CN109659563A - A kind of carbon nanotube silicon combined conductive agent and its preparation method and application - Google Patents
A kind of carbon nanotube silicon combined conductive agent and its preparation method and application Download PDFInfo
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- CN109659563A CN109659563A CN201811572368.XA CN201811572368A CN109659563A CN 109659563 A CN109659563 A CN 109659563A CN 201811572368 A CN201811572368 A CN 201811572368A CN 109659563 A CN109659563 A CN 109659563A
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- carbon nanotube
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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 discloses a kind of carbon nanotube silicon combined conductive agent, the carbon nanotube including fibre structure；And it is carried on the graininess nano-silicon of the carbon nano tube surface, the weight ratio of the nano-silicon and the carbon nanotube is 5:1~10:1.Suitable for lithium ion anode and negative electrode material, the usage amount of carbon nanotube is reduced, while improving its performance as conductive agent.
Description
Technical field
The present invention relates to conductive agent fields, and in particular to a kind of carbon nanotube silicon combined conductive agent and preparation method thereof
And application.
Background technique
Lithium ion secondary battery is a kind of novel high-energy secondary cell, with specific capacity is big, discharge voltage is high and steady, low
Warm nature can good, environmental-friendly, safety, the advantages that service life is long, self discharge is faint.The above-mentioned advantage of lithium ion secondary battery, causes
The attention and favor of countries in the world scientists, to promote the fast development of lithium ion secondary battery.Since the advent of the world, it is short
Between short recent two decades, it is a series of that lithium ion secondary battery has just been widely used in mobile phone, laptop, digital equipment etc.
In portable electronic product；Especially in recent years in the vehicles, aerospace, military affairs such as some key areas such as electric cars
The exploitation and application of the large-scale lithium ion secondary battery in equal fields are just unfolded in high gear.
The electrode reaction of lithium ion secondary battery includes the transmission of electronics and the transmission of ion, this requires that electrode will have
Good electric conductivity guarantees the unimpeded of electron propagation ducts；Necessary some pore structures, electrolyte of attracting deposit guarantee ion transmission
It is smooth.Only reach the requirement of these two aspects, just can guarantee that electrode active material has higher utilization rate and good circulation
Stability.The anode of lithium ion secondary battery generallys use stratiform cobalt acid lithium, lithium nickelate, lithium nickel cobalt dioxide or spinel lithium manganate etc.
As active material.But the poorly conductive of these active materials itself, therefore, when forming electrode, often using in activity
Conductive agent is added in substance to improve its electric conductivity.The cathode of lithium ion secondary battery is frequently with graphite type material, such as: sheet stone
Ink, graphite microspheres and modified graphite microballoon etc..These materials itself have preferable electric conductivity, in principle unnecessary addition
Conductive agent improves its electric conductivity, but a small amount of conductive agent, which is added, can improve the contact resistance between negative electrode active material, make electricity
The electric conductivity at extremely each position is consistent；Especially some fibre shape conductive agent can also improve negative electrode material bonding stability and
The pore structure for increasing electrode improves the cyclical stability of electrode in favor of electrolyte of attracting deposit.
Graphite, acetylene black and carbon fiber it is conductive it is good, density is small, stable structure and chemical stability characteristic, often
It is used as the conductive agent of lithium ion secondary battery anode material.If charge/discharge speed is slow, these conductive agents can be played
Performance.But if being big multiplying power fast charging and discharging, biggish polarization can be generated using the electrode of these conductive agents, leads to active matter
The utilization rate of matter declines.In order to improve the performance of lithium ion battery, the exploitation of novel conductive agent is extremely urgent, and the above problem is this
The problem of field urgent need to resolve.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carbon nanotube silicon combined conductive agents, are suitable for lithium ion
Anode and negative electrode material, reduce the usage amount of carbon nanotube, while improving its performance as conductive agent.
In order to solve the above technical problem, the present invention provides scheme be: a kind of carbon nanotube silicon combined conductive agent,
Carbon nanotube including fibre structure；And
It is carried on the graininess nano-silicon of the carbon nano tube surface, the weight ratio of the nano-silicon and the carbon nanotube
For 5:1~10:1.
Further, the carbon nanotube is multi-walled carbon nanotube, the caliber of the carbon nanotube is 3~100nm,
Length is 0.6~200um.
Further, the partial size of the nano-silicon is 5~100nm.
