CN106315553A - Lithium-ion-battery cathode material and preparing method thereof - Google Patents
Lithium-ion-battery cathode material and preparing method thereof Download PDFInfo
- Publication number
- CN106315553A CN106315553A CN201610656116.XA CN201610656116A CN106315553A CN 106315553 A CN106315553 A CN 106315553A CN 201610656116 A CN201610656116 A CN 201610656116A CN 106315553 A CN106315553 A CN 106315553A
- Authority
- CN
- China
- Prior art keywords
- negative material
- lithium ion
- ion battery
- carbon
- cnt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium-ion-battery cathode material and a preparing method thereof. The cathode material comprises carbon nanotubes and carbon nanosheets; the carbon nanotubes are distributed on the surfaces of the carbon nanosheets to form a three-dimensional conductive network structure, the tube diameter of the carbon nanotubes is 10 nm to 100 nm, and the thickness of the carbon nanosheets is 5 nm to 50 nm. Compared with an existing cathode material, the cathode material of the three-dimensional conductive network structure formed by the carbon nanotubes and the carbon nanosheets has the good electrochemical activity and electronic characteristics, can provide a good lithium-ion diffusion channel, volume expansion when lithium getting off is buffered, and a cathode sheet made from the cathode material has the excellent cycle performance and high magnification performance. In addition, the cathode material is prepared with the solid-solid pyrolysis method, has the advantages of being easy and convenient to operate, economical, low in energy consumption and convenient to produce in a large-scale mode, and has the good application prospects.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of lithium ion battery negative material and preparation side thereof
Method.
Background technology
Lithium ion battery because having that running voltage is high, specific energy high, safety is good, memory-less effect, self discharge little, acyclic
The advantages such as environment pollution and be considered as one of high energy battery that can meet Future Society sustainable development requirement.In recent years,
Lithium ion battery develops quickly, is widely used for the portable electronics such as mobile phone, digital camera, notebook computer, video camera and sets
Standby and space flight, aviation and navigational field, and start to be applied to electric automobile field.Therefore, various lithium ion battery for electric vehicles
The industry that various countries from now on give priority to will be become, also open more wide demand for China's electrokinetic cell industry development simultaneously
Space.
But, current lithium ion battery also cannot meet the energy density demand of sustainable growth.This opens with regard to an urgent demand
Send out high-energy-density, the battery material of high rate capability so that the energy density of lithium ion battery and power density meet current
Demand, and then promote the fast development of ev industry.Negative material be affect performance of lithium ion battery critical material it
One.Lithium ion battery negative material uses graphite in early days.But due to the energy density that it is relatively low, cannot meet at present
The electric motor car demand to high-energy-density.Therefore, find other negative material that can substitute for graphite and become the weight of people's research
Point.Preferably lithium ion battery negative material typically requires and meets following condition: (1) during the embedding-dealkylation reaction of lithium,
Current potential is low and current potential close to lithium metal, in order to ensure that battery has higher and stable output voltage；(2) have higher
Electrochemistry capacitance and higher efficiency for charge-discharge, to ensure that battery has higher energy density and less capacitance loss；(3)
On inside and the surface of electrode material, lithium ion has diffusion rate faster, to guarantee the kinetic factor of electrode process, from
And make battery that the needs of power type power supply with higher rate charge-discharge, can be met；(4) there is good electric conductivity；(5) have
Higher structural stability, chemical stability and heat stability, does not reacts with electrolyte, good to ensure that battery has
Cycle performance；(6) there is good electrode moulding performance；(7) preparation is easily, and aboundresources is cheap, to environment without dirt
Dye.Wherein, current lithium ion battery negative material mainly has graphite, amorphous carbons, CNT, silica-base material, tinbase material
Material, alloy material, transition metal oxide and two-dimension nano materials.
