CN106315553B - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium ion battery negative material and preparation method thereof, the negative material includes carbon nanotube and carbon nanosheet, the surface that the carbon nanotube is distributed in the carbon nanosheet forms three-dimensional conductive network structure, the caliber of the carbon nanotube is 10 ~ 100nm, and the thickness of the carbon nanosheet is 5 ~ 50 nm.Compared to existing negative material, the negative material for the three-dimensional conductive network structure that the present invention is formed by carbon nanotube and carbon nanosheet has good electro-chemical activity and characteristic electron, it is capable of providing good lithium ion diffusion admittance, buffer the volume expansion occurred when removal lithium embedded so that there is excellent cycle performance and high rate capability using the negative plate of the material.In addition, the negative material is had the advantages that easy to operate, economical, low energy consumption and be easy to implement large-scale production using the preparation method being pyrolyzed admittedly admittedly, there is preferable application prospect.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of lithium ion battery negative material and its preparation sides
Method.
Background technology
Lithium ion battery is because with operating voltage is high, higher than energy, safety is good, memory-less effect, self discharge are small, acyclic
Border pollute the advantages that and be considered as one of the high energy battery that can most meet future society sustainable development requirement.In recent years,
Lithium ion battery have developed rapidly, and is widely used for the portable electronics such as mobile phone, digital camera, laptop, video camera and sets
Standby and space flight, aviation and navigational field, and start to be applied to electric vehicle field.Therefore, various lithium ion battery for electric vehicle
The industry that will be given priority to as various countries from now on, while being also that China's power battery industry development opens more wide demand
Space.
However, current lithium ion battery also cannot be satisfied the energy density demand of sustainable growth.This is opened with regard to an urgent demand
Send out the battery material of high-energy density, high rate capability so that the energy density and power density of lithium ion battery meet current
Demand, and then push the fast development of ev industry.Negative material be influence performance of lithium ion battery critical material it
One.Early stage lithium ion battery negative material uses graphite.But due to its lower energy density, can no longer meet at present
Demand of the electric vehicle to high-energy density.Therefore, other weights that the negative material of graphite can be replaced to become people's research are found
Point.Ideal lithium ion battery negative material usually requires to meet following condition：（1）During embedding-dealkylation reaction of lithium,
Current potential is low and current potential close to lithium metal, to ensure that battery has higher and stable output voltage；（2）With higher
Electrochemistry capacitance and higher efficiency for charge-discharge, to ensure that battery has higher energy density and smaller capacitance loss；（3）
In the inside and surface of electrode material, lithium ion has faster diffusion rate, to ensure the kinetic factor of electrode process, from
And battery is enable to meet the needs of power type power supply with higher rate charge-discharge；（4）With good electric conductivity；（5）Have
Higher structural stability, chemical stability and thermal stability do not react with electrolyte, to ensure that it is good that battery has
Cycle performance；（6）With good electrode moulding performance；（7）It prepares and is easy, it is resourceful, it is cheap, to environment without dirt
Dye.Wherein, lithium ion battery negative material mainly has graphite, amorphous carbons, carbon nanotube, silica-base material, tinbase material at present
Material, alloy material, transition metal oxide and two-dimension nano materials.
It is vast that there is unique peacekeeping two-dimensional structure and higher electric conductivity to cause for carbon nanotube and carbon nanosheet
The interest of researcher.However simple carbon nanotube or carbon nanosheet lithiumation process can generate Li6The compound of C, leads to electrode
Electro-chemical activity, lithium storge quality and high rate performance it is poor.In view of this, it is necessory to existing lithium-ion electric
Pond negative material makees further improvement, so that it is had good electro-chemical activity and characteristic electron, and can improve the storage of lithium
Performance.
Invention content
It is an object of the present invention to：A kind of lithium ion battery negative material is provided in view of the deficiencies of the prior art,
The negative material has good electro-chemical activity and characteristic electron, while can improve the storge quality of lithium.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of lithium ion battery negative material, including carbon nanotube and carbon nanosheet, the carbon nanotube are distributed in described
The surface of carbon nanosheet forms three-dimensional conductive network structure, and the caliber of the carbon nanotube is 10 ~ 100nm, the carbon nanosheet
Thickness be 5 ~ 50 nm.
