CN104347858A - Lithium ion secondary cell cathode active material and preparation method thereof, lithium ion secondary cell cathode pole piece and lithium ion secondary cell - Google Patents
Lithium ion secondary cell cathode active material and preparation method thereof, lithium ion secondary cell cathode pole piece and lithium ion secondary cell Download PDFInfo
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- CN104347858A CN104347858A CN201310323914.7A CN201310323914A CN104347858A CN 104347858 A CN104347858 A CN 104347858A CN 201310323914 A CN201310323914 A CN 201310323914A CN 104347858 A CN104347858 A CN 104347858A
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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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- 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
- 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
The invention provides a lithium ion secondary cell cathode active material, the lithium ion secondary cell cathode active material comprises a silicon-based active substance and a nitrogen-doped carbon material, the silicon-based active substance is loaded on the surface of the nitrogen-doped carbon material, the silicon-based active substance is one or more of nano particles and nano wire, the nitrogen-doped carbon material is presented in a three dimensional net, and comprises several mutually crosslinked branches, at least a micropore is arranged on the nitrogen-doped carbon material and in the carbon material, and the material of the nitrogen-doped carbon material is nitrogen-doped carbon net. The lithium ion secondary cell cathode active material solves the problem of large volume change of the silicon material for making the cathode active material, easy shedding from a current collector and low conductivity in prior art. The invention also provides a preparation method of the lithium ion secondary cell cathode active material, a lithium ion secondary cell cathode pole piece containing the lithium ion secondary cell cathode active material and a lithium ion secondary cell containing the lithium ion secondary cell cathode active material.
Description
Technical field
The present invention relates to field of lithium ion secondary, particularly relate to a kind of negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery.
Background technology
Along with mancarried electronic aid and the requirement of electric automobile to energy density more and more higher, the research and development of high performance lithium ion secondary battery seem and become more and more important.
Pure silicon material because having higher theoretical capacity (up to 4200mAh/g), good embedding/deviate from ability becomes the new and effective storage lithium titanate cathode material of the most promising class.But silicon materials change in volume in the process of removal lithium embedded, more than 300%, it can be caused very easily to come off from collector, and the conductivity of silicon materials own is lower.Current industry mainly adopts nanometer, filming, Composite and designs multistage special construction four kinds of modes carries out modification to it, but effect is all undesirable, or preparation process is complicated, be difficult to realize commercialization, or the introducing of a large amount of inert matter greatly slackens the high power capacity advantage of pure silicon material.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of novel negative electrode of lithium ionic secondary battery, to solve when silicon materials in prior art do negative active core-shell material change in volume great Yi from the problem that collector comes off and conductivity is low.
First aspect, embodiments provide a kind of negative electrode of lithium ionic secondary battery, comprise the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
Preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 0.1% ~ 80% than content.
Preferably, the ratio of the diameter of the material with carbon element branch of described N doping and the particle diameter of described silicon-based active material nano particle is 1 ~ 10:1.
Preferably, the pore-size distribution of described micropore is at 0.5 ~ 500nm.
Preferably, pyrroles's type nitrogen is contained in described nitrogen-doped carbon net.Pyrroles's type nitrogen in nitrogen-doped carbon net can with Li
+be combined into key, there is good storage lithium performance.
Preferably, the material of described silicon-based active material is selected from one or more in elemental silicon, Si oxide and silicon alloy.
Compared with prior art, embodiment of the present invention first aspect provides a kind of negative electrode of lithium ionic secondary battery, the load of silicon-based active material is at the carbon material surface of N doping, silicon-based active material is combined with collector by the material with carbon element of N doping, carbon material surface and inner at least one place of N doping have micropore, the micropore of the material with carbon element of N doping can be the expansion headspace of silicon-based active material, and the material with carbon element of N doping is three-dimensional netted, the constraint that silicon-based active material after expansion is subject to the material with carbon element of N doping can not come off, to solve when silicon materials in prior art do negative active core-shell material change in volume great Yi from the problem that collector comes off and conductivity is low, substantially prolongs the useful life of negative electrode of lithium ionic secondary battery, nitrogen-doped carbon net can improve the whole conductivity of the material with carbon element composite material of silicon-based active material/N doping simultaneously, and nitrogen-doped carbon net self has the high power capacity that certain capacity adds silicon-based active material self, negative electrode of lithium ionic secondary battery is made to have high power capacity advantage.In addition, negative electrode of lithium ionic secondary battery cost is lower is easy to suitability for industrialized production.
