CN104347858B - Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery - Google Patents
Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery Download PDFInfo
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- CN104347858B CN104347858B CN201310323914.7A CN201310323914A CN104347858B CN 104347858 B CN104347858 B CN 104347858B CN 201310323914 A CN201310323914 A CN 201310323914A CN 104347858 B CN104347858 B CN 104347858B
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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
- H01M4/62—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Embodiments provide a kind of negative electrode of lithium ionic secondary battery, this negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping, silicon-based active material is supported on the carbon material surface of N doping, silicon-based active material is one or more in nano-particle and nano wire, the material with carbon element of N doping is three-dimensional netted, including the many branches being cross-linked with each other, the carbon material surface of N doping and at least one internal place have micropore, and the material of the material with carbon element of N doping is nitrogen-doped carbon net.This negative electrode of lithium ionic secondary battery solves the problem that change in volume great Yi when silicon materials do negative active core-shell material comes off from collector and electrical conductivity is low.The embodiment of the present invention additionally provides the preparation method of negative electrode of lithium ionic secondary battery, the cathode pole piece of lithium ion secondary battery comprising negative electrode of lithium ionic secondary battery and the lithium rechargeable battery comprising negative electrode of lithium ionic secondary battery.
Description
Technical field
The present invention relates to field of lithium ion secondary, particularly relate to a kind of lithium ion secondary battery negative pole and live
Property material and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery.
Background technology
Along with mancarried electronic aid and electric automobile are more and more higher to the requirement of energy density, high-performance lithium ion
The research and development of secondary cell seem and become more and more important.
Pure silicon material is because having higher theoretical capacity (up to 4200mAh/g), good intercalation/deintercalation energy
Power becomes the most promising class new and effective storage lithium titanate cathode material.But silicon materials are in the process of removal lithium embedded
Middle change in volume, more than 300%, can cause it easily to come off from collector, and the electrical conductivity of silicon materials own
Relatively low.Industry mainly uses nanorize, filming, Composite and designs four kinds of sides of multistage special construction at present
It is modified by formula, but effect is the most undesirable, or preparation process is complicated, it is difficult to realize commercialization,
Or the introducing of a large amount of inert matter has greatly slackened 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 lithium ion secondary battery negative pole work
Property material, solves when silicon materials in prior art do negative active core-shell material change in volume great Yi from collector
Come off the problem low with electrical conductivity.
First aspect, embodiments provides a kind of negative electrode of lithium ionic secondary battery, including silicon
Base active substance and the material with carbon element of N doping, described silicon-based active material is supported on the material with carbon element of described N doping
Surface, described silicon-based active material is one or more in nano-particle and nano wire, described silicon-based active
The particle diameter of material nano-particle is 1nm～1 μm, a diameter of the 1 of described nano wire～200nm and a length of
1～10 μm, the material with carbon element of described N doping is three-dimensional netted, and the material with carbon element of N doping includes that many are cross-linked with each other
Branch, a diameter of 1nm of described branch～10 μm, the carbon material surface of described N doping and internal extremely
Having micropore at few one, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, described nitrogen-doped carbon net
Middle nitrogen-atoms is combined with at least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen with carbon atom.
Preferably, described in described negative electrode of lithium ionic secondary battery, the mass ratio of silicon-based active material contains
Amount is 0.1%～80%.
Preferably, the diameter of the material with carbon element branch of described N doping and the grain of described silicon-based active material nano-particle
The ratio in footpath is 1～10:1.
Preferably, the pore-size distribution of described micropore is 0.5～500nm.
Preferably, containing pyrroles's type nitrogen in described nitrogen-doped carbon net.Pyrroles's type nitrogen in nitrogen-doped carbon net can be with
Li+In conjunction with bonding, there is good storage lithium performance.
Preferably, the material of described silicon-based active material one in elemental silicon, Si oxide and silicon alloy
Or it is several.
Compared with prior art, embodiment of the present invention first aspect provides a kind of lithium ion secondary battery negative pole work
Property material, silicon-based active material is supported on the carbon material surface of N doping, and silicon-based active material passes through N doping
Material with carbon element be combined with collector, the carbon material surface of N doping and at least one internal place have micropore, nitrogen
The micropore of the material with carbon element of doping can be the expansion headspace of silicon-based active material, and the carbon material of N doping
Material is in three-dimensional netted, and the silicon-based active material after expansion is not come off by the constraint of the material with carbon element of N doping,
Solve change in volume great Yi when silicon materials in prior art do negative active core-shell material to come off from collector and electricity
The problem that conductance is low, substantially prolongs the service life of negative electrode of lithium ionic secondary battery, simultaneously nitrogen
Doping carbon net can improve the whole conductivity of the material with carbon element composite of silicon-based active material/N doping, and
Nitrogen-doped carbon net self has certain capacity high power capacity plus silicon-based active material self so that lithium ion
Secondary battery negative pole active material has high power capacity advantage.Additionally, negative electrode of lithium ionic secondary battery
Cost is relatively low is prone to industrialized production.
Second aspect, embodiments provides the preparation side of a kind of negative electrode of lithium ionic secondary battery
Method, by the following method in one be prepared:
Method one: load silicon-based active material at nitrogen-doped carbon net surface by chemical vapour deposition technique, prepares lithium
Ion secondary battery negative active core-shell material；
Method two: load silicon-based active material at nitrogen-doped carbon net surface by magnetron sputtering method, prepares lithium ion
Secondary battery negative pole active material；
Method three: by ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide
Pyrolysis product and silicon precursor solution be blended and prepare mixed solution, described silicon precursor is γ-aminopropyl three second
Oxosilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and γ-methacryloxypropyl front three
One or more in TMOS, by heating in water bath after described mixed solution ultrasonic disperse, to described water-bath
System instills chelating agent, subsequently the mixed solution containing chelating agent is stirred reaction, by reacted product
Sinter after baking, prepare negative electrode of lithium ionic secondary battery；
Described negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping, institute
Stating silicon-based active material and be supported on the carbon material surface of described N doping, described silicon-based active material is nanometer
One or more in grain and nano wire, the particle diameter of described silicon-based active material nano-particle is 1nm～1 μm,
A diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, the material with carbon element of described N doping is three-dimensional
Netted, the material with carbon element of N doping includes the many branches being cross-linked with each other, a diameter of 1nm～10 μ of described branch
M, the carbon material surface of described N doping and at least one internal place have micropore, the material with carbon element of described N doping
Material be nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, graphite mould
At least one form in nitrogen and pyrroles's type nitrogen combines.
