CN108807935A - Lithium ion battery silicon substrate tinbase composite particles, preparation method, cathode and lithium ion battery comprising it - Google Patents
Lithium ion battery silicon substrate tinbase composite particles, preparation method, cathode and lithium ion battery comprising it Download PDFInfo
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- CN108807935A CN108807935A CN201810738713.6A CN201810738713A CN108807935A CN 108807935 A CN108807935 A CN 108807935A CN 201810738713 A CN201810738713 A CN 201810738713A CN 108807935 A CN108807935 A CN 108807935A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/362—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
- 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
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Present disclose provides a kind of lithium ion battery silicon substrate tinbase composite particles, preparation method, include its cathode and lithium ion battery, which is characterized in that the silicon substrate tinbase composite particles include：The oxide particle of hollow tin particles or hollow tin, and hollow tin particles or hollow tin oxide particle outer surface cladding silicon layer.The disclosure additionally provides the cathode for lithium rechargeable battery comprising the composite particles and the lithium rechargeable battery comprising the cathode.The preparation method of the composite particles of the disclosure is simple, and due to its hollow structure, which can effectively accommodate the volume expansion of silicon substrate and tin-based material in process of intercalation, to keep the stabilization of electrode structure.Moreover, external silica-base material can effectively prevent the reunion of nanometer tin particles, the stabilization of tin-based material is kept, it is hereby achieved that specific capacity is high, the composite cathode material of lithium ion battery of good cycle.
Description
The application is application No. is 2016110373036, and the applying date is on November 23rd, 2016, entitled " lithium from
The application for a patent for invention of sub- battery silicon substrate tinbase composite particles, preparation method, cathode and lithium ion battery comprising it "
Divisional application.
Technical field
This disclosure relates to a kind of lithium ion battery silicon substrate tinbase composite particles, preparation method, including the material is negative
Pole and lithium ion battery, specifically, this disclosure relates to a kind of hollow composite particles of lithium ion battery, preparation method, packet
Cathode containing the composite particles and lithium ion battery.
Background technology
The operation principle of lithium ion battery is that lithium is shifted in the form of ion between battery plus-negative plate, and battery completion is made to fill
The process of electric discharge, therefore lithium ion battery is otherwise known as " rocking chair batteries ".The selection of lithium ion cell positive negative material for
The energy density and cycle life of battery have vital influence.Currently, in various carbon materials, have laminar structured
Graphite-like carbon material be optimum as commercialized lithium ion battery negative material.But with electric vehicle and extensive storage
The development of energy, graphite material cannot meet the needs of lithium ion battery development.
Silicon is the second abundant element in the earth's crust, constitutes the 25.7% of earth's crust gross mass, and abundant reserves make its raw material
Source is sufficient.The theoretical specific capacity (4212mAh/g) of silicon is very high, compares traditional graphite cathode material, and silicium cathode material has bright
Aobvious specific capacity advantage.But the problem of silicium cathode, is, during electrochemical lithium storage, average each silicon atom combines 4.4
Lithium atom obtains Li22Si5Alloy phase, while the volume change of material reaches 300% or more.So huge bulk effect generates
Mechanicals efforts can make gradually to disengage between electrode active material and collector, and silicon activity mutually itself also can dusting, from
And the electrical contact with collector is lost, cause electrode cycle performance to decline rapidly.In addition, silicon itself is semi-conducting material, it is intrinsic
Conductivity is low, and only 6.7 × 10-4Conductive agent need to be added to improve the electronic conductance of electrode in S/cm.
Tinbase lithium storage materials have many advantages, such as that specific capacity is higher, it is convenient, cheap to prepare, stannous oxide (SnO), oxidation
Tin (SnO2) and the theoretical capacity of tin simple substance be respectively 875mAh/g and 782mAh/g and 990mAh/g.Tin-based material it is main
Problem is：Material structure is unstable, for the first time recycle coulombic efficiency it is low so that when as cell negative electrode material cycle performance compared with
Difference.The nanosizing of material can be such that problem is alleviated, but its larger specific surface area makes material be easy production in preparation process
It is raw to reunite.
There is still a need for one kind having height ratio capacity, the good negative material of cycle performance.