Wherein, carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has excellent power
, electricity and chemical property.And carbon nanosheet is characterized in its shape, since carbon nanosheet is that extraction crystal structure is minimum basic
Unit obtained material, thickness only has several atoms so big, and lateral dimension is usually micron or more, has high two dimension
Anisotropy；Its nanometric scale structure and high Two-Dimensional Anisotropic make carbon nanosheet have reactivity height, specific surface area
Greatly, the characteristics such as quantum limitation effect and high conductivity.Therefore, the present invention keeps one-dimensional carbon nanotube and two-dimensional carbon nanosheet logical
It crosses covalent bond to be combined to form three-dimensional conductive network structure, electro-chemical activity and the electronics that can effectively improve negative material are special
Property, so that it is had good cycle and high rate performance.
As a kind of improvement of lithium ion battery negative material of the present invention, the caliber of the carbon nanotube is 30 ~ 50nm, institute
The thickness for 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 the carbon nanotube is to be more than or wait
In 1000:1.
The second object of the present invention is：A kind of method preparing above-mentioned lithium ion battery negative material, the preparation are provided
Method includes the following steps:
Step 1：By nickel source and carbon nitrogen source in mass ratio 1:（1~15）Mixing, and 0.5~3h is ground at room temperature；
Step 2：It is warming up to 600~1000 DEG C under protective atmosphere and keeps the temperature 1~6h, obtains the negative material.
Wherein, when nickel source and higher carbon nitrogen source mass ratio, carbon nanotube is longer, more intensive；When nickel source and carbon nitrogen source matter
Amount than it is lower when, carbon nanotube is more sparse；It therefore, within the above range by nickel source and the setting of carbon nitrogen source mass ratio, can be effective
Control the pattern of carbon nanotube.
A kind of improvement of preparation method as lithium ion battery negative material of the present invention, the protective atmosphere be argon gas,
At least one of nitrogen and hydrogen nitrogen mixed gas.
A kind of improvement of preparation method as lithium ion battery negative material of the present invention, the nickel source are the nitre of metallic nickel
At least one of hydrochlorate, the chloride of metallic nickel, the acetate of metallic nickel, the sulfate of metallic nickel and dicyclopentadienyl nickel.
A kind of improvement of preparation method as lithium ion battery negative material of the present invention, the carbon nitrogen source are urea, three
At least one of poly cyanamid, dicyandiamide and cyanamide.
A kind of improvement of preparation method as lithium ion battery negative material of the present invention, nickel source described in step 1 and institute
It is 1 to state carbon nitrogen source mass ratio:5.
A kind of improvement of preparation method as lithium ion battery negative material of the present invention, the speed to heat up in step 2 are
1~10 DEG C/min.Wherein, when heating rate is faster, carbon nanotube obtained is shorter；When heating rate is slower, carbon obtained is received
Mitron is longer.
The beneficial effects of the present invention are：A kind of lithium ion battery negative material of the present invention, including carbon nanotube and carbon are received
Rice piece, the surface that the carbon nanotube is distributed in the carbon nanosheet form three-dimensional conductive network structure, the carbon nanotube
Caliber is 10 ~ 100nm, and the thickness of the carbon nanosheet is 5 ~ 50 nm.Compared to other existing negative materials（Such as silicon substrate
Material, tin-based material, alloy material, transition metal oxide etc.）, the three-dimensional that the present invention is formed by carbon nanotube and carbon nanosheet leads
The negative material of electric network structure has good electro-chemical activity and characteristic electron, is capable of providing good lithium ion diffusion
Channel buffers the volume expansion occurred when removal lithium embedded so that has excellent cycle performance and height using the negative plate of the material
High rate performance.In addition, the negative material using the preparation method being pyrolyzed admittedly admittedly, has, easy to operate, economical, low energy consumption and is convenient for
The advantages of accomplishing scale production has preferable application prospect.
