CN106602075A - Helical carbon nanofiber/super conductive carbon black binary conductive agent and lithium ion battery electrode material - Google Patents
Helical carbon nanofiber/super conductive carbon black binary conductive agent and lithium ion battery electrode material Download PDFInfo
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- CN106602075A CN106602075A CN201710004974.0A CN201710004974A CN106602075A CN 106602075 A CN106602075 A CN 106602075A CN 201710004974 A CN201710004974 A CN 201710004974A CN 106602075 A CN106602075 A CN 106602075A
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- carbon fiber
- conductive agent
- carbon black
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- nanometer carbon
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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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a helical carbon nanofiber/super conductive carbon black binary conductive agent. The preparation method comprises the following step: acidizing helical carbon nanofibers and super conductive carbon black in mixed acid to obtain the helical carbon nanofiber/super conductive carbon black binary conductive agent. The preparation method is easy to operate, low in cost, and suitable for industrial popularization. When the provided conductive agent is applied to a lithium ion battery, the conductive agent has high conductivity, and the specific charge and discharge capacities of the lithium ion battery can be increased. The specific discharge capacity can be up to 499.9mAh.g<-1>; the specific charge capacity can be up to 490.1mAh.g<-1>; the effectivity can be up to 99.7 percent; and superior specific charge and discharge capacities are still kept after 20 cycles.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of spiral nanometer carbon fiber/superconduction carbon black binary
Conductive agent and lithium ion battery electrode material.
Background technology
Conductive agent be in order to ensure electrode has good charge-discharge performance, adds when pole piece makes conductive materials,
Play a part of to collect micro-current between active material, between active material and collector, to reduce the contact resistance of electrode,
Accelerate the rate travel of electronics, while migration rate of the lithium ion in electrode material can be also effectively improved, so as to improve electricity
The efficiency for charge-discharge of pole.
The physical parameters such as the species of conductive agent, particle diameter, decentralization and content affect very big to lithium battery.It is high using electrical conductivity
Metal as conductive agent, can make battery that high power capacity and high circulation efficiency are kept in high current charge-discharge；Conductive agent contains
Amount also has significantly impact on the performance of battery, and at most bioactive agent composition excessively is few, and capacity is low；Then poorly conductive very little, battery holds
It is also easy to produce polarization；The granularity and degree of scatter of conductive agent also has a major impact to the performance of battery.
At present, many different types of conductive agents have been occurred in that on market.For example, particle conductive agent：Acetylene black, charcoal
Black, Delanium and native graphite etc.；Fibrous conductive agent：Metallic fiber, vapor phase method grown carbon fiber and CNT etc..So
And, but generally existing a common problem to conductive agent of the prior art, i.e. charge and discharge specific capacity is poor.
The content of the invention
It is an object of the invention to provide a kind of spiral nanometer carbon fiber/superconduction carbon black binary conductive agent and lithium ion battery
Electrode material, the conductive agent good conductivity that the present invention is provided simultaneously can improve the charge and discharge specific capacity of lithium ion battery.
In order to realize foregoing invention purpose, the present invention provides technical scheme below：
The invention provides a kind of preparation method of spiral nanometer carbon fiber/superconduction carbon black binary conductive agent, comprising following
Step：
Spiral nanometer carbon fiber and superconduction carbon black are acidified in mixed acid, spiral nanometer carbon fiber/superconduction is obtained
Carbon black binary conductive agent；
The mixed acid includes nitric acid and sulfuric acid.
Preferably, a diameter of 80～150nm of the spiral nanometer carbon fiber；
The pitch of the spiral nanometer carbon fiber is 50～200nm；
The spiral shell footpath of the spiral nanometer carbon fiber is 600～700nm.
Preferably, the mass ratio of the spiral nanometer carbon fiber and superconduction carbon black is 1:(1～2).
Preferably, the volume ratio of the nitric acid and sulfuric acid is 1:(1～3).
Preferably, the time of the acidifying is 1～5 hour.
The invention provides spiral nanometer carbon fiber/superconduction charcoal that the preparation method described in a kind of above-mentioned technical proposal is obtained
Black binary conductive agent.
