CN106486647A - A kind of composite cathode material for lithium ion cell and preparation method thereof and lithium ion battery - Google Patents
A kind of composite cathode material for lithium ion cell and preparation method thereof and lithium ion battery Download PDFInfo
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- CN106486647A CN106486647A CN201510546424.2A CN201510546424A CN106486647A CN 106486647 A CN106486647 A CN 106486647A CN 201510546424 A CN201510546424 A CN 201510546424A CN 106486647 A CN106486647 A CN 106486647A
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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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- 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
Embodiments provide a kind of composite cathode material for lithium ion cell, including the negative active core-shell material and modification alloy-layer on described negative active core-shell material surface, described negative active core-shell material is silicon based anode material, and the material of described alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.This composite negative pole material, by carrying out surface modification acquisition using the amorphous alloy of good conductivity low cost to silicon based anode material, has high power capacity, the advantage of low cost, long-life and high magnification charge/discharge characteristics.The embodiment of the present invention additionally provides the preparation method of this composite cathode material for lithium ion cell, and this preparation method is modified to silicon based anode material using amorphous alloy using liquid solution method, and process is simple, without high-temperature heat treatment, without complex device, low cost, there is widespread commercial prospect.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of composite cathode material for lithium ion cell and
Its preparation method and lithium ion battery.
Background technology
Negative material is one of critical material of lithium ion battery, lithium ion battery negative material newly developed in the recent period
In, silica-base material is high because of specific capacity, has great Commercial Prospect, thus receives the extensive pass of industry
Note.Though but silica-base material has the feature of high power capacity, in presence easy generation gas, charge and discharge process
Change in volume is big, the problem of cycle life difference and high rate performance difference.Therefore, lift the research of its electrical property
Just seem more urgent.
In order to solve the above problems, current industry mainly adopts nanorize, filming, Composite and design multistage
The modes such as special construction it is modified, but effect is all undesirable, and its most of solution is required to
High-temperature process, preparation process complexity is it is difficult to realize commercialization, or the introducing of a large amount of inert matter is very big
Weaken the high power capacity advantage of material.
Content of the invention
In consideration of it, embodiment of the present invention first aspect provides a kind of composite cathode material for lithium ion cell, to solve
Certainly the volumetric expansion in charge and discharge process of existing silicon based anode material is big, and poorly conductive therefore leads to lithium ion
Circulating battery stability is poor, the bad problem of high rate performance, and in prior art, silicon-based anode is material modified
Need to carry out high-temperature process, preparation is complicated, is unfavorable for the problem commercially produced.
In a first aspect, embodiments providing a kind of composite cathode material for lithium ion cell, including negative pole
The active material and modification alloy-layer on described negative active core-shell material surface, described negative active core-shell material is silicon substrate
Negative material, the material of described alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.
Preferably, the material of described alloy-layer is Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B,
Ni-Sn-P, Ni-Cu-P, Fe-Ni alloy/C.
Preferably, the quality of described alloy-layer accounts for the 1-40% of described composite negative pole material gross mass.
Preferably, the thickness of described alloy-layer is 50nm-40 μm.
Preferably, described silicon based anode material includes pure silicon material, Si-C composite material, silicon/conducting polymer
Composite, silicon/metal oxide composite.
Composite cathode material for lithium ion cell of the present invention is using the good amorphous alloy of inexpensive electric conductivity (such as
Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B, Ni-Sn-P, Ni-Cu-P, Fe-Ni etc.
The alloy of alloy-layer can be formed on silica-base material surface) surface modification is carried out to silicon based anode material, amorphous
Alloy-layer not only can be greatly improved the electric conductivity of negative material, promotes the fast transport of electronics and lithium ion,
Greatly improve the high rate performance of negative material, meanwhile, amorphous alloy layer is also used as protective layer, plays
The effect of cushion, effectively alleviates the volumetric expansion of silicon based anode material, considerably increases lithium ion battery
Cyclical stability, can also reduce the generation of SEI film simultaneously, reduce the generation of side reaction.