Description of the drawings
Fig. 1 is the SEM figures of negative material prepared by the embodiment of the present invention 1.
Fig. 2 is one of TEM figures of negative material prepared by the embodiment of the present invention 1.
Fig. 3 is the two of the TEM figures of negative material prepared by the embodiment of the present invention 1.
Fig. 4 is the XRD diagram of negative material prepared by the embodiment of the present invention 1 ~ 3.
Fig. 5 is the cycle performance figure of negative material prepared by the embodiment of the present invention 1.
Specific implementation mode
With reference to embodiment and Figure of description, the present invention is described in further detail, but the present invention
Embodiment it is without being limited thereto.
Embodiment 1
By dicyclopentadienyl nickel and melamine in mass ratio 1:2.5 mixing, and grind 1.5 hours at room temperature；Then in argon gas
800 DEG C of simultaneously insulation reaction 3 hours are heated to 5 DEG C/min under atmosphere, obtain the surface that carbon nanotube is distributed in carbon nanosheet
Form the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 40nm, draw ratio 3500:1；Carbon is received
The thickness of rice piece is 25nm.
Embodiment 2
By dicyclopentadienyl nickel and melamine in mass ratio 1:5 mixing, and grind 1.5 hours at room temperature；Then in argon gas gas
800 DEG C of simultaneously insulation reaction 3 hours are heated to 10 DEG C/min under atmosphere, obtain the surface shape that carbon nanotube is distributed in carbon nanosheet
At the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 40nm, draw ratio 2000:1；Carbon nanometer
The thickness of piece is 25nm.
Embodiment 3
By dicyclopentadienyl nickel and urea in mass ratio 1:10 mixing, and grind 1.5 hours at room temperature；Then under an argon atmosphere
800 DEG C of simultaneously insulation reaction 3 hours are heated to 5 DEG C/min, obtain the surface formation three that carbon nanotube is distributed in carbon nanosheet
Tie up the negative material of conductive network structure, wherein the caliber of carbon nanotube is 50nm, draw ratio 2500:1；Carbon nanosheet
Thickness is 20nm.
Embodiment 4
By dicyclopentadienyl nickel and urea in mass ratio 1:15 mixing, and grind 1.5 hours at room temperature；Then under an argon atmosphere
800 DEG C of simultaneously insulation reaction 3 hours are heated to 5 DEG C/min, obtain the surface formation three that carbon nanotube is distributed in carbon nanosheet
Tie up the negative material of conductive network structure, wherein the caliber of carbon nanotube is 100nm, draw ratio 1000:1；Carbon nanosheet
Thickness is 10nm.
Embodiment 5
By the nitrate of metallic nickel and dicyandiamide in mass ratio 1:10 mixing, and grind 3 hours at room temperature；Then in argon
1000 DEG C of simultaneously insulation reaction 6 hours are heated to 8 DEG C/min under gas atmosphere, obtain the table that carbon nanotube is distributed in carbon nanosheet
Face forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 10nm, draw ratio 2000:1；Carbon
The thickness of nanometer sheet is 5nm.
Embodiment 6
By the chloride of metallic nickel and cyanamide in mass ratio 1:12 mixing, and grind 0.5 hour at room temperature；Then exist
600 DEG C of simultaneously insulation reaction 1 hours are heated to 3 DEG C/min under argon gas atmosphere, carbon nanotube is obtained and is distributed in carbon nanosheet
Surface forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 20nm, draw ratio 1800:1；
The thickness of carbon nanosheet is 50nm.
Embodiment 7
By the acetate of metallic nickel and cyanamide in mass ratio 1:8 mixing, and grind 2 hours at room temperature；Then in argon
600 DEG C of simultaneously insulation reaction 5 hours are heated to 1 DEG C/min under gas atmosphere, obtain the table that carbon nanotube is distributed in carbon nanosheet
Face forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 30nm, draw ratio 1700:1；Carbon
The thickness of nanometer sheet is 30nm.
