from room temperature with the speed of 2 DEG C/min, and in dioxy
Change in carbon atmosphere and keep the temperature 2h, room temperature is finally cooled in argon atmosphere, obtains the cladded type lithium silicon that clad is lithium carbonate and close
Gold.
Performance evaluation
The charge-discharge property for the cladded type Li-Si alloy that embodiment 2 is prepared is analyzed.
It is in mass ratio that 70:20:10 is mixed by cladded type Li-Si alloy, conductive carbon and binder prepared by embodiment 2
It is even, electrode is prepared, wherein binder is Kynoar (PVDF)/polytetrafluoroethylene (PTFE) (PTFE) (5:5 mass ratio).Using
CR2016 type button cell carries out electro-chemical test, and battery assembly operates in the glove box full of Ar gas.Electrolyte is addition
1mol/L lithium hexafluoro phosphate/the ethylene carbonate of 10% (volume fraction) fluorinated ethylene carbonate (FEC): dimethyl carbonate
(LiPF6/ EC:DMC (volume ratio 1:1)).Diaphragm is ENTEK ET20-26.Electricity is carried out using blue electric (LAND) test macro
Pond charge-discharge test, test temperature are 25 DEG C.
Test result are as follows: first charge-discharge current density is 100mAg-1, charge and discharge blanking voltage is 1.2~0.01V.
By the Mass Calculation charging and discharging capacity of entire composite material.Test results are shown in figure 6.It will be appreciated from fig. 6 that cladded type lithium silicon closes
Golden specific discharge capacity is 1714.0 mAhg-1, charge specific capacity 1668.8mAhg-1, first charge-discharge efficiency 97.3%.
Illustrate that the Li-Si alloy of cladded type can effectively improve first charge-discharge efficiency.
The cladded type Li-Si alloy that embodiment 2 is prepared is tested as the cycle performance of negative electrode material, is tested
Method are as follows: electrode preparation, electrolyte, test temperature are same as above.Test results are shown in figure 7.As shown in Figure 7, the present invention provides
Cladded type Li-Si alloy as negative electrode material, there is preferable cycle performance, initial charge specific capacity is 1668.8mAhg-1, after recycling 4 times, charge specific capacity 1722.3mAhg-1, after recycling 11 times, charge specific capacity 1727.3mAhg-1,
After preliminary electrode activates, charge specific capacity is increased.Thus illustrate cladded type Li-Si alloy conduct provided by the invention
Negative electrode material has preferable cycle performance.
It the first charge-discharge current density for the cladded type Li-Si alloy that embodiment 4 is prepared according to the method described above and fills
Discharge cut-off voltage is tested, test result are as follows: first charge-discharge current density is 100mAg-1, charge and discharge blanking voltage
For 1.2~0.01V.By the Mass Calculation charging and discharging capacity of entire composite material.Test results are shown in figure 8.It can by Fig. 8
Know, cladded type Li-Si alloy specific discharge capacity is 843.3mAhg-1, charge specific capacity is 756.4 mAhg-1, first charge discharge efficiency
111.5%.Illustrate that the Li-Si alloy of cladded type can effectively improve first charge-discharge efficiency.
The cladded type Li-Si alloy that embodiment 4 is prepared according to the method described above as negative electrode material cycle performance into
Row test, test results are shown in figure 9, and as shown in Figure 9, the charge specific capacity of cladded type Li-Si alloy is 756.4mAhg-1,
The charge specific capacity that circulation is 5 times is 635mAhg-1, the charge specific capacity that circulation is 10 times is 607.4mAhg-1, recycle 15 times
Charge specific capacity be 586mAhg-1, the charge specific capacity that circulation is 20 times is 575.6 mAhg-1.It follows that of the invention
The cladded type Li-Si alloy of offer has preferable cycle performance as negative electrode material.
In conclusion cladded type Li-Si alloy provided by the invention not only has high first charge-discharge as negative electrode material
Specific capacity, and have preferable cycle performance, stability preferable.In addition, the present invention is carried out Li-Si alloy using clad
The problem of cladding, it is high to efficiently solve Li-Si alloy activity, operating difficulties.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of cladded type Li-Si alloy, including Li-Si alloy matrix and clad, from composition, the clad includes carbonic acid
One of lithium, carbon and lithium fluoride are a variety of；The clad with a thickness of 3~15nm.
2. cladded type Li-Si alloy according to claim 1, which is characterized in that from composition, the Li-Si alloy matrix
Including Li2Si、Li13Si4、Li22Si5、Li12Si7、Li7Si3And Li15Si4One of or it is a variety of.
3. cladded type Li-Si alloy according to claim 1 or 2, which is characterized in that the clad is in cladded type lithium silicon
Mass content in alloy is 8%~30%.
4. the preparation method of any one of claims 1 to 3 cladded type Li-Si alloy, comprising the following steps:
When the clad is lithium carbonate, the preparation method of the cladded type Li-Si alloy is the following steps are included: in argon gas gas
Under atmosphere, after Li-Si alloy matrix is warming up to 180~400 DEG C, isothermal holding is carried out, is then down to room temperature, obtaining clad is
The cladded type Li-Si alloy of lithium carbonate；The isothermal holding carries out under carbon dioxide atmosphere；
When the clad is carbon, the preparation method of the cladded type Li-Si alloy the following steps are included: under an argon atmosphere,
500~900 DEG C are warming up to after Li-Si alloy matrix and carbon source are mixed, 60~180min is kept the temperature, is then down to room temperature, is wrapped
Coating is the cladded type Li-Si alloy of carbon；
Alternatively, when the clad is carbon, the preparation method of the cladded type Li-Si alloy the following steps are included: in argon gas and
Under the mixed atmosphere of toluene, after silicon powder is warming up to 780~820 DEG C, 55~65min is kept the temperature, room temperature is then down to, obtains silicon-carbon
Composite material；Under an argon atmosphere, 650~850 DEG C will be warming up to after Si-C composite material and lithium mix, heat preservation 90~
Then 180min is down to room temperature, obtain the cladded type Li-Si alloy that clad is carbon；
When the clad is lithium fluoride, the preparation method of the cladded type Li-Si alloy the following steps are included: by perfluor oneself
After alkane and Li-Si alloy matrix are stirred, 80~120 DEG C are warming up to, continues to be stirred, obtaining clad is lithium fluoride
Cladded type Li-Si alloy.
5. the preparation method according to claim 4, which is characterized in that the preparation method of the Li-Si alloy matrix include with
Lower step: under an argon atmosphere, mixing silicon powder and lithium piece according to the atom mass rate of Li-Si alloy matrix, it is warming up to 380~
After 420 DEG C, 160~200min is kept the temperature, room temperature is then down to, obtains Li-Si alloy matrix.
6. the preparation method according to claim 4, which is characterized in that when the clad is carbon, the Li-Si alloy
The mixing of matrix and carbon source includes: to mix Li-Si alloy matrix and carbon source in tetrahydrofuran, then again removes tetrahydrofuran
It removes.
7. preparation method according to claim 4 or 5, which is characterized in that when the clad is carbon, the lithium atom
Molar ratio with silicon atom in Si-C composite material is 1.7~4.4:1.
8. preparation method according to claim 4 or 5, which is characterized in that described complete when the clad is lithium fluoride
The mass ratio of fluorine hexane and Li-Si alloy matrix is 1:1~1.5.
9. any one of any one of claims 1 to 3 cladded type Li-Si alloy and claim 4~8 preparation method
Application of the cladded type Li-Si alloy being prepared as negative electrode material.
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