CN109860538A - A kind of lithium battery silicon-carbon cathode slurry and preparation method thereof, lithium ion battery - Google Patents
A kind of lithium battery silicon-carbon cathode slurry and preparation method thereof, lithium ion battery Download PDFInfo
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Abstract
The present invention provides a kind of lithium battery silicon-carbon cathode slurry, the component including following mass fraction: 10~30 parts of silicon-carbon；70~90 parts of graphite；First 1~3 part of conductive agent；Second 0.1~1 part of conductive agent；3~5 parts of binder；40~70 parts of water, wherein binder is polyacrylic acid, and the second conductive agent is the linear carbon nanotube of overlength, contains dispersing agent sodium carboxymethylcellulose in carbon nanotube.The present invention prepares a kind of stabilization and has reversible silicon-carbon cathode slurry, after the completion of slurry preparation, after standing about 0.5 hour, slurry tends towards stability, in g., jelly-like is similar to, slurry viscosity will not increase as time increases, and placement for a long time will not occur settling and lamination；Before coating, slurry is dispersed, slurry restores flow regime again；After standing about 0.5 hour, slurry is in be conducive to store for a long time similar to g., jelly-like again, does not influence subsequent Painting effect, surface density stabilization, levelling.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly, to a kind of lithium battery silicon-carbon cathode slurry and its preparation
Method, lithium ion battery.
Background technique
At present, with lithium electricity industry to high capacity, long-life batteries demand it is growing, people are to lithium ion battery
More stringent requirements are proposed for performance.Capacity of lithium ion battery is relatively low to have become a bottleneck for restricting battery industry development, finds
The positive electrode and negative electrode material of more height ratio capacity have become a developing direction in battery material field.
Current commercialized negative electrode material is carbon, and since lithium ion battery commercialization, the research of carbon material obtains length
The progress of foot, actual specific capacity improve quickly, already close to the theoretical value of 372mAh/g, it is very difficult to there is the space of promotion again.Silicon tool
It has many good qualities, rich reserves on the earth, cost is relatively low, environmental sound.Silicon theoretical specific capacity (4200mAh/ with higher
And lower intercalation potential, thus be a kind of very promising lithium ion battery negative material g).Silicon-carbon cathode slurry
Due to the expansion characteristics of silicon carbon material, suitable binder need to be used, a kind of stable silicon-carbon cathode slurry is prepared, to rear
Continuous coating plays an important role, and then is conducive to improve battery core consistency.
Existing graphite cathode slurry system comparative maturity, mainly include cathode main material, conductive agent, binder, aqueous solvent,
Wherein conductive agent conduction feature is dot type, and binder uses sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR), and CMC is viscous
Knot agent plays thickening and slurry stabilization in the slurry, and SBR plays cementation.Existing graphite cathode slurry preparation is completed initial
State, slurry tend towards stability, but under static conditions as time increases, and slurry will appear the wild effects such as sedimentation, layering,
Can have an adverse effect to coating.
Summary of the invention
In view of this, the present invention is directed to propose a kind of lithium battery silicon-carbon cathode slurry and preparation method thereof, lithium ion battery,
To solve the problem of that slurry will appear sedimentation, layering to existing negative electrode slurry as time increases under static conditions.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of lithium battery silicon-carbon cathode slurry, the component including following mass fraction:
10~30 parts of silicon-carbon；
70~90 parts of graphite；
First 1~3 part of conductive agent；
Second 0.1~1 part of conductive agent；
3~5 parts of binder；
40~70 parts of water,
Wherein, binder is polyacrylic acid, and the second conductive agent is the linear carbon nanotube of overlength, contains in carbon nanotube and divides
Powder sodium carboxymethylcellulose.
By adopting the above technical scheme, sodium carboxymethylcellulose plays the role of dispersing Nano carbon tubes.
Further, the draw ratio of carbon nanotube is (15000~3000): 1, diameter is 1~100nm, carboxymethyl cellulose
Plain sodium and the mass ratio of carbon nanotube are (4~5): 100.
Further, carbon nanotube is single-walled carbon nanotube, and the first conductive agent is one of SP or VGCF or two
The combination of kind.
By adopting the above technical scheme, pipe good conductivity of the pipe electric conductivity of single than multi-walled carbon nanotube, performance
It is more excellent.
The preparation method of above-mentioned lithium battery silicon-carbon cathode slurry the following steps are included:
Step 1: by 1~3 part of the first conductive agent, 0.1~1 part of the second conductive agent, 1.5~2.5 parts of binder, water 20~
35 parts of dispersions obtain the first mixture；
Step 2: 10~30 parts of silicon-carbon are added in above-mentioned first mixture, dispersion obtains the second mixture；
Step 3: 70~90 parts of graphite are added in above-mentioned second mixture, dispersion obtains third mixture；
Step 4: adding 1.5~2.5 parts of binder, 20~35 parts of water in above-mentioned third mixture, and dispersion obtains silicon-carbon
Negative electrode slurry.
Further, it is 15~20m/s that linear velocity is dispersed in step 1, and dispersion temperature is 20~30 DEG C, and jitter time is
100~150min.