Second aspect, embodiments provides a kind of preparation method of negative electrode of lithium ionic secondary battery, and the one is by the following method prepared:
Method one: by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material, obtained negative electrode of lithium ionic secondary battery;
Method two: by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material, obtained negative electrode of lithium ionic secondary battery;
Method three: by the pyrolysis product of ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide and the blended obtained mixed solution of silicon precursor solution, described silicon precursor is γ-aminopropyl three ethoxy silane, γ-(2, 3-epoxy third oxygen) one or more in propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane, by heating water bath after described mixed solution ultrasonic disperse, complexing agent is instilled in described water-bath system, subsequently by the mixed solution stirring reaction containing complexing agent, by sintering after reacted product baking, obtained negative electrode of lithium ionic secondary battery,
Described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
Preferably, described in method one by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material be: get nitrogen-doped carbon net and be placed in tube furnace, tube furnace is vacuumized, by volume for the ratio of 1:0.1 ~ 10 passes into silicon source SiH
4and protective gas, control throughput is 30 ~ 300sccm, with the heating rate of 1 ~ 50 DEG C/min by being warming up to 500 ~ 1300 DEG C in tube furnace and being incubated 3 ~ 60min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Preferably, described in method two by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material be: get nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0 ~ 10
-2pa, to pass into throughput be the protective gas of 10 ~ 300sccm is 1 ~ 10Pa to pressure in magnetron sputtering cavity, and control power is 10 ~ 200W, at 100 ~ 400 DEG C of sputtering 1 ~ 10min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Preferably; the mass ratio of ionic liquid pyrolysis product described in method three and described silicon precursor is 1:0.1 ~ 5; described complexing agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate; mixed solution constant temperature containing complexing agent 50 ~ 100 DEG C is stirred lower reaction 0.5 ~ 5h; reacted product is toasted 1 ~ 24h under 50 ~ 100 DEG C of vacuum; proceed in atmosphere sintering furnace, under protective gas atmosphere, 500 ~ 1300 DEG C of sintering 1 ~ 10h, are cooled to room temperature subsequently again.
Preparation method's technique of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides is simple and convenient, and cost is low, is easy to suitability for industrialized production.
The third aspect, embodiments provide a kind of cathode pole piece of lithium ion secondary battery, described cathode pole piece of lithium ion secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
A kind of cathode pole piece of lithium ion secondary battery long service life that the embodiment of the present invention third aspect provides and conductivity is good.
Fourth aspect, embodiments provide a kind of lithium rechargeable battery, described lithium rechargeable battery is by cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
The lithium rechargeable battery long service life that embodiment of the present invention fourth aspect provides and conductivity is good.
Embodiment of the present invention first aspect provides a kind of negative electrode of lithium ionic secondary battery, the load of silicon-based active material is at the carbon material surface of N doping, silicon-based active material is combined with collector by the material with carbon element of N doping, carbon material surface and inner at least one place of N doping have micropore, the micropore of the material with carbon element of N doping can be the expansion headspace of silicon-based active material, and the material with carbon element of N doping is three-dimensional netted, the constraint that silicon-based active material after expansion is subject to the material with carbon element of N doping can not come off, to solve when silicon materials in prior art do negative active core-shell material change in volume great Yi from the problem that collector comes off and conductivity is low, substantially prolongs the useful life of negative electrode of lithium ionic secondary battery, nitrogen-doped carbon net can improve the whole conductivity of the material with carbon element composite material of silicon-based active material/N doping simultaneously, and nitrogen-doped carbon net self has the high power capacity that certain capacity adds silicon-based active material self, negative electrode of lithium ionic secondary battery is made to have high power capacity advantage.In addition, negative electrode of lithium ionic secondary battery cost is lower is easy to suitability for industrialized production.Preparation method's technique of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides is simple and convenient, and cost is low, is easy to suitability for industrialized production.A kind of cathode pole piece of lithium ion secondary battery that the embodiment of the present invention third aspect provides and the lithium rechargeable battery long service life that fourth aspect provides and conductivity is good.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the SEM Electronic Speculum figure of the negative electrode of lithium ionic secondary battery that the embodiment of the present invention one obtains.
Fig. 2 is the structural representation of nitrogen-doped carbon net in the obtained negative electrode of lithium ionic secondary battery of the embodiment of the present invention two.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of novel negative electrode of lithium ionic secondary battery, to solve when silicon materials in prior art do negative active core-shell material change in volume great Yi from the problem that collector comes off and conductivity is low.Embodiment of the present invention second aspect provides the preparation method of described negative electrode of lithium ionic secondary battery, and technique is simple and convenient, and cost is low, is easy to suitability for industrialized production.The embodiment of the present invention third aspect provides the cathode pole piece of lithium ion secondary battery comprising described negative electrode of lithium ionic secondary battery, and embodiment of the present invention fourth aspect provides the lithium rechargeable battery comprising described negative electrode of lithium ionic secondary battery.