The invention provides spiral nanometer carbon fiber/superconduction charcoal that the preparation method described in a kind of above-mentioned technical proposal is obtained
Spiral nanometer carbon fiber described in black binary conductive agent or above-mentioned technical proposal/superconduction carbon black binary conductive agent is used as lithium-ion electric
The application of pond electrode material conductive agent.
Present invention also offers a kind of lithium ion battery electrode material, the component comprising following weight portion：
7～8 parts of electrode active material；
Spiral nanometer carbon fiber/1～2 part of superconduction carbon black binary conductive agent；
1 part of binding agent.
Preferably, the electrode active material is positive active material；
The positive active material is one or more in LiFePO4, cobalt acid lithium, LiMn2O4 and nickel cobalt manganese.
Preferably, the electrode active material is negative electrode active material；
The negative electrode active material is graphite, carbonaceous mesophase spherules, petroleum coke, thermal decomposed resins carbon, alloy type negative material
With one or more in the nitride-based negative material of lithium-containing transition metal.
The invention provides a kind of preparation method of spiral nanometer carbon fiber/superconduction carbon black binary conductive agent, spiral is received
Rice carbon fiber and superconduction carbon black are acidified in mixed acid, obtain spiral nanometer carbon fiber/superconduction carbon black binary conductive agent.
In the present invention, the acidifying can increase the quantity of the oxy radicals such as spiral nanometer carbon fiber surface hydroxyl and carboxyl, improve spiral shell
The dispersiveness of rotation carbon nano-fiber；Spiral nanometer carbon fiber fills superconduction carbon black pellet hole, can form good conductive network.
The carbon net of spiral nanometer carbon fiber has the layer structure of similar graphite, can store up lithium, interlayer of its interlamellar spacing than graphite with interlayer
Away from bigger, Li is more beneficial for+It is embedding de-.The helicoidal structure of spiral nanometer carbon fiber and big specific surface area, can absorb and
Storage electrolyte, and improve the ability of electrode opposing destruction, improve the comprehensive electrochemical of electrode material.According to embodiment
As a result understand, the conductive agent that the present invention is provided is applied to after lithium ion battery, and specific discharge capacity is up to 499.9mAhg-1, charge
Specific capacity is up to 490.1mAhg-1, efficiency still maintains excellent discharge and recharge ratio 20 times later up to 99.7%, in circulation
Capacity.
Description of the drawings
Fig. 1 is schemed by the embodiment of the present invention using 0.2 μm of SEM of spiral nanometer carbon fiber；
Fig. 2 is schemed by the embodiment of the present invention using the 200nm SEM of spiral nanometer carbon fiber；
Fig. 3 is schemed by the embodiment of the present invention using the 50nm SEM of spiral nanometer carbon fiber；
Fig. 4 is front 20 specific discharge capacities of embodiment of the present invention difference conductive agent；
Fig. 5 is the first charge-discharge curve of embodiment of the present invention difference conductive agent；
Fig. 6 is HCNf and Super P with 0:The VA characteristic curve of battery during 1 mixing；
Fig. 7 is HCNf and Super P with 1:The VA characteristic curve of battery during 2 mixing；
Fig. 8 is HCNf and Super P with 1:The VA characteristic curve of battery during 1 mixing；
Fig. 9 is HCNf and Super P with 2:The VA characteristic curve of battery during 1 mixing；
Figure 10 is HCNf and Super P with 1:The VA characteristic curve of battery during 0 mixing；
Figure 11 is the AC impedance curve of the battery that embodiment of the present invention difference conductive agent is obtained.
Specific embodiment
The invention provides a kind of preparation method of spiral nanometer carbon fiber/superconduction carbon black binary conductive agent, comprising following
Step：
Spiral nanometer carbon fiber and superconduction carbon black are acidified in mixed acid, spiral nanometer carbon fiber/superconduction is obtained
Carbon black binary conductive agent；
The mixed acid includes nitric acid and sulfuric acid.