Preferably, silicon-based active is loaded by chemical vapour deposition technique at nitrogen-doped carbon net surface described in method one
Material is: takes nitrogen-doped carbon net and is placed in tube furnace, by tube furnace evacuation, is 1:0.1～10 by volume
Ratio be passed through silicon source SiH4And protective gas, controlling throughput is 30～300sccm, with 1～50 DEG C/min
Heating rate by being warming up to 500～1300 DEG C in tube furnace and being incubated 3～60min, be then cooled to room temperature,
Prepare negative electrode of lithium ionic secondary battery.
Preferably, silicon-based active material is loaded by magnetron sputtering method at nitrogen-doped carbon net surface described in method two
For: take nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0～10-2Pa, is passed through air-flow
Amount be the protective gas of 10～300sccm be 1～10Pa to pressure in magnetron sputtering cavity, control power be
10～200W, sputter 1～10min at 100～400 DEG C, be then cooled to room temperature, prepare lithium rechargeable battery
Negative active core-shell material.
Preferably, ionic liquid pyrolysis product described in method three with the mass ratio of described silicon precursor is
1:0.1～5, described chelating agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate, will contain
Have the mixed solution constant temperature 50 of chelating agent～100 DEG C of lower reactions 0.5～5h of stirring, by reacted product in
Toast 1～24h under 50～100 DEG C of vacuum, then proceed in atmosphere sintering furnace, under protective gas atmosphere
500～1300 DEG C of sintering 1～10h, are then cooled to room temperature.
The preparation side of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides
Method technique is simple and convenient, low cost, it is easy to industrialized production.
The third aspect, embodiments provides a kind of cathode pole piece of lithium ion secondary battery, described lithium ion
Secondary battery negative pole pole piece includes the material with carbon element of silicon-based active material and N doping, and described silicon-based active material is born
Being loaded in the carbon material surface of described N doping, described silicon-based active material is in nano-particle and nano wire
Planting or several, the particle diameter of described silicon-based active material nano-particle is 1nm～1 μm, the diameter of described nano wire
Being 1～200nm and a length of 1～10 μm, the material with carbon element of described N doping is three-dimensional netted, the carbon of N doping
Material includes the many branches being cross-linked with each other, a diameter of 1nm of described branch～10 μm, described N doping
Carbon material surface and at least one internal place have micropore, and the material of the material with carbon element of described N doping is N doping
Carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen
At least one form combine.
The embodiment of the present invention third aspect provide a kind of cathode pole piece of lithium ion secondary battery length in service life and
Electrical conductivity is good.
Fourth aspect, embodiments provides a kind of lithium rechargeable battery, described lithium ion secondary electricity
Pond is made up of cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell, institute
State cathode pole piece of lithium ion secondary battery and include collector and the lithium ion secondary electricity being coated on described collector
Pond negative active core-shell material, described negative electrode of lithium ionic secondary battery includes that silicon-based active material and nitrogen are mixed
Miscellaneous material with carbon element, described silicon-based active material is supported on the carbon material surface of described N doping, described silica-based work
Property material is one or more in nano-particle and nano wire, the grain of described silicon-based active material nano-particle
Footpath is 1nm～1 μm, and a diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, described nitrogen is mixed
Miscellaneous material with carbon element is three-dimensional netted, and the material with carbon element of N doping includes the many branches being cross-linked with each other, described branch
A diameter of 1nm～10 μm, the carbon material surface of described N doping and at least one internal place there is micropore,
The material of the material with carbon element of described N doping is nitrogen-doped carbon net, nitrogen-atoms and carbon atom in described nitrogen-doped carbon net
Combine with at least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen.
Lithium rechargeable battery length in service life and electrical conductivity that embodiment of the present invention fourth aspect provides are good.
Embodiment of the present invention first aspect provides a kind of negative electrode of lithium ionic secondary battery, silicon-based active
Material is supported on the carbon material surface of N doping, and silicon-based active material passes through material with carbon element and the collector of N doping
In conjunction with, the carbon material surface of N doping and at least one internal place, there is micropore, the material with carbon element of N doping micro-
Hole can be the expansion headspace of silicon-based active material, and the material with carbon element of N doping is three-dimensional netted, swollen
Silicon-based active material after swollen is not come off by the constraint of the material with carbon element of N doping, solves in prior art
The problem that when silicon materials do negative active core-shell material, change in volume great Yi comes off from collector and electrical conductivity is low, greatly
Extending greatly the service life of negative electrode of lithium ionic secondary battery, nitrogen-doped carbon net can improve simultaneously
The whole conductivity of the material with carbon element composite of silicon-based active material/N doping, and nitrogen-doped carbon net self tool
There is certain capacity high power capacity plus silicon-based active material self so that lithium ion secondary battery negative pole activity
Material has high power capacity advantage.Additionally, negative electrode of lithium ionic secondary battery cost is relatively low is prone to industry
Metaplasia is produced.The system of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides
Preparation Method technique is simple and convenient, low cost, it is easy to industrialized production.The embodiment of the present invention third aspect provides
A kind of cathode pole piece of lithium ion secondary battery and fourth aspect provide lithium rechargeable battery long for service life
And electrical conductivity is good.
The advantage of the embodiment of the present invention will partly illustrate, and a part according to description is
It will be apparent that or can be known by the enforcement of the embodiment of the present invention.
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 prepares.
Fig. 2 is nitrogen-doped carbon net in the negative electrode of lithium ionic secondary battery that the embodiment of the present invention two prepares
Structural representation.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that general for the art
For logical technical staff, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvement
And retouching, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of novel negative electrode of lithium ionic secondary battery, solves
When in prior art of having determined, silicon materials do negative active core-shell material, change in volume great Yi comes off and conductance from collector
The problem that rate is low.Embodiment of the present invention second aspect provides described negative electrode of lithium ionic secondary battery
Preparation method, technique is simple and convenient, low cost, it is easy to industrialized production.Embodiment of the present invention third party
Face 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 comprising described negative electrode of lithium ionic secondary battery
Ion secondary battery.
First aspect, embodiments provides a kind of negative electrode of lithium ionic secondary battery, including silicon
Base active substance and the material with carbon element of N doping, described silicon-based active material is supported on the material with carbon element of described N doping
Surface, described silicon-based active material is one or more in nano-particle and nano wire, described silicon-based active
The particle diameter of material nano-particle is 1nm～1 μm, a diameter of the 1 of described nano wire～200nm and a length of
1～10 μm, the material with carbon element of described N doping is three-dimensional netted, and the material with carbon element of N doping includes that many are cross-linked with each other
Branch, a diameter of 1nm of described branch～10 μm, the carbon material surface of described N doping and internal extremely
Having micropore at few one, the material of the material with carbon element of described N doping is nitrogen-doped carbon net, described nitrogen-doped carbon net
Middle nitrogen-atoms is combined with at least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen with carbon atom.