First aspect, embodiments provide a kind of negative electrode of lithium ionic secondary battery, comprise the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
Preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 0.1% ~ 80% than content.More preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 5% ~ 50% than content.Further preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 15% ~ 30% than content.
Preferably, the diameter of the material with carbon element branch of described N doping is 30nm ~ 5 μm.
Preferably, the pore-size distribution of described micropore is at 0.5 ~ 500nm.More preferably, the pore-size distribution of described micropore is at 2 ~ 100nm.
Preferably, the ratio of the diameter of the material with carbon element branch of described N doping and the particle diameter of described silicon-based active material nano particle is 1 ~ 10:1.
Carbon material surface or the inside of N doping have microcellular structure, or have microcellular structure at the carbon material surface of N doping and inside.
Preferably, pyrroles's type nitrogen is contained in described nitrogen-doped carbon net.Pyrroles's type nitrogen in nitrogen-doped carbon net can with Li
+be combined into key, there is good storage lithium performance.
Preferably, the material of described silicon-based active material is selected from one or more in elemental silicon, Si oxide and silicon alloy.
Preferably, the particle diameter of described silicon-based active material nano particle is 30nm ~ 200nm.
Preferably, the nano wire of described silicon-based active material and the diameter of nanometer rods are 10 ~ 100nm and length is 2 ~ 5 μm.
Embodiment of the present invention first aspect provides a kind of negative electrode of lithium ionic secondary battery, the load of silicon-based active material is at the carbon material surface of N doping, silicon-based active material is combined with collector by the material with carbon element of N doping, carbon material surface and inner at least one place of N doping have micropore, the micropore of the material with carbon element of N doping can be the expansion headspace of silicon-based active material, and the material with carbon element of N doping is three-dimensional netted, the constraint that silicon-based active material after expansion is subject to the material with carbon element of N doping can not come off, to solve when silicon materials in prior art do negative active core-shell material change in volume great Yi from the problem that collector comes off and conductivity is low, substantially prolongs the useful life of negative electrode of lithium ionic secondary battery, nitrogen-doped carbon net can improve the whole conductivity of the material with carbon element composite material of silicon-based active material/N doping simultaneously, and nitrogen-doped carbon net self has the high power capacity that certain capacity adds silicon-based active material self, negative electrode of lithium ionic secondary battery is made to have high power capacity advantage.In addition, negative electrode of lithium ionic secondary battery cost is lower is easy to suitability for industrialized production.
Second aspect, embodiments provides a kind of preparation method of negative electrode of lithium ionic secondary battery, and the one is by the following method prepared:
Method one: by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material, obtained negative electrode of lithium ionic secondary battery;
Method two: by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material, obtained negative electrode of lithium ionic secondary battery;
Method three: by the pyrolysis product of ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide and the blended obtained mixed solution of silicon precursor solution, described silicon precursor is γ-aminopropyl three ethoxy silane, γ-(2, 3-epoxy third oxygen) one or more in propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane, by heating water bath after described mixed solution ultrasonic disperse, complexing agent is instilled in described water-bath system, subsequently by the mixed solution stirring reaction containing complexing agent, by sintering after reacted product baking, obtained negative electrode of lithium ionic secondary battery,
Described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
Preferably, described in method one by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material be: get nitrogen-doped carbon net and be placed in tube furnace, tube furnace is vacuumized, by volume for the ratio of 1:0.1 ~ 10 passes into silicon source SiH
4and protective gas, control throughput is 30 ~ 300sccm, with the heating rate of 1 ~ 50 DEG C/min by being warming up to 500 ~ 1300 DEG C in tube furnace and being incubated 3 ~ 60min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.Get nitrogen-doped carbon net and be placed in quartz ampoule, tube furnace is vacuumized, by volume for the ratio of 1:0.1 ~ 10 passes into silicon source SiH
4and protective gas, control throughput is 30 ~ 300sccm, with the heating rate of 1 ~ 50 DEG C/min by being warming up to 500 ~ 1300 DEG C in tube furnace and being incubated 3 ~ 60min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Preferably, described in method two by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material be: get nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0 ~ 10