Invention content
For existing silicon substrate, the volume expansion of Tin Composite Material, tin are reunited, electrode structure is unstable and cycle performance
The problem of difference, present disclose provides a kind of high performance silicon tin composite lithium ion battery cathode materials.
Specifically, present disclose provides the hollow materials that a kind of nano silicone coats tin.The material is aoxidized with metal
Object coats tin-based material, and prepare tinbase hollow nano material by removal template method on it as template.Pass through chemical gas again
Mutually deposition, the method for liquid phase in-situ deposition coat silicon substrate negative electrode material layer in tinbase hollow nano material surface, and it is multiple to form silicon tin
Close hollow nano structure.It is swollen that the hollow structure can effectively accommodate the volume of silicon substrate and tin-based material in process of intercalation
It is swollen, to keep the stabilization of electrode structure.Moreover, external silica-base material can effectively prevent the reunion of nanometer tin particles, keep
The stabilization of tin-based material, it is hereby achieved that specific capacity is high, the composite cathode material of lithium ion battery of good cycle.
According to the disclosure technical solution, a kind of lithium ion battery silicon substrate tinbase composite particles are provided,
Including：
The oxide particle of hollow tin particles or hollow tin, and
In the silicon layer of the outer surface cladding of the oxide particle of hollow tin particles or hollow tin.
Preferably, the grain size of the silicon substrate tinbase composite particles in 15nm between 250nm, the hollow tin particles or
The hollow diameters of the oxide particle of hollow tin are between 5nm-200nm.
Preferably, the silicon substrate tinbase composite particles can be spherical, polyhedron shape or rodlike, when being rodlike, major diameter
Than that can be 2：1 to 10：1.
Preferably, the thickness of the silicon layer of the cladding is 10nm to 50nm, more preferable 10nm to 20nm.
According to another technical solution of the disclosure, a kind of lithium ion battery silicon substrate tinbase composite particles are provided
Preparation method includes the following steps：
(1) oxide template is prepared by any one of Hydrolyze method, sol-gel method and decomposition method or directly adopted
Use nano particle as oxide template；
(2) tin-based material is coated to oxide template described in step (1) by situ deposition method：
(3) template in the material that removal step (2) obtains in lye, and by nonessential reduction process to obtain
The oxide particle of hollow tin or hollow tin particles；
(4) the surface coated Si of the hollow particle obtained by as chemical vapour deposition technique or in situ deposition method in step (3)
Layer is to form the hollow composite particles of silicon substrate tinbase.
Preferably, this approach includes the following steps：
(1) masterplate is prepared
Oxide template is prepared by Hydrolyze method or any one of sol-gel method and decomposition method or is directly used
Nano particle is as oxide template.
Hydrolyze method preparation process is：By water, alcohol and lye according to (5~40)：(94~55)：The volume ratio of (1~5) is mixed
It closes, hydrolysis presoma is added, after reacting 10min~3h at 5-50 DEG C, obtained suspension is centrifuged, and is obtained after washing
Granular formwork.
Sol-gel method preparation process is：The salting liquid of metal ion is added in a certain amount of organic solvent, is prepared into
Then gelling agent and surfactant is added dropwise in the solution of a concentration of 1~3mol/L under 60~80 degree, gel is formed, by gel
Heat preservation ageing 2~for 24 hours after, under 600~800 degree heat treatment 1~3h, obtain granular formwork；
Decomposition method preparation process is：It is heat-treated 1~3h under 600~800 degree to nano level metal salt in an inert atmosphere,
Obtain oxide template.
(2) tin-based material is coated
Tin-based material is coated to the oxide template in step (1) by situ deposition method, the specific steps are：By step
(1) granular formwork obtained is dispersed in 50~100ml deionized waters, and the stannic acid of 0.5~2mol/L of 50~100ml is added
Salt reacts 1-5 hours in 60 degree to 80 degree temperature ranges, and of the oxide cladding of tin will be obtained after product centrifugation washing
Grain.
(3) template is removed
Prepare 0.5~3mol/L lye, by the product of step (2) under 70 degree to 90 degree in lye react 0.5~
2h obtains the oxide particle of hollow tin after centrifugation washing, includes hollow tin particles in the hollow composite particles
When, the oxide particle of hollow tin is reduced to by hollow tin particles by the method for magnesium thermit or hydrogen reducing.