Preferably, described in described negative electrode of lithium ionic secondary battery, the mass ratio of silicon-based active material contains
Amount is 0.1%～80%.It is highly preferred that silicon-based active described in described negative electrode of lithium ionic secondary battery
The quality of material is 5%～50% than content.It is further preferred that described lithium ion secondary battery negative pole is active
The quality of silicon-based active material described in material is 15%～30% than content.
Preferably, a diameter of 30nm of the material with carbon element branch of described N doping～5 μm.
Preferably, the pore-size distribution of described micropore is 0.5～500nm.It is highly preferred that the aperture of described micropore is divided
Cloth is 2～100nm.
Preferably, the diameter of the material with carbon element branch of described N doping and the grain of described silicon-based active material nano-particle
The ratio in footpath is 1～10:1.
The carbon material surface of N doping or inside have a microcellular structure, or at the carbon material surface of N doping and interior
Portion has microcellular structure.
Preferably, containing pyrroles's type nitrogen in described nitrogen-doped carbon net.Pyrroles's type nitrogen in nitrogen-doped carbon net can be with
Li+In conjunction with bonding, there is good storage lithium performance.
Preferably, the material of described silicon-based active material one in elemental silicon, Si oxide and silicon alloy
Or it is several.
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 a diameter of the 10 of nanometer rods～100nm and a length of
2～5 μm.
Embodiment of the present invention first aspect provides a kind of negative electrode of lithium ionic secondary battery, silicon-based active
Material is supported on the carbon material surface of N doping, and silicon-based active material passes through material with carbon element and the collector of N doping
In conjunction with, the carbon material surface of N doping and at least one internal place, there is micropore, the material with carbon element of N doping micro-
Hole can be the expansion headspace of silicon-based active material, and the material with carbon element of N doping is three-dimensional netted, swollen
Silicon-based active material after swollen is not come off by the constraint of the material with carbon element of N doping, solves in prior art
The problem that when silicon materials do negative active core-shell material, change in volume great Yi comes off from collector and electrical conductivity is low, greatly
Extending greatly the service life of negative electrode of lithium ionic secondary battery, nitrogen-doped carbon net can improve simultaneously
The whole conductivity of the material with carbon element composite of silicon-based active material/N doping, and nitrogen-doped carbon net self tool
There is certain capacity high power capacity plus silicon-based active material self so that lithium ion secondary battery negative pole activity
Material has high power capacity advantage.Additionally, negative electrode of lithium ionic secondary battery cost is relatively low is prone to industry
Metaplasia is produced.
Second aspect, embodiments provides the preparation side of a kind of negative electrode of lithium ionic secondary battery
Method, by the following method in one be prepared:
Method one: load silicon-based active material at nitrogen-doped carbon net surface by chemical vapour deposition technique, prepares lithium
Ion secondary battery negative active core-shell material；
Method two: load silicon-based active material at nitrogen-doped carbon net surface by magnetron sputtering method, prepares lithium ion
Secondary battery negative pole active material；
Method three: by ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide
Pyrolysis product and silicon precursor solution be blended and prepare mixed solution, described silicon precursor is γ-aminopropyl three second
Oxosilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and γ-methacryloxypropyl front three
One or more in TMOS, by heating in water bath after described mixed solution ultrasonic disperse, to described water-bath
System instills chelating agent, subsequently the mixed solution containing chelating agent is stirred reaction, by reacted product
Sinter after baking, prepare negative electrode of lithium ionic secondary battery；
Described negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping, institute
Stating silicon-based active material and be supported on the carbon material surface of described N doping, described silicon-based active material is nanometer
One or more in grain and nano wire, the particle diameter of described silicon-based active material nano-particle is 1nm～1 μm,
A diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, the material with carbon element of described N doping is three-dimensional
Netted, the material with carbon element of N doping includes the many branches being cross-linked with each other, a diameter of 1nm～10 μ of described branch
M, the carbon material surface of described N doping and at least one internal place have micropore, the material with carbon element of described N doping
Material be nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, graphite mould
At least one form in nitrogen and pyrroles's type nitrogen combines.
Preferably, silica-based work is loaded by chemical vapour deposition technique at nitrogen-doped carbon net surface described in method one
Property material is: taking nitrogen-doped carbon net is placed in tube furnace, by tube furnace evacuation, is 1:0.1～10 by volume
Ratio be passed through silicon source SiH4And protective gas, controlling throughput is 30～300sccm, with 1～50 DEG C/min
Heating rate by being warming up to 500～1300 DEG C in tube furnace and being incubated 3～60min, be then cooled to room temperature,
Prepare negative electrode of lithium ionic secondary battery.Take nitrogen-doped carbon net to be placed in quartz ampoule, tube furnace is taken out
Vacuum, the ratio for 1:0.1～10 is passed through silicon source SiH by volume4And protective gas, controlling throughput is
30～300sccm, 500～1300 DEG C will be warming up to the heating rate of 1～50 DEG C/min in tube furnace and be incubated
3～60min, it is then cooled to room temperature, prepares negative electrode of lithium ionic secondary battery.
Preferably, silicon-based active material is loaded by magnetron sputtering method at nitrogen-doped carbon net surface described in method two
For: take nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0～10-2Pa, is passed through air-flow
Amount be the protective gas of 10～300sccm be 1～10Pa to pressure in magnetron sputtering cavity, control power be
10～200W, sputter 1～10min at 100～400 DEG C, be then cooled to room temperature, prepare lithium rechargeable battery
Negative active core-shell material.Take nitrogen-doped carbon net and be placed in magnetron sputtering cavity, load onto silicon target, be evacuated to 0～10-2Pa,
Being passed through the protective gas that throughput is 10～300sccm is 1～10Pa to pressure in magnetron sputtering cavity, controls
Power is 10～200W, sputters 1～10min at 100～400 DEG C, is then cooled to room temperature, prepares lithium ion two
Primary cell negative active core-shell material.