CNT and carbon nanosheet have a unique peacekeeping two-dimensional structure and higher electric conductivity causes vast
The interest of researcher.But simple CNT or carbon nanosheet lithiumation process can generate Li6The compound of C, causes electrode
Electro-chemical activity, the storge quality of lithium and high rate performance the most poor.In view of this, necessary to existing lithium-ion electric
Pond negative material is made further to improve so that it is possesses good electro-chemical activity and characteristic electron, and can improve the storage of lithium
Performance.
Summary of the invention
An object of the present invention is: provide a kind of lithium ion battery negative material for the deficiencies in the prior art,
This negative material possesses good electro-chemical activity and characteristic electron, can improve the storge quality of lithium simultaneously.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of lithium ion battery negative material, including CNT and carbon nanosheet, described CNT is distributed in described carbon and receives
The surface of rice sheet forms three-dimensional conductive network structure, and the caliber of described CNT is 10 ~ 100nm, the thickness of described carbon nanosheet
Degree is 5 ~ 50 nm.
Wherein, CNT is as monodimension nanometer material, lightweight, and hexagonal structure connects perfection, has the power of excellence
, electricity and chemical property.And the feature of carbon nanosheet is its shape, owing to carbon nanosheet is to extract crystal structure minimum substantially
Unit gained material, its thickness only has several atom so big, and lateral dimension is usually more than micron, has high two dimension
Anisotropy；Its nanometric scale structure and high Two-Dimensional Anisotropic, make carbon nanosheet have reactive high, specific surface area
Greatly, the characteristic such as quantum limitation effect and high conductivity.Therefore, the present invention makes the carbon nanosheet of one-dimensional CNT and two dimension lead to
Cross covalent bond to combine and form three-dimensional conductive network structure, it is possible to the electro-chemical activity and the electronics that are effectively improved negative material are special
Property so that it is possess good circulation and high rate performance.
As a kind of improvement of lithium ion battery negative material of the present invention, the caliber of described CNT is 30 ~ 50nm, institute
The thickness stating carbon nanosheet is 15 ~ 35nm.
As a kind of improvement of lithium ion battery negative material of the present invention, the draw ratio of described CNT for more than or etc.
In 1000:1.
The two of the purpose of the present invention are: providing a kind of method preparing above-mentioned lithium ion battery negative material, this is prepared
Method comprises the following steps:
Step one: by nickel source and carbon nitrogen source 1:(1 in mass ratio～15) mixing, and grind 0.5～3h at room temperature；
Step 2: be warming up to 600～1000 DEG C under protective atmosphere and be incubated 1～6h, i.e. preparing described negative material.
Wherein, when nickel source and carbon nitrogen source mass ratio are the highest, CNT is the longest, the most intensive；When nickel source and carbon nitrogen source matter
Amount ratio is time the lowest, and CNT is the most sparse；Therefore, nickel source and carbon nitrogen source mass ratio are set within the above range, it is possible to effectively
Control the pattern of CNT.
As a kind of improvement of the preparation method of lithium ion battery negative material of the present invention, described protective atmosphere be argon,
At least one in nitrogen and hydrogen nitrogen mixed gas.
As a kind of improvement of the preparation method of lithium ion battery negative material of the present invention, described nickel source is the nitre of metallic nickel
At least one in hydrochlorate, the chloride of metallic nickel, the acetate of metallic nickel, the sulfate of metallic nickel and dicyclopentadienyl nickel.
As a kind of improvement of the preparation method of lithium ion battery negative material of the present invention, described carbon nitrogen source be carbamide, three
At least one in poly cyanamid, dicyandiamide and cyanamide.
As a kind of improvement of the preparation method of lithium ion battery negative material of the present invention, nickel source described in step one and institute
Stating carbon nitrogen source mass ratio is 1:5.
As a kind of improvement of the preparation method of lithium ion battery negative material of the present invention, the speed heated up in step 2 is
1～10 DEG C/min.Wherein, when programming rate is the fastest, prepared CNT is the shortest；When programming rate is the slowest, prepared carbon is received
Mitron is the longest.