Embodiment of the present invention first aspect provide a kind of composite cathode material for lithium ion cell, have high power capacity,
The advantage of low cost, long-life and high magnification charge/discharge characteristics, solves existing silicon based anode material in charge and discharge
In electric process, volumetric expansion is big, and poorly conductive therefore leads to lithium ion battery cyclical stability poor, forthright again
The bad problem of energy.
Second aspect, embodiments provides a kind of preparation of above-mentioned composite cathode material for lithium ion cell
Method, comprises the following steps：
(1) take negative active core-shell material, adopt HF solution to be surface-treated to remove surface oxide layer to it,
Then washed, described negative active core-shell material is silicon based anode material；
(2) negative active core-shell material after above-mentioned surface treatment is sequentially placed into stannum dichloride sensitizing solution and two respectively
In Palladous chloride. activating solution, stirring, then filter, washing, make described negative active core-shell material surface active, shape
Become reaction center, the negative active core-shell material after being activated；
(3) negative active core-shell material after above-mentioned activation is placed in chemical plating fluid, by electroless plating method described
Negative active core-shell material surface forms alloy-layer, then through filtering, washing, after being dried, obtain lithium ion battery multiple
Close negative material, described chemical plating fluid is the solion containing the metal constituting described alloy-layer, described lithium
Ion battery composite negative pole material includes negative active core-shell material and modifies the conjunction on described negative active core-shell material surface
Layer gold, the material of described alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.
Preferably, the material of described alloy-layer is Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B,
Ni-Sn-P, Ni-Cu-P, Fe-Ni alloy/C.
Preferably, in described plating process, reaction temperature is 20-95 DEG C, and the response time is 20min-4h.
Preferably, the quality of described alloy-layer accounts for the 1-40% of described composite negative pole material quality.
Preferably, the thickness of described alloy-layer is 50nm-40 μm.
Preferably, described silicon based anode material includes pure silicon material, Si-C composite material, silicon/conducting polymer
Composite, silicon/metal oxide composite.
Preferably, the mass concentration of described HF solution is 5-15%.
Preferably, described stannum dichloride sensitizing solution is the mixed solution that stannum dichloride is formed with hydrochloric acid, wherein two
The concentration of stannic chloride is 2-20g/L, and the concentration of hydrochloric acid is 20-80mL/L；Described palladium chloride activating solution is two
The mixed solution that Palladous chloride. is formed with hydrochloric acid, the wherein concentration of palladium chloride are 0.5-2g/L, and the concentration of hydrochloric acid is
10-30mL/L.
The preparation method of the composite cathode material for lithium ion cell that embodiment of the present invention second aspect provides, adopts
Liquid solution method is surface-treated to silicon based anode material using amorphous alloy, obtains good modification
Effect, the method preparation process is simple, without high-temperature heat treatment, without complex device, with traditional CVD,
The expensive surface modification method such as high-temperature heat treatment is compared, and the method cost substantially reduces, environmental friendliness,
Beneficial to commercially producing, prospect is extensive.
The third aspect, embodiments provides a kind of lithium ion battery negative electrode, including collector and
It is coated in lithium ion battery negative material on described collector, binding agent and conductive agent, described lithium-ion electric
Pond negative material is described in the above-mentioned first aspect of the present invention or the present invention above-mentioned second aspect preparation method is obtained
Composite cathode material for lithium ion cell.
Fourth aspect, embodiments provides a kind of lithium ion battery, described lithium ion battery by lithium from
Sub- negative pole piece of battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described lithium ion battery
Cathode pole piece is the lithium ion battery negative electrode described in the above-mentioned third aspect of the present invention.
The lithium ion battery that fourth aspect present invention provides has good cyclical stability and high rate performance.
The advantage of the embodiment of the present invention will partly illustrate in the following description, and a part according to description is
It will be apparent that or can be known by the enforcement of the embodiment of the present invention.