(4) silicon layer is coated
Silicon is coated on to the surface of the hollow particle obtained by step (3) as chemical vapour deposition technique and in situ deposition method.
Chemical vapour deposition technique step is：Hollow particle prepared by the step of taking 0.1~1g (3), passes through silane gas checking solution
Or silicon chloride adds the method for hydrogen to deposit silicon on its surface.
The in situ deposition method step of silicon is：Hollow particle prepared by step (3) is passed through into liquid-phase silicone chlorination in a kettle
Object adds the method for hydrogen to deposit silicon on its surface.
Step (1) described alcohol is methanol, ethyl alcohol, propyl alcohol, butanol or amylalcohol；The hydrolysis presoma is esters of silicon acis, such as silicon
One or more of acid butyl ester, methyl silicate, silester, silicic acid diethylester.The lye is one kind in urea, ammonium hydroxide
Or it is several.The salt of the metal ion is nitrate, sulfate, the phosphorus of Al, Mg, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn or Zr
Hydrochlorate, carbonate, silicate or chlorate.The organic solvent includes one kind or several in ethylene glycol monomethyl ether and ethylene glycol ethyl ether
Kind.The surfactant includes dodecyl sodium sulfate, stearic acid, one or more of lecithin.The gelling agent packet
Containing one or more of butyl titanate and silester.It includes aluminium oxide Al to be formed by oxide template particle2O3, oxidation
Magnesium MgO, calcium oxide CaO, titanium dioxide TiO2, manganese oxide MnO and manganese dioxide MnO2, ferrous oxide FeO, ferroso-ferric oxide
Fe3O4, cobalt oxide CoO, cobaltosic oxide Co3O4, nickel oxide NiO, cuprous oxide Cu2O, copper oxide CuO, zinc oxide ZnO and oxygen
Change zirconium ZrO2.Preferably, the oxide template grain size of synthesis is between 5nm~200nm.
Step (2) described stannate includes sodium stannate, potassium stannate, magnesium stannate, calcium stannate.The oxide of the tin includes oxygen
Change stannous SnO and stannic oxide SnO2。
Lye includes potassium hydroxide and sodium hydroxide used by step (3).Preferably, the hollow tin particles of formation or
The hollow diameters of the oxide particle of hollow tin are between 5nm~200nm.
The grain size of hollow composite particles is between 15nm~250nm obtained by step (4).Preferably, the silicon of the cladding
The thickness of layer is 10nm to 50nm, more preferable 10nm to 20nm.
According to another technical solution of the disclosure, it is compound to provide the silicon substrate tinbase prepared according to the preparation method
Particle.
According to another technical solution of the disclosure, a kind of cathode for lithium rechargeable battery is provided, is wrapped
Include above-mentioned silicon substrate tinbase composite particles.Preferably, the cathode further includes conductive agent, binder；Wherein, the conductive agent is
At least one of carbon black, acetylene black, natural graphite, carbon nanotube, graphene, carbon fiber or mixture；The binder is
Polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvingl ether, polyimides, benzene
At least one of ethylene-butadiene copolymer, sodium carboxymethylcellulose or mixture；Preferably, negative electrode active material, conduction
Agent, binder ratio be：The mass fraction of negative electrode active material is 50~99.5wt%, and conductive agent is 0.1~40wt%, is glued
Knot agent is 0.1~40wt%.
According to another technical solution of the disclosure, a kind of secondary cell is provided comprising above-mentioned cathode；It is preferred that
Ground, the secondary cell further include anode, diaphragm, electrolyte；Wherein, the just extremely common lithium battery anode, wherein wrapping
The non-limitative example of the active material contained includes：Cobalt acid lithium, LiMn2O4, lithium nickelate, LiFePO4, lithium titanate, nickel-cobalt-manganese
The metal composite oxide etc. of ternary system or lithium；The diaphragm include aramid fiber diaphragm, nonwoven cloth diaphragm, polyethene microporous membrane,
One kind in polypropylene screen, polypropylene-polyethylene bilayer or sandwich diaphragm and its ceramic coating layer diaphragm；The electrolyte packet
Containing electrolyte and solvent；Electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)、LiBOB、
At least one of LiCl, LiBr, LiI or mixture；Solvent includes propylene carbonate (PC), dimethyl carbonate (DMC), carbon
Sour methyl ethyl ester (EMC), 1,2- dimethoxy-ethanes (DME), ethylene carbonate, propene carbonate, butylene, carbonic acid diethyl
At least one of ester, methyl propyl carbonate, acetonitrile, ethyl acetate, ethylene sulfite or several mixtures.
