CN105633346A - Silicon anode of lithium-ion battery and preparation method of silicon anode and lithium-ion battery - Google Patents
Silicon anode of lithium-ion battery and preparation method of silicon anode and lithium-ion battery Download PDFInfo
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- CN105633346A CN105633346A CN201610207948.3A CN201610207948A CN105633346A CN 105633346 A CN105633346 A CN 105633346A CN 201610207948 A CN201610207948 A CN 201610207948A CN 105633346 A CN105633346 A CN 105633346A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 invention provides a silicon anode of a lithium-ion battery. The silicon anode comprises a silicon anode electrode plate and a porous conductive barrier layer, wherein the porous conductive barrier layer is compounded on the surface of the silicon anode electrode plate. A porous conductive material is compounded on a traditional silicon anode electrode plate; and a silicon anode electrode plate structure with the conductive barrier layer is formed on one surface, loaded with a silicon material, of the electrode plate. Through improvement of the silicon anode material structure by the conductive barrier layer, improvement of the cycle performance of the silicon anode material and improvement of the rate capability can be relatively simply and conveniently achieved. The corresponding preparation method of the silicon anode provided by the invention is simple and feasible, and has a large-scale application prospect.
Description
Technical field
The present invention relates to technical field of lithium ion, it is specifically related to a kind of lithium ion battery silicium cathode and preparation method, lithium ion battery.
Background technology
Lithium ion battery generally includes positive pole, negative pole, barrier film, electrolytic solution and housing, have operating voltage height, specific energy height, have extended cycle life, weight is light, self-discharge is few, memory-less effect and ratio of performance to price advantages of higher, has become the main alternative of the field rechargeable type power supplys such as superpower electric vehicle, man-made satellite, aerospace. Therefore lithium ion battery and associated materials thereof become the research focus of scientific research personnel.
But, along with people are for the higher requirement of cell container in electronics and long circulation life, the performance of existing lithium ion battery little by little cannot meet application demand. Wherein one of key factor determining performance of lithium ion battery is exactly negative material, and existing commercial lithium-ion batteries adopts graphite negative electrodes material mostly. This type of material has and has extended cycle life and the advantage of low cost. But, graphite negative electrodes materials theory capacity is lower, only 372mAh/g, and so low energy density cannot meet growing portable electronics, and energy storage establishes device and electromobile for the requirement of energy density. Therefore, develop the Novel cathode material for lithium ion battery with high-energy-density and seem more and more urgent.
Silicon receives much concern as a kind of negative material with very high theoretical capacity, it is reported that silicon has the theoretical specific capacity (4200mAh/g) of superelevation and lower de-lithium current potential (< 0.5V), and the voltage platform of silicon is a little more than graphite, when charging, difficulty causes surface analysis lithium, and safety performance is better. Enrich owing to it has reserves concurrently, the features such as cost is lower and discharge platform is lower and one of ideal chose becoming energy-density lithium ion battery negative material. But, the embedding of lithium ion of silicium cathode material in charge and discharge process works and deviating from, can make the Swelling and contraction of silicon materials experience 400%. Volume change so big in working cycle, the mechanicals efforts of generation can make the efflorescence gradually of silicium cathode material, causes structure to cave in, electrode active material and collector is finally caused to depart from, lose electrical contact so that electronics path is cut off, and finally causes cycle performance of battery greatly to reduce; In addition, due to this kind of volume effect, the continuous cracked meeting of silicium cathode material makes the SEI film of surface formation unstable, with the destruction of electrode structure, constantly form new SEI film at the silicon face exposed, exacerbate corrosion and the capacity attenuation of silicon so that charging efficiency is lower. Thus, the reason of these two aspects will make the cycle performance of silicium cathode material very poor.
Therefore, how to improve the cycle performance of silicon, obtain a kind of silicium cathode lithium-ion-power cell, be the Focal point and difficult point of current silicon based anode material research, be also forward position, this area scholar's problem demanding prompt solution.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of lithium ion silicium cathode and its preparation method, lithium ion battery, silicium cathode provided by the invention has better monolithic conductive, obviously improves the stable circulation performance of silicon cathode lithium ion battery.
The present invention provides a kind of lithium ion battery silicium cathode, comprises silicium cathode electrode slice and is compounded in the porous, electrically conductive interlayer on its surface.