Brief description
Fig. 1 is SEM figure under 500nm enlargement ratio for the commercialization silica flour used by the embodiment of the present invention；
Fig. 2 is SEM figure under 1 μm of enlargement ratio for the commercialization silica flour used by the embodiment of the present invention；
Fig. 3 is SEM under 1 μm of enlargement ratio for the embodiment of the present invention one composite cathode material for lithium ion cell
Figure；
Fig. 4 is SEM under 2 μm of enlargement ratios for the embodiment of the present invention one composite cathode material for lithium ion cell
Figure.
Specific embodiment
Described below is the preferred implementation of the embodiment of the present invention it is noted that general for the art
For logical technical staff, on the premise of without departing from embodiment of the present invention principle, some improvement can also be made
And retouching, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of composite cathode material for lithium ion cell, to solve existing silicon
The volumetric expansion in charge and discharge process of base negative material is big, poorly conductive, therefore leads to lithium ion battery to circulate
Stability is poor, the bad problem of high rate performance, and in prior art, the material modified needs of silicon-based anode are carried out
High-temperature process, preparation is complicated, is unfavorable for the problem commercially produced.
In a first aspect, embodiments providing a kind of composite cathode material for lithium ion cell, including negative pole
The active material and modification alloy-layer on described negative active core-shell material surface, described negative active core-shell material is silicon substrate
Negative material, the material of described alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.
Preferably, the material of described alloy-layer is Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B,
Ni-Sn-P, Ni-Cu-P, Fe-Ni alloy/C.
Preferably, the quality of described alloy-layer accounts for the 1-40% of described composite negative pole material gross mass.It is highly preferred that
The quality of described alloy-layer accounts for the 10-20% of described composite negative pole material gross mass.
Preferably, the thickness of described alloy-layer is 50nm-40 μm.It is highly preferred that the thickness of described alloy-layer
For 1-25 μm.
Preferably, described silicon based anode material includes pure silicon material, Si-C composite material, silicon/conducting polymer
Composite, silicon/metal oxide composite.
Composite cathode material for lithium ion cell of the present invention is using the good amorphous alloy of inexpensive electric conductivity (such as
Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B, Ni-Sn-P, Ni-Cu-P, Fe-Ni etc.
The alloy of alloy-layer can be formed on silica-base material surface) surface modification is carried out to silicon based anode material, amorphous
Alloy-layer not only can be greatly improved the electric conductivity of negative material, promotes the fast transport of electronics and lithium ion,
Greatly improve the high rate performance of negative material, meanwhile, amorphous alloy layer is also used as protective layer, plays
The effect of cushion, effectively alleviates the volumetric expansion of silicon based anode material, considerably increases lithium ion battery
Cyclical stability, can also reduce the generation of SEI film simultaneously, reduce the generation of side reaction.
Embodiment of the present invention first aspect provide a kind of composite cathode material for lithium ion cell, have high power capacity,
The advantage of low cost, long-life and high magnification charge/discharge characteristics, solves existing silicon based anode material in charge and discharge
In electric process, volumetric expansion is big, and poorly conductive therefore leads to lithium ion battery cyclical stability poor, forthright again
The bad problem of energy.
Second aspect, embodiments provides a kind of preparation of above-mentioned composite cathode material for lithium ion cell
Method, comprises the following steps：
(1) take negative active core-shell material, adopt HF solution to be surface-treated to remove surface oxide layer to it,
Then washed, described negative active core-shell material is silicon based anode material；
(2) negative active core-shell material after above-mentioned surface treatment is sequentially placed into stannum dichloride sensitizing solution and two respectively
In Palladous chloride. activating solution, stirring, then filter, washing, make described negative active core-shell material surface active, shape
Become reaction center, the negative active core-shell material after being activated；
(3) negative active core-shell material after above-mentioned activation is placed in chemical plating fluid, by electroless plating method described
Negative active core-shell material surface forms alloy-layer, then through filtering, washing, after being dried, obtain lithium ion battery multiple
Close negative material, described chemical plating fluid is the solion containing the metal constituting described alloy-layer, described lithium
Ion battery composite negative pole material includes negative active core-shell material and modifies the conjunction on described negative active core-shell material surface
Layer gold, the material of described alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.