-2pa, to pass into throughput be the protective gas of 10 ~ 300sccm is 1 ~ 10Pa to pressure in magnetron sputtering cavity, and control power is 10 ~ 200W, at 100 ~ 400 DEG C of sputtering 1 ~ 10min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.Get nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0 ~ 10
-2pa, to pass into throughput be the protective gas of 10 ~ 300sccm is 1 ~ 10Pa to pressure in magnetron sputtering cavity, and control power is 10 ~ 200W, at 100 ~ 400 DEG C of sputtering 1 ~ 10min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Preferably; the mass ratio of ionic liquid pyrolysis product described in method three and described silicon precursor is 1:0.1 ~ 5; described complexing agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate; mixed solution constant temperature containing complexing agent 50 ~ 100 DEG C is stirred lower reaction 0.5 ~ 5h; reacted product is toasted 1 ~ 24h under 50 ~ 100 DEG C of vacuum; proceed in atmosphere sintering furnace, under protective gas atmosphere, 500 ~ 1300 DEG C of sintering 1 ~ 10h, are cooled to room temperature subsequently again.Get ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide is placed in ceramic crucible, proceed in tube furnace, pass into protective gas, to 400 ~ 800 DEG C be warming up to the heating rate of 1 ~ 10 DEG C/min in tube furnace and be incubated 1 ~ 10h, be cooled to room temperature subsequently, obtained ionic liquid pyrolysis product, subsequently by described ionic liquid pyrolysis product and the blended obtained mixed solution of silicon precursor solution, described silicon precursor is γ-aminopropyl three ethoxy silane, γ-(2,3-epoxy third oxygen) one or more in propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane, the mass ratio of described ionic liquid pyrolysis product and described silicon precursor is 1:0.1 ~ 5, by described mixed solution ultrasonic disperse 5 ~ 60min, with being placed on heating water bath to 50 ~ 100 DEG C in container, complexing agent is instilled in described container, described complexing agent is citric acid, tartaric acid, one or more of EDTA and sodium succinate, mixed solution constant temperature containing complexing agent 50 ~ 100 DEG C is stirred lower reaction 0.5 ~ 5h subsequently, reacted product is toasted 1 ~ 24h under 50 ~ 100 DEG C of vacuum, proceed to again in atmosphere sintering furnace, 500 ~ 1300 DEG C of sintering 1 ~ 10h under protective gas atmosphere, be cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
More preferably, nitrogen-doped carbon net obtains in the following manner: the pyrolysis of one or more in the chemical vapour deposition (CVD) of one or more in the pyrolysis of one or more in polypyridine, polypyrrole, Polyaniline and its derivative, aniline, pyrroles, pyridine and its derivatives or ionic liquid 3-methyl-butvl pyridine dicyan amine salt and 1-ethyl-3-methylimidazole cdicynanmide and derivative thereof.Organic molecule, as carbon source, forms nitrogen-doped carbon net in pyroprocess, and in described nitrogen-doped carbon net, nitrogen-atoms is combined with at least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen with carbon atom.And, in pyrolysis process, organic molecule decomposites micro-molecular gas, and micro-molecular gas is overflowed from the carbon material surface of N doping, thus N doping carbon material surface or inner form microcellular structure, or N doping carbon material surface and innerly form microcellular structure.
Further preferably, described nitrogen-doped carbon net one of as follows preparation:
The high-temperature decomposition of one or more in polypyridine, polypyrrole, Polyaniline and its derivative: by softex kw (CTAB, (C
16h
33) N (CH
3)
3br, 7.3g) be dissolved in the HCl(120mL of ice-water bath, 1mol/L) in solution, ultrasonic disperse is even, then by ammonium persulfate (APS, 13.7g) add wherein, form the suspension-turbid liquid of white at once, stir after 0.5 hour, add pyrrole monomer (Py again, 8.3mL), filter after insulation reaction 24h at 4 DEG C, by the HCl solution washing of black precipitate 1mol/L that obtains three times, again with pure water washing to solution be colourless neutrality, then sediment at 80 DEG C dry 24 hours, finally dried sediment is placed in tube furnace, passes into 5%H
2/ Ar gaseous mixture, sinters 2 hours can obtain nitrogen-doped carbon net at 700 DEG C; Or
The chemical vapour deposition technique of one or more in aniline, pyrroles, pyridine and its derivatives: tube furnace is vacuumized, reaction gas is done with the pyridine monomer (pyridine) of Ar load gasification, Ar throughput controls as 50ml/min, warming and cooling rate 30 DEG C/min, 6 hours are incubated at 700 DEG C, treat that tube furnace is cooled to room temperature, obtain nitrogen-doped carbon net; Or
The high-temperature decomposition of one or more in ionic liquid 3-methyl-butvl pyridine dicyan amine salt and 1-ethyl-3-methylimidazole cdicynanmide and derivative thereof: get ionic liquid 3-methyl-butvl pyridine dicyan amine salt and be placed in alumina crucible, proceed in tube furnace, pass into protective gas, to 600 DEG C be warming up to the heating rate of 2 DEG C/min in tube furnace and be incubated 2h, be cooled to room temperature subsequently, obtained ionic liquid pyrolysis product; Subsequently described ionic liquid pyrolysis product is proceeded in atmosphere sintering furnace, pass into reducing atmosphere, the product after baking is sintered 4h at 500 DEG C of temperature, is cooled to room temperature subsequently, obtains nitrogen-doped carbon net.
Preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 0.1% ~ 80% than content.More preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 5% ~ 50% than content.Further preferably, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 15% ~ 30% than content.
Preferably, the diameter of the material with carbon element branch of described N doping is 30nm ~ 5 μm.
Preferably, the pore-size distribution of described micropore is at 0.5 ~ 500nm.More preferably, the pore-size distribution of described micropore is at 2 ~ 100nm.
Preferably, the ratio of the diameter of the material with carbon element branch of described N doping and the particle diameter of described silicon-based active material nano particle is 1 ~ 10:1.
Carbon material surface or the inside of N doping have microcellular structure, or have microcellular structure at the carbon material surface of N doping and inside.
Preferably, pyrroles's type nitrogen is contained in described nitrogen-doped carbon net.Pyrroles's type nitrogen in nitrogen-doped carbon net can with Li
+be combined into key, there is good storage lithium performance.
Preferably, the material of described silicon-based active material is selected from one or more in elemental silicon, Si oxide and silicon alloy.
Preferably, the particle diameter of described silicon-based active material nano particle is 30nm ~ 200nm.
Preferably, the nano wire of described silicon-based active material and the diameter of nanometer rods are 10 ~ 100nm and length is 2 ~ 5 μm.
Preparation method's technique of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides is simple and convenient, and cost is low, is easy to suitability for industrialized production.
The third aspect, embodiments provide a kind of cathode pole piece of lithium ion secondary battery, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
A kind of cathode pole piece of lithium ion secondary battery long service life that the embodiment of the present invention third aspect provides and conductivity is good.The same first aspect of optimal way of wherein said negative electrode of lithium ionic secondary battery.
Fourth aspect, embodiments provide a kind of lithium rechargeable battery, described lithium rechargeable battery is by cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
The lithium rechargeable battery long service life that embodiment of the present invention fourth aspect provides and conductivity is good.The same first aspect of optimal way of wherein said negative electrode of lithium ionic secondary battery.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.The embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable is changed and implements.
Embodiment one
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
By softex kw (CTAB, (C
16h
33) N (CH
3)
3br, 7.3g) be dissolved in the HCl(120mL of ice-water bath, 1mol/L) in solution, ultrasonic disperse is even, then by ammonium persulfate (APS, 13.7g) add wherein, form the suspension-turbid liquid of white at once, stir after 0.5 hour, add pyrrole monomer (Py again, 8.3mL), filter after insulation reaction 24h at 4 DEG C, by the HCl solution washing of black precipitate 1mol/L that obtains three times, again with pure water washing to solution be colourless neutrality, then sediment at 80 DEG C dry 24 hours, finally dried sediment is placed in tube furnace, passes into 5%H
2/ Ar gaseous mixture, sinters 2 hours can obtain nitrogen-doped carbon net at 700 DEG C.
(2) load silicon-based active material
Nitrogen-doped carbon net is placed in quartz ampoule, tube furnace is vacuumized, by volume for the ratio of 1:1 passes into silicon source SiH
4and H
2, control throughput is 120sccm, with the heating rate of 10 DEG C/min by being warming up to 600 DEG C in tube furnace and being incubated 10min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Through XRD analysis, in negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, and adopting weight ammonium chloride method to record its quality than content is 21.3%.Carbon material surface and inner at least one place of N doping have micropore, and adopt nitrogen adsorption methods, calculate through BET and BJH, micropore size is distributed between 0.5 ~ 4nm.Through XPS analysis, nitrogen-atoms exists with the form of pyridine type nitrogen and pyrroles's type nitrogen.Fig. 1 is the SEM Electronic Speculum figure of the negative electrode of lithium ionic secondary battery that the embodiment of the present invention one obtains.As shown in Figure 1, described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, the material with carbon element of N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter about 50 ~ 80nm of branch, the distribution of silicon-based active material nano particle very evenly and particle diameter at about 10nm.This structure takes full advantage of the three-dimensional conductive network of the material with carbon element of N doping, and the monolithic conductive characteristic of low conductivity on material of silicon-based active material does not almost affect.Meanwhile, the micropore of the material with carbon element of N doping effectively can reduce the impact of silicon-based active mass volume change on the material monolithic life-span.
Embodiment two
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
Vacuumized by tube furnace, do reaction gas with the pyridine monomer (pyridine) of Ar load gasification, Ar throughput controls, for 50ml/min, warming and cooling rate 30 DEG C/min, to be incubated 6 hours, to treat that tube furnace is cooled to room temperature, obtain nitrogen-doped carbon net at 700 DEG C.