Embodiment 8
By the sulfate of metallic nickel and cyanamide in mass ratio 1:14 mixing, and grind 2.5 hours at room temperature；Then exist
700 DEG C of simultaneously insulation reaction 4 hours are heated to 7 DEG C/min under argon gas atmosphere, carbon nanotube is obtained and is distributed in carbon nanosheet
Surface forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 35nm, draw ratio 3000:1；
The thickness of carbon nanosheet is 35nm.
Embodiment 9
By the sulfate of metallic nickel, the nitrate of metallic nickel and cyanamide in mass ratio 0.5:0.5:1 mixing, and in room temperature
Lower grinding 3 hours；Then 900 DEG C of simultaneously insulation reaction 3.5 hours are heated to 5 DEG C/min under an argon atmosphere, obtain carbon and receives
The surface that mitron is distributed in carbon nanosheet forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is
40nm, draw ratio 4500:1；The thickness of carbon nanosheet is 28nm.
Embodiment 10
By the nitrate, cyanamide and dicyandiamide in mass ratio 1 of metallic nickel:5:5 mixing, and grind 3 hours at room temperature；
Then 1000 DEG C and insulation reaction 6 hours are heated to 8 DEG C/min under an argon atmosphere, obtain carbon nanotube and be distributed in carbon and receives
The surface of rice piece forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is 25nm, and draw ratio is
5000:1；The thickness of carbon nanosheet is 40nm.
Embodiment 11
By the chloride of metallic nickel, the acetate of metallic nickel, melamine and dicyandiamide in mass ratio 0.5:0.5:2.5:
2.5 mixing, and grind 1.5 hours at room temperature；Then 800 DEG C and insulation reaction 3 are heated to 5 DEG C/min under an argon atmosphere
Hour, obtain the negative material that carbon nanotube is distributed in the surface formation three-dimensional conductive network structure of carbon nanosheet, wherein carbon
The caliber of nanotube is 40nm, draw ratio 6000:1；The thickness of carbon nanosheet is 25nm.
Embodiment 12
By the nitrate of metallic nickel, the acetate of metallic nickel, melamine and urea in mass ratio 0.5:0.5:2.5:2.5
Mixing, and grind 1.5 hours at room temperature；Then 800 DEG C are heated to 5 DEG C/min under an argon atmosphere and insulation reaction 3 is small
When, obtain the negative material that carbon nanotube is distributed in the surface formation three-dimensional conductive network structure of carbon nanosheet, wherein carbon is received
The caliber of mitron is 38nm, draw ratio 6500:1；The thickness of carbon nanosheet is 32nm.
Embodiment 13
By the nitrate, cyanamide and urea in mass ratio 1 of metallic nickel:2.5:2.5 mixing, and 1.5 are ground at room temperature
Hour；Then 1000 DEG C of simultaneously insulation reaction 1.5 hours are heated to 5 DEG C/min under an argon atmosphere, obtain carbon nanotube point
Cloth forms the negative material of three-dimensional conductive network structure on the surface of carbon nanosheet, wherein the caliber of carbon nanotube is 30nm, long
Diameter ratio is 5000:1；The thickness of carbon nanosheet is 15nm.
Embodiment 14
By the nitrate of metallic nickel, the chloride of metallic nickel and urea in mass ratio 0.5:0.5:5 mixing, and at room temperature
Grinding 1.5 hours；Then 600 DEG C of simultaneously insulation reaction 3 hours are heated to 5 DEG C/min in a nitrogen atmosphere, obtain carbon nanometer
The surface that pipe is distributed in carbon nanosheet forms the negative material of three-dimensional conductive network structure, wherein the caliber of carbon nanotube is
50nm, draw ratio 5500:1；The thickness of carbon nanosheet is 35nm.
Embodiment 15
By the nitrate of metallic nickel, the chloride of metallic nickel, melamine, dicyandiamide and cyanamide in mass ratio 0.5:
0.5:1.5:1.5:2 mixing, and grind 1.5 hours at room temperature；Then 1000 DEG C are heated to 5 DEG C/min in a nitrogen atmosphere
And insulation reaction 3 hours, it obtains carbon nanotube and is distributed in the surface of carbon nanosheet and form the cathode of three-dimensional conductive network structure
Material, wherein the caliber of carbon nanotube is 40nm, draw ratio 7000:1；The thickness of carbon nanosheet is 30nm.