The beneficial effects of the present invention is: one lithium ion battery negative material of the present invention, receive including CNT and carbon
Rice sheet, described CNT is distributed in the surface of described carbon nanosheet and forms three-dimensional conductive network structure, described CNT
Caliber is 10 ~ 100nm, and the thickness of described carbon nanosheet is 5 ~ 50 nm.Compared to other existing negative material (such as silicon substrate
Material, tin-based material, alloy material, transition metal oxide etc.), the three-dimensional that the present invention is formed by CNT and carbon nanosheet is led
The negative material of electric network structure possesses good electro-chemical activity and characteristic electron, and it can provide good lithium ion to spread
Passage, the volumetric expansion occurred during buffering removal lithium embedded so that use the negative plate of this material to have cycle performance and the height of excellence
High rate performance.Additionally, this negative material uses the preparation method of solid solid pyrolysis, have easy and simple to handle, economy, energy consumption are low and are easy to
The advantage accomplished scale production, has preferable application prospect.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the negative material of the embodiment of the present invention 1 preparation.
Fig. 2 is one of TEM figure of negative material of the embodiment of the present invention 1 preparation.
Fig. 3 is the two of the TEM figure of the negative material of the embodiment of the present invention 1 preparation.
Fig. 4 is the XRD figure of the negative material of the embodiment of the present invention 1 ~ 3 preparation.
Fig. 5 is the cycle performance figure of the negative material of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below in conjunction with detailed description of the invention and Figure of description, the present invention is described in further detail, but the present invention
Embodiment be not limited to this.
Embodiment 1
Dicyclopentadienyl nickel and tripolycyanamide 1:2.5 in mass ratio are mixed, and grinds 1.5 hours at room temperature；Then in argon gas atmosphere
Under be heated to 800 DEG C and insulation reaction 3 hours with 5 DEG C/min, i.e. prepare CNT and be distributed in the surface of carbon nanosheet and formed
The negative material of three-dimensional conductive network structure, wherein, the caliber of CNT is 40nm, and draw ratio is 3500:1；Carbon nanosheet
Thickness be 25nm.
Embodiment 2
Dicyclopentadienyl nickel and tripolycyanamide 1:5 in mass ratio are mixed, and grinds 1.5 hours at room temperature；The most under an argon atmosphere
It is heated to 800 DEG C of also insulation reaction 3 hours with 10 DEG C/min, i.e. prepares CNT and be distributed in the surface formation three of carbon nanosheet
The negative material of dimension conductive network structure, wherein, the caliber of CNT is 40nm, and draw ratio is 2000:1；Carbon nanosheet
Thickness is 25nm.
Embodiment 3
Dicyclopentadienyl nickel and carbamide 1:10 in mass ratio are mixed, and grinds 1.5 hours at room temperature；The most under an argon atmosphere with 5
DEG C/min is heated to 800 DEG C and insulation reaction 3 hours, i.e. prepare CNT and be distributed in the surface of carbon nanosheet and form three-dimensional and lead
The negative material of electric network structure, wherein, the caliber of CNT is 50nm, and draw ratio is 2500:1；The thickness of carbon nanosheet
For 20nm.
Embodiment 4
Dicyclopentadienyl nickel and carbamide 1:15 in mass ratio are mixed, and grinds 1.5 hours at room temperature；The most under an argon atmosphere with 5
DEG C/min is heated to 800 DEG C and insulation reaction 3 hours, i.e. prepare CNT and be distributed in the surface of carbon nanosheet and form three-dimensional and lead
The negative material of electric network structure, wherein, the caliber of CNT is 100nm, and draw ratio is 1000:1；The thickness of carbon nanosheet
For 10nm.