Preferably, described porous, electrically conductive interlayer comprises porous, electrically conductive carbon material layer, porous, electrically conductive metal level or porous, electrically conductive organic matter layer.
Preferably, the mass ratio of the silica flour in described porous, electrically conductive interlayer and silicium cathode electrode slice is (1��10): 1.
Preferably, the thickness of described porous, electrically conductive interlayer is 0.1��20 ��m; The aperture of described porous, electrically conductive interlayer is 0.05��10 ��m.
Preferably, described porous, electrically conductive carbon material layer comprises one or more in graininess carbon material, one dimension fibre carbon material and graphene sheet layer carbon material.
Preferably, described one dimension fibre carbon material comprises carbon nanofiber cloth.
Preferably, the mass surface density of the carbon fiber on described silicium cathode electrode slice is 0.1��20mg/cm2��
The present invention provides the preparation method of a kind of lithium ion battery silicium cathode, comprises the following steps:
The load that porous, electrically conductive interlayer is placed on silicium cathode electrode slice has the one side of silicium cathode, after roll-in, obtains lithium ion battery silicium cathode.
Preferably, described silicium cathode electrode slice is obtained after preparation by silica flour;
The granularity of described silica flour is 20nm��30 ��m.
Present invention also offers a kind of lithium ion battery, comprise the lithium ion battery silicium cathode described in technique scheme any one or the lithium ion battery silicium cathode prepared by technique scheme any one.
The present invention provides a kind of lithium ion battery silicium cathode, comprises silicium cathode electrode slice and is compounded in the porous, electrically conductive interlayer on its surface. Compared with prior art, porous conductive material is compounded on traditional silicium cathode electrode slice by the present invention, has the one side of silicon materials in electrode slice load, forms the silicium cathode electrode slice structure with conduction interlayer. This kind of conduction interlayer is for the improvement on silicium cathode material structure, it is possible to easier realizes the raising of silicium cathode material cycle performance and the raising of high rate performance; Avoid the existing volume change being cushioned silicon by the minimizing of silicon grain size and the preparation of silicon carbon composite material, the inherent defect of the preparation process complexity existed, the preparation method of corresponding silicium cathode provided by the invention is simple, easy, possesses the prospect of large-scale application. Experimental result shows, silicium cathode electrode slice provided by the invention is under the circulating current of 4A/g, and capacity remains��40%; Adopt the lithium ion battery of silicium cathode electrode slice provided by the invention, it is possible to realize lower 40 stable circulation of 200mA/g (capacity keeps more than 90%).
Accompanying drawing explanation
Fig. 1 is the silicium cathode electrode slice simplified schematic diagram with porous, electrically conductive interlayer provided by the invention;
Fig. 2 is the cross section Electronic Speculum figure of silicium cathode electrode slice prepared by the embodiment of the present invention 1;
Fig. 3 be the embodiment of the present invention 1 prepare there is conductive carbon fibre interlayer and without cycle performance curve under 100mA/g electric current of the silicium cathode electrode slice of electro-conductive fiber interlayer;
Fig. 4 is the high rate performance of the silicium cathode electrode slice with conductive carbon fibre interlayer prepared by the embodiment of the present invention 1.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, it is understood that these describe just for the features and advantages of the present invention instead of the restriction to patent requirements of the present invention are described further.
The all raw materials of the present invention, be not particularly limited its source, that commercially buy or prepare according to ordinary method well known to those skilled in the art.
The all raw materials of the present invention, are not particularly limited its purity, and the present invention preferably adopts the purity requirement of analytical pure or field of lithium ion battery routine.
The present invention provides a kind of lithium ion battery silicium cathode, comprises silicium cathode electrode slice and is compounded in the porous, electrically conductive interlayer on its surface.