The negative material prepared by above-described embodiment 1 is taken to carry out SEM and TEM tests respectively, test result is shown in Fig. 1 ~ 3.
By Fig. 1 ~ 3 it is found that the carbon negative pole material of three-dimensional conductive network structure of the present invention is compared with traditional graphite cathode, carbon
Nanotube is distributed in as ion channel on the surface of carbon nanosheet, and forms three-dimensional by Covalent bonding together with carbon nanosheet
Conductive network is conducive to embedding-de- dynamic performance for improving lithium ion；And since carbon nanotube is evenly distributed in carbon nanometer
On piece, this pattern are conducive to infiltration of the electrolyte to negative material；Therefore, negative material of the present invention can be such that negative plate has excellent
Different cycle performance and high rate performance.
The negative material prepared by above-described embodiment 1 ~ 3 is taken to carry out XRD tests respectively, test result is shown in Fig. 4.
As shown in Figure 4, the XRD spectrum of negative material of the present invention shows 25oDiffraction maximum, it belongs to（002）Crystal face, without
Nickel source in proportion has no effect on the diffraction maximum position of carbon and Ni in negative material with carbon nitrogen source.
Cycle performance test is carried out using the lithium ion battery that the negative material prepared by above-described embodiment 1 is assembled into, is surveyed
Test result is shown in Fig. 5.
As shown in Figure 5, negative material of the present invention shows good cyclical stability, still kept after 300 cycles compared with
High charge/discharge capacity, therefore the negative material of the present invention has excellent cycle performance.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in above-mentioned specific implementation mode, every those skilled in the art exist
Made any conspicuously improved, replacement or modification all belongs to the scope of protection of the present invention on the basis of the present invention.This
Outside, although having used some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (8)
1. a kind of lithium ion battery negative material, it is characterised in that：Including carbon nanotube and carbon nanosheet, the carbon nanotube point
Cloth forms three-dimensional conductive network structure on the surface of the carbon nanosheet by Covalent bonding together, and the caliber of the carbon nanotube is
The thickness of 10 ~ 100nm, the carbon nanosheet are 5 ~ 50 nm.
2. lithium ion battery negative material according to claim 1, it is characterised in that：The caliber of the carbon nanotube is 30
The thickness of ~ 50nm, the carbon nanosheet are 15 ~ 35nm.
3. lithium ion battery negative material according to claim 1, it is characterised in that：The draw ratio of the carbon nanotube is
More than or equal to 1000:1.
4. a kind of preparation method of lithium ion battery negative material according to claim 1, which is characterized in that including following
Step:
Step 1：By nickel source and carbon nitrogen source in mass ratio 1:（1~15）Mixing, and 0.5~3h is ground at room temperature；The carbon nitrogen
Source is at least one of urea, melamine, dicyandiamide and cyanamide；
Step 2：It is warming up to 600~1000 DEG C under protective atmosphere and keeps the temperature 1~6h, obtains the negative material.
5. the preparation method of lithium ion battery negative material according to claim 4, it is characterised in that：The protective atmosphere
For at least one of argon gas, nitrogen and hydrogen nitrogen mixed gas.
6. the preparation method of lithium ion battery negative material according to claim 4, it is characterised in that：The nickel source is gold
Belong at least one in the sulfate and dicyclopentadienyl nickel of the nitrate of nickel, the chloride of metallic nickel, the acetate of metallic nickel, metallic nickel
Kind.
7. the preparation method of lithium ion battery negative material according to claim 4, it is characterised in that：Described in step 1
Nickel source and the carbon nitrogen source mass ratio are 1:5.
8. the preparation method of lithium ion battery negative material according to claim 4, it is characterised in that：It heats up in step 2
Speed be 1~10 DEG C/min.
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