The application further provides a kind of preparation method of above-mentioned carbon nanotube silicon combined conductive agent, including with
Lower step:
S1, in mass ratio 5:1~10:1 weigh carbon nanotube and nano-silicon, form mixture, by dispersing agent and described mixed
It closes object to be dispersed in organic solvent, wherein the dispersing agent accounts for 12.5~25wt% of the mixture, and lasting dispersion is straight
To the slurry for forming carbon nanotube and nano-silicon total content is 5.6~6.2wt%；
S2, the slurry is ground, obtains carbon nanotube silicon combined conductive agent.
Further, the dispersing agent is macromolecule dispersing agent.
Further, the dispersing agent is polyvinylpyrrolidone or polyvinyl alcohol.
Further, being dispersed under vacuum condition in the step S1.
Further, the carbon nanotube silicon combined conductive agent apply in lithium ion secondary battery anode material or
Ion secondary battery cathode material lithium；
The lithium ion secondary battery anode material is LiCoO2、LiPFeO4、LiNiO2、LiCoxNi1-xO2, spinel manganese
Sour lithium LiMn2O4And the LiMn2O4 added with cobalt acid lithium, wherein 0 < x < 1；
The ion secondary battery cathode material lithium be flake graphite, modified natural graphite microballoon, artificial graphite microspheres, in
Between phase carbosphere or carbon fiber.
Beneficial effects of the present invention: it is suitable for lithium ion anode and negative electrode material, reduces the usage amount of carbon nanotube, together
When improve its performance as conductive agent.
Detailed description of the invention
Fig. 1 is the SEM image of conductive agent in the embodiment of the present invention 1.
Fig. 2 is the lithium ion secondary battery anode material LiCoO using different conductive agents2Under the discharge-rate of 1C, put
The relation curve of capacitance and cycle-index.
Fig. 3 is the ion secondary battery cathode material lithium graphite using different conductive agents under 1.5C discharge-rate, electric discharge
The relation curve of capacity and cycle-index.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with
It more fully understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Case study on implementation 1
The N-Methyl pyrrolidone (NMP) of 4.69kg is weighed as solvent, polyvinylpyrrolidone (PVP) 60g is added, point
After dissipating, nano-silicon 75g is added, carbon nanotube (CNTs) 175g is added after low speed disperses and carries out high-speed stirred, until shape
The slurry for being 6.2% at solid content.
The slurry is carried out grinding processing using sand mill or colloid mill, obtains conductive agent.
The SEM image of the conductive agent is as shown in Figure 1, it can be seen that nano-silicon is uniformly dispersed in carbon nanotube.
Take the anode active material of lithium ion secondary battery LiCoO of 5.08g2, 0.88g slurry sample, 0.08g's is just very viscous
Agent PVDF to be tied, is added in NMP, disperse 240~300 minutes in vacuum high speed disperser, viscosity controls 4000~
6000cp (is adjusted) by the additional amount of NMP, 150 meshes discharging, in 16 μm of thickness of aluminium foil (specification 350x0.016mm)
60~80 μm of upper film is dried in 100 DEG C of vacuum drying ovens, and the electrode slice of φ 16 is made in punching.With 16 μm of thickness
Cellgard2400 is diaphragm, LiPF6Solution is that electrolyte forms simulated battery, is measured in 1C electric discharge with 141mAh/g's
Specific discharge capacity reaches 95% when 0.2C.
In order to make it easy to understand, the application also further provides embodiment 2~4, specific preparation process and embodiment 1
It is similar, and electrode slice preparation, simulated battery assembling and test are carried out to embodiment 2~4 referring to the technique of embodiment 1.
In addition, the application also further provides two reference examples, reference examples 1 and reference examples 2, out together as control
Method in sample reference implementation example 1 carries out electrode slice preparation to reference examples 1,2, simulated battery assembles and test, wherein embodiment 2
~4 and reference examples 1,2 in every component proportion, and specific test result is as shown in table 1.
Table 1
Table 1 indicates the composition and positive electrode LiCoO when conductive agent preparation2Form the chemical property of electrode.
It can be seen from Table 1 that, in 1C electric discharge, being used as and being led using not the embodiment of the present application in the embodiment of the present application
When the specific discharge capacity of electric agent is compared to using individual carbon nanotube or nano-silicon as conductive agent, obtain significantly mentioning
It is high.