The present invention does not have particular/special requirement to the source of the spiral nanometer carbon fiber, using well known to those skilled in the art
Spiral nanometer carbon fiber, can be specifically commercially available spiral nanometer carbon fiber.In the present invention, the spiral nanometer
The diameter of carbon fiber is preferably 80～150nm, most preferably more preferably 90～130nm, 100～120nm.In the present invention,
The pitch of the spiral nanometer carbon fiber is preferably 50～200nm, most preferably more preferably 80～180nm, 100～150nm.
In the present invention, the spiral shell footpath of the spiral nanometer carbon fiber is preferably 600～700nm, more preferably 620～680nm, most preferably
For 640～660nm.
In the present invention, the spiral nanometer carbon fiber is preferably first carrying out dried process using front.In the present invention, institute
State dried process to be preferably vacuum dried.In the present invention, the vacuum drying vacuum is preferably -0.07～-0.1MPa,
Can be specifically -0.07MPa, -0.08MPa, -0.09MPa or -1MPa.In the present invention, the vacuum drying temperature is excellent
Elect 100～120 DEG C, more preferably 105～115 DEG C, most preferably 108～113 DEG C as；The vacuum drying time is preferably
6～10 hours, can be specifically 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
The present invention does not have particular/special requirement to the source of the conductive black, using conduction well-known to those skilled in the art
Carbon black, it is specific such as commercially available conductive black.In the present invention, the conductive black is preferably the special close high TIMCAL of Switzerland
Superconduction carbon black, model：SUPER P.
The present invention preferably first will be again acidified after spiral nanometer carbon fiber and the mixing of superconduction carbon black.In the present invention, institute
The mixing for stating spiral nanometer carbon fiber and superconduction carbon black is preferably ball milling mixing.In the present invention, the ball milling mixing preferably exists
Carry out in planetary ball mill.In the present invention, the material of the ball milling abrading-ball is preferably agate；The ball of the mechanical milling process
Material ratio preferably 1:(1～3), can be specifically 1:1、1:2 or 1:3.In the present invention, the abrading-ball be preferably divided into greatly,
Middle or small three size grades, the quantity ratio preferably 1 of the large, medium and small three-level abrading-ball:3:2.In the present invention, the ball milling
Rotating speed be preferably 4000～5000rpm, most preferably more preferably 4200～4800rpm, 4400～4600rpm；The ball
The time of mill is preferably 10～20 minutes, more preferably 12～18 minutes, most preferably 14～16 minutes.In the present invention, institute
State ball milling and enable to the more uniform of spiral nanometer carbon fiber and the mixing of superconduction carbon black, and also can be fine by spiral nanometer carbon
Dimension is interrupted, and reduces the draw ratio of spiral nanometer carbon fiber, improves the dispersiveness of spiral nanometer carbon fiber.
In the present invention, the mass ratio of the spiral nanometer carbon fiber and superconduction carbon black is preferably 1:(1～2), more preferably
For 1:(1.2～1.8), most preferably 1:(1.4～1.6).
In the present invention, the mass concentration of the nitric acid is preferably 97～99%, specifically can for 97%, 98% or
99%.In the present invention, the mass concentration of the sulfuric acid is preferably 97～99%, can be specifically 97%, 98% or 99%.
In the present invention, the volume ratio of the nitric acid and sulfuric acid is preferably 1:(1～3), more preferably 1:(1.5～2.5), most preferably
1:(1.8～2.3).The present invention does not have to the mixture of the spiral nanometer carbon fiber and superconduction carbon black with the relative amount of mixed acid
There is particular/special requirement, the mixture of spiral nanometer carbon fiber and superconduction carbon black is immersed in mixed acid.
In the present invention, the acidifying is preferably carried out under ultrasound condition；The frequency of the ultrasound is preferably 30～
40KHz, more preferably 32～38KHz, most preferably 34～36KHz；The time of the acidifying is preferably 1～5 hour, specifically
It can be 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.In the present invention, the acidifying is preferably carried out at room temperature.At this
In invention, the acidifying can increase the quantity of the oxy radicals such as spiral nanometer carbon fiber surface hydroxyl and carboxyl, improve spiral
The dispersiveness of carbon nano-fiber.