Lithium ion battery silicium cathode of the present invention is a kind of lithium ion battery silicium cathode with porous, electrically conductive interlayer. The mass ratio of described porous, electrically conductive interlayer and silicium cathode electrode slice is not particularly limited by the present invention, those skilled in the art can select according to practical condition, compound situation and product performance, the mass ratio of porous, electrically conductive interlayer of the present invention and silicium cathode electrode slice is preferably (1��10)��1, it is more preferably (2��9): 1, it is more preferably (3��8): 1, it is most preferred that be (4��7): 1. The thickness of described porous, electrically conductive interlayer is not particularly limited by the present invention, those skilled in the art can select according to practical condition, compound situation and product performance, the thickness of porous, electrically conductive interlayer of the present invention is preferably 0.1��20 ��m, it is more preferably 1��15 ��m, it is more preferably 3��13 ��m, it is most preferred that be 5��10 ��m; The aperture of described porous, electrically conductive interlayer is preferably 0.05��10 ��m, it is more preferable to be 0.1��8 ��m, it is more preferable to be 0.5��5 ��m, it is most preferred that be 1��3 ��m.
The material of described porous, electrically conductive interlayer is not particularly limited by the present invention, with porous conductive material well known to those skilled in the art, those skilled in the art can select according to practical condition, compound situation and product performance, porous, electrically conductive interlayer of the present invention preferably includes porous, electrically conductive carbon material layer, porous, electrically conductive metal level or porous, electrically conductive organic matter layer, it is more preferable to be porous, electrically conductive carbon material layer; Porous, electrically conductive interlayer of the present invention and layered porous electro-conductive material, described porous conductive material can be porous, electrically conductive carbon material, porous, electrically conductive metallic substance or porous, electrically conductive organic materials. The material of described porous, electrically conductive carbon material layer is not particularly limited by the present invention, with porous, electrically conductive carbon material well known to those skilled in the art, those skilled in the art can select according to practical condition, compound situation and product performance, porous, electrically conductive carbon material of the present invention preferably includes one or more in graininess carbon material, one dimension fibre carbon material and graphene sheet layer carbon material, it is more preferably graininess carbon material, one dimension fibre carbon material or graphene sheet layer carbon material, it is most preferred that be one dimension fibre carbon material. Described one dimension fibre carbon material is not particularly limited by the present invention, and with one dimension fibre carbon material well known to those skilled in the art, the present invention is preferably carbon nanofiber cloth.
The present invention better improves the conductivity of silicium cathode sheet and the performance of lithium cell, and when described conduction interlayer is porous, electrically conductive carbon material layer, the mass surface density of the carbon fiber on the silicium cathode electrode slice of silicium cathode provided by the invention is preferably 0.1��20mg/cm2, it is more preferable to it is 1��15mg/cm2, it is more preferable to it is 5��12mg/cm2, it is most preferred that it is 7��10mg/cm2. The concrete definition of described compound is not particularly limited by the present invention, with the definition of compound well known to those skilled in the art, in the present invention can for roll-in, coated and doping in one or more.
Described lithium ion battery silicon negative electrode sheet is not particularly limited by the present invention, with the silicium cathode electrode slice of lithium ion battery well known to those skilled in the art, those skilled in the art can understand the silicium cathode electrode slice of lithium ion battery of the present invention, i.e. silicium cathode sheet, except silicium cathode active material, it is preferable that also comprise cathode conductive agent, binding agent, solvent and collector etc.
Silicium cathode active material of the present invention is not particularly limited, and with lithium ion battery silicium cathode active material well known to those skilled in the art, negative active core-shell material of the present invention is preferably silica flour; Silica flour of the present invention is more preferably the silica flour of nanoscale and/or the silica flour of micro-meter scale, and the granularity of the silica flour of nanoscale of the present invention is preferably 20��500nm, it is more preferable to be 50��450nm, it is more preferable to be 100��400nm, it is most preferred that be 200��300nm; The granularity of the silica flour of micro-meter scale of the present invention is preferably 0.5��30 ��m, it is more preferable to be 1��25 ��m, it is more preferable to be 5��20 ��m, it is most preferred that be 10��15 ��m.
Cathode conductive agent of the present invention is not particularly limited, with cathode conductive agent well known to those skilled in the art, those skilled in the art can select according to practical condition, compound situation and product performance, cathode conductive agent of the present invention preferably includes acetylene black, Graphene, graphitized carbon black or other charcoal systems (carbon system) electro-conductive material, it is more preferable to be acetylene black or graphitized carbon black.