Embodiment 5
By nitrate and the dicyandiamide 1:10 in mass ratio mixing of metallic nickel, and grind 3 hours at room temperature；Then at argon gas
It is heated to 1000 DEG C of also insulation reaction 6 hours with 8 DEG C/min under atmosphere, i.e. prepares CNT and be distributed in the surface shape of carbon nanosheet
Becoming the negative material of three-dimensional conductive network structure, wherein, the caliber of CNT is 10nm, and draw ratio is 2000:1；Carbon nanometer
The thickness of sheet is 5nm.
Embodiment 6
By chloride and the cyanamide 1:12 in mass ratio mixing of metallic nickel, and grind 0.5 hour at room temperature；Then at argon
It is heated to 600 DEG C of also insulation reaction 1 hours with 3 DEG C/min under atmosphere, i.e. prepares CNT and be distributed in the surface of carbon nanosheet
Forming the negative material of three-dimensional conductive network structure, wherein, the caliber of CNT is 20nm, and draw ratio is 1800:1；Carbon is received
The thickness of rice sheet is 50nm.
Embodiment 7
By acetate and the cyanamide 1:8 in mass ratio mixing of metallic nickel, and grind 2 hours at room temperature；Then at argon gas
It is heated to 600 DEG C of also insulation reaction 5 hours with 1 DEG C/min under atmosphere, i.e. prepares CNT and be distributed in the surface shape of carbon nanosheet
Becoming the negative material of three-dimensional conductive network structure, wherein, the caliber of CNT is 30nm, and draw ratio is 1700:1；Carbon nanometer
The thickness of sheet is 30nm.
Embodiment 8
By sulfate and the cyanamide 1:14 in mass ratio mixing of metallic nickel, and grind 2.5 hours at room temperature；Then at argon
It is heated to 700 DEG C of also insulation reaction 4 hours with 7 DEG C/min under atmosphere, i.e. prepares CNT and be distributed in the surface of carbon nanosheet
Forming the negative material of three-dimensional conductive network structure, wherein, the caliber of CNT is 35nm, and draw ratio is 3000:1；Carbon is received
The thickness of rice sheet is 35nm.
Embodiment 9
The sulfate of metallic nickel, the nitrate of metallic nickel and cyanamide 0.5:0.5:1 in mass ratio are mixed, and grinds at room temperature
Grind 3 hours；It is heated to 900 DEG C of also insulation reaction 3.5 hours with 5 DEG C/min the most under an argon atmosphere, i.e. prepares CNT
The surface being distributed in carbon nanosheet forms the negative material of three-dimensional conductive network structure, and wherein, the caliber of CNT is 40nm,
Draw ratio is 4500:1；The thickness of carbon nanosheet is 28nm.
Embodiment 10
The nitrate of metallic nickel, cyanamide and dicyandiamide 1:5:5 in mass ratio is mixed, and grinds 3 hours at room temperature；Then
It is heated to 1000 DEG C of also insulation reaction 6 hours with 8 DEG C/min under an argon atmosphere, i.e. prepares CNT and be distributed in carbon nanosheet
Surface formed three-dimensional conductive network structure negative material, wherein, the caliber of CNT is 25nm, and draw ratio is 5000:
1；The thickness of carbon nanosheet is 40nm.
Embodiment 11
The chloride of metallic nickel, the acetate of metallic nickel, tripolycyanamide and dicyandiamide 0.5:0.5:2.5:2.5 in mass ratio are mixed
Close, and grind 1.5 hours at room temperature；It is heated to 800 DEG C of also insulation reaction 3 hours the most under an argon atmosphere with 5 DEG C/min,
I.e. prepare the negative material that CNT is distributed in the surface formation three-dimensional conductive network structure of carbon nanosheet, wherein, carbon nanometer
The caliber of pipe is 40nm, and draw ratio is 6000:1；The thickness of carbon nanosheet is 25nm.