The product that preferred pair acidifying of the present invention is obtained is post-processed, and obtains spiral nanometer carbon fiber/superconduction carbon black binary
Conductive agent.In the present invention, the post processing is preferably comprised the steps of：
Acidizing product to obtaining is washed, and obtains solid product；
The solid product is dried, spiral nanometer carbon fiber/superconduction carbon black binary conductive agent is obtained.
In the present invention, detergent used by the washing is preferably water.Concrete operations of the present invention to the washing do not have
Particular/special requirement, acidizing product can be washed to neutrality.
In the present invention, the drying to the solid product is preferably vacuum dried.In the present invention, the vacuum drying
Vacuum be preferably -0.07～-0.1MPa, can be specifically -0.07MPa, -0.08MPa, -0.09MPa or -1MPa.
In the present invention, the vacuum drying temperature is preferably 100～120 DEG C, more preferably 105～115 DEG C, most preferably 108～
113℃；The vacuum drying time is preferably 3～5 hours, can be specifically 3 hours, 4 hours or 5 hours.
The invention provides spiral nanometer carbon fiber/superconduction charcoal that the preparation method described in a kind of above-mentioned technical proposal is obtained
Black binary conductive agent.
The invention provides a kind of spiral nanometer carbon fiber described in above-mentioned technical proposal/superconduction carbon black binary conductive agent conduct
The application of lithium ion battery electrode material conductive agent.
Present invention also offers a kind of lithium ion battery electrode material, the component comprising following weight portion：
7～8 parts of electrode active material；
Spiral nanometer carbon fiber/1～2 part of superconduction carbon black binary conductive agent；
1 part of binding agent.
On the basis of the content of binding agent, the lithium ion battery electrode material that the present invention is provided includes 1 part of binding agent.This
The bright species to the binding agent does not have special restriction, using lithium ion battery electrode material well known to those skilled in the art
With binding agent；In the present invention, the binding agent is preferably carboxymethylcellulose calcium, LA132, LA133, polyvinyl alcohol and gathers
One or more in tetrafluoroethene.
On the basis of 1 part of binding agent, the lithium ion battery electrode material that the present invention is provided includes 7～8 parts of electrode activity things
Matter, preferably 7.2～7.8 parts, more preferably 7.4～7.6 parts.
In the present invention, the electrode active material can be positive active material, when the electrode active material is for just
During the active material of pole, the lithium ion battery electrode material is positive electrode；The positive active material be preferably LiFePO4,
One or more in cobalt acid lithium, LiMn2O4 and nickel cobalt manganese.The present invention does not have special limit to the source of the positive active material
System, using the above-mentioned concrete material of anode material for lithium-ion batteries well known to those skilled in the art.
In the present invention, the electrode active material can also be negative electrode active material, when the electrode active material is
During negative electrode active material, the lithium ion battery electrode material is negative material；The negative electrode active material be preferably graphite, in
Between in phase carbosphere, petroleum coke, thermal decomposed resins carbon, alloy type negative material and the nitride-based negative material of lithium-containing transition metal
One or more.
On the basis of 1 part of binding agent, the lithium ion battery electrode material that the present invention is provided includes 1～2 part of spiral nanometer carbon
Fiber/superconduction carbon black binary conductive agent, preferably 1.2～1.8 parts, more preferably 1.4～1.6 parts.In the present invention, the spiral shell
Rotation carbon nano-fiber/superconduction carbon black binary conductive agent is the spiral nanometer carbon fibre that preparation method described in above-mentioned technical proposal is obtained
Spiral nanometer carbon fiber described in dimension/superconduction carbon black binary conductive agent or above-mentioned technical proposal/superconduction carbon black binary conductive agent,
This is no longer repeated.
The present invention does not have particular/special requirement to the preparation method of the electrode material, using well-known to those skilled in the art
The preparation method of electrode material is prepared.
The present invention is provided spiral nanometer carbon fiber/superconduction carbon black binary conductive agent with reference to embodiment and lithium ion
The electrode material of battery is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
By spiral nanometer carbon fiber in vacuum drying chamber, it is vacuum dried 8 hours under 110 DEG C, -0.1MPa.