Further, it is 8~10m/s that linear velocity is dispersed in step 2, and dispersion temperature is 20~30 DEG C, jitter time 30
~60min.
Further, it is 8~10m/s that linear velocity is dispersed in step 3, and dispersion temperature is 20~30 DEG C, and jitter time is
100~150min.
Further, it is 8~10m/s that linear velocity is dispersed in step 4, and dispersion temperature is 20~30 DEG C, jitter time 60
~90min.
Further, fineness≤30 μm for the silicon-carbon cathode slurry that step 4 obtains, the viscosity of silicon-carbon cathode slurry are
2000~4000mpa*s.
Using the lithium ion battery of above-mentioned lithium battery silicon-carbon cathode slurry.
Compared with the existing technology, lithium battery silicon-carbon cathode slurry of the present invention and preparation method thereof, lithium ion battery
It has the advantage that
The present invention under the basis of silicon carbon material, using corpuscular first conductive agent and with the second conductive agent group of line style
Close, binder polyacrylic acid simultaneously accurately compounds each component, prepare a kind of stabilization and there is reversible silicon-carbon cathode slurry,
After the completion of slurry preparation, after standing about 0.5 hour, slurry tends towards stability, and in g., jelly-like is similar to, slurry viscosity will not be with
The increase of time and increase, placing will not occur settling and lamination for a long time；Before coating, slurry is dispersed, is starched
Material restores flow regime again, and the viscosity of slurry also keeps stablizing within a certain period of time；After standing about 0.5 hour, slurry is in class again
It is similar to g., jelly-like, is conducive to store for a long time, does not influence subsequent Painting effect, surface density stabilization, levelling.
Detailed description of the invention
Fig. 1 is the viscosity change of lithium battery silicon-carbon cathode slurry of the present invention；
Fig. 2 is the molecular structure of sodium carboxymethylcellulose；
Fig. 3 is the molecular structure of polyacrylic acid；
Fig. 4 is the invertibity schematic diagram of lithium battery silicon-carbon cathode slurry of the present invention.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to examples and drawings, the present invention will be described in detail.
Embodiment 1
A kind of lithium battery silicon-carbon cathode slurry, the component including following mass fraction: 12 parts of silicon-carbon；80 parts of graphite；First
2 parts of conductive agent；Second 0.3 part of conductive agent；5 parts of binder；50 parts of water,
Wherein, binder is polyacrylic acid, and the first conductive agent is SP, and the second conductive agent is the linear carbon nanotube of overlength,
The draw ratio of carbon nanotube is 1.5 ten thousand~30,000, and diameter is 1~100nm.Sodium carboxymethylcellulose, carboxylic are mixed in carbon nanotube
Sodium carboxymethylcellulose pyce and the mass ratio of carbon nanotube are 4:100~5:100.
Embodiment 2
The preparation method of lithium battery silicon-carbon cathode slurry described in embodiment 1, comprising the following steps:
Step 1: by 2 parts of the first conductive agent, 0.3 part of the second conductive agent, 2.5 parts of binder, 25 parts of water dispersions, discrete lines
Speed is 15m/s, and dispersion temperature is 25 DEG C, and jitter time 120min obtains the first mixture；
Step 2: 12 parts of silicon-carbon are added in above-mentioned first mixture, dispersion, dispersion linear velocity is 8m/s, dispersion temperature
It is 25 DEG C, jitter time 30min obtains the second mixture；
Step 3: 80 parts of graphite are added in above-mentioned second mixture, dispersion, dispersion linear velocity is 8m/s, dispersion temperature
It is 25 DEG C, jitter time 120min obtains third mixture；
Step 4: adding 2.5 parts of binder, 25 parts of water, dispersion in above-mentioned third mixture, and dispersion linear velocity is 8m/
S, dispersion temperature are 25 DEG C, and jitter time 60min obtains silicon-carbon cathode slurry, the fineness of obtained silicon-carbon cathode slurry≤
30 μm, the viscosity of silicon-carbon cathode slurry is 2000~4000mpa*s.
The present invention is under the basis of silicon carbon material, using binder polyacrylic acid and corpuscular first conductive agent and line style
The second conductive agent combination, prepare a kind of lithium battery silicon-carbon cathode slurry.This slurry does not need other spies after the completion of preparation
Different agitating device can keep stablizing, will not be caused by and stand for a long time in certain time slurry, and slurry settles, point
Layer phenomenon, influences subsequent Painting effect.
The slurry solids content is 40% or so, basic with ordinary graphite negative electrode slurry under the original state purchased
Unanimously, slurry enters stable state about after 0.5h, and in g., jelly-like is similar to, the viscosity of slurry will not increase as time increases
Add, phenomena such as sedimentation, layering will not occur in slurry.Most importantly slurry of the invention has invertibity, before coating, passes through
Dispersion restores flow regime similar to the slurry of g., jelly-like, and the viscosity of slurry also keeps stablizing (see Fig. 1) within a certain period of time,
Slurry can smooth 150 mesh of mistake sieve.After standing about 0.5h, slurry is in have negative different from ordinary graphite similar to g., jelly-like again
The characteristic of pole slurry is conducive to store for a long time, does not influence subsequent Painting effect, surface density stabilization, levelling.