Embodiment 12
The nitrate of metallic nickel, the acetate of metallic nickel, tripolycyanamide and carbamide 0.5:0.5:2.5:2.5 in mass ratio are mixed
Close, and grind 1.5 hours at room temperature；It is heated to 800 DEG C of also insulation reaction 3 hours the most under an argon atmosphere with 5 DEG C/min,
I.e. prepare the negative material that CNT is distributed in the surface formation three-dimensional conductive network structure of carbon nanosheet, wherein, carbon nanometer
The caliber of pipe is 38nm, and draw ratio is 6500:1；The thickness of carbon nanosheet is 32nm.
Embodiment 13
The nitrate of metallic nickel, cyanamide and carbamide 1:2.5:2.5 in mass ratio is mixed, and grinds 1.5 hours at room temperature；
It is heated to 1000 DEG C of also insulation reaction 1.5 hours with 5 DEG C/min the most under an argon atmosphere, i.e. prepares CNT and be distributed in carbon
The surface of nanometer sheet forms the negative material of three-dimensional conductive network structure, and wherein, the caliber of CNT is 30nm, and draw ratio is
5000:1；The thickness of carbon nanosheet is 15nm.
Embodiment 14
The nitrate of metallic nickel, the chloride of metallic nickel and carbamide 0.5:0.5:5 in mass ratio are mixed, and grinds at room temperature
1.5 hour；It is heated to 600 DEG C of also insulation reaction 3 hours with 5 DEG C/min the most in a nitrogen atmosphere, i.e. prepares CNT and divide
Cloth forms the negative material of three-dimensional conductive network structure on the surface of carbon nanosheet, and wherein, the caliber of CNT is 50nm, long
Footpath is than for 5500:1；The thickness of carbon nanosheet is 35nm.
Embodiment 15
By the nitrate of metallic nickel, the chloride of metallic nickel, tripolycyanamide, dicyandiamide and cyanamide 0.5:0.5 in mass ratio:
1.5:1.5:2 mixing, and grind 1.5 hours at room temperature；It is heated to 1000 DEG C with 5 DEG C/min the most in a nitrogen atmosphere and protects
Temperature reaction 3 hours, i.e. prepares the negative material that CNT is distributed in the surface formation three-dimensional conductive network structure of carbon nanosheet,
Wherein, the caliber of CNT is 40nm, and draw ratio is 7000:1；The thickness of carbon nanosheet is 30nm.
Taking the negative material prepared by above-described embodiment 1 and carry out SEM and TEM test respectively, test result is shown in Fig. 1 ~ 3.
From Fig. 1 ~ 3, the carbon negative pole material of three-dimensional conductive network structure of the present invention compared with traditional graphite cathode, carbon
Nanotube is distributed on the surface of carbon nanosheet as ion channel, and is combined formation three-dimensional with carbon nanosheet by covalent bond
Conductive network, is conducive to improving embedding-de-dynamic performance of lithium ion；And owing to CNT is evenly distributed in carbon nanometer
On sheet, this pattern is conducive to the infiltration of electrolyte anticathode material；Therefore, that negative plate can be made to have is excellent for negative material of the present invention
Different cycle performance and high rate performance.
Taking the negative material prepared by above-described embodiment 1 ~ 3 and carry out XRD test respectively, test result is shown in Fig. 4.
As shown in Figure 4, the XRD figure spectrum of negative material of the present invention manifests 25oDiffraction maximum, it belongs to (002) crystal face, and not
Nickel source in proportion and carbon nitrogen source have no effect on the diffraction maximum position of carbon and Ni in negative material.
The lithium ion battery using the negative material prepared by above-described embodiment 1 to be assembled into is circulated performance test, surveys
Test result is shown in Fig. 5.
As shown in Figure 5, negative material of the present invention shows good cyclical stability, still keeps relatively after 300 circulations
High charge/discharge capacity, therefore the negative material of the present invention has the cycle performance of excellence.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula changes and revises.Therefore, the invention is not limited in that above-mentioned detailed description of the invention, every those skilled in the art exist
Any conspicuously improved, replacement done on the basis of the present invention or modification belong to protection scope of the present invention.This
Outward, although employing some specific terms in this specification, but these terms are merely for convenience of description, not to the present invention
Constitute any restriction.