In the disclosure, unless otherwise defined, the numberical range includes arbitrary subrange therein, and can be recognized
To be to disclose any number therein.
In the disclosure, the composite particles can be spherical, Polyhedral Particles shape or rodlike, when being rodlike, length
Diameter ratio can be 2：1 to 10：1.In the disclosure, the grain size of the composite particles and the hollow tin particles or hollow
Tin oxide particle hollow diameters be by electron microscope analysis, nitrogen adsorption pore volume analysis or laser particle size analysis measure
Or be calculated.
Silicon substrate tinbase composite particles prepared by the disclosure, preparation method is simple, and material source is abundant.And since its is hollow
Structure, the particle can effectively accommodate the volume expansion of silicon substrate and tin-based material in process of intercalation, to keep electrode knot
The stabilization of structure.Moreover, external silica-base material can effectively prevent the reunion of nanometer tin particles, the stabilization of tin-based material is kept, from
And specific capacity height can be obtained, the composite cathode material of lithium ion battery of good cycle.
Description of the drawings
Fig. 1 is the structural schematic diagram of silicon substrate tinbase composite particles prepared by the disclosure.
Fig. 2 is the preparation method of spherical nanoparticle prepared by the disclosure, and wherein a indicates that the template prepared, b indicate cladding
The template of tin-based material, c indicate that the hollow tin-based material of removing template, d is gone to indicate to remove the hollow composite particles of removing template.
The schematic diagram of variation when Fig. 3 is the spherical hollow composite particles embedding and removing of the disclosure, wherein left side is original
Beginning state, centre are the state after embedding lithium, and right side is the state after de- lithium.
Fig. 4 and Fig. 5 is the electron scanning micrograph of hollow composite particles prepared by embodiment of the disclosure 1.
Fig. 6 be embodiment of the disclosure 1 prepare hollow composite particles as negative material when cycle performance figure, wherein
Circular dot indicates that charge specific capacity, square point indicate that specific discharge capacity, triangle point indicate coulombic efficiency.
Fig. 7 is the transmission electron microscope photo of hollow composite particles prepared by embodiment of the disclosure 2.
Fig. 8 be embodiment of the disclosure 2 prepare hollow composite particles as negative material when cycle performance figure, wherein
Solid dot indicates that specific discharge capacity, hollow dots indicate coulombic efficiency.
Fig. 9 is the transmission electron microscope photo of hollow composite particles prepared by embodiment of the disclosure 3.
Figure 10 be embodiment of the disclosure 3 prepare hollow composite particles as negative material when cycle performance figure, wherein
The data point of top indicates that coulombic efficiency, the data point of lower section indicate specific discharge capacity.
Figure 11 is the transmission electron microscope photo of hollow composite particles prepared by embodiment of the disclosure 4.
Figure 12 be embodiment of the disclosure 4 prepare hollow composite particles as negative material when cycle performance figure, wherein
The data point of triangle indicates that coulombic efficiency, circular data point indicate specific discharge capacity.
Figure 13 be the disclosure comparative example 1 prepare solid silicon/stannic oxide composite particles as negative material when
Cycle performance figure, wherein the closed square data point of top indicates coulombic efficiency, the circle of lower section and the data point of hollow square
It indicates to be charged and discharged specific capacity respectively.
Figure 14 be the disclosure comparative example 2 prepare stannic oxide hollow sphere as negative material when cycle performance
Figure, wherein round and square data point indicates to be charged and discharged specific capacity respectively.
Specific implementation mode
The disclosure will be described in detail by specific implementation mode below, it is to be noted that, following implementation is only used for
Understand the disclosure, rather than in order to limit the scope of the present disclosure.
Fig. 1 shows the illustrative grain structure of the disclosure, is respectively from left to right spherical shape, polyhedral, rodlike,
Middle outer layer indicates silicon layer, and intermediate representation tin-based material, inside is hollow.