(2) load silicon-based active material
Nitrogen-doped carbon net is put into and is placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 10
-3pa, to pass into throughput be the protective gas of 30sccm is 3.0Pa to pressure in magnetron sputtering cavity, and control power is 80W, at 200 DEG C of sputtering 2min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, and the load of described silicon-based active material is at the carbon material surface of described N doping.Through XRD analysis, in negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, and adopting weight ammonium chloride method to record its quality than content is 23.6%.From SEM, the material with carbon element of N doping is three-dimensional netted, and the material with carbon element of N doping comprises the many branches be cross-linked with each other, and the diameter about 300 ~ 500nm of branch, the diameter of nano silicon particles is between 100 ~ 200nm.Carbon material surface and inner at least one place of N doping have micropore, and adopt nitrogen adsorption methods, calculate through BET and BJH, micropore size is distributed between 50 ~ 150nm.Through XPS analysis, nitrogen-atoms exists with pyridine type nitrogen, pyrroles's type nitrogen and graphite nitrogen three kinds of forms.Fig. 2 is the structural representation of nitrogen-doped carbon net in the negative electrode of lithium ionic secondary battery that obtains of the embodiment of the present invention.As shown in Figure 2, in nitrogen-doped carbon net, nitrogen-atoms and carbon atom are combined with the various ways in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen usually.
Embodiment three
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
Get ionic liquid 3-methyl-butvl pyridine dicyan amine salt and be placed in alumina crucible, proceed in tube furnace, pass into protective gas, will 600 DEG C are warming up to the heating rate of 2 DEG C/min in tube furnace and be incubated 2h, be cooled to room temperature subsequently, obtained ionic liquid pyrolysis product, subsequently described ionic liquid pyrolysis product is added obtained mixed solution in the aqueous solution of γ-aminopropyl three ethoxy silane, the mass ratio of described ionic liquid pyrolysis product and described γ-aminopropyl three ethoxy silane is 8:5, by described mixed solution ultrasonic disperse 30min with being placed on heating water bath to 85 DEG C in container, aqueous citric acid solution is instilled and constant temperature 85 DEG C of stirring reaction 2h in described container, reacted solution is filtered, filter residue is toasted 12h under 80 DEG C of vacuum, proceed in atmosphere sintering furnace, pass into reducing atmosphere, product after baking is sintered 4h at 500 DEG C of temperature, be cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, and the load of described silicon-based active material is at the carbon material surface of described N doping.Through XRD analysis, in negative electrode of lithium ionic secondary battery, silicon-based active material is the mixture of silicon and SiOx, and adopting weight ammonium chloride method to record its quality than content is 19.9%.From SEM, the material with carbon element of N doping is three-dimensional netted, and the material with carbon element of N doping comprises the many branches be cross-linked with each other, and the diameter about 50 ~ 100nm of branch, the diameter of nano silicon particles is between 5 ~ 10nm.Carbon material surface and inner at least one place of N doping have micropore, and adopt nitrogen adsorption methods, calculate through BET and BJH, micropore size is distributed between 10 ~ 50nm.Through XPS analysis, nitrogen-atoms exists with pyridine type nitrogen, pyrroles's type nitrogen and graphite nitrogen three kinds of forms.
Comparative example one
Pitch is placed in quartz ampoule, passes into 5%H
2/ Ar gaseous mixture, sinters to obtain carbonization in 2 hours, then is vacuumized by tube furnace at 700 DEG C, by volume for the ratio of 1:1 passes into silicon source SiH
4and H
2, control throughput is 120sccm, with the heating rate of 10 DEG C/min by being warming up to 600 DEG C in tube furnace and being incubated 10min, is cooled to room temperature subsequently, obtained carbon/silicon compound lithium ion secondary battery negative pole active material.
Comparative example two
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
By softex kw (CTAB, (C
16h
33) N (CH
3)
3br, 7.3g) be dissolved in the HCl(120mL of ice-water bath, 1mol/L) in solution, ultrasonic disperse is even, then by ammonium persulfate (APS, 13.7g) add wherein, form the suspension-turbid liquid of white at once, stir after 0.5 hour, add pyrrole monomer (Py again, 8.3mL), filter after insulation reaction 24h at 4 DEG C, by the HCl solution washing of black precipitate 1mol/L that obtains three times, again with pure water washing to solution be colourless neutrality, then sediment at 80 DEG C dry 24 hours, finally dried sediment is placed in tube furnace, passes into 5%H
2/ Ar gaseous mixture, sinters 2 hours can obtain nitrogen-doped carbon net at 700 DEG C.