Claims (9)
1. a lithium ion battery negative material, it is characterised in that: include that CNT and carbon nanosheet, described CNT divide
Cloth forms three-dimensional conductive network structure on the surface of described carbon nanosheet, and the caliber of described CNT is 10 ~ 100nm, described
The thickness of carbon nanosheet is 5 ~ 50 nm.
Lithium ion battery negative material the most according to claim 1, it is characterised in that: the caliber of described CNT is 30
~ 50nm, the thickness of described carbon nanosheet is 15 ~ 35nm.
Lithium ion battery negative material the most according to claim 1, it is characterised in that: the draw ratio of described CNT is
More than or equal to 1000:1.
4. the preparation method of a lithium ion battery negative material according to claim 1, it is characterised in that include following
Step:
Step one: by nickel source and carbon nitrogen source 1:(1 in mass ratio～15) mixing, and grind 0.5～3h at room temperature；
Step 2: be warming up to 600～1000 DEG C under protective atmosphere and be incubated 1～6h, i.e. preparing described negative material.
The preparation method of lithium ion battery negative material the most according to claim 4, it is characterised in that: described protective atmosphere
For at least one in argon, nitrogen and hydrogen nitrogen mixed gas.
The preparation method of lithium ion battery negative material the most according to claim 4, it is characterised in that: described nickel source is gold
Belong at least in the nitrate of nickel, the chloride of metallic nickel, the acetate of metallic nickel, the sulfate of metallic nickel and dicyclopentadienyl nickel
Kind.
The preparation method of lithium ion battery negative material the most according to claim 4, it is characterised in that: described carbon nitrogen source is
At least one in carbamide, tripolycyanamide, dicyandiamide and cyanamide.
The preparation method of lithium ion battery negative material the most according to claim 4, it is characterised in that: described in step one
Nickel source and described carbon nitrogen source mass ratio are 1:5.
The preparation method of lithium ion battery negative material the most according to claim 4, it is characterised in that: step 2 heats up
Speed be 1～10 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610656116.XA CN106315553B (en) | 2016-08-11 | 2016-08-11 | A kind of lithium ion battery negative material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610656116.XA CN106315553B (en) | 2016-08-11 | 2016-08-11 | A kind of lithium ion battery negative material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106315553A true CN106315553A (en) | 2017-01-11 |
| CN106315553B CN106315553B (en) | 2018-07-24 |
Family
ID=57740678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610656116.XA Expired - Fee Related CN106315553B (en) | 2016-08-11 | 2016-08-11 | A kind of lithium ion battery negative material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106315553B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352528A (en) * | 2017-08-31 | 2017-11-17 | 清华大学 | A kind of preparation method and nano chain of metal oxide nano chain |
| CN111211300A (en) * | 2020-01-10 | 2020-05-29 | 南昌大学 | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof |
| CN114671427A (en) * | 2022-03-21 | 2022-06-28 | 中国人民解放军国防科技大学 | Composite nanomaterial of carbon nano sheet in-situ loaded carbon nano tube and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346293A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN103915632A (en) * | 2014-03-24 | 2014-07-09 | 复旦大学 | Self-supporting nitrogen-doped carbon nanotube lithium air cell cathode and preparation method thereof |
| CN104538595A (en) * | 2014-12-10 | 2015-04-22 | 南京师范大学 | Lithium ion battery cathode material embedded nano metal loaded carbon nanosheet as well as preparation method and application thereof |
| CN104860294A (en) * | 2015-04-20 | 2015-08-26 | 复旦大学 | Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof |
| CN105449214A (en) * | 2016-01-12 | 2016-03-30 | 广西师范大学 | Lithium ion battery cathode material of which nano particles embedded into carbon nanosheet and preparation method of lithium ion battery cathode material |
-
2016