Binding agent of the present invention is not particularly limited, with binding agent well known to those skilled in the art, those skilled in the art can select according to practical condition, compound situation and product performance, binding agent of the present invention be preferably in polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinyl alcohol and carboxymethyl cellulose one or more; Collector of the present invention is not particularly limited, with the collector for silicium cathode electrode slice well known to those skilled in the art, those skilled in the art can select according to practical condition, compound situation and product performance, and collector of the present invention is preferably Copper Foil, aluminium foil or other sheet metals (such as stainless steel etc.).
Negative active core-shell material of the present invention, ratio between conductive agent and binding agent is not particularly limited, with conventional ratio well known to those skilled in the art, those skilled in the art can according to practical condition, compound situation and product performance are selected, negative active core-shell material of the present invention, the mass ratio of conductive agent and binding agent is preferably (9��3): (0.5��3.5): (0.5��3.5), it is more preferably (8��4): (1��3): (1��3), it most preferably is (7��5): (1.5��2.5): (1.5��2.5).
Present invention also offers the preparation method of a kind of lithium ion battery silicium cathode, it is characterised in that, comprise the following steps:
The load that porous, electrically conductive interlayer is placed on silicium cathode electrode slice has the one side of silicium cathode, after roll-in, obtains lithium ion battery silicium cathode.
The present invention is to, in described preparation method, the optimum principles such as the selection of the raw material of described lithium ion battery silicium cathode and ratio, as without dated especially, with the equal one_to_one corresponding in aforementioned lithium ion battery silicium cathode, this is no longer going to repeat them.
The source of described porous, electrically conductive interlayer is not particularly limited by the present invention, with preparation method well known to those skilled in the art preparation or commercially available buy, when conduction interlayer of the present invention is preferably carbon nanofiber cloth, described preparation method preferably adopts electrospinning process, obtains having the flexible carbon cloth of good electroconductibility and uniqueness. The step of described preparation has preferably:
The solution of high-molecular-weight organic material is carried out spinning and obtains organism non-woven fabrics; then the shape looks of nanofiber are kept by subzero treatment in air subsequently; the then pyroprocessing under rare gas element (argon gas, nitrogen etc.) is protected, it is possible to obtain carbon nanofiber cloth. The spinning solution that spinning uses comprises: polyacrylonitrile (PAN) solution, polyvinylpyrrolidone (PVP) solution, polyvinyl alcohol (PVA) solution or epoxidized ethylene (PEO) solution.
The source of described silicium cathode electrode slice is not particularly limited by the present invention, and with preparation method well known to those skilled in the art preparation or commercially available buy, the preparation process of silicium cathode electrode slice of the present invention has preferably:
The first preparation method is tradition preparation method: take the various materials required for the pure silicium cathode electrode slice of preparation, comprise: silica flour, conductive agent, binding agent and collector, wherein the mass ratio of silica flour, conductive agent and binding agent is preferably (9��3): (0.5��3.5): (0.5��3.5), concrete optimum principle is consistent with aforementioned silicium cathode electrode slice. Wherein, silica flour is preferably dimensioned to be 20nm��5 ��m, it is more preferable to be 50nm��3 ��m, it is more preferable to be 0.1 ��m��1 ��m, it is most preferred that be 0.3 ��m��0.7 ��m. Conductive agent is preferably acetylene black or graphitized carbon black, binding agent is preferably the compound binding agent of polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose or two or more binding agents above-mentioned, e.g., collector is preferably Copper Foil or other sheet metals (stainless steel etc.). After said components material is taken according to mass ratio, grind in specific solvent (such as N-methyl pyrrole network alkane ketone, water), obtain even silicium cathode slurry. By the coating of this slurry on a current collector, it is positioned in vacuum drying oven after so that solvent volatilizees completely, obtains dring silicon negative electrode sheet.
2nd kind of preparation method is: directly disperseed by solvent (such as water, ethanol) by silica flour, by coating on above-mentioned collector and solvent volatilization, obtains silicium cathode electrode slice.
The concrete parameter of described roll-in is not particularly limited by the present invention, those skilled in the art can carry out selecting and adjusting according to practical condition, compound situation and product performance, the pressure of roll-in of the present invention is preferably 0.5��5MPa, it is more preferable to be 1��4MPa, it is most preferred that be 2��3MPa; The number of times of roll-in of the present invention is preferably 2��5 times, it is more preferable to be 2��4 times, it is most preferred that be 2��3 times.