(2) load silicon-based active material
Nitrogen-doped carbon net is placed in quartz ampoule, tube furnace is vacuumized, by volume for the ratio of 1:1 passes into silicon source SiH
4and H
2, control throughput is 80sccm, with the heating rate of 10 DEG C/min by being warming up to 1000 DEG C in tube furnace and being incubated 20min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Through XRD analysis, in negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, and adopting weight ammonium chloride method to record its quality than content is 22.1%.From SEM, the material with carbon element of N doping is three-dimensional netted, and the material with carbon element of N doping comprises the many branches be cross-linked with each other, and the diameter about 50 ~ 80nm of branch, the domain size distribution of nano silicon particles is between 1 ~ 3 μm.Adopt nitrogen adsorption methods, calculate through BET and BJH, micropore size is distributed between 0.5 ~ 4nm.Through XPS analysis, nitrogen-atoms exists with the form of pyridine type nitrogen and pyrroles's type nitrogen.
Comparative example three
A preparation method for negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
Vacuumized by tube furnace, do reaction gas with the pyridine monomer (pyridine) of Ar load gasification, Ar throughput controls, for 100ml/min, warming and cooling rate 50 DEG C/min, to be incubated 4 hours, to treat that tube furnace is cooled to room temperature, obtain nitrogen-doped carbon net at 1000 DEG C.
(2) load silicon-based active material
Nitrogen-doped carbon net is put into and is placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 10
-3pa, to pass into throughput be the protective gas of 30sccm is 3.0Pa to pressure in magnetron sputtering cavity, and control power is 80W, at 200 DEG C of sputtering 2min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery.
Through XRD analysis, in negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, and adopting weight ammonium chloride method to record its quality than content is 22.1%.From SEM, the material with carbon element of N doping is three-dimensional netted, and the material with carbon element of N doping comprises the many branches be cross-linked with each other, and the diameter of branch about 15 ~ 30 μm, the diameter of nano silicon particles is between 300 ~ 500nm.Adopt nitrogen adsorption methods, calculate through BET and BJH, micropore size is distributed between 1 ~ 5 μm.Through XPS analysis, nitrogen-atoms exists with pyridine type nitrogen, pyrroles's type nitrogen and graphite nitrogen three kinds of forms.
The preparation of cathode pole piece of lithium ion secondary battery
By negative electrode of lithium ionic secondary battery obtained in above-described embodiment one and conductive agent (Timcal, Super-p and SFG-6) mix, then the Kynoar PVDF(Arkmer of 8% is added, HSV900), 1-METHYLPYRROLIDONE solution NMP, stir, above-mentioned mixed slurry is uniformly coated in the copper foil current collector of 10 μm, under 110 DEG C and vacuum condition, toasts 12h, namely obtain cathode pole piece of lithium ion secondary battery.Wherein, the formula of lithium ion secondary battery negative pole mixed slurry is (mass ratio): negative electrode of lithium ionic secondary battery: super-p:SFG-6:PVDF=92:3:1:4.
The preparation of lithium rechargeable battery
Above-mentioned cathode pole piece of lithium ion secondary battery is made 2016 type button cells, wherein, adopt lithium metal to electrode, barrier film is celgard C2400, and electrolyte is 1.3M LiPF
6eC and DEC(volume ratio be 3:7) solution.
Negative electrode of lithium ionic secondary battery obtained in embodiment two, embodiment three and comparative example one ~ comparative example three all herewith processes.
Effect example is the beneficial effect providing powerful support for the embodiment of the present invention, provides effect example as follows, in order to evaluate and test the performance of the product that the embodiment of the present invention provides.
By buckle type lithium-ion secondary cell obtained in embodiment one ~ embodiment three and comparative example one ~ comparative example three with the current charges of 100mA/1g active material to voltage for 0.001V, then constant voltage is until electric current is less than 10mA/1g active material; Shelve 10min; By above-mentioned button cell with the current discharge of 100mA/1g active material to 2.5V.Complete above-mentionedly to fill, discharge of electricity process is designated as 1 and fills/discharge of electricity circulation.The formula of the coulombic efficiency first of buckle type lithium-ion secondary cell and capability retention is as follows respectively, outcome record in Table 1:
Coulombic efficiency (%)=initial charge capacity/discharge capacity × 100% first first;
Discharge capacity × 100% of the discharge capacity/1st time circulation of capability retention (%)=n-th time circulation of n-th circulation.