Preferably, the material of described alloy-layer is Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B,
Ni-Sn-P, Ni-Cu-P, Fe-Ni alloy/C.
Preferably, the quality of described alloy-layer accounts for the 1-40% of described composite negative pole material gross mass.It is highly preferred that
The quality of described alloy-layer accounts for the 10-20% of described composite negative pole material gross mass.
Preferably, the thickness of described alloy-layer is 50nm-40 μm.It is highly preferred that the thickness of described alloy-layer
For 1-25 μm.
Preferably, described silicon based anode material includes pure silicon material, Si-C composite material, silicon/conducting polymer
Composite, silicon/metal oxide composite.
Preferably, the mass concentration of described HF solution is 5-15%.The time that described HF solution surface is processed
It can be 10-25 minute.
In step (1), the operation of washing is the HF solution in order to clean silicon based anode material surface, and washing can
Carry out 1-3 time.
Preferably, described stannum dichloride sensitizing solution is the mixed solution that stannum dichloride is formed with hydrochloric acid, wherein two
The concentration of stannic chloride is 2-20g/L, and the concentration of hydrochloric acid is 20-80mL/L；Described palladium chloride activating solution is two
The mixed solution that Palladous chloride. is formed with hydrochloric acid, the wherein concentration of palladium chloride are 0.5-2g/L, and the concentration of hydrochloric acid is
10-30mL/L.
In step (2), the negative active core-shell material after surface treatment is first placed in stannum dichloride sensitizing solution and carries out
Activation, the time of stirring can be 5-40min, then be placed in palladium chloride activating solution and activated, stirring when
Between can be 5-40min.
In step (3), the concrete reaction temperature of plating process, response time and system pH are according to reality
Depending on the alloy-layer metal species to be coated with of border, can be with stirring operation.Preferably, described plating process
In, reaction temperature is 20-95 DEG C, and the response time is 20min-4h.
Described washing includes washing, and also can further include organic solvent washing.Organic solvent can be ethanol.
Described chemical plating fluid is the solion containing the metal constituting described alloy-layer, for example, the material of alloy-layer
Matter is Ni-P, and chemical plating fluid can be the solution containing Ni ion and phosphoric acid hydrogen radical ion.Specifically, chemical plating
Liquid can be actually needed preparation according to chemical plating.
Reducing agent, stabilizer, buffer agent, chelating agent and accelerator is may also include in described chemical plating fluid.Described
Reducing agent can be sodium dihydric hypophosphite, and stabilizer can be thiourea, ammonium sulfate, and buffer agent can be chlorination
Ammonium, Sodium Acetate Trihydrate, chelating agent can be lactic acid, citric acid, and accelerator can be sodium citrate.
The preparation method of the composite cathode material for lithium ion cell that embodiment of the present invention second aspect provides, adopts
Liquid solution method is surface-treated to silicon based anode material using amorphous alloy, obtains good modification
Effect, the method preparation process is simple, without high-temperature heat treatment, without complex device, with traditional CVD,
The expensive surface modification method such as high-temperature heat treatment is compared, and the method cost substantially reduces, environmental friendliness,
Beneficial to commercially producing, prospect is extensive.
The third aspect, embodiments provides a kind of lithium ion battery negative electrode, including collector and
It is coated in lithium ion battery negative material on described collector, binding agent and conductive agent, described lithium-ion electric
Pond negative material is described in the above-mentioned first aspect of the present invention or the present invention above-mentioned second aspect preparation method is obtained
Composite cathode material for lithium ion cell.
Fourth aspect, embodiments provides a kind of lithium ion battery, described lithium ion battery by lithium from
Sub- negative pole piece of battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described lithium ion battery
Cathode pole piece is the lithium ion battery negative electrode described in the above-mentioned third aspect of the present invention.