Fig. 2 and Fig. 3 shows preparation method, the preparation of the material of other shapes by taking spherical hollow composite material as an example
Method is similar therewith, and details are not described herein.
The schematic diagram of variation when Fig. 4 is the spherical hollow composite particles embedding and removing of the disclosure, wherein left side is original
Beginning state, centre are the state after embedding lithium, and right side be the state taken off after lithium, the change when embedding and removing of the material of other shapes
Change is similar therewith, and details are not described herein.As seen from Figure 4, the hollow composite particles of the disclosure are in embedding and removing (i.e. charge and discharge
Electric process) when volume change it is small.
The preparation process of composite material is described in detail by the following examples, those skilled in the art can be according to following system
Standby process obtains the scheme of the disclosure.
Embodiment 1
(1) 60ml deionized waters are mixed in beaker, the positive silicon of 10ml is added in 25% ammonium hydroxide of 150ml ethyl alcohol and 15ml
Simultaneously 50min is stirred at room temperature in acetoacetic ester.It centrifuges and is washed with deionized to obtain the silica template that grain size is 130nm.
(2) product in 1g steps (1) is added in 100ml deionized waters, ultrasonic disperse 30min.1mol/L is added
Sodium stannate solution 50ml, stir simultaneously react 2h under 70 degree.It centrifuges and is washed with deionized to obtain product.
(3) potassium hydroxide solution for preparing 1.5mol/L, is added the product in step (2), stirs and is reacted under 75 degree
1h.It centrifuges and is washed with deionized to obtain the stannic oxide hollow ball that grain size is 150nm.
(4) product of step 0.5g steps (3) is put into tube furnace, under protection of argon gas by silane gas checking solution with
The flow of 100sccm reacts 2h at 450 degree.Obtain silicon/stannic oxide hollow ball that grain size is 170nm.
Prepared active material, conductive black and binder polyacrylic acid are pressed 85：10：5 mass ratio is uniformly mixed,
Negative electrode slurry is made by solvent of deionized water, is applied on copper foil and negative plate is made, and the vacuum drying overnight at 60 DEG C.
Electro-chemical test is carried out using CR2025 type button cells, is analytically pure metal lithium sheet to electrode, and electrolyte is 1M LiPF6
Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1：1) solution, battery diaphragm are Celgard-2320 (micropores
Polypropylene screen).The assembly of battery is carried out in the glove box full of argon gas, as shown in fig. 6, after material chemical conversion prepared by the method
Capacity stablizes the capacity retention ratio about 81% at about 900mAh/g, 100 cycles under the current density of 600mA/g.
Embodiment 2
(1) using ethylene glycol monomethyl ether as solvent, the iron nitrate solution 100ml of 2mol/L is configured.It stirs and distinguishes under 70 degree
Dodecyl sodium sulfate, butyl titanate and the silester of 10ml is added.After forming brown colloidal sol uniformly, stable, at 70 degree
Lower ageing colloidal sol 2h, and it is dried under reduced pressure 3h under 90 degree.Product is taken out, calcines 3h under 600 degree in Muffle furnace, obtaining grain size is
The nanometer blocky-shaped particle of the di-iron trioxide of 50nm.
(2) product in 2g steps (1) is added in 100ml deionized waters, ultrasonic disperse 30min.1mol/L is added
Stannic acid potassium solution 30ml, stir simultaneously react 2h under 60 degree.It centrifuges and is washed with deionized to obtain product.
(3) potassium hydroxide solution for preparing 1mol/L, is added the product in step (2), stirs and reacts 2h under 80 degree.
It centrifuges and is washed with deionized to obtain the stannic oxide hollow particle that grain size is 60nm.Hollow particle is mixed with magnesium powder, is set
In tube furnace, 700 degree of reaction 3h are downloaded in atmosphere of inert gases, magnesia is removed with acetic acid, centrifuges and be washed with deionized water
The tin hollow particle that grain size is 60nm is obtained after washing.
(4) product of step 1g steps (3) is put into reaction kettle, using silicon tetrachloride as silicon source, passes through catalytic hydrogenation
Method deposits silicon on stannic oxide hollow particle surface, forms silicon/tin composite hollow particle that grain size is 80nm.