By spiral nanometer carbon fiber (HCNf) and superconduction carbon black (Super P) with 1:2 mass ratio is planetary in 4500rpm
Ball milling 15 minutes in ball mill.
Ball milling rear screw carbon nano-fiber/superconduction carbon black is immersed in into the nitration mixture of nitric acid and sulfuric acid, and (volume ratio is 1:2) it is molten
It is ultrasonically treated 3 hours with the supersonic frequency of 35KHz in liquid.
It is washed with deionized to neutrality, is vacuum dried 4 hours under 115 DEG C, -0.1MPa, obtains spiral nanometer carbon fine
Dimension/superconduction carbon black binary conductive agent.
Embodiment 2
By spiral nanometer carbon fiber in vacuum drying chamber, it is vacuum dried 6 hours under 100 DEG C, -0.0.08MPa.
By spiral nanometer carbon fiber (HCNf) and superconduction carbon black (Super P) with 1:1 mass ratio is planetary in 4600rpm
Ball milling 18 minutes in ball mill.
Ball milling rear screw carbon nano-fiber/superconduction carbon black is immersed in into the nitration mixture of nitric acid and sulfuric acid, and (volume ratio is 1:1) it is molten
It is ultrasonically treated 2 hours with the supersonic frequency of 35KHz in liquid.
It is washed with deionized to neutrality, is vacuum dried 5 hours under 115 DEG C, -0.1MPa, obtains spiral nanometer carbon fine
Dimension/superconduction carbon black binary conductive agent.
Comparative example 1
By spiral nanometer carbon fiber in vacuum drying chamber, it is vacuum dried 6.5 hours under 105 DEG C, -0.0.9MPa.
By spiral nanometer carbon fiber (HCNf) and superconduction carbon black (Super P) with 0:1 mass ratio is planetary in 4200rpm
Ball milling 15 minutes in ball mill.
Ball milling rear screw carbon nano-fiber/superconduction carbon black is immersed in into the nitration mixture of nitric acid and sulfuric acid, and (volume ratio is 1:3) it is molten
It is ultrasonically treated 4 hours with the supersonic frequency of 40KHz in liquid.
It is washed with deionized to neutrality, is vacuum dried 4.5 hours under 115 DEG C, -0.1MPa, obtains spiral nanometer carbon
Fiber/superconduction carbon black binary conductive agent.
Comparative example 2
By spiral nanometer carbon fiber in vacuum drying chamber, it is vacuum dried 7 hours under 120 DEG C, -0.1MPa.
By spiral nanometer carbon fiber (HCNf) and superconduction carbon black (Super P) with 2:1 mass ratio is planetary in 4900rpm
Ball milling 20 minutes in ball mill.
Ball milling rear screw carbon nano-fiber/superconduction carbon black is immersed in into the nitration mixture of nitric acid and sulfuric acid, and (volume ratio is 1:2) it is molten
It is ultrasonically treated 3 hours with the supersonic frequency of 38KHz in liquid.
It is washed with deionized to neutrality, is vacuum dried 5 hours under 110 DEG C, -0.1MPa, obtains spiral nanometer carbon fine
Dimension/superconduction carbon black binary conductive agent.
Comparative example 3
By spiral nanometer carbon fiber in vacuum drying chamber, it is vacuum dried 7.5 hours under 100 DEG C, -0.1MPa.
By spiral nanometer carbon fiber (HCNf) and superconduction carbon black (Super P) with 1:0 mass ratio is planetary in 5000rpm
Ball milling 20 minutes in ball mill.
Ball milling rear screw carbon nano-fiber/superconduction carbon black is immersed in into the nitration mixture of nitric acid and sulfuric acid, and (volume ratio is 1:2) it is molten
It is ultrasonically treated 2 hours with the supersonic frequency of 35KHz in liquid.
It is washed with deionized to neutrality, is vacuum dried 4.5 hours under 115 DEG C, -0.1MPa, obtains spiral nanometer carbon
Fiber/superconduction carbon black binary conductive agent.