The lithium ion battery that fourth aspect present invention provides has good cyclical stability and high rate performance.
Below, point multiple embodiments are further detailed to the embodiment of the present invention taking commercialization silica flour as a example.
Wherein, the embodiment of the present invention is not limited to following specific embodiment.In the range of constant principal right, can
Implemented with suitable carrying out change.
Embodiment one
A kind of preparation method of composite cathode material for lithium ion cell, comprises the steps：
(1) take 1g commercialization silica flour, the HF solution using 200mL 5% mass concentration is surface-treated
10min, and cleaned 3 times using deionized water；
(2) the commercialization silica flour after above-mentioned surface treatment is added in 50mL stannum dichloride sensitizing solution and carries out
Activation, the wherein concentration of stannum dichloride are 15g/L, and the concentration of hydrochloric acid is 60mL/L, stirs 20min, mistake
Filter, washing；It is added to afterwards in 20mL palladium chloride activating solution, wherein the concentration of palladium chloride is 0.5g/L,
The concentration of hydrochloric acid is 10mL/L, stirs 20min, filters, washing, so that commercialization silicon powder surface is activated, shape
Become reaction center, the commercialization silica flour after being activated；
(3) the commercialization silica flour after activation is added in chemical plating fluid, 70 DEG C of stirring 60min, describedization
Plating solution is 2g NiSO4·7H2O, 3g NaH2PO2, 3g NaC2H3O2·3H2O (Sodium Acetate Trihydrate), 2.5g
Na3C6H5O7·2H2O (sodium citrate) and 0.1mg thiourea are added to formed in 100mL deionized water mixed
Close solution, after the completion of reaction, filter, gained material is washed, after being dried, obtain surface modification Ni-P alloy-layer
Composite cathode material for lithium ion cell, the thickness of alloy-layer is about 5 μm, mass percent shared by alloy-layer
It is about 7%, alloy layer thickness and mass fraction can adjust according to the quality of reactant and response time.
Fig. 1, Fig. 2 are commercialization silica flour used by the embodiment of the present invention respectively in 500nm and 1 μm of enlargement ratio
Under SEM figure；Fig. 3, Fig. 4 are the embodiment of the present invention one gained composite cathode material for lithium ion cell difference
SEM figure under 1 μm and 2 μm of enlargement ratios.It can be seen that commercialization silicon powder surface has rib
Angle, becomes block, gap hole is larger；Modified silica flour is gained lithium ion battery composite cathode of the present invention
Material surface is smooth, has spherical characteristics, between granule, gap is little, also a small amount of amorphous solid thing filling.
Embodiment two
A kind of preparation method of composite cathode material for lithium ion cell, comprises the steps：
(1) take 1g commercialization silica flour, the HF solution using 200mL 5% mass concentration is surface-treated
20min, and cleaned 3 times using deionized water；
(2) the commercialization silica flour after above-mentioned surface treatment is added in 100mL stannum dichloride sensitizing solution and carries out
Activation, the wherein concentration of stannum dichloride are 20g/L, and the concentration of hydrochloric acid is 80mL/L, stirs 30min, mistake
Filter, washing；It is added to afterwards in 50mL palladium chloride activating solution, wherein the concentration of palladium chloride is 2g/L,
The concentration of hydrochloric acid is 16.3mL/L, stirs 25min, filters, washing, so that commercialization silicon powder surface is activated,
Form reaction center, the commercialization silica flour after being activated；
(3) the commercialization silica flour after activation is added in chemical plating fluid, solution ph is maintained at 7-8,
92 ± 1 DEG C of stirrings keep 3h, and described chemical plating fluid is 8g Na2H2PO2·H2O, 4g six hydration nickel sulfate, 2.8g
Ammonium chloride, 1.6g citric acid, 3.2g sodium citrate and 1g Na2WO4·2H2O, is added to shape in 200mL water
The mixed solution becoming, filtration after having reacted, deionized water cleans products therefrom, 80 DEG C of drying, obtains table
The composite cathode material for lithium ion cell of Ni-W-P alloy-layer is modified in face.Alloy layer thickness is about 12 μm, closes
Shared by layer gold, mass percent is about 14%.