Prepared active material, conductive black and binder polyacrylic acid are pressed 85：10：5 mass ratio is uniformly mixed,
Negative electrode slurry is made by solvent of deionized water, is applied on copper foil and negative plate is made, and the vacuum drying overnight at 60 DEG C.
Electro-chemical test is carried out using CR2025 type button cells, is analytically pure metal lithium sheet to electrode, and electrolyte is 1M LiPF6
Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1：1) solution, battery diaphragm are Celgard-2320 (micropores
Polypropylene screen).The assembly of battery is carried out in the glove box full of argon gas, as shown in figure 8, after material chemical conversion prepared by the method
Capacity stablizes the capacity retention ratio about 83% at about 1300mAh/g, 100 cycles under the current density of 600mA/g.
Embodiment 3
(1) using ethylene glycol monomethyl ether as solvent, the zinc nitrate solution 100ml of 2mol/L is configured.It stirs and distinguishes under 80 degree
Dodecyl sodium sulfate, butyl titanate and the silester of 20ml is added.After forming brown colloidal sol uniformly, stable, at 80 degree
Lower ageing colloidal sol 2h, and it is dried under reduced pressure 3h under 90 degree.Product is taken out, calcines 3h under 600 degree in Muffle furnace, obtaining grain size is
The nanometer spherical particle of the zinc oxide of 100nm.
(2) product in 3g steps (1) is added in 100ml deionized waters, ultrasonic disperse 30min.1mol/L is added
Sodium stannate solution 40ml, stir simultaneously react 0.5h under 60 degree.It centrifuges and is washed with deionized to obtain product.
(3) potassium hydroxide solution for preparing 2mol/L, is added the product in step (2), stirs and reacts 2h under 80 degree.
It centrifuges and is washed with deionized to obtain the stannous oxide hollow ball that grain size is 120nm.
(4) product of 1g steps (3) is put into reaction kettle, using silicon tetrachloride as silicon source, passes through the method for catalytic hydrogenation
Silicon is deposited on stannic oxide hollow particle surface, forms silicon/stannous oxide composite hollow ball that grain size is 150nm.
Prepared active material, conductive black and binder polyacrylic acid are pressed 85：10：5 mass ratio is uniformly mixed,
Negative electrode slurry is made by solvent of deionized water, is applied on copper foil and negative plate is made, and the vacuum drying overnight at 60 DEG C.
Electro-chemical test is carried out using CR2025 type button cells, is analytically pure metal lithium sheet to electrode, and electrolyte is 1M LiPF6
Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1：1) solution, battery diaphragm are Celgard-2320 (micropores
Polypropylene screen).The assembly of battery is carried out in the glove box full of argon gas, as shown in Figure 10, material chemical conversion prepared by the method
Capacity stablizes the capacity retention ratio about 90% at about 900mAh/g, 100 cycles under the current density of 600mA/g afterwards.
Embodiment 4
(1) it is that the alumina particle of 80nm is added in 100ml deionized waters to take 3g grain sizes, ultrasonic disperse 30min.It is added
The stannic acid potassium solution 50ml of 1mol/L is stirred and is reacted 2h under 70 degree.It centrifuges and is washed with deionized to obtain product.
(2) potassium hydroxide solution for preparing 2mol/L, is added the product in step (1), stirs and reacts 2h under 80 degree.
It centrifuges and is washed with deionized to obtain the stannic oxide hollow ball that grain size is 100nm.
(3) product of step (2) is put into tube furnace, under protection of argon gas by silane gas checking solution with 200sccm
Flow 1.5h is reacted at 450 degree.Obtain silicon/stannic oxide hollow ball that grain size is 140nm.
Prepared active material, conductive black and binder polyacrylic acid are pressed 85：10：5 mass ratio is uniformly mixed,
Negative electrode slurry is made by solvent of deionized water, is applied on copper foil and negative plate is made, and the vacuum drying overnight at 60 DEG C.
Electro-chemical test is carried out using CR2025 type button cells, is analytically pure metal lithium sheet to electrode, and electrolyte is 1M LiPF6
Ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1：1) solution, battery diaphragm are Celgard-2320 (micropores
Polypropylene screen).The assembly of battery is carried out in the glove box full of argon gas, as shown in figure 12, material chemical conversion prepared by the method
Capacity stablizes the capacity retention ratio about 77% at about 850mAh/g, 100 cycles under the current density of 600mA/g afterwards.