As shown in Fig. 2, wherein Mix indicates that using the application, as conductive agent, CNTs is indicated to be used as using carbon nanotube and be led
Electric agent, AB indicates to do conductive agent using acetylene black, as seen from Figure 1, using the anode material of lithium battery of the application, capacitance
It is better than carbon nanotube with cyclical stability and acetylene black does conductive agent.
Case study on implementation 6
Conductive agent preparation method is the same as case study on implementation 1.
Take 2.8g lithium-ion negative pole active material modified graphite microballoon HMSG, 2.94g electrocondution slurry, 0.14g binder
SBR, 0.04g thickener CMC, are added in NMP, disperse 240~300 minutes in vacuum high speed disperser, and viscosity control exists
4000~5000cp (is adjusted) by the additional amount of NMP, and the discharging of 150 meshes, in 16 μm of thickness of aluminium foils, (specification is
60~80 μm of film on 350x0.016mm) are dried in 100 DEG C of vacuum drying ovens, and the electrode slice of φ 16 is made in punching.With thickness
16 μm of Cellgard2400 is diaphragm, LiPF6Solution is that electrolyte forms simulated battery, and measuring has in 1.5C electric discharge
The specific discharge capacity of 269mAh/g reaches 87% when 0.5C.
In addition, the application also further provides embodiment 7~10, specific preparation process is similar to Example 1, and
Electrode slice preparation, simulated battery assembling and test method are carried out referring to the technique of embodiment 6, embodiment 7~10 is carried out respectively
Test.
In addition, the application also further provides two reference examples, reference examples 3 and reference examples 4, equally as control
Method in reference implementation example 6 carries out electrode slice preparation to reference examples 3,4, simulated battery assembles and test, wherein embodiment 7
~10 and reference examples 3,4 in every component proportion, and specific test result is as shown in table 2.
Table 2
Table 2 indicates the chemical property of composition and negative electrode material graphite HMSG composition electrode when prepared by conductive agent.
As can be seen from Table 2, using the ion cathode material lithium of the application, in 1.5C electric discharge, specific discharge capacity is obtained
Apparent raising.
As shown in figure 3, Mix indicates to be used as conductive agent using the application, CNTs indicates to use carbon nanotube as conductive agent,
Conductive agent is not used without expression, as seen from Figure 3, discharge capacity and cyclical stability of the electrode under the discharge-rate of 1.5C
It is better than carbon nanotube and does not have to conductive agent.
Nano-silicon has the characteristics that purity is high, partial size is small, is evenly distributed, and large specific surface area, high surface and pine dress
Density is low.Although itself dispersibility is not very ideal, with carbon nanotube it is compound after, the agglomeration of the two is obvious good
Turn, so that dispersion performance is significantly promoted.Nano-silicon larger problem of volume change during deintercalate lithium ions simultaneously utilizes
Compound is formed after carbon nanotube is compound and has buffered its volume change, is maintained material structure and is stablized.
Si powder is dispersed in the dispersible carriers such as carbon pipe, graphite, forms two-phase or multiphase system of stable and uniform.?
In charge and discharge process, Si is the activated centre of electrochemical reaction, although carbon carrier also has a removal lithium embedded performance, it is main rise from
The effect of son, the transmission channel of electronics and structural support.Si/C composite material is due to being dispersed in elasticity and volume for nano-silicon
In the small carbon parent of effect, the volume change of electrode not only can be reduced, reduce electrode surface solid electrolyte film since volume becomes
It is destroyed caused by change, and silicon is wrapped in carbon, can prevent the reunion of nano-silicon active body, to improve the circulation of material
Stability.
In addition, the addition of nano-silicon, advantageously reduces the usage amount of carbon nanotube, significantly reduces cost.
Find that the caliber of carbon nanotube has considerable influence in the present invention.Generally, caliber is bigger, and the length of carbon pipe is got over
It is short.Effect is best when the carbon nanotube of 10~50nm of caliber is used as conductive agent, because of its caliber, moderate length, relative to caliber
For bigger carbon nanotube, pipe number is more, for, the longer carbon nanotube of length smaller relative to caliber, mutual
Winding is slighter, is easier to disperse.So advantageously forming effective conductive network.Only has effective conductive mesh
Network could act on each other together with nano-silicon, form a kind of synergistic effect.