Scan image (SEM, VEGA3, the Czech of spiral nanometer carbon fiber used by above-described embodiment
TESCAN companies) as shown in Figures 1 to 3, wherein, Fig. 1 is used 0.2 μm of SEM of spiral nanometer carbon fiber by the embodiment of the present invention
Figure；Fig. 2 is schemed by the embodiment of the present invention using the 200nm SEM of spiral nanometer carbon fiber；Fig. 3 is used by the embodiment of the present invention
The 50nm SEM figures of spiral nanometer carbon fiber.From Fig. 1～3, the spiral of the spiral nanometer carbon fiber that the present embodiment is used
Structural integrity, without breakage.
The conductive agent for preparing is assembled into battery by the present invention, carries out various tests, involved battery component：With reality
It is GND conductive agent to apply the conductive agent that example 1～2 and comparative example 1～3 obtain, with graphite (AGP-8, Shenzhen Bei Teruixin
Energy and material limited company) be negative active core-shell material, the pure lithium of metal (99.9% high-purity lithium piece) be anode electrode, electrolyte
(LiPF6-EC/DEC) LBC305-01 (Shenzhen Xinzhoubang Technology Co., Ltd), assembles CR2032 button cells (2032 types
Battery case).
Battery testing parameter setting：Battery testing LAND battery test systems, model CT2001A (the blue electricity in Wuhan City
Electronics limited company), charging/discharging voltage scope be 0.005～3.0V, current density 50mAh/g.Circulating battery volt-ampere is special
Property test using Shanghai occasion China electrochemical workstation CH1660E, frequency be 100mHZ～100kHZ, voltage amplitude is 5mV.
Obtain being tested as follows after the battery for assembling：
Cycle performance is tested：20 circulations are carried out under 0.1C, HCNf additions is investigated to battery charging and discharging specific capacity
Affect, as a result as shown in table 1 and Fig. 4～5.Wherein, table 1 for first with the 20th charging and discharging capacity and cycle efficieny；Fig. 4 is
Front 20 specific discharge capacities of embodiment of the present invention difference conductive agent；Fig. 5 is filling first for embodiment of the present invention difference conductive agent
Discharge curve.
Table 1 first with the 20th charging and discharging capacity and cycle efficieny
It is the purer spiral nanometer carbon fiber conductive agent of conductive agent that the present invention is claimed, pure super from table 1 and Fig. 4～5
Lead carbon black conductive agent and other conductive agents have more excellent charging and discharging capacity, specific discharge capacity is up to 499.9mAhg-1,
Charge specific capacity is up to 490.1mAhg-1, efficiency still maintains excellent charge and discharge 20 times later up to 99.7%, in circulation
Electric specific capacity.
VA characteristic curve is tested：As shown in Fig. 6～10.Wherein, Fig. 6 is HCNf and Super P with 0:Battery during 1 mixing
VA characteristic curve；Fig. 7 is HCNf and Super P with 1:The VA characteristic curve of battery during 2 mixing；Fig. 8 be HCNf with
Super P are with 1:The VA characteristic curve of battery during 1 mixing；Fig. 9 is HCNf and Super P with 2:The volt-ampere of battery during 1 mixing
Characteristic curve；Figure 10 is HCNf and Super P with 1:The VA characteristic curve of battery during 0 mixing.
The invertibity of the electrochemical reaction of material can pass through the peak value electricity of relatively more each cyclic voltammetry curve oxidation and reduction
Stream and current potential situation are obtained：Peak point current difference is bigger, and the difference between reduction potential and oxidizing potential is less, illustrates the pole of material
Change situation is less, good reversibility.
From Fig. 6～10, spiral nanometer carbon fiber and Super P ratio 1:When 2 (scheme of embodiment 1),
From the beginning of electrode is circulated from second, reduction peak is symmetric with oxidation peak and peak shape is consistent, and reduction peak and oxidation peak-to-peak value are electric
Position is essentially identical, reduces irreversibility.When the ratio of spiral nanometer carbon fiber and Super P is 1:2 add as conductive agent
When, half-cell has good invertibity.