Comparative example 1
Other than without step (1) and (3), obtained according to the method for preparing particle same as Example 1 solid
Silicon/stannic oxide particle, and battery is prepared according to the method for preparing battery same as Example 1 and tests its electrochemistry
Can, as a result as shown in figure 13.As can be seen from Figure 13, the space expanded due to lacking receiving, material fragmentation, poor circulation,
Under the current density of 600mA/g after 100 cycles, battery specific capacity falls to approximately 100mAh/g from about 600mAh/g,
Capacity retention ratio under 100 cycles is only about 16.7%.
Comparative example 2
Other than without step (4), hollow titanium dioxide is obtained according to the method for preparing particle same as Example 1
Tin particles, and battery is prepared according to the method for preparing battery same as Example 1 and tests its chemical property, as a result as schemed
Shown in 14.As can be seen from Figure 14, reunited in cyclic process due to tin, lose hollow-core construction, it is close in the electric current of 600mA/g
The cycle performance of battery under degree falls to approximately 400mAh/g, the capacity retention ratio under 100 cycles from about 800mAh/g
Only about 50%.
The initial specific capacities of the hollow composite particles provided according to the disclosure are can be seen that according to Fig. 6-14, are recycled for 100 times
The capacity retention ratio after specific capacity and 100 cycles afterwards is all much higher than the analog value in comparative example.
Can be seen that the hollow composite particles of disclosure offer according to above experimental result can effectively accommodate silicon substrate
With volume expansion of the tin-based material in process of intercalation, to keep the stabilization of electrode structure, and specific capacity height, cyclicity are obtained
The good composite cathode material of lithium ion battery of energy.
Claims (10)
1. a kind of lithium ion battery silicon substrate tinbase composite particles, which is characterized in that the silicon substrate tinbase composite particles include：
The oxide particle of hollow tin particles or hollow tin, and
In the silicon layer of the outer surface of the hollow tin particles or the oxide particle of hollow tin cladding.
2. silicon substrate tinbase composite particles according to claim 1, wherein
The grain size of the silicon substrate tinbase composite particles in 15nm between 250nm, the hollow tin particles or hollow tin
The size of the cavity of oxide particle is between 5nm-200nm.
3. silicon substrate tinbase composite particles according to claim 1, wherein
The silicon substrate tinbase composite particles are spherical, polyhedron shapes or rodlike, when being rodlike, draw ratio 2：1 to 10：1.
4. silicon substrate tinbase composite particles according to claim 1, wherein
The thickness of the silicon layer of the cladding is 10nm to 50nm.
5. a kind of lithium ion battery preparation method of silicon substrate tinbase composite particles, includes the following steps：
(a1) 60ml deionized waters are mixed in beaker, the positive silicic acid second of 10ml is added in 25% ammonium hydroxide of 150ml ethyl alcohol and 15ml
Simultaneously 50min is stirred at room temperature in ester, centrifuges and is washed with deionized to obtain the silica template that grain size is 130nm,
(a2) product in 1g steps (a1) is added in 100ml deionized waters, ultrasonic disperse 30min is added 1mol/L's
Sodium stannate solution 50ml is stirred and is reacted 2h under 70 degree, centrifuge and be washed with deionized to obtain product,
(a3) potassium hydroxide solution for preparing 1.5mol/L, is added the product in step (a2), stirs and reacts 1h under 75 degree,
It centrifuges and is washed with deionized to obtain the stannic oxide hollow ball that grain size is 150nm,
(a4) product of step 0.5g steps (a3) is put into tube furnace, under protection of argon gas by silane gas checking solution with
The flow of 100sccm reacts 2h at 450 degree, obtains silicon/stannic oxide hollow ball that grain size is 170nm, or
(b1) using ethylene glycol monomethyl ether as solvent, the iron nitrate solution 100ml of 2mol/L is configured, stirs and is separately added under 70 degree
Dodecyl sodium sulfate, butyl titanate and the silester of 10ml, it is old under 70 degree after forming brown colloidal sol uniformly, stable