Embodiment three
A kind of preparation method of composite cathode material for lithium ion cell, comprises the steps：
(1) take 1g commercialization silica flour, the HF solution using 100mL10% mass concentration is carried out at surface
Reason 15min, and cleaned 3 times using deionized water；
(2) the commercialization silica flour after above-mentioned surface treatment is added in 50mL stannum dichloride sensitizing solution and carries out
Activation, the wherein concentration of stannum dichloride are 10g/L, and the concentration of hydrochloric acid is 20mL/L, stirs 20min, mistake
Filter, washing；It is added to afterwards in 30mL palladium chloride activating solution, wherein the concentration of palladium chloride is 1g/L,
The concentration of hydrochloric acid is 20mL/L, stirs 20min, filters, washing, so that commercialization silicon powder surface is activated, shape
Become reaction center, the commercialization silica flour after being activated；
(3) the commercialization silica flour after activation is added in chemical plating fluid, controls 9.0,88 ± 2 DEG C of pH anti-
Answer 3h, described chemical plating fluid is 10g NiSO4·6H2O, 0.5g SnCl2·2H2O, 10g NaH2PO2·H2O,
17.5g Na3C6H5O7·2H2O, 15g (NH4)2SO4It is added to shape in 500mL deionized water with 2mL lactic acid
The mixed solution becoming, filtration after having reacted, deionized water cleans products therefrom, 80 DEG C of drying, obtains table
The composite cathode material for lithium ion cell of Ni-Sn-P alloy-layer is modified in face.Alloy layer thickness is about 25 μm, closes
Shared by layer gold, mass percent is about 23%.
Example IV
A kind of preparation method of composite cathode material for lithium ion cell, comprises the steps：
(1) take 1g commercialization silica flour, the HF solution using 100mL10% mass concentration is carried out at surface
Reason 15min, and cleaned 3 times using deionized water；
(2) the commercialization silica flour after above-mentioned surface treatment is added in 50mL stannum dichloride sensitizing solution and carries out
Activation, the wherein concentration of stannum dichloride are 8g/L, and the concentration of hydrochloric acid is 36mL/L, stirs 20min, filters,
Washing；It is added to afterwards in 20mL palladium chloride activating solution, wherein the concentration of palladium chloride is 0.5g/L, salt
The concentration of acid is 30mL/L, stirs 20min, filters, washing, so that commercialization silicon powder surface is activated, is formed
Reaction center, the commercialization silica flour after being activated；
(3) the commercialization silica flour after activation is added in chemical plating fluid, 85 DEG C of stirring reactions 40min, institute
Stating chemical plating fluid is 0.5g nickel sulfate, 4.5g cobaltous sulfate, and, as reducing agent, 0.4g is no for 8g sodium dihydric hypophosphite
Water citric acid acid sodium is added to the deionized water of 200mL as stabilizer and 0.6g ammonium chloride as buffer agent
The mixed solution of middle formation, it is 9.0 that ammonia spirit controls pH, filtration after having reacted, and deionized water is cleaned
Products therefrom, dries, obtains the composite cathode material for lithium ion cell of surface modification Ni-Co-P alloy-layer.Close
Layer gold thickness is about 2 μm, and shared by alloy-layer, mass percent is about 3%.