Table 1. buckle type lithium-ion secondary cell test result
As can be seen from Table 1, the obtained negative electrode of lithium ionic secondary battery of the embodiment of the present invention one ~ embodiment three compares with negative electrode of lithium ionic secondary battery silicon/carbon composite that the comparative example one under equal temperature obtains and has long cycle life, high capacity and efficiency first, this is because nitrogen-doped carbon net itself has the capacity higher than carbon and conductivity, the micropore of the material with carbon element of N doping effectively can reduce the impact of silicon-based active mass volume change on the material monolithic life-span simultaneously.The negative electrode of lithium ionic secondary battery that the negative electrode of lithium ionic secondary battery that the embodiment of the present invention one ~ embodiment three obtains obtains with the comparative example two and three under equal temperature compares, the collocation that its silicon-based active material nano particle size and the material with carbon element branch diameter of N doping and the material with carbon element micropore size of N doping distribute is more reasonable, conductivity is high, has higher capacity, first efficiency and cycle life.
Claims (10)
1. a negative electrode of lithium ionic secondary battery, it is characterized in that, comprise the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
2. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, the quality of silicon-based active material described in described negative electrode of lithium ionic secondary battery is 0.1% ~ 80% than content.
3. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, the ratio of the diameter of the material with carbon element branch of described N doping and the particle diameter of described silicon-based active material nano particle is 1 ~ 10:1.
4. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, the pore-size distribution of described micropore is at 0.5 ~ 500nm.
5. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, containing pyrroles's type nitrogen in described nitrogen-doped carbon net.
6. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, is characterized in that, the material of described silicon-based active material is selected from one or more in elemental silicon, Si oxide and silicon alloy.
7. a preparation method for negative electrode of lithium ionic secondary battery, is characterized in that, the one is by the following method prepared:
Method one: by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material, obtained negative electrode of lithium ionic secondary battery;
Method two: by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material, obtained negative electrode of lithium ionic secondary battery;
Method three: by the pyrolysis product of ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide and the blended obtained mixed solution of silicon precursor solution, described silicon precursor is γ-aminopropyl three ethoxy silane, γ-(2, 3-epoxy third oxygen) one or more in propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane, by heating water bath after described mixed solution ultrasonic disperse, complexing agent is instilled in described water-bath system, subsequently by the mixed solution stirring reaction containing complexing agent, by sintering after reacted product baking, obtained negative electrode of lithium ionic secondary battery,
Described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
8. the preparation method of a kind of negative electrode of lithium ionic secondary battery as claimed in claim 7, is characterized in that,
Described in method one by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material be: get nitrogen-doped carbon net and be placed in tube furnace, tube furnace is vacuumized, by volume for the ratio of 1:0.1 ~ 10 passes into silicon source SiH
4and protective gas, control throughput is 30 ~ 300sccm, with the heating rate of 1 ~ 50 DEG C/min by being warming up to 500 ~ 1300 DEG C in tube furnace and being incubated 3 ~ 60min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery;
Described in method two by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material be: get nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0 ~ 10
-2pa, to pass into throughput be the protective gas of 10 ~ 300sccm is 1 ~ 10Pa to pressure in magnetron sputtering cavity, and control power is 10 ~ 200W, at 100 ~ 400 DEG C of sputtering 1 ~ 10min, is cooled to room temperature subsequently, obtained negative electrode of lithium ionic secondary battery;
The mass ratio of ionic liquid pyrolysis product described in method three and described silicon precursor is 1:0.1 ~ 5; described complexing agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate; mixed solution constant temperature containing complexing agent 50 ~ 100 DEG C is stirred lower reaction 0.5 ~ 5h; reacted product is toasted 1 ~ 24h under 50 ~ 100 DEG C of vacuum; proceed to again in atmosphere sintering furnace; under protective gas atmosphere, 500 ~ 1300 DEG C of sintering 1 ~ 10h, are cooled to room temperature subsequently.
9. a cathode pole piece of lithium ion secondary battery, it is characterized in that, described cathode pole piece of lithium ion secondary battery comprises collector and is coated in the negative electrode of lithium ionic secondary battery on described collector, described negative electrode of lithium ionic secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
10. a lithium rechargeable battery, it is characterized in that, described lithium rechargeable battery is by cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described cathode pole piece of lithium ion secondary battery comprises the material with carbon element of silicon-based active material and N doping, the load of described silicon-based active material is at the carbon material surface of described N doping, described silicon-based active material is one or more in nano particle and nano wire, the particle diameter of described silicon-based active material nano particle is 1nm ~ 1 μm, the diameter of described nano wire is 1 ~ 200nm and length is 1 ~ 10 μm, the material with carbon element of described N doping is three-dimensional netted, the material with carbon element of N doping comprises the many branches be cross-linked with each other, the diameter of described branch is 1nm ~ 10 μm, carbon material surface and inner at least one place of described N doping have micropore, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, at least one form in graphite mould nitrogen and pyrroles's type nitrogen combines.
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| CN104347858B (en) | 2016-12-28 |
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