The principle that slurry of the invention can be formed: the second conductive agent is the linear carbon nanotube of overlength, and good conductivity contains admittedly
Measure low, carbon nanotube is mixed with dispersing agent sodium carboxymethylcellulose, sodium carboxymethylcellulose (structural formula is shown in Fig. 2) and polyacrylic acid
(structural formula is shown in Fig. 3) is physical crosslinking by hydrogen bond action, along with the draw ratio of carbon nanotube is big, enhances polyacrylic acid
Pseudoplastic behavior, formed be similar to g., jelly-like slurry, to make slurry long-time stable under this state.
Slurry of the invention has reversible principle: soft-agglomerated particle is formd according to experimental phenomena carbon nanotube, it is soft
Agglomerated particle can be opened by stirring.As shown in figure 4, starting to stir or increase shear rate, carbon nanotube order increases
Add, the viscosity of slurry reduces.Stop stirring or reduce shear rate, carbon nanotube order reduces, and the viscosity of slurry increases.
Carbon nanotube needs the regular hour from orderly restoring unordered, and there are time-dependences for the viscosity of the slurry under low sheraing.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of lithium battery silicon-carbon cathode slurry, it is characterised in that: the component including following mass fraction:
10~30 parts of silicon-carbon；
70~90 parts of graphite；
First 1~3 part of conductive agent；
Second 0.1~1 part of conductive agent；
3~5 parts of binder；
40~70 parts of water,
Wherein, binder is polyacrylic acid, and the second conductive agent is the linear carbon nanotube of overlength, is mixed with carboxylic first in carbon nanotube
Base sodium cellulosate.
2. lithium battery silicon-carbon cathode slurry according to claim 1, it is characterised in that: the draw ratio of carbon nanotube is
(15000~3000): 1, diameter is 1~100nm, and the mass ratio of sodium carboxymethylcellulose and carbon nanotube is (4~5): 100.
3. lithium battery silicon-carbon cathode slurry according to claim 1, it is characterised in that: carbon nanotube is single
Pipe, the first conductive agent are one of SP or VGCF or two kinds of combination.
4. the according to claim 1, preparation method of lithium battery silicon-carbon cathode slurry described in 2,3 any one, it is characterised in that:
The following steps are included:
Step 1: by 1~3 part of the first conductive agent, 0.1~1 part of the second conductive agent, 1.5~2.5 parts of binder, 20~35 parts of water
Dispersion obtains the first mixture；
Step 2: 10~30 parts of silicon-carbon are added in above-mentioned first mixture, dispersion obtains the second mixture；
Step 3: 70~90 parts of graphite are added in above-mentioned second mixture, dispersion obtains third mixture；
Step 4: adding 1.5~2.5 parts of binder, 20~35 parts of water in above-mentioned third mixture, and dispersion obtains silicon-carbon cathode
Slurry.
5. the preparation method of lithium battery silicon-carbon cathode slurry according to claim 4, it is characterised in that: disperse in step 1
Linear velocity is 15~20m/s, and dispersion temperature is 20~30 DEG C, and jitter time is 100~150min.
6. the preparation method of lithium battery silicon-carbon cathode slurry according to claim 4, it is characterised in that: disperse in step 2
Linear velocity is 8~10m/s, and dispersion temperature is 20~30 DEG C, and jitter time is 30~60min.
7. the preparation method of lithium battery silicon-carbon cathode slurry according to claim 4, it is characterised in that: disperse in step 3
Linear velocity is 8~10m/s, and dispersion temperature is 20~30 DEG C, and jitter time is 100~150min.
8. the preparation method of lithium battery silicon-carbon cathode slurry according to claim 4, it is characterised in that: disperse in step 4
Linear velocity is 8~10m/s, and dispersion temperature is 20~30 DEG C, and jitter time is 60~90min.
9. the preparation method of lithium battery silicon-carbon cathode slurry according to claim 4, it is characterised in that: what step 4 obtained
Fineness≤30 μm of silicon-carbon cathode slurry, the viscosity of silicon-carbon cathode slurry are 2000~4000mpa*s.
10. a kind of lithium ion battery using lithium battery silicon-carbon cathode slurry described in claim 1-3 any one.
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| CN111313005A (en) * | 2020-02-29 | 2020-06-19 | 江西远东电池有限公司 | Silicon-carbon negative electrode slurry mixing method |
| CN111313005B (en) * | 2020-02-29 | 2021-02-26 | 江西远东电池有限公司 | Silicon-carbon negative electrode slurry mixing method |
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| CN114335690A (en) * | 2021-12-31 | 2022-04-12 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN114335690B (en) * | 2021-12-31 | 2024-09-24 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN114927679A (en) * | 2022-03-07 | 2022-08-19 | 上海兰钧新能源科技有限公司 | Lithium battery negative electrode slurry and preparation method thereof |
| CN114927679B (en) * | 2022-03-07 | 2024-05-24 | 上海兰钧新能源科技有限公司 | Lithium battery negative electrode slurry and manufacturing method thereof |
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