Preferably, ionic liquid pyrolysis product described in method three with the mass ratio of described silicon precursor is
1:0.1～5, described chelating agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate, will contain
Have the mixed solution constant temperature 50 of chelating agent～100 DEG C of lower reactions 0.5～5h of stirring, by reacted product in
Toast 1～24h under 50～100 DEG C of vacuum, then proceed in atmosphere sintering furnace, under protective gas atmosphere
500～1300 DEG C of sintering 1～10h, are then cooled to room temperature.Take ionic liquid 3-methyl-butvl pyridine cdicynanmide
Salt or 1-ethyl-3-methylimidazole cdicynanmide are placed in ceramic crucible, proceed in tube furnace, are passed through protectiveness gas
Body, will be warming up to 400～800 DEG C with the heating rate of 1～10 DEG C/min and is incubated 1～10h in tube furnace, with
After be cooled to room temperature, prepare ionic liquid pyrolysis product；Subsequently by before described ionic liquid pyrolysis product and silicon
Body solution blending prepares mixed solution, and described silicon precursor is γ-aminopropyl three ethoxy silane, γ-(2,3-
Epoxy the third oxygen) one in propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane
Or several, described ionic liquid pyrolysis product is 1:0.1～5 with the mass ratio of described silicon precursor；By described mixed
Close solution ultrasonic disperse 5～60min, be subsequently placed in container that heating in water bath is to 50～100 DEG C, to described container
Middle instillation chelating agent, described chelating agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate,
Subsequently by the mixed solution constant temperature 50 containing chelating agent～100 DEG C of lower reactions 0.5～5h of stirring, by reacted product
Thing toasts 1～24h under 50～100 DEG C of vacuum, then proceeds in atmosphere sintering furnace, under protective gas atmosphere
500～1300 DEG C of sintering 1～10h, are then cooled to room temperature, prepare negative electrode of lithium ionic secondary battery.
It is highly preferred that nitrogen-doped carbon net obtains in the following manner: polypyridine, polypyrrole, polyaniline and spread out
One or several in the pyrolytic of one or more in biology, aniline, pyrroles, pyridine and its derivatives
Kind chemical gaseous phase deposition or ionic liquid 3-methyl-butvl pyridine dicyan amine salt and 1-ethyl-3-methylimidazole two
The pyrolytic of one or more in cyanamide and derivant thereof.Organic molecule is as carbon source, in pyroprocess
Middle formation nitrogen-doped carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, graphite mould nitrogen
Combine with at least one form in pyrroles's type nitrogen.And, in pyrolysis process, organic molecule decomposes
Going out micro-molecular gas, micro-molecular gas escapes from the carbon material surface of N doping, thus at the carbon material of N doping
Material surface or be internally formed microcellular structure, or at the carbon material surface of N doping be internally formed microcellular structure.
It is further preferred that one of the as follows preparation of described nitrogen-doped carbon net:
The high-temperature decomposition of one or more in polypyridine, polypyrrole, Polyaniline and its derivative: by 16
Alkyl trimethyl ammonium bromide (CTAB, (C16H33)N(CH3)3Br, 7.3g) it is dissolved in the HCl(120 of ice-water bath
ML, 1mol/L) in solution, ultrasonic disperse is uniform, then Ammonium persulfate. (APS, 13.7g) is added it
In, form the suspension of white at once, after stirring 0.5 hour, add pyrrole monomer (Py, 8.3mL),
Filter after insulation reaction 24h at 4 DEG C, the HCl solution of black precipitate 1mol/L obtained is washed
Wash three times, then with pure water washing to solution be colourless neutrality, then precipitate at 80 DEG C be dried 24
Hour, finally dried precipitate is placed in tube furnace, is passed through 5%H2/ Ar gaseous mixture, 700
Sinter at DEG C 2 hours i.e. can get nitrogen-doped carbon net；Or
The chemical vapour deposition technique of one or more in aniline, pyrroles, pyridine and its derivatives: by tube furnace
Evacuation, does reaction gas with the pyridine monomer (pyridine) of Ar load gasification, and the control of Ar throughput is
50ml/min, 30 DEG C/min of warming and cooling rate, be incubated 6 hours at 700 DEG C, treat that tube furnace is cooled to room temperature,
Obtain nitrogen-doped carbon net；Or
Ionic liquid 3-methyl-butvl pyridine dicyan amine salt and 1-ethyl-3-methylimidazole cdicynanmide and derivant thereof
In the high-temperature decomposition of one or more: take ionic liquid 3-methyl-butvl pyridine dicyan amine salt and be placed in oxidation
In aluminum crucible, proceed to, in tube furnace, be passed through protective gas, with the heating rate of 2 DEG C/min by tube furnace
It is warming up to 600 DEG C and is incubated 2h, being then cooled to room temperature, preparing ionic liquid pyrolysis product；Subsequently by institute
State ionic liquid pyrolysis product to proceed to, in atmosphere sintering furnace, be passed through reducing atmosphere, the product after baking is existed
Sinter 4h at a temperature of 500 DEG C, be then cooled to room temperature, obtain nitrogen-doped carbon net.
Preferably, described in described negative electrode of lithium ionic secondary battery, the mass ratio of silicon-based active material contains
Amount is 0.1%～80%.It is highly preferred that silicon-based active described in described negative electrode of lithium ionic secondary battery
The quality of material is 5%～50% than content.It is further preferred that described lithium ion secondary battery negative pole is active
The quality of silicon-based active material described in material is 15%～30% than content.
Preferably, a diameter of 30nm of the material with carbon element branch of described N doping～5 μm.
Preferably, the pore-size distribution of described micropore is 0.5～500nm.It is highly preferred that the aperture of described micropore is divided
Cloth is 2～100nm.
Preferably, the diameter of the material with carbon element branch of described N doping and the grain of described silicon-based active material nano-particle
The ratio in footpath is 1～10:1.
The carbon material surface of N doping or inside have a microcellular structure, or at the carbon material surface of N doping and interior
Portion has microcellular structure.
Preferably, containing pyrroles's type nitrogen in described nitrogen-doped carbon net.Pyrroles's type nitrogen in nitrogen-doped carbon net can be with
Li+In conjunction with bonding, there is good storage lithium performance.
Preferably, the material of described silicon-based active material one in elemental silicon, Si oxide and silicon alloy
Or it is several.
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 a diameter of the 10 of nanometer rods～100nm and a length of
2～5 μm.
The preparation side of a kind of negative electrode of lithium ionic secondary battery that embodiment of the present invention second aspect provides
Method technique is simple and convenient, low cost, it is easy to industrialized production.
The third aspect, embodiments provides a kind of cathode pole piece of lithium ion secondary battery, described lithium ion
Secondary battery negative pole pole piece includes that collector and the lithium ion secondary battery negative pole being coated on described collector are lived
Property material, described negative electrode of lithium ionic secondary battery includes the carbon material of silicon-based active material and N doping
Material, described silicon-based active material is supported on the carbon material surface of described N doping, and 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, a diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, described N doping
Material with carbon element is three-dimensional netted, and the material with carbon element of N doping includes the many branches being cross-linked with each other, described branch straight
Footpath is 1nm～10 μm, and the carbon material surface of described N doping and at least one internal place have micropore, described
The material of the material with carbon element of N doping is nitrogen-doped carbon net, and in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyrrole
At least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen combines.