The positive electrode that the present invention can be used includes: cobalt acid lithium, LiFePO4, lithium nickelate, lithium nickel cobalt dioxide, spinel manganese
Sour lithium, LiMn2O4 and added with spinel lithium manganate of cobalt acid lithium etc..Negative electrode material includes: graphite, flake graphite, spherolith
Ink, modified graphite microballoon (MSG), carbonaceous mesophase spherules (MCMB) etc..
The application method of CNTs-Si combined conductive agent is with other conductive agents in the present invention, and the material of total good conductivity can be with
The additive amount of moderate reduction combined conductive agent.Such as positive pole material of lithium cobalt acid, additive amount 3%；If spinel lithium manganate,
Additive amount is 7%, even more；LiFePO4, additive amount will reach 15%.
The electric conductivity of negative electrode material is generally preferable, and the additive amount of combined conductive agent is generally 1~3%.Conductive agent additional amount
Very few, conductive network is not intensive enough；Conductive agent additional amount is excessive, and waste is not said, while increasing the dosage of binder, reduces
The specific capacity of electrode.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (8)
1. a kind of carbon nanotube silicon combined conductive agent, which is characterized in that the carbon nanotube including fibre structure；And
It is carried on the graininess nano-silicon of the carbon nano tube surface, the nano-silicon and the weight ratio of the carbon nanotube are 5:
1~10:1.
2. as described in claim 1, which is characterized in that the carbon nanotube is multi-walled carbon nanotube, the carbon nanotube
Caliber be 3~100nm, length be 0.6~200um.
3. carbon nanotube silicon combined conductive agent as described in claim 1, which is characterized in that the partial size of the nano-silicon is
5~100nm.
4. a kind of preparation method of carbon nanotube silicon combined conductive agent according to any one of claims 1 to 3, special
Sign is, comprising the following steps:
S1, in mass ratio 5:1~10:1 weigh carbon nanotube and nano-silicon, mixture are formed, by dispersing agent and the mixture
Dispersed in organic solvent, wherein the dispersing agent accounts for 12.5~25wt% of the mixture, and lasting dispersion is until shape
The slurry for being 5.6~6.2wt% at carbon nanotube and nano-silicon total content；
S2, the slurry is ground, obtains carbon nanotube silicon combined conductive agent.
5. preparation method as claimed in claim 4, which is characterized in that the dispersing agent is macromolecule dispersing agent.
6. preparation method as claimed in claim 5, which is characterized in that the dispersing agent is polyvinylpyrrolidone or polyethylene
Alcohol.
7. preparation method as claimed in claim 4, which is characterized in that in the step S1, dispersed under vacuum condition.
8. a kind of application of carbon nanotube silicon combined conductive agent according to any one of claims 1 to 3, feature exist
In the carbon nanotube silicon combined conductive agent is applied in lithium ion secondary battery anode material or lithium ion secondary battery cathode
Pole material；
The lithium ion secondary battery anode material is LiCoO2、LiPFeO4、LiNiO2、LiCoxNi1-xO2, spinel lithium manganate
LiMn2O4And the LiMn2O4 added with cobalt acid lithium, wherein 0 < x < 1；
The ion secondary battery cathode material lithium is flake graphite, modified natural graphite microballoon, artificial graphite microspheres, interphase
Carbosphere or carbon fiber.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048123A (en) * | 2019-04-29 | 2019-07-23 | 苏州聚龙能源科技有限公司 | Silicon/carbon/graphite in lithium ion batteries alkene few-wall carbon nanotube waterborne conductive agent and preparation method thereof |
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| CN106684342A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silicon-carbon nanotube microspheres and metal lithium compound thereof, and preparation method and application |
| CN110048123A (en) * | 2019-04-29 | 2019-07-23 | 苏州聚龙能源科技有限公司 | Silicon/carbon/graphite in lithium ion batteries alkene few-wall carbon nanotube waterborne conductive agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684342A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silicon-carbon nanotube microspheres and metal lithium compound thereof, and preparation method and application |
| CN110048123A (en) * | 2019-04-29 | 2019-07-23 | 苏州聚龙能源科技有限公司 | Silicon/carbon/graphite in lithium ion batteries alkene few-wall carbon nanotube waterborne conductive agent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048123A (en) * | 2019-04-29 | 2019-07-23 | 苏州聚龙能源科技有限公司 | Silicon/carbon/graphite in lithium ion batteries alkene few-wall carbon nanotube waterborne conductive agent and preparation method thereof |
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Application publication date: 20190419 |