The detailed process of described preparation method is not particularly limited by the present invention, and those skilled in the art can carry out selecting and adjusting according to practical condition, compound situation and product performance, and the detailed process of preparation method of the present invention is preferably:
The silicium cathode electrode slice adopting above-mentioned tradition preparation method to prepare is carried out punching, obtains the silicium cathode electrode slice of desired shape. Then carbon nanofiber cloth above-mentioned steps prepared, shears according to the shape of silicium cathode electrode slice after punching. Subsequently, carbon nanofiber cloth is placed on silicium cathode electrode slice, namely it is placed on electrode slice and says that load has the one side of silicium cathode, after both are carried out repeatedly roll-in by roll squeezer, make carbon nanofiber cloth can be attached on silicium cathode electrode slice, remove roll-in process is failed be attached to carbon fiber cracked on silicium cathode electrode slice subsequently, obtain having the silicium cathode electrode slice of conduction interlayer.
It is the silicium cathode electrode slice schematic diagram with porous, electrically conductive interlayer provided by the invention see Fig. 1, Fig. 1.
The invention also discloses the above-mentioned application of silicium cathode electrode slice in high-energy density type energy storage device with conduction interlayer, concrete, the present invention provides a kind of lithium ion battery, comprises the lithium ion battery silicium cathode described in technique scheme any one or the lithium ion battery silicium cathode prepared by technique scheme any one.
The present invention is to optimum principles such as the selection of described lithium ion battery silicium cathode and ratios, as dated especially in nothing, and with the equal one_to_one corresponding in aforementioned lithium ion battery silicium cathode, this is no longer going to repeat them. Other structures of described lithium ion battery and selection are not particularly limited by the present invention, with lithium ion battery well known to those skilled in the art.
Porous conductive material is compounded on traditional silicium cathode electrode slice by applying pressure or add the modes such as binding agent by the present invention, has the one side of silicon materials in electrode slice load, forms the silicium cathode electrode slice structure with conduction interlayer. This kind of conduction interlayer is for the improvement on silicium cathode material structure, it is possible to easier realizes the raising of silicium cathode material cycle performance and the raising of high rate performance; Avoid the existing volume change being cushioned silicon by the minimizing of silicon grain size and the preparation of silicon carbon composite material, the inherent defect of the preparation process complexity existed, the preparation method of corresponding silicium cathode provided by the invention is simple, easy, possesses the prospect of large-scale application. Experimental result shows, silicium cathode electrode slice provided by the invention is under the circulating current of 4A/g, and capacity remains��40%; Adopt the lithium ion battery of silicium cathode electrode slice provided by the invention, it is possible to realize lower 40 stable circulation of 200mA/g (capacity keeps more than 90%).
In order to understand the present invention further, a kind of lithium ion battery silicium cathode provided by the invention and preparation method thereof, lithium ion battery being described below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Select the commercialization nano silica fume (��100nm) of Sigma-Aldrich as active material, acetylene black prepares silicium cathode slurry as conductive agent, the polyvinylidene difluoride (PVDF) solution (solvent is N-Methyl pyrrolidone) of 5wt% as binding agent. Wherein, the mass ratio of nano silica fume, conductive agent and binding agent is 60:20:20. Then, being coated on Copper Foil by mixed uniformly slurry, through drying, make the silicium cathode electrode slice that thickness is 20 ��m, face mass density is 0.6mg/cm2��
With polyacrylonitrile (PAN, molecular weight is 150000, Sigma-Aldrich) it is solute, dimethyl formamide (DMF, Chemical Reagent Co., Ltd., Sinopharm Group) it is solvent, preparation concentration is that the PAN solution of 8.5wt% is as spinning precursor liquid. Carrying out spinning by single syringe needle electrostatic spinning machine, spinning condition is: the spinning voltage that syringe needle place applies is 16��19kV, and the syringe speed of injecting is: 19.00mL/min, and the distance between collecting board and syringe needle is 21cm. The PAN non-woven fabrics obtained by electrostatic spinning first by processing 3 hours at air atmosphere 280 DEG C; then at rare gas element (argon gas) protects lower 1000 DEG C, carbonization obtains flexible carbon fibre cloth in 8 hours, and wherein the diameter of carbon nanofiber is 150��200nm.