Change colloidal sol 2h, and be dried under reduced pressure 3h under 90 degree, take out product, 3h is calcined under 600 degree in Muffle furnace, it is 50nm to obtain grain size
Di-iron trioxide nanometer blocky-shaped particle,
(b2) product in 2g steps (b1) is added in 100ml deionized waters, ultrasonic disperse 30min is added 1mol/L's
Stannic acid potassium solution 30ml is stirred and is reacted 2h under 60 degree, centrifuge and be washed with deionized to obtain product,
(b3) potassium hydroxide solution for preparing 1mol/L, is added the product in step (b2), stirs and reacts 2h under 80 degree, from
The heart simultaneously is washed with deionized to obtain the stannic oxide hollow particle that grain size is 60nm, and hollow particle is mixed with magnesium powder, is placed in
In tube furnace, 700 degree of reaction 3h are downloaded in atmosphere of inert gases, magnesia is removed with acetic acid, centrifuges and be washed with deionized
The tin hollow particle that grain size is 60nm is obtained afterwards,
(b4) product of step 1g steps (b3) is put into reaction kettle, using silicon tetrachloride as silicon source, passes through the side of catalytic hydrogenation
Method deposits silicon on stannic oxide hollow particle surface, forms silicon/tin composite hollow particle that grain size is 80nm, or
(c1) using ethylene glycol monomethyl ether as solvent, the zinc nitrate solution 100ml of 2mol/L is configured, stirs and is separately added under 80 degree
Dodecyl sodium sulfate, butyl titanate and the silester of 20ml, it is old under 80 degree after forming brown colloidal sol uniformly, stable
Change colloidal sol 2h, and be dried under reduced pressure 3h under 90 degree, takes out product, calcine 3h under 600 degree in Muffle furnace, obtaining grain size is
The nanometer spherical particle of the zinc oxide of 100nm,
(c2) product in 3g steps (c1) is added in 100ml deionized waters, ultrasonic disperse 30min is added 1mol/L's
Sodium stannate solution 40ml is stirred and is reacted 0.5h under 60 degree, centrifuge and be washed with deionized to obtain product,
(c3) potassium hydroxide solution for preparing 2mol/L, is added the product in step (c2), stirs and reacts 2h under 80 degree, from
The heart simultaneously is washed with deionized to obtain the stannous oxide hollow ball that grain size is 120nm,
(c4) product of 1g steps (c3) is put into reaction kettle, it is heavy by the method for catalytic hydrogenation using silicon tetrachloride as silicon source
Product silicon forms silicon/stannous oxide composite hollow ball that grain size is 150nm on stannic oxide hollow particle surface, or
(d1) it is that the alumina particle of 80nm is added in 100ml deionized waters to take 3g grain sizes, and ultrasonic disperse 30min is added
The stannic acid potassium solution 50ml of 1mol/L is stirred and is reacted 2h under 70 degree, centrifuge and be washed with deionized to obtain product,
(d2) potassium hydroxide solution for preparing 2mol/L, is added the product in step (d1), stirs and reacts 2h under 80 degree, from
The heart simultaneously is washed with deionized to obtain the stannic oxide hollow ball that grain size is 100nm,
(d3) product of step (d2) is put into tube furnace, under protection of argon gas by silane gas checking solution with 200sccm's
Flow reacts 1.5h at 450 degree, obtains silicon/stannic oxide hollow ball that grain size is 140nm.
6. a kind of cathode for lithium ion battery comprising silicon substrate tinbase according to any one of claims 1-5 is multiple
Close particle.
7. the cathode according to claim 6 for lithium ion battery, the cathode further includes conductive agent and binder；Its
In, the conductive agent is carbon black, natural graphite, carbon nanotube, graphene, one kind in carbon fiber or mixture；The bonding
Agent is polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvingl ether, polyamides Asia
At least one of amine, styrene-butadiene copolymer, sodium carboxymethylcellulose or mixture.
8. the cathode according to claim 7 for lithium ion battery, wherein
The carbon black is acetylene black.
9. the cathode according to claim 7 or 8 for lithium ion battery, wherein the negative electrode active material described is led
Electric agent, the binder ratio be：The mass fraction of the negative electrode active material is 50~99.5wt%, and the conductive agent is
0.1~40wt%, the binder are 0.1~40wt%.
10. a kind of lithium ion battery comprising according to the cathode described in any one of claim 7-9.
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