Embodiment five
A kind of preparation method of composite cathode material for lithium ion cell, comprises the steps：
(1) take 1g commercialization silica flour, the HF solution using 100mL10% mass concentration is carried out at surface
Reason 25min, and cleaned 3 times using deionized water；
(2) the commercialization silica flour after above-mentioned surface treatment is added in 200mL stannum dichloride sensitizing solution and carries out
Activation, the wherein concentration of stannum dichloride are 18g/L, and the concentration of hydrochloric acid is 60mL/L, stirs 30min, mistake
Filter, washing；It is added to afterwards in 250mL palladium chloride activating solution, wherein the concentration of palladium chloride is 1.5g/L,
The concentration of hydrochloric acid is 21mL/L, stirs 20min, filters, washing, so that commercialization silicon powder surface is activated, shape
Become reaction center, the commercialization silica flour after being activated；
(3) the commercialization silica flour after activation is added in chemical plating fluid, 30 DEG C of stirring reactions 2h, describedization
Plating solution is 7g nickel sulfate, and 15g sodium citrate is added in 200mL deionized water, adds 11.6mL
Ammonia, stirs, and then adds 6g sodium hypophosphite and 9g Ferrous ammonium sulfate again, and stirring 1h is formed
Mixed solution, controls pH to be 9.2, filtration after having reacted, and deionized water cleans products therefrom, dries,
Obtain the composite cathode material for lithium ion cell of surface modification Fe-Ni alloy/C layer.Alloy layer thickness is about 18 μm,
Shared by alloy-layer, mass percent is about 16%.
The preparation of lithium ion battery negative electrode
Preparation-obtained composite cathode material for lithium ion cell in the embodiment of the present invention one to embodiment five is divided
Do not mix homogeneously with conductive agent (Super-p), be subsequently adding the sodium alginate binding agent of 10wt%, stirring is all
Even, obtain mixed slurry, above-mentioned mixed slurry is uniformly coated in 10 μm of copper foil current collector, at 110 DEG C
Toast 12h with vacuum condition, that is, obtain lithium ion battery negative electrode.Wherein, the formula of negative material is
(mass ratio) active substance：Super-P：Sodium alginate=70：10：20.
The preparation of lithium ion battery
Preparation-obtained lithium ion battery negative electrode in the embodiment of the present invention one to embodiment five is done respectively
Become 2032 type button cells, wherein, electrode is adopted with lithium metal, barrier film is celgard C2300, electrolyte
For 1.0M LiPF6EC and DEC (volume ratio be 1:1) solution.
Effect example
It is that the beneficial effect that embodiment of the present invention technical scheme is brought provides powerful support for, the following property of special offer
Can test：
Lithium electricity charge and discharge cycles test
Preparation-obtained button cell in the embodiment of the present invention one to embodiment five is lived with 100mA/g respectively
Current discharge to the voltage of property material is 0.01V, shelves 10mins afterwards；Again by above-mentioned button cell with
The electric current of 100mA/g active substance charges to 1.5V.Complete above-mentioned fill, discharge of electricity process be designated as 1 fill/electricity
Discharge cycles.The formula of the coulombic efficiency first of battery and capability retention is as follows respectively：
Discharge capacity × 100% of coulombic efficiency (%)=initial charge capacity/first first；
What discharge capacity/1st time of the capability retention (%) of n-th circulation=n-th circulation was circulated puts
Capacitance × 100%.
Button cell test result is as shown in table 1：
Table 1
To sum up, the preparation method of the composite cathode material for lithium ion cell that the above embodiment of the present invention provides, adopts
Liquid solution method carries out surface modification using amorphous alloy to silicon based anode material, and amorphous alloy layer is not only
The electric conductivity of negative material can be greatly improved, greatly improve the high rate performance of negative material, meanwhile, no fixed
Shape alloy-layer can also effectively alleviate the volumetric expansion of silicon based anode material, considerably increases lithium ion battery
Cyclical stability is so that composite cathode material for lithium ion cell has high power capacity, low cost, long-life and height
The advantage of multiplying power charge/discharge characteristics, and said method preparation process of the present invention is simple, without high-temperature heat treatment,
Without complex device, compared with surface modification method expensive with traditional CVD, high-temperature heat treatment etc.,
The method cost substantially reduces, environmental friendliness, and beneficial to commercially producing, prospect is extensive.
Claims (15)
1. a kind of composite cathode material for lithium ion cell is it is characterised in that including negative active core-shell material and repairing
The alloy-layer on described negative active core-shell material surface for the decorations, described negative active core-shell material is silicon based anode material, institute
The material stating alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.