- 2016-08-11 CN CN201610656116.XA patent/CN106315553B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346293A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN103915632A (en) * | 2014-03-24 | 2014-07-09 | 复旦大学 | Self-supporting nitrogen-doped carbon nanotube lithium air cell cathode and preparation method thereof |
| CN104538595A (en) * | 2014-12-10 | 2015-04-22 | 南京师范大学 | Lithium ion battery cathode material embedded nano metal loaded carbon nanosheet as well as preparation method and application thereof |
| CN104860294A (en) * | 2015-04-20 | 2015-08-26 | 复旦大学 | Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof |
| CN105449214A (en) * | 2016-01-12 | 2016-03-30 | 广西师范大学 | Lithium ion battery cathode material of which nano particles embedded into carbon nanosheet and preparation method of lithium ion battery cathode material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352528A (en) * | 2017-08-31 | 2017-11-17 | 清华大学 | A kind of preparation method and nano chain of metal oxide nano chain |
| CN111211300A (en) * | 2020-01-10 | 2020-05-29 | 南昌大学 | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof |
| CN114671427A (en) * | 2022-03-21 | 2022-06-28 | 中国人民解放军国防科技大学 | Composite nanomaterial of carbon nano sheet in-situ loaded carbon nano tube and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106315553B (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110620223B (en) | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof | |
| Zhang et al. | Constructing ultra-thin Ni-MOF@ NiS2 nanosheets arrays derived from metal organic frameworks for advanced all-solid-state asymmetric supercapacitor | |
| CN102013330B (en) | Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof | |
| CN103326007B (en) | The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof | |
| CN102496719A (en) | Silicon/graphene composite material, and preparation method and application of the same | |
| CN105304872B (en) | A kind of preparation method of nickel ion doping cobalt sulfide/conductive substrates composite | |
| CN104966824A (en) | Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof | |
| CN103236528B (en) | A kind of germanium carbon graphite alkene composite material and its preparation method and application | |
| CN103441246A (en) | Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material | |
| CN103290246A (en) | Preparation method of three-dimensional nano porous tin-base alloy for lithium-ion battery negative electrode | |
| US20220216477A1 (en) | Pre-lithiated silicon-carbon multilayer composite negative electrode material for lithium ion batteries and preparation method thereof | |
| CN109616331A (en) | A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof | |
| He et al. | ZnO/CoO@ NiCoS nanohybrids with double heterogeneous interface for high-performance hybrid supercapacitors | |
| CN104953105B (en) | A kind of lithium ion battery SnOxThe preparation method of/carbon nano tube compound material | |
| CN107634193B (en) | Porous ferrous sulfide nanowire and nitrogen-doped carbon composite material as well as preparation method and application thereof | |
| WO2022151648A1 (en) | High-capacity highly stable silicon-carbon negative electrode material and preparation method therefor | |
| CN106315553A (en) | Lithium-ion-battery cathode material and preparing method thereof | |
| CN104269520A (en) | Li2FeTiO4-G composite positive electrode material taking graphene as carrier and preparation method of Li2FeTiO4-G composite positive electrode material | |
| CN106025297A (en) | Electrode preparation method of new energy source automobile fuel cell | |
| Zhao et al. | A novel capacitive negative electrode material of Fe3N | |
| Weng et al. | In situ growth of silicon carbide interface enhances the long life and high power of the mulberry-like Si-based anode for lithium-ion batteries | |
| CN103066249B (en) | Cobalt-based complex oxide/graphene composite material as well as preparation method and application thereof | |
| Chen et al. | Controllable synthesis of cobalt oxide nanoflakes on three-dimensional porous cobalt networks as high-performance cathode for alkaline hybrid batteries | |
| CN106783196B (en) | Preparation method of polyhedral ferric oxide nano material | |
| Yu et al. | Fabrication and electrochemical performance of Al-Doped ZnO nanosheets on graphene-based flexible substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180724 Termination date: 20190811 |