The embodiment of the present invention third aspect provide a kind of cathode pole piece of lithium ion secondary battery length in service life and
Electrical conductivity is good.The same first aspect of optimal way of wherein said negative electrode of lithium ionic secondary battery.
Fourth aspect, embodiments provides a kind of lithium rechargeable battery, described lithium ion secondary electricity
Pond is made up of cathode pole piece of lithium ion secondary battery, anode pole piece, barrier film, nonaqueous electrolytic solution and shell, institute
State cathode pole piece of lithium ion secondary battery and include collector and the lithium ion secondary electricity being coated on described collector
Pond negative active core-shell material, described negative electrode of lithium ionic secondary battery includes that silicon-based active material and nitrogen are mixed
Miscellaneous material with carbon element, described silicon-based active material is supported on the carbon material surface of described N doping, described silica-based work
Property material is one or more in nano-particle and nano wire, the grain of described silicon-based active material nano-particle
Footpath is 1nm～1 μm, and a diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, described nitrogen is mixed
Miscellaneous material with carbon element is three-dimensional netted, and the material with carbon element of N doping includes the many branches being cross-linked with each other, described branch
A diameter of 1nm～10 μm, the carbon material surface of described N doping and at least one internal place there is micropore,
The material of the material with carbon element of described N doping is nitrogen-doped carbon net, nitrogen-atoms and carbon atom in described nitrogen-doped carbon net
Combine with at least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen.
Lithium rechargeable battery length in service life and electrical conductivity that embodiment of the present invention fourth aspect provides are good.
The same first aspect of optimal way of wherein said negative electrode of lithium ionic secondary battery.
Divide multiple embodiment that the embodiment of the present invention is further detailed below.The embodiment of the present invention does not limits
Due to following specific embodiment.In the range of constant principal right, carrying out change that can be suitable is implemented.
Embodiment one
The preparation method of a kind of negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
By cetyl trimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br, 7.3g) it is dissolved in frozen water
The HCl(120mL, 1mol/L of bath) in solution, ultrasonic disperse is uniform, then by Ammonium persulfate. (APS, 13.7
G) be added thereto, formed at once white suspension, after stirring 0.5 hour, add pyrrole monomer (Py,
8.3mL), filter after insulation reaction 24h at 4 DEG C, by black precipitate 1mol/L that obtains
HCl solution wash three times, then with pure water washing to solution be colourless neutrality, then precipitate at 80 DEG C
Under be dried 24 hours, finally dried precipitate is placed in tube furnace, is passed through 5%H2/ Ar mixes
Gas, sinter at 700 DEG C 2 hours i.e. can get nitrogen-doped carbon net.
(2) load silicon-based active material
Nitrogen-doped carbon net is placed in quartz ampoule, and by tube furnace evacuation, the ratio for 1:1 is passed through by volume
Silicon source SiH4And H2, control throughput is 120sccm, with the heating rate of 10 DEG C/min by tube furnace
It is warming up to 600 DEG C and is incubated 10min, being then cooled to room temperature, preparing lithium ion secondary battery negative pole activity material
Material.
In XRD analysis, negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, adopts
Recording its quality than content by weight ammonium chloride method is 21.3%.The carbon material surface of N doping and inside are at least
Having micropore at one, use nitrogen adsorption methods, calculate through BET and BJH, micropore size is distributed in 0.5～4nm
Between.Through XPS analysis, nitrogen-atoms is presented in pyridine type nitrogen and pyrroles's type nitrogen.Fig. 1 is that the present invention is real
Execute the SEM Electronic Speculum figure of the negative electrode of lithium ionic secondary battery that example one prepares.As it is shown in figure 1, described lithium
Ion secondary battery negative active core-shell material includes the material with carbon element of silicon-based active material and N doping, described silica-based work
Property material is supported on the carbon material surface of described N doping, and the material with carbon element of N doping is three-dimensional netted, N doping
Material with carbon element include the many branches being cross-linked with each other, the diameter of branch about 50～80nm, silicon-based active material nanometer
The distribution of granule is extremely uniformly and particle diameter is at about 10nm.This structure takes full advantage of the material with carbon element of N doping
Three-dimensional conductive network, the monolithic conductive characteristic of material is had little to no effect by the low conductivity of silicon-based active material.
Meanwhile, the micropore of the material with carbon element of N doping can effectively reduce the change of silicon-based active mass volume to material entirety
The impact in life-span.
Embodiment two
The preparation method of a kind of negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
By tube furnace evacuation, do reaction gas, Ar gas with the pyridine monomer (pyridine) of Ar load gasification
Flow-control is 50ml/min, 30 DEG C/min of warming and cooling rate, is incubated 6 hours, treats that tube furnace is cold at 700 DEG C
But to room temperature, nitrogen-doped carbon net is obtained.
(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, is passed through gas
Flow be the protective gas of 30sccm be 3.0Pa to pressure in magnetron sputtering cavity, control power is 80W,
Sputter 2min at 200 DEG C, be then cooled to room temperature, prepare negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping,
Described silicon-based active material is supported on the carbon material surface of described N doping.Through XRD analysis, lithium ion secondary
In battery cathode active material, silicon-based active material is elemental silicon, uses weight ammonium chloride method to record its mass ratio
Content is 23.6%.From the point of view of SEM, the material with carbon element of N doping is three-dimensional netted, and the material with carbon element of N doping includes
The many branches being cross-linked with each other, the diameter of branch about 300～500nm, the diameter of nano silicon particles is 100～200
Between nm.The carbon material surface of N doping and at least one internal place have micropore, use nitrogen adsorption methods,
Calculating through BET and BJH, micropore size is distributed between 50～150nm.Through XPS analysis, nitrogen-atoms is with pyrrole
Pyridine type nitrogen, pyrroles's type nitrogen and three kinds of forms of graphite nitrogen exist.Fig. 2 is the lithium ion two that the embodiment of the present invention prepares
The structural representation of nitrogen-doped carbon net in primary cell negative active core-shell material.As in figure 2 it is shown, nitrogen in nitrogen-doped carbon net
Atom is generally combined with the various ways in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen with carbon atom.