AC impedance curve is tested：The AC impedance curve (range of scanned frequencies 0.01Hz～100kHz) of its battery is as schemed
Shown in 11, Figure 11 is the AC impedance curve of the battery that embodiment of the present invention difference conductive agent is obtained.As shown in Figure 11, exchange resistance
Anti- curve is made up of the semicircle of a high frequency region and the line segment of low frequency range.Intercept on transverse axis for electrode material resistance, HCNf
With the ratio of Super P 0:1、1:2、1:1、2:1、1:Resistance value when 0 be respectively 225 Ω, 150 Ω, 200 Ω, 175 Ω,
325Ω.1:During 2 this ratio, slope of a curve is very big, shows that the conductive diffusion coefficient of negative material is big, conducts electricity very well,
Charge-discharge velocity is high.
As seen from the above embodiment, the invention provides a kind of spiral nanometer carbon fiber/superconduction carbon black binary conductive agent
Preparation method, will be acidified after spiral nanometer carbon fiber and the mixing of superconduction carbon black in mixed acid, obtain spiral nanometer carbon fine
Dimension/superconduction carbon black binary conductive agent.Acidifying of the present invention can increase spiral nanometer carbon fiber surface hydroxyl and carboxyl etc. and contain
The quantity of oxygen groups, improves the dispersiveness of spiral nanometer carbon fiber.Spiral nanometer carbon fiber fills superconduction carbon black pellet hole, can
Form good conductive network.The carbon net of spiral nanometer carbon fiber has the layer structure of similar graphite, can store up lithium with interlayer, its
Interlamellar spacing is bigger than the interlamellar spacing of graphite, is more beneficial for Li+It is embedding de-.The helicoidal structure of spiral nanometer carbon fiber and big ratio
Surface area, can absorb and store electrolyte, and improve the ability that electrode opposing is destroyed, and improve the comprehensive electrochemistry of electrode material
Performance.It can be seen from the result of embodiment, the conductive agent that the present invention is provided is applied to after lithium ion battery, and specific discharge capacity is reachable
499.9mAh·g-1, charge specific capacity is up to 490.1mAhg-1, efficiency still protects for 20 times later up to 99.7%, in circulation
Hold excellent charging and discharging capacity.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of spiral nanometer carbon fiber/superconduction carbon black binary conductive agent, comprises the steps of：
Spiral nanometer carbon fiber and superconduction carbon black are acidified in mixed acid, spiral nanometer carbon fiber/superconduction carbon black is obtained
Binary conductive agent；
The mixed acid includes nitric acid and sulfuric acid.
2. preparation method according to claim 1, it is characterised in that a diameter of the 80 of the spiral nanometer carbon fiber～
150nm；
The pitch of the spiral nanometer carbon fiber is 50～200nm；
The spiral shell footpath of the spiral nanometer carbon fiber is 600～700nm.
3. preparation method according to claim 1 and 2, it is characterised in that the spiral nanometer carbon fiber and superconduction carbon black
Mass ratio be 1:(1～2).
4. preparation method according to claim 1, it is characterised in that the volume ratio of the nitric acid and sulfuric acid is 1:(1～
3)。
5. the preparation method according to claim 1 or 4, it is characterised in that the time of the acidifying is 1～5 hour.
6. the spiral nanometer carbon fiber that the preparation method described in Claims 1 to 5 any one is obtained/superconduction carbon black binary is conductive
Agent.
7. spiral nanometer carbon fiber described in claim 6/superconduction carbon black binary conductive agent is led as lithium ion battery electrode material
The application of electric agent.
8. a kind of lithium ion battery electrode material, the component comprising following weight portion：
7～8 parts of electrode active material；
Spiral nanometer carbon fiber described in claim 6/1～2 part of superconduction carbon black binary conductive agent；
1 part of binding agent.
9. lithium ion battery electrode material according to claim 8, it is characterised in that the electrode active material is positive pole
Active material；
The positive active material is one or more in LiFePO4, cobalt acid lithium, LiMn2O4 and nickel cobalt manganese.
10. lithium ion battery electrode material according to claim 8, it is characterised in that the electrode active material is negative
Pole active material；
The negative electrode active material is graphite, carbonaceous mesophase spherules, petroleum coke, thermal decomposed resins carbon, alloy type negative material and contains
One or more in the nitride-based negative material of lithium transition-metal.
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