2. composite cathode material for lithium ion cell as claimed in claim 1 is it is characterised in that described conjunction
The material of layer gold is Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B, Ni-Sn-P, Ni-Cu-P,
Fe-Ni alloy/C.
3. composite cathode material for lithium ion cell as claimed in claim 1 is it is characterised in that described conjunction
The quality of layer gold accounts for the 1-40% of described composite negative pole material gross mass.
4. composite cathode material for lithium ion cell as claimed in claim 1 is it is characterised in that described conjunction
The thickness of layer gold is 50nm-40 μm.
5. composite cathode material for lithium ion cell as claimed in claim 1 is it is characterised in that described silicon
Base negative material includes pure silicon material, Si-C composite material, silicon/conductive polymer composite, silicon/metal oxygen
Compound composite.
6. a kind of preparation method of composite cathode material for lithium ion cell is it is characterised in that include following walking
Suddenly：
(1) take negative active core-shell material, adopt HF solution to be surface-treated to remove surface oxide layer to it,
Then washed, described negative active core-shell material is silicon based anode material；
(2) negative active core-shell material after above-mentioned surface treatment is sequentially placed into stannum dichloride sensitizing solution and two respectively
In Palladous chloride. activating solution, stirring, then filter, washing, make described negative active core-shell material surface active, shape
Become reaction center, the negative active core-shell material after being activated；
(3) negative active core-shell material after above-mentioned activation is placed in chemical plating fluid, by electroless plating method described
Negative active core-shell material surface forms alloy-layer, then through filtering, washing, after being dried, obtain lithium ion battery multiple
Close negative material, described chemical plating fluid is the solion containing the metal constituting described alloy-layer, described lithium
Ion battery composite negative pole material includes negative active core-shell material and modifies the conjunction on described negative active core-shell material surface
Layer gold, the material of described alloy-layer is to carry out the alloy of chemical plating and no electro-chemical activity.
7. the preparation method of composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In, the material of described alloy-layer is Ni-P, Ni-W-P, Ni-Co-P, Ni-B, Ni-Cu, Ni-P-B, Ni-Sn-P,
Ni-Cu-P, Fe-Ni alloy/C.
8. the preparation method of composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In in described plating process, reaction temperature is 20-95 DEG C, and the response time is 20min-4h.
9. the preparation method of composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In the quality of described alloy-layer accounts for the 1-40% of described composite negative pole material quality.
10. the preparation method of composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In the thickness of described alloy-layer is 50nm-40 μm.
The preparation method of 11. composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In, described silicon based anode material include pure silicon material, Si-C composite material, silicon/conductive polymer composite,
Silicon/metal oxide composite.
The preparation method of 12. composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In the mass concentration of described HF solution is 5-15%.
The preparation method of 13. composite cathode material for lithium ion cell as claimed in claim 6, its feature exists
In the mixed solution that described stannum dichloride sensitizing solution is formed with hydrochloric acid for stannum dichloride, wherein stannum dichloride
Concentration is 2-20g/L, and the concentration of hydrochloric acid is 20-80mL/L；Described palladium chloride activating solution be palladium chloride with
The mixed solution that hydrochloric acid is formed, the wherein concentration of palladium chloride are 0.5-2g/L, and the concentration of hydrochloric acid is
10-30mL/L.
A kind of 14. lithium ion battery negative electrodes are it is characterised in that including collector and being coated in described collection
Lithium ion battery negative material on fluid, binding agent and conductive agent, described lithium ion battery negative material is
Composite cathode material for lithium ion cell as described in claim 1-5.
A kind of 15. lithium ion batteries are it is characterised in that described lithium ion battery is by lithium ion battery negative pole
Piece, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described lithium ion battery negative electrode is power
Profit requires the lithium ion battery negative electrode described in 14.
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| CN108832077A (en) * | 2018-04-25 | 2018-11-16 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of Copper-cladding Aluminum Bar core-shell structure Si-C composite material |
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