Embodiment three
The preparation method of a kind of negative electrode of lithium ionic secondary battery, comprises the following steps:
Take ionic liquid 3-methyl-butvl pyridine dicyan amine salt to be placed in alumina crucible, proceed in tube furnace,
It is passed through protective gas, 600 DEG C will be warming up to the heating rate of 2 DEG C/min in tube furnace and be incubated 2h, with
After be cooled to room temperature, prepare ionic liquid pyrolysis product；Subsequently by described ionic liquid pyrolysis product add γ-
The aqueous solution of aminopropyl three ethoxy silane prepares mixed solution, described ionic liquid pyrolysis product and described γ-
The mass ratio of aminopropyl three ethoxy silane is 8:5, and described mixed solution ultrasonic disperse 30min is subsequently placed at appearance
In device, heating in water bath is to 85 DEG C, instills aqueous citric acid solution constant temperature 85 DEG C stirring reaction 2h in described container,
Reacted solution is filtered, filtering residue is toasted under 80 DEG C of vacuum 12h, proceeds in atmosphere sintering furnace, logical
Enter reducing atmosphere, the product after baking is sintered 4h at a temperature of 500 DEG C, is then cooled to room temperature, prepare
Negative electrode of lithium ionic secondary battery.
Described negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping, institute
State silicon-based active material and be supported on the carbon material surface of described N doping.Through XRD analysis, lithium ion secondary electricity
In the negative active core-shell material of pond, silicon-based active material is the mixture of silicon and SiOx, uses weight ammonium chloride method to record
Its quality is 19.9% than content.From the point of view of SEM, the material with carbon element of N doping is three-dimensional netted, N doping
Material with carbon element includes the many branches being cross-linked with each other, the diameter of branch about 50～100nm, the diameter of nano silicon particles
Between 5～10nm.The carbon material surface of N doping and at least one internal place have micropore, use nitrogen
Absorption method, calculates through BET and BJH, and micropore size is distributed between 10～50nm.Through XPS analysis,
Nitrogen-atoms exists with pyridine type nitrogen, pyrroles's type nitrogen and three kinds of forms of graphite nitrogen.
Comparative example one
Colophonium is placed in quartz ampoule, is passed through 5%H2/ Ar gaseous mixture, sinters to obtain 2 hours carbon at 700 DEG C
Change, then by tube furnace evacuation, the ratio for 1:1 is passed through silicon source SiH by volume4And H2, control air-flow
Amount is 120sccm, will be warming up to 600 DEG C with the heating rate of 10 DEG C/min and is incubated 10min in tube furnace,
It is then cooled to room temperature, prepares carbon/silicon compound lithium ion secondary battery negative pole active material.
Comparative example two
The preparation method of a kind of negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
By cetyl trimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br, 7.3g) it is dissolved in frozen water
The HCl(120mL, 1mol/L of bath) in solution, ultrasonic disperse is uniform, then by Ammonium persulfate. (APS, 13.7
G) be added thereto, formed at once white suspension, after stirring 0.5 hour, add pyrrole monomer (Py,
8.3mL), filter after insulation reaction 24h at 4 DEG C, by black precipitate 1mol/L that obtains
HCl solution wash three times, then with pure water washing to solution be colourless neutrality, then precipitate at 80 DEG C
Under be dried 24 hours, finally dried precipitate is placed in tube furnace, is passed through 5%H2/ Ar mixes
Gas, sinter at 700 DEG C 2 hours i.e. can get nitrogen-doped carbon net.
(2) load silicon-based active material
Nitrogen-doped carbon net is placed in quartz ampoule, and by tube furnace evacuation, the ratio for 1:1 is passed through by volume
Silicon source SiH4And H2, control throughput is 80sccm, will rise with the heating rate of 10 DEG C/min in tube furnace
Temperature is to 1000 DEG C and is incubated 20min, is then cooled to room temperature, prepares lithium ion secondary battery negative pole activity material
Material.
In XRD analysis, negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, adopts
Recording its quality than content by weight ammonium chloride method is 22.1%.From the point of view of SEM, the material with carbon element of N doping in
Three-dimensional netted, the material with carbon element of N doping includes the many branches being cross-linked with each other, the diameter of branch about 50～80nm,
The particle diameter of nano silicon particles is distributed between 1～3 μm.Use nitrogen adsorption methods, calculate through BET and BJH,
Micropore size is distributed between 0.5～4nm.Through XPS analysis, nitrogen-atoms is with pyridine type nitrogen and pyrroles's type nitrogen
Form exists.
Comparative example three
The preparation method of a kind of negative electrode of lithium ionic secondary battery, comprises the following steps:
(1) nitrogen-doped carbon net is prepared
By tube furnace evacuation, do reaction gas, Ar gas with the pyridine monomer (pyridine) of Ar load gasification
Flow-control is 100ml/min, 50 DEG C/min of warming and cooling rate, is incubated 4 hours, treats tube furnace at 1000 DEG C
It is cooled to room temperature, obtains nitrogen-doped carbon net.
(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, is passed through gas
Flow be the protective gas of 30sccm be 3.0Pa to pressure in magnetron sputtering cavity, control power is 80W,
Sputter 2min at 200 DEG C, be then cooled to room temperature, prepare negative electrode of lithium ionic secondary battery.
In XRD analysis, negative electrode of lithium ionic secondary battery, silicon-based active material is elemental silicon, adopts
Recording its quality than content by weight ammonium chloride method is 22.1%.From the point of view of SEM, the material with carbon element of N doping in
Three-dimensional netted, the material with carbon element of N doping includes the many branches being cross-linked with each other, the diameter of branch about 15～30 μm,
The diameter of nano silicon particles is between 300～500nm.Use nitrogen adsorption methods, calculate through BET and BJH,
Micropore size is distributed between 1～5 μm.Through XPS analysis, nitrogen-atoms with pyridine type nitrogen, pyrroles's type nitrogen and
Three kinds of forms of graphite nitrogen exist.
The preparation of cathode pole piece of lithium ion secondary battery
By above-described embodiment one prepares negative electrode of lithium ionic secondary battery and conductive agent (Timcal,
Super-p and SFG-6) mix homogeneously, it is subsequently adding the Kynoar PVDF(Arkmer of 8%,
HSV900), N-Methyl pyrrolidone solution NMP, stir, above-mentioned mixed slurry be uniformly coated on
In the copper foil current collector of 10 μm, under 110 DEG C and vacuum condition, toast 12h, i.e. obtain lithium ion secondary electricity
Pond cathode pole piece.Wherein, the formula of lithium ion secondary battery negative pole mixed slurry is (mass ratio): lithium ion
Secondary battery negative pole active material: 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, electrode is used
Lithium metal, barrier film is celgard C2400, and electrolyte is 1.3M LiPF6EC and DEC(volume ratio be
3:7) solution.
The lithium ion secondary battery cathode prepared in embodiment two, embodiment three and comparative example one～comparative example three
Pole active material the most herewith processes.
Effect example is the beneficial effect providing powerful support for the embodiment of the present invention, it is provided that effect example is as follows,
In order to evaluate and test the performance of the product that the embodiment of the present invention provides.