The silicium cathode electrode slice obtained and flexible carbon fibre cloth are obtained, respectively through punching, the circular piece that diameter is 1cm, then carbon cloth is placed on the one side that circular silicium cathode electrode slice load has silicon, by both by 3 roll-ins, carbon fiber is made to be attached on silicium cathode electrode slice, forming the silicium cathode electrode slice with conduction interlayer, the quality of interlayer of wherein conducting electricity is 1.56mg.
See the silicium cathode electrode slice cross section Electronic Speculum figure that Fig. 2, Fig. 2 are reality prepared by the embodiment of the present invention 1.
The silicium cathode electrode slice with porous, electrically conductive interlayer above-mentioned steps of the present invention prepared carries out Performance Detection, and concrete steps are as follows:
Using metal lithium sheet as negative pole; microporous polypropylene membrane (Celgard2400) is as barrier film; the silicium cathode electrode slice with conduction interlayer is as positive pole; 1mol/LLiPF6 NSC 11801 and the diethyl carbonate mixed solution of 1:1 (solvent to be volume ratio be) is as electrolytic solution; the glove box of argon gas shielded is assembled into CR2032 button cell; carrying out charge-discharge test, test procedure is 200mA/g, and discharge and recharge interval is 0.001��1.2V.
See Fig. 3, Fig. 3 be the embodiment of the present invention 1 prepare there is conductive carbon fibre interlayer and without cycle performance curve under 100mA/g electric current of the silicium cathode electrode slice of electro-conductive fiber interlayer. As shown in Figure 3, pure silicium cathode material almost will cannot carry out discharge and recharge after 10 circulations, and the silicium cathode electrode slice in the present invention with porous, electrically conductive fiber interlayer can realize lower 40 stable circulation of 200mA/g (capacity keeps more than 90%). And after 40 circulations, by can be calculated, the capacity contribution of silicon is��2700mAh/g.
In addition, above-mentioned electrode slice is carried out high rate performance test, it is the high rate performance of the silicium cathode electrode slice with conductive carbon fibre interlayer prepared by the embodiment of the present invention 1 see Fig. 4, Fig. 4. As shown in Figure 4, under 0.4,0.65,1,2,2.5 and 4A/g current density, the capacity contribution of silicon is respectively 3240,2600,2250,1678,1400 and 870mAh/g.
Embodiment 2
Select the commercialization nano silica fume (��100nm) of Sigma-Aldrich as active material, acetylene black prepares silicium cathode slurry as conductive agent, the polyvinylidene difluoride (PVDF) solution (solvent is N-Methyl pyrrolidone) of 5wt% as binding agent. Wherein, the mass ratio of nano silica fume, conductive agent and binding agent is 60:20:20. Then, being coated on Copper Foil by mixed uniformly slurry, through drying, make the silicium cathode electrode slice that thickness is 26 ��m, face mass density is 1.17mg/cm2��
Same flexible carbon nanofiber cloth is prepared with electrospinning process in embodiment 1.
The silicium cathode electrode slice obtained and flexible carbon fibre cloth are obtained, respectively through punching, the circular piece that diameter is 1cm, then carbon cloth is placed on the one side that circular silicium cathode electrode slice load has silicon, by both by 3 roll-ins, carbon fiber is made to be attached on silicium cathode electrode slice, forming the silicium cathode electrode slice with conduction interlayer, the quality of interlayer of wherein conducting electricity is 2.5mg.
The silicium cathode electrode slice with porous, electrically conductive interlayer above-mentioned steps of the present invention prepared carries out Performance Detection, and concrete steps are as follows:
Using metal lithium sheet as negative pole; microporous polypropylene membrane (Celgard2400) is as barrier film; the silicium cathode electrode slice with conduction interlayer is as positive pole; 1mol/LLiPF6 NSC 11801 and the diethyl carbonate mixed solution of 1:1 (solvent to be volume ratio be) is as electrolytic solution; the glove box of argon gas shielded is assembled into CR2032 button cell; carrying out charge-discharge test, test procedure is 200mA/g, and discharge and recharge interval is 0.001��1.2V.
The silicium cathode electrode slice in this embodiment with porous, electrically conductive fiber interlayer can realize lower 40 stable circulation of 200mA/g (capacity keeps more than 90%). And after 40 circulations, by can be calculated, the capacity contribution of silicon is��3000mAh/g.