The buckle type lithium-ion secondary electricity that will prepare in embodiment one～embodiment three and comparative example one～comparative example three
Pond charges to voltage as 0.001V with the electric current of 100mA/1g active substance, and then constant voltage is until electric current is less than
10mA/1g active substance；Shelve 10min；By above-mentioned button cell with the electricity of 100mA/1g active substance
Stream is discharged to 2.5V.Complete above-mentioned to fill, discharge of electricity process is designated as 1 and fills/discharge of electricity circulation.Buckle type lithium-ion
The formula of the coulombic efficiency first of secondary cell and capability retention is as follows, result record in Table 1:
Discharge capacity × 100% of coulombic efficiency (%)=initial charge capacity/first first；
Putting of the discharge capacity/1st time circulation of the capability retention (%) of n-th circulation=n-th circulation
Capacitance × 100%.
Table 1. buckle type lithium-ion secondary cell test result
From table 1 it follows that the lithium ion secondary battery negative pole that the embodiment of the present invention one～embodiment three prepare
Negative electrode of lithium ionic secondary battery silicon/carbon that active material prepares with the comparative example one at equal temperature is multiple
Condensation material compares and has long cycle life, high capacity and efficiency first, this is because nitrogen-doped carbon net this
Body has capacity more higher than carbon and electrical conductivity, and the micropore of the material with carbon element of N doping can effectively reduce silicon simultaneously
The impact on material bulk life time of the base active substance change in volume.The embodiment of the present invention one～embodiment three prepare
The lithium ion secondary that negative electrode of lithium ionic secondary battery prepares with the comparative example two and three at equal temperature
Battery cathode active material compares, its silicon-based active material nano-particle size and the material with carbon element branch of N doping
The collocation of the material with carbon element micropore size distribution of diameter and N doping is more reasonable, and electrical conductivity is high, has higher appearance
Amount, first efficiency and cycle life.
Claims (10)
1. a negative electrode of lithium ionic secondary battery, it is characterised in that include silicon-based active material and
The material with carbon element of N doping, described silicon-based active material is supported on the carbon material surface of described N doping, described silicon
Base active substance is one or more in nano-particle and nano wire, described silicon-based active material nano-particle
Particle diameter be 1nm～1 μm, a diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, described
The material with carbon element of N doping is three-dimensional netted, and the material with carbon element of N doping includes the many branches being cross-linked with each other, described
A diameter of 1nm of branch～10 μm, the three-dimensional netted carbon material surface of described N doping or inside have micropore
Structure, or the three-dimensional netted carbon material surface of described N doping and inside has microcellular structure, and described nitrogen is mixed
The material of miscellaneous material with carbon element is nitrogen-doped carbon net, and in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type
At least one form in nitrogen, 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, it is characterised in that
Described in described negative electrode of lithium ionic secondary battery, the quality of silicon-based active material than content is
0.1%～80%.
3. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, it is characterised in that
The diameter of the material with carbon element branch of described N doping with the ratio of 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, it is characterised in that
The pore-size distribution of described micropore is 0.5～500nm.
5. a kind of negative electrode of lithium ionic secondary battery as claimed in claim 1, it is characterised 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, it is characterised in that
One or more in elemental silicon, Si oxide and silicon alloy of the material of described silicon-based active material.
7. the preparation method of a negative electrode of lithium ionic secondary battery, it is characterised in that by with lower section
One in method is prepared:
Method one: load silicon-based active material at nitrogen-doped carbon net surface by chemical vapour deposition technique, prepares lithium
Ion secondary battery negative active core-shell material；
Method two: load silicon-based active material at nitrogen-doped carbon net surface by magnetron sputtering method, prepares lithium ion
Secondary battery negative pole active material；
Method three: by ionic liquid 3-methyl-butvl pyridine dicyan amine salt or 1-ethyl-3-methylimidazole cdicynanmide
Pyrolysis product and silicon precursor solution be blended and prepare mixed solution, described silicon precursor is γ-aminopropyl three second
Oxosilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane and γ-methacryloxypropyl front three
One or more in TMOS, by heating in water bath after described mixed solution ultrasonic disperse, to described water-bath
System instills chelating agent, subsequently the mixed solution containing chelating agent is stirred reaction, by reacted product
Sinter after baking, prepare negative electrode of lithium ionic secondary battery；
Described negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping, institute
Stating silicon-based active material and be supported on the carbon material surface of described N doping, described silicon-based active material is nanometer
One or more in grain and nano wire, the particle diameter of described silicon-based active material nano-particle is 1nm～1 μm,
A diameter of the 1 of described nano wire～200nm and a length of 1～10 μm, the material with carbon element of described N doping is three-dimensional
Netted, the material with carbon element of N doping includes the many branches being cross-linked with each other, a diameter of 1nm～10 μ of described branch
M, the three-dimensional netted carbon material surface of described N doping or inside has a microcellular structure, or described N doping
Three-dimensional netted carbon material surface and inside have microcellular structure, and the material of the material with carbon element of described N doping is that nitrogen is mixed
Miscellaneous carbon net, in described nitrogen-doped carbon net, nitrogen-atoms and carbon atom are with pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen
In at least one form combine.
The preparation method of a kind of negative electrode of lithium ionic secondary battery the most as claimed in claim 7, its
It is characterised by,
Described in method one by chemical vapour deposition technique at nitrogen-doped carbon net surface load silicon-based active material it is:
Take nitrogen-doped carbon net to be placed in tube furnace, by tube furnace evacuation, be that the ratio of 1:0.1～10 is led to by volume
Enter silicon source SiH4And protective gas, controlling throughput is 30～300sccm, with the intensification of 1～50 DEG C/min
Speed, by being warming up to 500～1300 DEG C in tube furnace and being incubated 3～60min, is then cooled to room temperature, prepares lithium
Ion secondary battery negative active core-shell material；
Described in method two by magnetron sputtering method at nitrogen-doped carbon net surface load silicon-based active material it is: take nitrogen
Doping carbon net is placed in magnetron sputtering cavity, loads onto silicon target, is evacuated to 0～10-2Pa, being passed through throughput is
The protective gas of 10～300sccm is 1～10Pa to pressure in magnetron sputtering cavity, controls power and is
10～200W, sputter 1～10min at 100～400 DEG C, be then cooled to room temperature, prepare lithium rechargeable battery
Negative active core-shell material；
Ionic liquid pyrolysis product described in method three is 1:0.1～5 with the mass ratio of described silicon precursor, described
Chelating agent is one or more of citric acid, tartaric acid, EDTA and sodium succinate, by mixing containing chelating agent
Close solution constant temperature 50～100 DEG C of lower reactions 0.5～5h of stirring, reacted product is dried under 50～100 DEG C of vacuum
Roasting 1～24h, then proceed in atmosphere sintering furnace, 500～1300 DEG C of sintering 1～10h under protective gas atmosphere,
It is then cooled to room temperature.
9. a cathode pole piece of lithium ion secondary battery, it is characterised in that described lithium ion secondary battery negative pole
Pole piece includes collector and the negative electrode of lithium ionic secondary battery being coated on described collector, described
Negative electrode of lithium ionic secondary battery includes the material with carbon element of silicon-based active material and N doping, described silica-based
Active substance is supported on the carbon material surface of described N doping, and described silicon-based active material is nano-particle and receives
One or more in rice noodle, the particle diameter of described silicon-based active material nano-particle is 1nm～1 μm, described in receive
A diameter of the 1 of rice noodle～200nm and a length of 1～10 μm, the material with carbon element of described N doping is three-dimensional netted,
The material with carbon element of N doping includes the many branches being cross-linked with each other, a diameter of 1nm of described branch～10 μm, institute
Three-dimensional netted carbon material surface or the inside of stating N doping have microcellular structure, or the three-dimensional of described N doping
Reticulated carbon material surface and inside have microcellular structure, and 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 in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen
At least one form combines.
10. a lithium rechargeable battery, it is characterised in that described lithium rechargeable battery is by lithium ion two
Primary cell cathode pole piece, anode pole piece, barrier film, nonaqueous electrolytic solution and shell composition, described lithium ion secondary
Negative pole piece of battery includes that the material with carbon element of silicon-based active material and N doping, described silicon-based active material are supported on
The carbon material surface of described N doping, described silicon-based active material be the one in nano-particle and nano wire or
Several, the particle diameter of described silicon-based active material nano-particle is 1nm～1 μm, described nano wire a diameter of
1～200nm and a length of 1～10 μm, the material with carbon element of described N doping is three-dimensional netted, the carbon material of N doping
Material includes the many branches being cross-linked with each other, a diameter of 1nm of described branch～10 μm, the three of described N doping
Dimension reticulated carbon material surface or inside have microcellular structure, or the three-dimensional netted material with carbon element table of described N doping
Face and inside have microcellular structure, and the material of the material with carbon element of described N doping is nitrogen-doped carbon net, and described nitrogen is mixed
In miscellaneous carbon net, nitrogen-atoms and carbon atom are with at least one form in pyridine type nitrogen, graphite mould nitrogen and pyrroles's type nitrogen
In conjunction with.
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| PCT/CN2014/072429 WO2015014120A1 (en) | 2013-07-29 | 2014-02-24 | Negative active material of lithium-ion secondary battery and preparation method therefor, negative plate of lithium-ion secondary battery, and lithium-ion secondary battery |
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| CN105098185B (en) | 2014-04-29 | 2018-08-14 | 华为技术有限公司 | Composite negative pole material and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery |
| CN106898738B (en) | 2015-12-18 | 2019-07-23 | 华为技术有限公司 | A kind of negative electrode of lithium ionic secondary battery and preparation method, cathode pole piece of lithium ion secondary battery and lithium ion secondary battery |
| CN106941165A (en) * | 2017-04-13 | 2017-07-11 | 乐延伟 | A kind of silica carbon composition lithium ion electromagnetism negative active core-shell material and preparation method thereof |
| CN108821292B (en) * | 2017-05-05 | 2021-07-23 | 储晞 | Method and device for producing silicon monoxide |
| CN107799742A (en) * | 2017-09-28 | 2018-03-13 | 浙江工业大学 | A kind of lithium battery load porous carbon negative pole material of silicon bio-based N doping and preparation method thereof |
| CN109755506A (en) * | 2018-12-18 | 2019-05-14 | 宁波革鑫新能源科技有限公司 | A kind of Si-C composite material and preparation method thereof |
| CN112216833A (en) * | 2020-11-11 | 2021-01-12 | 榆林学院 | WS (WS)2/TiO2Preparation method of/nitrogen-doped graphene nanocomposite |
| CN113054172A (en) * | 2021-03-11 | 2021-06-29 | 珠海冠宇电池股份有限公司 | Nitrogen-doped graphene-coated silicon-based material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2333879A1 (en) * | 2008-09-30 | 2011-06-15 | Sumitomo Bakelite Co., Ltd. | Carbon material for negative electrode of lithium secondary battery, negative electrode of lithium secondary battery, lithium secondary battery and method for producing carbon material for negative electrode of lithium secondary battery |
| CN102804463A (en) * | 2009-06-18 | 2012-11-28 | 株式会社Lg化学 | Cathode active material for a lithium rechargeable battery and a production method therefor |
| CN102891314A (en) * | 2011-07-19 | 2013-01-23 | 张少波 | Nitrogen silicon carbide as cathode material |
| CN103022478A (en) * | 2011-09-28 | 2013-04-03 | 比亚迪股份有限公司 | Lithium ion battery cathode material and preparation method thereof and lithium ion battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4747607B2 (en) * | 2004-02-24 | 2011-08-17 | 住友金属工業株式会社 | Anode material for non-aqueous secondary battery and method of manufacturing |
| CN101527357B (en) * | 2009-04-24 | 2012-05-16 | 清华大学 | Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor |
| US8753545B2 (en) * | 2010-03-03 | 2014-06-17 | 3M Innovative Properties Company | Composite negative electrode materials |
| CN102637874B (en) * | 2012-04-11 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN102651476B (en) * | 2012-05-28 | 2015-01-28 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon carbide composite anode material and preparation method thereof |
| CN103219517B (en) * | 2013-04-15 | 2015-01-21 | 中南大学深圳研究院 | Preparation method for nitrogen-doped porous carbon sphere-sulfur composite positive material |
-
2013
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- 2014-02-24 WO PCT/CN2014/072429 patent/WO2015014120A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2333879A1 (en) * | 2008-09-30 | 2011-06-15 | Sumitomo Bakelite Co., Ltd. | Carbon material for negative electrode of lithium secondary battery, negative electrode of lithium secondary battery, lithium secondary battery and method for producing carbon material for negative electrode of lithium secondary battery |
| CN102804463A (en) * | 2009-06-18 | 2012-11-28 | 株式会社Lg化学 | Cathode active material for a lithium rechargeable battery and a production method therefor |
| CN102891314A (en) * | 2011-07-19 | 2013-01-23 | 张少波 | Nitrogen silicon carbide as cathode material |
| CN103022478A (en) * | 2011-09-28 | 2013-04-03 | 比亚迪股份有限公司 | Lithium ion battery cathode material and preparation method thereof and lithium ion battery |
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