Embodiment 3
Select the commercialization nano silica fume (��100nm) of Sigma-Aldrich as active material, acetylene black prepares silicium cathode slurry as conductive agent, the polyvinylidene difluoride (PVDF) solution (solvent is N-Methyl pyrrolidone) of 5wt% as binding agent. Wherein, the mass ratio of nano silica fume, conductive agent and binding agent is 60:20:20. Then, being coated on Copper Foil by mixed uniformly slurry, through drying, make the silicium cathode electrode slice that thickness is 32 ��m, face mass density is 1.96mg/cm2��
Same flexible carbon nanofiber cloth is prepared with electrospinning process in embodiment 1.
The silicium cathode electrode slice obtained and flexible carbon fibre cloth are obtained, respectively through punching, the circular piece that diameter is 1cm, then carbon cloth is placed on the one side that circular silicium cathode electrode slice load has silicon, by both by 3 roll-ins, carbon fiber is made to be attached on silicium cathode electrode slice, forming the silicium cathode electrode slice with conduction interlayer, the quality of interlayer of wherein conducting electricity is 2.59mg.
The silicium cathode electrode slice with porous, electrically conductive interlayer above-mentioned steps of the present invention prepared carries out Performance Detection, and concrete steps are as follows:
Using metal lithium sheet as negative pole; microporous polypropylene membrane (Celgard2400) is as barrier film; the silicium cathode electrode slice with conduction interlayer is as positive pole; 1mol/LLiPF6 NSC 11801 and the diethyl carbonate mixed solution of 1:1 (solvent to be volume ratio be) is as electrolytic solution; the glove box of argon gas shielded is assembled into CR2032 button cell; carrying out charge-discharge test, test procedure is 200mA/g, and discharge and recharge interval is 0.001��1.2V.
The silicium cathode electrode slice in this embodiment with porous, electrically conductive fiber interlayer can realize lower 30 stable circulation of 200mA/g (capacity keeps more than 90%). And after 30 circulations, by can be calculated, the capacity contribution of silicon is��2900mAh/g.
Above a kind of lithium ion battery silicium cathode provided by the invention and preparation method thereof, lithium ion battery are described in detail; apply specific case herein the principle of the present invention and enforcement mode to have been set forth; illustrating just for helping the method understanding the present invention and core concept thereof of above embodiment; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; the present invention can also carry out some improvement and modification, and these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a lithium ion battery silicium cathode, it is characterised in that, comprise silicium cathode electrode slice and it is compounded in the porous, electrically conductive interlayer on its surface.
2. silicium cathode according to claim 1, it is characterised in that, described porous, electrically conductive interlayer comprises porous, electrically conductive carbon material layer, porous, electrically conductive metal level or porous, electrically conductive organic matter layer.
3. silicium cathode according to claim 1, it is characterised in that, the mass ratio of the silica flour in described porous, electrically conductive interlayer and silicium cathode electrode slice is (1��10): 1.
4. silicium cathode according to claim 1, it is characterised in that, the thickness of described porous, electrically conductive interlayer is 0.1��20 ��m; The aperture of described porous, electrically conductive interlayer is 0.05��10 ��m.
5. silicium cathode according to claim 2, it is characterised in that, described porous, electrically conductive carbon material layer comprises one or more in graininess carbon material, one dimension fibre carbon material and graphene sheet layer carbon material.
6. silicium cathode according to claim 5, it is characterised in that, described one dimension fibre carbon material comprises carbon nanofiber cloth.
7. silicium cathode according to claim 6, it is characterised in that, the mass surface density of the carbon fiber on described silicium cathode electrode slice is 0.1��20mg/cm2��
8. the preparation method of a lithium ion battery silicium cathode, it is characterised in that, comprise the following steps:
The load that porous, electrically conductive interlayer is placed on silicium cathode electrode slice has the one side of silicium cathode, after roll-in, obtains lithium ion battery silicium cathode.
9. preparation method according to claim 8, it is characterised in that, described silicium cathode electrode slice is obtained after preparation by silica flour;
The granularity of described silica flour is 20nm��30 ��m.
10. a lithium ion battery, it is characterised in that, comprise the lithium ion battery silicium cathode described in claim 1��7 any one or the lithium ion battery silicium cathode prepared by claim 8��9 any one.
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